Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149

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Journal of the Taiwan Institute of Chemical Engineers

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

Green production of bioactive components from herbal origins

through one-pot oxidation/polymerization reactions and application as
a corrosion inhibitor for mild steel in HCl solution
Motahhare Keramatinia, Bahram Ramezanzadeh∗, Mohammad Mahdavian
Department of Surface Coatings and Corrosion, Institute for Color Science and Technology, P.O. Box 16765-654, Tehran, Iran

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

Article history: Biopolymers such as polydopamine and polyserotonin are effective corrosion inhibitors for the acidic-
Received 20 June 2019 induced corrosion of steel. Despite the excellent corrosion inhibition activity of these compounds,
Revised 25 September 2019
they are not cost-effective and readily available in a large scale. In this study, for the first time, a
Accepted 9 October 2019
cheap and easy methodology was followed for obtaining the modified Nettle extract including the oxi-
Available online 24 October 2019
dized/dimerized bio-active products such as serotonin and histamine. The Nettle extract (NTE) and oxi-
Keywords: dized Nettle extract components (ONTE) were characterized by Fourier transform infrared spectroscopy
Bio-active products (FT-IR), scanning electron microscope (SEM), UV-visible spectroscopy, and thermal gravimetric analysis
Oxidized Nettle extract (ONTE) (TGA). The NTE was oxidized under the alkaline condition at an ambient temperature. Finally, 600 ppm
Corrosion inhibitor NTE and ONTE were separately added to 1 mol L−1 HCl solution to reduce the steel corrosion rate. The
EIS corrosion inhibition activity of the utilized inhibitors was assessed by electrochemical impedance spec-
troscopy (EIS) and potentiodynamic polarization (PDP) techniques. The surface features were examined by
SEM, atomic force microscope (AFM), and water contact angle test. The obtained results displayed that
the ONTE inhibitor resulted in the higher inhibition efficiency than the NTE. The maximum inhibition ef-
ficiency, i.e. 93.40%, was obtained in the case of the acidic solution inhibited by 600 ppm ONTE after 1.5 h.
Results of the polarization test and surface analyses proved the ONTE inhibitor components adsorption
on the active metal sites, especially on the anodic areas. In studying of effects of temperature on the cor-
rosion rate of mild steel the positive effect of ONTE on the mild steel corrosion mitigation was noticed.
It was shown that the adsorption of the inhibitor on the metal surface obeyed the Langmuir isotherm in
both physisorption and chemisorption forms.
© 2019 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Diluted HCl and H2 SO4 solutions (i.e. 0.5 and 1 mol L−1 ) have
been extensively used in the acid pickling/descaling processes to
eliminate the oxides, scales, oils and other organic/inorganic con-
taminations from the metal/alloy surface [1,2]. However, even di-
luted acidic solutions are strong enough to cause undesirable met-
als and alloys corrosion. The acidic solutions corrosiveness degree
can be reduced by adding small quantities of the corrosion in-
hibitors, which is a practical and cost-effective approach compared
to other protection methods [3–8]. Several parameters, including
the degree of effectiveness, cost, easy availability, and being eco-
friendly should be taken into consideration when choosing an in-
hibitor [9,10]. Unfortunately, despite the high corrosion inhibition
∗
Corresponding author.
E-mail addresses: ramezanzadeh-bh@icrc.ac.ir, ramezanzadeh@aut.ac.ir
Ramezanzadeh).
activity most of the conventional corrosion inhibitors are not eco-
friendly materials. So, this matter forced the researchers to find
non-toxic inhibitive compounds [9,11].
In this regard, eco-friendly materials such as surfactants [12,13]
and ionic liquids (ILs) [14,15] are introduced. Kowsari et al. stud-
ied the imidazolium-based ionic liquid inhibition impact toward
the steel corrosion in 1 mol L−1 HCl media. The polarization re-
sults revealed that in the presence of 100 mg/L imidazolium-based
ILs, the steel corrosion in HCl solution was noticeably mitigated
by a mixed inhibition mechanism [16]. The synthesis of an am-
photeric surfactant and a di-cationic surfactant based on pyridine
was studied by Hegazy et al. After that, the inhibition effects of
the obtained inhibitors were studied on a series of metals in acidic
solutions. Since the structures of these components include many
double bonds and heteroatoms, they can chemically interact with
the steel surface and retard the corrosive ions access to the sur-
face [17]. Recently, biopolymers have been noticed as a novel class
(B. of fortified eco-friendly corrosion inhibitors. These polymers are

