j m a t e r r e s t e c h n o l .

2 0 1 7;6(2):158170

Available online at www.sciencedirect.com

www.jmrt.com.br

Original Article

Inhibition effect of bamboo leaves extract on cold

rolled steel in Cl3 CCOOH solution

Xianghong Li a,b, , Shuduan Deng a , Nan Li b , Xiaoguang Xie c

a Yunnan Key Laboratory of Wood Adhesives and Glue Products, Southwest Forestry University, Kunming, China
b Faculty of Science, Southwest Forestry University, Kunming, China
c School of Chemical Science and Technology, Yunnan University, Kunming, China

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

Article history: The corrosion inhibition by Dendrocalamus brandisii leaves extract (DBLE)/major avonoid of
Received 30 January 2016 cold rolled steel (CRS) in trichloroacetic acid (Cl3 CCOOH) solution was investigated by weight
Accepted 14 September 2016 loss, electrochemical techniques and atomic force microscope (AFM). The adsorption mode
Available online 9 November 2016 of four major compounds (rutin, vientin, isovientin and orientin) on Fe (001) surface was
theoretically investigated by molecular dynamics (MD). The results show that DBLE is a
Keywords: good inhibitor, and the maximum inhibition efciency is higher than 95%. The adsorption
Corrosion inhibitor of DBLE on CRS surface obeys Langmuir isotherm with exothermic process. DBLE behaves
Trichloroacetic acid as a mixed inhibitor. AFM results conrm that DBLE could retard the corrosion of CRS in
Steel Cl3 CCOOH. The inhibitive action of each avonoid is lower than DBLE, and follows the order:
Bamboo leaves extract rutin > vientin > isovientin > orientin. The major avonoids in DBLE are adsorbed onto Fe
Flavonoids adsorption (001) surface through FBS (avones backbone structure) with a nearby at orientation.
2016 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier
Editora Ltda. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

Up to now, many plant extracts have been reported as

1. Introduction
Using inhibitors is one of the most practical methods for
metals protection against corrosion, especially in acid media
[1]. With more and more restrictive environmental regula-
tions, the research in the eld of corrosion inhibitors has been
addressed toward the goal of using cheap and effective com-
pounds at low or zero environmental impact. Biodegradable
plant extract could be obtained by simple extraction process
from rich natural resources. Thus, the main advantage of using
plant extracts as corrosion inhibitors are both economic and
environmental.
effective corrosion inhibitors of steel in inorganic acids (HCl,
H2 SO4 , H3 PO4 ), such as henna [2,3], Nypa fruticans Wurmb [4],
Zenthoxylum alatum [5], Mentha pulegium [6], olive [7], Phyllan-
thus amarus [8], Damsissa [9], Occimum viridis [10,11], Murraya
koenigii [12], lupine [13], Ananas comosus [14], Lasianthera
africana [15], Strychnos nux-vomica [16], Justicia gendarussa [17],
Oxandra asbeckii [18], Ferula assa-foetida [19], coffee [20], fruit
peel [21], Halfabar [22], Kopsia Singapurenis [23], Jasminum nud-
iorum [24], ginkgo [25], Artemisia pallens [26], Salvia ofcinalis
[27], Osmanthus fragran [28], Uncaria gambir [29], garlic peel [30],
Neolamarckia cadamba [31], Z. alatum [32], Acalypha indica L.
[33], Acer truncatum [34], Acer buergerianum [35], Tagetes erecta

Corresponding author.
E-mail: xianghong-li@163.com (X. Li).
http://dx.doi.org/10.1016/j.jmrt.2016.09.002
2238-7854/ 2016 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier Editora Ltda. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170 159

[36], Musa paradisica [37] and Geissospermum leave [38]. It is

Table 1 The experimentally measured and calculated
found that the inhibition performance of plant extract is pH values of Cl3 CCOOH solutions.
normally ascribed to the presence in their composition of
c (Cl3 COOH) Measured pH Calculated pH
complex organic species like tannins, alkaloids and nitrogen
bases, carbohydrates, amino acids, proteins and hydrolysis 0.05 M 1.34 1.38
products. These organic compounds always contain the 0.1 M 1.10 1.13
0.2 M 0.85 0.95
adsorption centers of polar functional groups with N, S, O
0.3 M 0.74 0.77
atoms as well as conjugated double bonds or aromatic rings
0.4 M 0.66 0.69
in their molecular structures. 0.5 M 0.57 0.62
However, there have been lower attentions for plant
extracts as corrosion inhibitors in organic acid medium. In
these chemical reagents are obtained from Shanghai Chem-
2012, Piper nigrum L. leaves extract [39] was reported as an
ical Reagent Company of China. The aggressive solutions of
effective corrosion inhibitor for steel in citric acid (H3 C6 H5 O7 ).
0.050.5 M Cl3 CCOOH were prepared by dilution of AR grade
As another frequently used organic acid, trichloroacetic acid
Cl3 CCOOH with distilled water. The ionization equilibrium
(Cl3 CCOOH) is widely used in cellulose industry [40], and in the
constant (Ka ) of Cl3 CCOOH is 2.2 101 (pKa = 0.66, 20 C). The
production of TCA Na-salt used as an herbicide. Cl3 CCOOH
experimentally measured and calculated pH values are listed
shows strong corrosiveness on metal, so there is a great
in Table 1; clearly in good agreement with the theoretically
need to add inhibitor to protect metals in Cl3 CCOOH solu-
calculated pH values.
tion [40]. In 1974, Sampat and Vora [41] investigated the
DBLE was extracted from D. brandisii leaves using 80%
corrosion inhibition of aluminum in Cl3 CCOOH by some
(percent by volume) C2 H5 OH water solution at 75 C for 2 h
methyl pyridine derivatives. Since the 21st Century, xylenol
in our laboratory, as described in our earlier work [48,50].
orange [40], amino acetanilides [42], sulphathiazole [43] and
The production rate is about 9.7%. Fourier transform infrared
2-acetylphenothiazine [44] have been reported as effective
spectroscopy (FTIR) of DBLE and the average content of total
inhibitors for aluminum in Cl3 CCOOH solution. However,
avonoids in DBLE (about 28%) were fully studied in our recent
after carefully checking out the published references, there
paper [48]. The concentration range of DBLE was 10200 mg l1 .
is almost no report about the corrosion inhibition of steel in
Cl3 CCOOH solution, specially for plant extract inhibitors.
2.2. Weight loss and electrochemical measurements
In our laboratory, much work has been conducted to study
the inhibition by bamboo leaves extract on the corrosion
CRS sheets of 2.5 cm 2.0 cm 0.06 cm were abraded by a
of metals in various media. The main reason is that bam-
series of emery paper (grade 320500800) and then washed
boo leaves are abundant resources (about 1200 species and
with distilled water and degreased with acetone. The weight
70 genera of bamboo in the world) with fast and continu-
loss and electrochemical measurements have been described
ous renewal. Most