https://doi.org/10.1016/j.jtice.2019.10.005
1876-1070/© 2019 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149
Fig. 1. Chemical structure of some important biomolecules ingredients existed in the Nettle extract.
naturally present in all vivid organisms. Therefore, they are called
advance renewable and biodegradable materials with few adverse
effects on the environment and human health compared to other
materials [18–20].
Charitha et al. reported 90% inhibition efficiency for the cor-
rosion control of 6061 Al-alloy in the presence of a carbohydrate
biopolymer [21]. Sodium alginate was applied as an inhibitor for
corrosion control of various metals. Jmiai et al. showed 83% inhi-
bition at a concentration of 0.1 mg/L on copper in 1 mol L−1 hy-
drochloric acid medium [22]. In another research, the Arabino-
galactan (AG) biopolymer inhibition effect on the carbon steel cor-
rosion in 1 mol L−1 HCl was analyzed by polarization, EIS, and
gravimetric measurements. The inhibition efficiency was promoted
by increasing AG concentration [23]. Solomon et al. utilized sev-
eral dextran biopolymers with different molecular weights as ef-
fective corrosion inhibitors. They found that the dextran biopoly-
mer with a weight of 10 0,0 0 0–20 0,0 0 0 daltons led to the inhibi-
tion efficiency equal to 51.38% for steel in the H2 SO4 solution [24].
Despite the good inhibition activity of most of the biopoly-
mers against acidic-induced corrosion of metals, they are almost
expensive. So the researchers have decided to provide biopolymers
from natural sources. In this regard, a group of biopolymers has
been obtained from the biomass feedstock. The biomass feedstock
can be derived from the animal and herbal origins [25,26]. There
are too many herbal biomass materials which have been utilized
as green corrosion inhibitors [27,28]. For instance, the extract of
khillah seeds [29] and 5-hydroxytryptophan were used as effective
inhibitors for steel corrosion in the acidic environment. At the prior
research, the effects of inhibitor concentration and in the later the
effects of temperature and concentration were studied [30]. The
extract of the Nettle leaves in HCl, NaCl, H2 SO4 solutions was used
as a green inhibitor in several studies [31,32]. According to litera-
ture, it is noticed that the Nettle leaves extract is a green source of
different bioactive components like histamine, serotonin, quercetin,
rutin, tannins, kaempferol, formic acid, and salicylic acid [33–35].
The mentioned organic compounds are active inhibitive reagents
135
for effective metal corrosion mitigation in the acidic solution due
to the presence of lots of heteroatoms in their structures [36,37].
The chemical structures of a few of these bioactive components are
presented in Fig. 1.
Like dopamine, serotonin is a neurotransmitter existed in the
nervous system. Nako et al. reported that the serotonin can be
polymerized in the presence of an alkaline buffer solution simi-
lar to the polydopamine synthesis methodology [38,39]. Serotonin
is also existed in the human body and plays different roles [40].
Quercetin is a flavonoid that has anti-cancer properties. Also, his-
tamine is a biogenic amine that can be found in the fermented
pieces of stuff and beverages [41,42]. The presence of even low
amounts of these components in the Nettle leaves makes it a good
corrosion inhibitor. Various approaches are employed to promote
the effectiveness of the inhibitors derived from the plant biomass.
Ramezanzadeh et al. amended the inhibition efficiency of the Net-
tle leaves extract to 95% in neutral chloride-containing solution in
the presence of cerium cations [43]. In another research, the ele-
phant grass extract was mixed with several halides such as am-
monium chloride and potassium iodide to improve its inhibition
performance [44].
In this study, for the first time, the bio-active corrosion in-
hibitors were obtained through oxidation modification of the Net-
tle leaves extract components (like serotonin and histamine). FT-IR,
TGA, and UV–Vis analyses were applied to verify the ONTE chem-
ical structure. Finally, the electrochemical analyses, including EIS
and polarization, were conducted to verify the corrosion inhibition
effect of ONTE for the mild steel samples submerged in 1 mol L−1
hydrochloric acid solution.
2. Experimental
2.1. Raw materials
St-12 mild steel coupons with a dimension of 3 cm × 5 cm ×
0.2 cm were used as a working electrode. HCl 37% and tris
136 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149
(hydroxymethyl) aminomethane were procured from Merck Co.
and Sigma-Aldrich Co., respectively. The Nettle leaves were pre-
pared from the Northern regions of Iran.
2.2. Sample preparation
2.2.1. Nettle extract preparation procedure
At first, the Nettle leaves were dried in the ambient tempera-
ture. Then, the powdered leaves were added to the deionized wa-
ter (DI) and heated at 70 °C for 4 h. Finally, the solution was filtered
and the obtained pasty material was heated at 60 °C for 24 h. The
obtained residue was used as a primary source of biopolymer com-
pounds.
2.2.2. Synthesis of ONTE
The Nettle extract powder was first dissolved in DI water
(7 mg/mL) for one day. Then, the tris buffer was added to the
solution until reaching a pH of 9.14 [38]. The reaction continued
for five days at room temperature. At this condition, the oxidized
forms of the bioactive components like serotonin and histamine
can be obtained. However, the other parts of the Nettle leave ei-
ther remained unchanged in soluble form or destroyed in the al-
kaline media. The ONTE collected by the centrifugation (20 0 0 rpm)
was washed by DI water for several times to remove the unreacted
components. Finally, the ONTE powder was obtained by drying at
55 °C in a vacuum.
2.3. Characterization
2.3.1. Sample characterization
The NTE and ONTE chemical structures were assessed by FT-IR
analysis. Measurements were performed on a Perkin Elmer (Fron
pier model) spectrophotometer. The wavenumber range for the ob-
tained spectra was 40 0–40 0 0 cm−1 . The UV-visible test was carried
out by Optizen 3220 instrument on the highly diluted solutions in-
cluding NTE and ONTE. The morphologies of NTE and ONTE pow-
ders were inspected using a scanning electron microscope (SEM).
Gravimetric measurements were executed on a Perkin Elmer TGA
analyzer (model Pyris 6) under a nitrogen atmosphere and at the
heating rate of 10 °C min−1 from 25 to 600 °C.
2.3.2. Surface characterization
In order to inspect the surface topography of the steel plates
dipped in the acidic solutions without and with inhibitors an AFM
instrument of Dualscope DS 95–200, DME was employed. Also, a
comparison of the surface chemistry of the samples was done by
determining the water contact angle values on the uninhibited and
inhibited steel samples by an OCA 15 plus test instrument at 25 °C.
DI was used as the test liquid. The morphology of the plate surface
was analyzed by Phillips XL 30 model SEM instrument. Also, the
structure of the film deposited on the metal surface in the best-
inhibited sample was investigated by FT-IR and grazing incidence
X-ray diffraction (GIXRD). GIXRD pattern was obtained by PHILIPS
XRD PW1730 model (Cu/kα radiation, λ = 1.54A).
2.3.3. Electrochemical experiments
The inhibition behavior of 600 ppm NTE and ONTE on the steel
corrosion mitigation in 1 mol L−1 HCl solution was evaluated by EIS
and polarization tests. Polarization measurements were conducted
in the potential range of ± 250 mV around the open circuit poten-
tial (OCP) at a scan rate of 1 mV/s. EIS measurements were car-
ried out in an electrochemical cell consisting of saturated Calomel
(SC), mild steel, and platinum as a reference, working and counter
electrodes, respectively. The frequency range of 10−2 –104 Hz with
10 mV step potential was selected for EIS measurements. The OCP
values of the steel samples immersed in the HCl solutions without
and with inhibitors (600 ppm) were recorded by ProsKit MT-1860
manual voltmeter during 420 min.
2.3.4. Weight loss measurements
In this method, the steel panels were submerged in the 1 HCl
solutions without and with inhibitors. At first, the panels were
polished with emery papers (grade 40 0–10 0 0) and subsequently
cleaned with acetone. Then, they were weighed and then sub-
merged in the acidic solutions (1 M HCl solution). The panels were
removed from the solution after 0.5, 1, 1.5, and 2 h and dried. Af-
ter that, the weights of the plates were recorded again. Finally,
the corrosion rate and inhibition efficiency values were calculated
through Eqs. (1) and 2.
m0 − m
η= × 100 (1)
m0
W
Corrosion rate = (2)
A.t
Where m0 is the weight loss of the blank sample that was im-
mersed in the acid solution without inhibitor and m is the weight
loss of the samples dipped in the acidic solution with inhibitor. A is
the surface area in m2 and t is the immersion time.
3. Results and discussion
3.1. Characterization of NTE and ONTE samples
The FT-IR spectra of the NTE and ONTE samples are shown in
Fig. 2. The Nettle extract components contain aromatic rings and
several functional groups like C–O, O–H, C–N, and C–H [45]. In the
FT-IR spectrum of the Nettle extract, the O–H stretching vibration
is observed at 3417 cm−1 . Also, the observable shoulder in the ab-
sorption region of over 30 0 0 cm−1 can be attributed to the N–H
bond stretching. The peaks appeared in 1650 cm−1 and 1450 cm−1
wavenumbers suggest the C=C bond in the aromatic ring. The ab-
sorption band observed at 1130 cm−1 is referred to the C–O or C–N
stretching vibration. The peaks detected in the FT-IR spectrum of
NTE confirm the presence of some important functional groups of
the Nettle leaves components such as histamine, serotonin, rutin,
and quercetin [46].
In the presence of basic buffer (tris) the serotonin and quercetin
can be oxidized according to the following reactions: (1) dimeriza-
tion/trimerization of the serotonin and histamine molecules, and
(2) oxidation of the serotonin and quercetin molecules [37,42–45].
The oxidation mechanism is complicated; however, some possible
structures are presented in Fig. 3. Observation of the absorption
bands related to C=O at 1667 cm−1 and 1790 cm−1 reveals that the
Nettle extract components were successfully oxidized. The other
absorption peaks appeared at 873.52 cm−1 , 1076 cm−1 , 1425 cm−1 ,
2924 cm−1 , 3147 cm−1 , and 3418 cm−1 are attributed to the C–H
bending vibration in the aromatic ring, C–N or C–O stretching, C=C
aromatic, alkyl C–H stretching, aromatic C–H stretching and O–H,
respectively.
The UV–vis absorption spectra of the NTE and ONTE samples in
l mol L−1 HCl are shown in Fig. 4. As can be seen, the bright brown
color of NTE changed to bright gray after the oxidation process.
The UV absorption peaks observed at 202 nm and 300 nm are re-
lated to the π -π ∗ and n-π ∗ electronic transitions, respectively. The
π -π ∗ transition is represented by C=C double bonds in the aro-
matic rings existed in the Nettle extract. It seems that the peaks
shifted to lower wavelengths in the ONTE structure which is at-
tributed to the oxidation of the organic structures in the oxidized
Nettle extract. The presence of several C=O functional groups in
the ONTE components has made a hypsochromic shift in the n-
π ∗ transition. Additionally, the peak related to the n-π ∗ transition
 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149 137

Fig. 2. FT-IR spectra (a) NTE and (b) ONTE.

H
N

Dimerized serotonin
OH
H 2N HO

NH 2
N
H

HO O NH2
H 2N HO
HO 5 days, O
OH ambient temperature, Oxidized serotonin
N
HN
O
O
and basic pH H
N
NH 2
NH OH N N
HO

N N Dimerized histamine
H H

O
O

O O

O Oxidized quercetin
O O

Nettle extract Oxidized Nettle extract

Fig. 3. Possible structures of ONTE in effect of oxidation on the alkaline PH.

in the NTE sample is broader than the ONTE sample. Whereas a
partly sharp peak observed in 252.2 nm is related to C=O in the
ONTE sample. It corroborates that the absorbance took place in the
higher wavelengths in the NTE sample.
The morphology of the NTE and ONTE samples is shown in
Fig. 5 (a and b). It is evident from the SEM images that the NTE
particles have an irregular morphology and are almost in aggre-
gated form. The ONTE sample shows regular morphology probably
due to the polymerization or dimerization of the NTE components
like serotonin [47].
TGA measurements were performed to study the thermal sta-
bility and the amount of the residual components in the NTE and
ONTE samples, as shown in Fig. 6. Results show that the thermal
decomposition behavior of the NTE sample is different from ONTE.
138 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149

Fig. 4. UV–Visible spectra corresponded to NTE and ONTE extract.

Fig. 5. SEM images in two magnification of (a1 ,a2 ) NTE and (b1 ,b2 ) ONTE powders.

There are four decomposition steps in the TGA plot of the NTE
sample, while three mass loss steps were seen in the plot of the
oxidized sample. The first decomposition stage fell out in the range
of 35–120 °C, referring to the loss of the physically captured water.
The second mass loss step occurred in the range of 120–200 °C for
the NTE sample, indicating structural water removal. This weight
loss step cannot be seen in the TGA plot of the ONTE sample. The
most mass loss magnitude (about 33%) occurred within the tem-
perature range of 20 0–40 0 °C is attributed to the OH functional
group decomposition [48]. Results reveal that the degradation of
the functional groups of the ONTE sample occurred at higher tem-
peratures compared with NTE one. According to the DTG plots, it
is obvious that the thermal degradation rate in the NTE sample is
higher than the ONTE sample. This observation reveals the greater
thermal stability of the ONTE sample than NTE one. According to
the literature, the pyrolysis of the OH functional groups occurs at
lower temperatures compared to the C=O groups, whereas the de-
composition of amines, carbonyl, and carboxyl groups took place
 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149
Fig. 6. TGA plots corresponded to the NTE and ONTE powders.
Table 1
Results obtained from TGA plots of the NTE and ONTE samples.
Sample Weight loss%
35–120 °C 120–200 °C
NTE 6.5% 8.5%
ONTE 6.5% 1%
at the higher temperatures. Therefore, the greater thermal stability
of the ONTE sample than NTE can be attributed to the presence of
more thermally stable C=O functional groups in the ONTE sample
than NTE one. The weight loss occurred in the temperature range
of 40 0–60 0 °C is attributed to the aromatic rings decomposition. In
addition, the residual weight percentage in the ONTE sample is 9%
higher than the NTE one, confirming the greater thermal stability
of the former. Table 1 presents the TGA data briefly.
3.2. Electrochemical measurements
The NTE and ONTE corrosion inhibition activities against the
steel corrosion in the acidic media were studied by EIS and polar-
ization tests. The OCP values changes for the panels exposed to the
1 mol L−1 HCl dilutions without and with 600 ppm NTE and ONTE
at different immersion times are presented in Fig. 7. Fig. 7 shows
that as the immersion time elapsed the OCP of the blank sam-
ple went in a negative direction. On the other hand, the OCP of
the samples subjected to the NTE and ONTE containing solutions
shifted to less negative values compared to the blank sample. The
increase of OCP in the presence of NTE and ONTE inhibitors can be
attributed to the adsorption of the inhibitors on the anodic sites of
metal.
Fig. 8 shows the Nyquist and Bode diagrams of the mild steel
panels exposed to 1 mol L−1 HCl solutions in the absence and pres-
ence of NTE and ONTE. Since the acid pickling process duration
is almost too short, the measurement was done in a short time.
An only one-time constant is observed in the curves of all sam-
ples. This observation indicates that the corrosion reaction is un-
der charge transfer control. Therefore, the impedance plots were
fitted by a simple equivalent circuit. The obtained electrochemical
parameters including total resistance (Rt ), which is the summation
of charge transfer resistance (Rct ) and inhibitor film resistance (Rf ),
non-ideal double-layer capacitance (Y0 ), phase shift coefficient (n),
and the computed capacitance values are shown in Table 2. The
capacitance was computed according to the Eq. (3) [49], where Rt
139
Total remained
mass (%) at 600 °C
20 0–40 0 °C >400 °C
31.7% 9.5% 45.23%
27% 11.7% 54.86%
is the total resistance and Rs is the solution resistance
1 1 
1 (n−1)/n
Cdl = Y0 /n + (3)
Rs Rt
Results show that as the immersion time elapsed the Cdl de-
creased, indicating the double layer thickness increment due to the
water molecules replacement with the inhibitor molecules at the
steel/electrolyte interface [50].
The Nyquist semicircular shape remained unchanged after the
addition of 600 ppm NTE and ONTE to 1 mol L−1 HCl olution. In
other words, the corrosion mechanism did not change after the ad-
dition of the inhibitors [51]. By comparing the diameters of the
semicircles in the blank sample, NTE, and ONTE plots, one can
be clearly seen is that the ONTE could efficiently retard the iron
dissolution rate. Results reveal that the charge transfer resistance
has significantly increased in the presence of green inhibitors. The
most increase in impedance was observed for the ONTE sample.
This result confirms that the Nettle leaves extract corrosion in-
hibition activity was improved through an oxidation modification
mechanism.
According to Table 2 and Fig. 8 results, the addition of NTE and
ONTE to the HCl solution resulted in the remarkable increase of
Rt . The maximum Rt value is obtained for the ONTE sample af-
ter 1.5 h immersion time. This observation reveals that the ONTE
molecules adsorption on the metal surface could effectively retard
the iron dissolution rate in the HCl solution. Another important
parameter is “n” which means the phase shift coefficient. The in-
crease of “n” with the immersion time progress was observed for
the samples containing the green inhibitor, evidencing the surface
heterogeneity reduction due to the inhibitor molecules adsorption
on the metal surface [52,53]. The inhibition efficiency (ηEIS ,%) was
estimated by Eq. (4) [53]. The highest inhibition efficiency was ob-
tained for the ONTE sample at 90 min. Obtaining an inhibition ef-
ficiency of 93.4% indicates that ONTE molecules could effectively
retard the corrosion of steel in HCl solution
Rt (inhibited ) − Rt (uninhibited )
(ηEIS , % ) = × 100 (4)
Rt (inhibited )
140 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149

Fig. 7. OCP curves for mild steel in 1 mol L−1 HCl solutions (for 5 h) without, and with 600 ppm of NTE and ONTE.

Table 2
Electrochemical impedance parameters related to mild steel in 1 mol L−1 HCl, without and with 600 ppm NTE and ONTE as a new inhibitor.

Sample Immersion time (min) Rt (Ω.cm2 ) CPE Cdl (μF·cm−2 ) log |Z 10 mHz | (Ω.cm2 ) Phase angle (°) Chi squared

Y0 (μΩ−1 .cm−2 .sn ) n

Blank 30 37.46 183.6 0.83 567.84 1.59 18.59 0.0033618

60 45.24 133.9 0.87 296.23 1.67 15.13 0.0036788
90 48.82 123.63 0.89 237.92 1.70 14.02 0.0051107
120 44.45 321.9 0.83 665.21 1.67 3.009 0.0033618
NTE 30 515.4 85.78 0.77 334.31 2.71 48.21 0.0071275
60 571.5 72.85 0.79 231.22 2.76 49.94 0.0062427
90 597.5 65.63 0.81 175.87 2.77 49.95 0.0058467
120 579.5 63.19 0.81 168.97 2.76 49.34 0.0057745
ONTE 30 405.7 133.50 0.80 486.01 2.61 34.17 0.0020712
60 661.3 98.60 0.83 278.58 2.82 31.70 0.0019607
90 739.2 91.83 0.84 240.74 2.87 31.43 0.0022734
120 718.4 86.53 0.84 225.76 2.86 31.44 0.0023682

Fig. 9 illustrates the Tafel plots for the samples submerged in
the acidic media without and with inhibitor after 5 h. The main
parameters that can be obtained from the polarization plots are
Ecorr (potential of corrosion), and icorr (corrosion current density).
With looking at Fig. 9, it can be understood that the Ecorr and
icorr values are affected in the presence of the inhibitors compared
to the blank sample. Results display that the Ecorr slightly shifted to
a more positive value in the presence of NTE. Since the Ecorr shift
in the inhibited solution compared to the blank sample is lower
than 85 mV, it can be concluded that the NTE and ONTE can be
considered as mixed-type inhibitors [54]. It is obvious that the Ecorr
was moved to a more negative value in the presence of the ONTE
inhibitor. On the other hand, the change in the anodic branch
shape and the slope is more pronounced than the cathodic one.
This evidences that the ONTE acted as a mixed-type inhibitor with
preponderantly anodic reaction preventative action. The change in
the anodic branch shape after the addition of ONTE suggests that
the anodic reaction mechanism has been changed due to the ONTE
molecules interaction with the iron surface. The ONTE molecules
include C=O and N–H groups with the capability of electron shar-
ing and bonding with the iron cations [55,56]. Another observation
from Fig. 9 is that the anodic and cathodic branches of the inhib-
ited samples shifted to the lower current densities compared to
blank sample. Lower anodic/cathodic branches current densities of
the ONTE sample than NTE means that the oxidized/polymerized
molecules of NTE could form a more effective barrier film over the
metal surface in subjection to the HCl solution.
3.3. Effects of temperature
The effects of temperature on the action of the inhibitor in mild
steel corrosion mitigation at various temperatures were studied by
the weight-loss method. Table 3 shows the data obtained from the
weight loss measurement at different temperatures (25, 35 and
55 °C) during 2 h immersion. Subsequently, other parameters like
corrosion rate and inhibition efficiency were estimated. It can be
seen that the corrosion rate increased with increasing the temper-
ature from 25 to 55 °C. This is due to the increase in the inhibitor
molecules’ displacement capability at higher temperatures [57,58].
Although the corrosion rate increased by increasing the temper-
ature, the presence of NTE and ONTE inhibitors is beneficial for
the mitigation of the acid-induced corrosion of metal. For exam-
ple, the corrosion rate decreased from 33.33 m2 h−1 for the blank
sample to 16 g m2 h−1 for the acidic solution including the ONTE.
The plot of the corrosion rate of the mild steel versus temperature
at the same time (after 1.5 h) for three samples (Blank, NTE, and
 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149 141

Fig. 8. Nyquist and Bode plots for mild steel specimens immersed in 1 mol L−1 HCl solutions (a1 ,a2 ) without, (b1 ,b2 ) with 600 ppm NTE, and (c1 ,c2 ) with 600 ppm ONTE; the
symptoms and solid lines are related to the experimental and fitting and data, respectively.

ONTE) is shown in Fig. 10. It is obvious that a decreasing trend is
seen with adding the inhibitors. Meanwhile, the change of the plot
slope decreased in the presence of the inhibitors in the 1 mol L−1
HCl solution. Therefore, the obtained results are in good agreement
with the previous researches.
3.4. Adsorption isotherms
Adsorption mechanism in terms of the thermodynamic point of
view was studied. To this end, the best agreement of the experi-
mental data with different isotherms such as Langmuir, Frumkin,
142 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149

Fig. 9. Potentiodynamic polarization curves after 5 h immersion of mild steel in 1 mol L−1 HCl without and with 600 ppm inhibitor.

Table 3
Values obtained from weight loss method for the mild steel sample immersed in 1 mol L−1 HCl solution without and with
600 ppm NTE and ONTE inhibitors in the different temperature during 1.5 h immersion.

Sample Temperature (°C) W (g) Corrosion rate (g m−2 h−1 ) Inhibition efficiency

Blank 25 0.0012 8 –
35 0.0013 8.6 –
55 0.0050 33.3 –
NTE 25 0.0008 5.3 33.33
35 0.0009 6 30.77
55 0.0011 7.3 78
ONTE 25 0.0007 4.6 41.66
35 0.0011 6.8 15.38
55 0.0024 16 52

and Temkin was checked. The adsorption isotherm explains the Table 4
Thermodynamic parameters for adsorption of NTE and ONTE inhibitors onto the
correlation between the concentration of the inhibitors in solution
steel surface in 1 mol L−1 HCl solution at ambient temperature.
and the surface coverage of the inhibitors on the metal surface
[59,60]. The best fitting of the experimental data obtained from EIS Sample R2 kads (L g−1 ) Gads (Kj mol−1 )
analysis was acquired with Langmuir isotherm as shown in Fig. 11. NTE 0.9866 25 −25.09
Langmuir adsorption isotherm is expressed with Eq. (5) [5]. ONTE 0.9967 22.22 −24.79

Cinh 1
= + Cinh
θ Kads
Where Cinh is the concentration of the inhibitor in solution and θ
is the surface coverage. The calculated adsorption constants (Kads )
for NTE and ONTE were 25 L g−1 and 22.22 L g−1 , respectively. The
correlation coefficients of 0.9866 and 0.9967, as well as a slop near
1, were obtained for NTE and ONTE samples, respectively. These re-
sults reveal that the experimental data were well fitted by a Lang-
muir isotherm. This means that the adsorption of inhibitors on the
metal surface is in monolayer form and there is no connection be-
tween the adsorbed inhibitor molecules on the surface. The ther-
modynamic parameter of the standard free energy (Gads ) was cal-
culated by Eq. (6).
Gads = −R T ln (55.5 kads )
Where 55.5 is the molar concentration of water, R, T, and kads
are the gas constant, temperature in kelvin and adsorption con-
stant, respectively. The obtained values for Gads are reported in
Table 4. According to literature, the values of Gads more than
−20 kJ mol−1 explain a physisorption mechanism of adsorption and
(5)
the values lower than −40 kJ mol−1 validate the chemisorption
mechanism [58,61]. The calculated values of Gads in this study
are between −20 and −40 kJ mol−1 , confirming that the adsorption
of inhibitor molecules on the metal surface occurred in both ph-
ysisorption and chemisorption forms.
3.5. Surface analysis
The surface morphology analysis of the steel panels after 5 h ex-
posure to the uninhibited and inhibited HCl solutions was done by
an SEM analysis and the images related to these samples are illus-
trated in Fig. 12. Meanwhile, the smooth surface of the as-received
(6)
mild steel sample is obvious in Fig. 12. Results reveal that the sur-
face of the plate exposed to the acidic solution without inhibitor is
strongly damaged and many holes/defects were produced, indicat-
ing the severe steel surface corrosion. However, the surface of the
plate immersed in the acidic solution with NTE is almost smoother
than the blank sample, indicating the lower degree of damage due
 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149 143

Fig. 10. Corrosion rate of mild steel without (Blank) and with inhibitor (NTE and ONTE) at the different in the acidic solution.

Fig. 11. Langmuir adsorption isotherm of NTE and ONTE inhibitors in 1 mol L−1 HCl at 298 K.

to the effective role of NTE molecules in iron dissolution rate con- Table 5
Roughness parameters extracted from AFM micrographs.
trol. In the presence of ONTE, all cracks and holes were approxi-
mately diminished and the lowest steel surface damages occurred. Sample Sy (nm) Sz (nm) Sa (nm) Sq (nm)
These observations prove that the ONTE could form a more protec- as received 65 13.9
tive film than NTE on the steel surface [55,62]. It seems that the Blank 1930 1868 270 336
oxidation/polymerization of Nettle molecules resulted in the gen- NTE 954 861 101 129
eration of larger inhibitive molecules with higher corrosion inhibi- ONTE 742 616 71.1 87.2

tion activity.
Additionally, the investigation of the surface morphology was
performed by AFM analysis (Fig. 13.). The roughness parameters
magnitudes including Sy (maximum height), SZ (ten-point height),
and Sa (arithmetical mean height) are given in Table 5. As it is evi-
dent from the presented results, the blank sample surface is almost
rough. A reason for this phenomenon is the severe surface damage
due to acidic solution attacks [63]. However, the surface rough-
ness drastically decreased in the case of the solution inhibited by
NTE. In the HCl solution containing the oxidized Nettle (ONTE), the
surface roughness (Sa ) reached 71.1 nm. This result proves that the
ONTE adsorption on the steel surface could significantly reduce the
surface damage due to corrosion.
The results obtained from the water contact angle examination
on the surface of the samples exposed to the acidic solution with-
out and with two different inhibitors are given in Fig. 14.
Water contact angle magnitudes for the blank, NTE and ONTE
samples were 45˚, 67˚ and 90˚, respectively. The surface free energy
(γ sv ) was estimated by the Neumann’s [64] and Young’s equations
[65].
The ascending trend of contact angle value is attributed to
the decrease of the surface hydrophilicity due to the inhibitor
molecules absorption [66]. All of these observations prove that the
144 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149
Fig. 12. SEM images for mild steel after 5 h immersion in 1 mol L−1 HCl (a) as received sample, in absence of inhibitor (b) Blank and presence of inhibitors (c) 600 ppm NTE
and (d) 600 ppm ONTE.
inhibitor molecules could adsorb on the metal surface and de-
crease its hydrophilic nature.
X-ray diffraction patterns were provided from the surface of
the steel samples immersed in the acidic solutions without and
with ONTE. According to Fig. 15, the XRD pattern of the blank
sample shows different peaks related to the corrosion products
such as FeOOH at 2θ = 64.92°, Fe2 O3 at 2θ = 33.5°, and Fe metal
in 2θ = 44.87° [67,68]. In the ONTE sample, the metal submerged
in the HCl solution containing 600 ppm of ONTE, the intensity of
the peak related to the iron oxides significantly decreased and the
peak related to Fe increased. These results prove that the corrosion
reactions were controlled by a competitive layer formation on the
metal surface.
A deeper understanding of the chemical nature of the protec-
tive layer formed on the metal surface was carried out by FT-IR
analysis (Fig. 16). The spectrum “a” is related to the mild steel
plate exposed to HCl solution after 5 h. It can be seen that the
FT-IR spectrum of the blank sample consists of different types
of corrosion products such as γ -FeO(OH), β -FeO(OH), and Fe2 O3 .
The most appeared absorption peaks at 1051 cm−1 , 1162 cm−1 ,
and 1632 cm−1 belong to the destructive lepidocrocite phase (β -
FeO(OH)) [69]. These consequences confirm that the mild steel was
corroded under the acidic condition. The spectrum “b” is related to
the synthesized ONTE powder. The main peaks of ONTE were ex-
plained in Section 3.2. The spectrum “c” is related to the plate ex-
posed to the HCl solution containing 600 ppm ONTE. It can be seen
that the shift of vibrational frequencies took place. For example in
the spectrum “c”, it was realized that the FeO–OH at 1051 cm−1
has shifted to 1038 cm−1 , and the O–H bending at 1448 cm−1 has
shifted to1457 cm−1 . Also, new vibrations are observed in the spec-
trum of the mild steel sample exposed to ONTE containing solu-
tion. The vibrations of C–N bending in 1258 cm−1 and C≡N in
2337 cm−1 are absent in the spectrum of the sample exposed to
blank solution. The obtained results confirmed that the inhibitor
 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149 145

Fig. 13. The 2D and 3D AFM micrographs of steel samples immersed in 1 mol L−1 HCl solutions (a1 , a2 ) as received sample, (b1 , b2 ) after 5 h immersion in 1 mol L−1 HCl
solutions without inhibitor, (c1 ,c2 ) with 600 ppm NTE, and (d1 ,d2 ) with 600 ppm ONTE.
146 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149

Fig. 14. Contact angle of the mild steel samples dipped in 1 mol L−1 HCl solutions without and with NTE and ONTE inhibitors.

Fig. 15. GIXRD patterns of the steel sample immersed in the acidic solutions (for 5 h) (A) without and (B) with ONTE inhibitor.

molecules could successfully interact with the mild steel surface
[24,70,71].
3.6. The mechanism of NTE/ONTE corrosion inhibition
Fig. 17 schematically presents the adsorption mechanism of the
inhibitive compounds of NTE and ONTE on the corrosion sites of
the steel coupons subjected to 1 mol L−1 HCl solutions. NTE and
ONTE molecules include π -electrons and heteroatoms (like O and
N) in their structures that can bond with the metal surface and re-
duce the corrosion rate. Since the iron cations can be generated on
the anodic sites of the metal surface, the chloride ions can electro-
statically adsorb on the metal surface. As a result, the positively
changed NTE and ONTE molecules adsorb on the metal surface
 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149 147

Fig. 16. (a) FT-IR spectrum of the mild steel sample subjected to 1 mol L−1 HCl solution without inhibitor for 5 h, (b) FT-IR spectrum of the ONTE synthesized inhibitor,
(c) FT-IR spectrum of the metal surface undergone by 1 mol L−1 HCl solution including 600 ppm ONTE inhibitor.

Cl -
Cl -
Cl -
mild steel

Physisorption Chemisorption

Fig. 17. The proposed mechanisms for the NTE and ONTE inhibitors against steel corrosion in acidic solution.

through a physisorption mechanism. In addition to the physisorp-
tion mechanism, the inhibitors molecules could adsorb on the an-
odic sites through the chemisorption mechanism. Accordingly, the
heteroatoms existed in the NTE and ONTE compounds can share
the electron pairs with the vacant orbital of Fe. O–H, N–H, and NH2
are the most important functional groups present in the NTE com-
ponents. Whereas in the ONTE sample, the С=O functional groups
are the most important functional groups. Since the Fe-carbonyl
complex is stronger than the Fe–hydroxyl complex, the better inhi-
bition behavior of the ONTE sample compared to NTE is expected.
The C=O ligand has more ability than O–H to produce Fe d-orbital
splitting according to spectrochemical ligand series but the O–H
dominantly participates in hydrogen bonding. Moreover, the dimer-
ized/polymerized serotonin molecules present in the ONTE show
the higher capability of film formation on the steel surface than
NTE [63,72]. The ONTE molecules with greater molecular weight
and lower –OH groups than NTE form a more barrier film with
lower hydrophilicity and higher protection properties.
3.7. Economic comparison of the biopolymer-based corrosion
inhibitors
Nowadays, using eco-friendly inhibitors has become a hot topic
of recent researches. Bio-compatible based corrosion inhibitors
such as chitosan, dextran, polydopamine, and etc. are used for this
purpose. These materials are expensive and their availability is not
easy. Table 6 reveals a concise comparison between the commer-
cial corrosion inhibitors consumed for the corrosion mitigation of
the steel samples in the acidic solution from both the efficiencies
and costs points of views [24,73,74]. The green bio-active inhibitor
considered in this study is not as pure as the common biopoly-
148 M. Keramatinia, B. Ramezanzadeh and M. Mahdavian / Journal of the Taiwan Institute of Chemical Engineers 105 (2019) 134–149
Table 6
The comprehensive comparison between some biopolymer corrosion inhibitors used in acidic so-
lution for the mild steel protection.
Biopolymer Cost ($/50 gr) Type of solution
Chitosan 60–70 1 M HCl
Polydopamine 220–240 1 M HCl
Dextran 120–130 15% H2 SO4
ONTE 27–30 1 M HCl
mers but provided higher inhibition efficiencies with lower syn-
thesis price.
4. Conclusion
Synthesis of the green and bio-active components was carried
out during 5 days at ambient temperature and pH=9.14. The FT-IR
and UV–Vis analyses indicated that the oxidation of the Nettle ex-
tract molecules was successfully done. Then, the inhibition activity
of the obtained compound (ONTE) and Nettle extract was examined
in HCl solution on the mild steel surface and maximum inhibition
efficiency of 93.4% was obtained for ONTE after 1.5 h immersion.
Langmuir adsorption isotherm was a good model for explaining the
adsorption behavior of the experimental data. The values of Gads
confirmed that the adsorption of inhibitors onto the mild steel sur-
face is in chemical and physical forms. The surface analysis results
ascertained that the interactions between the ONTE molecules and
the metal surface are stronger than the NTE molecules. The ONTE
molecules owing to their higher molecular weight than NTE and
the presence of higher C=O groups could form a more inhibitive
film on the steel surface.
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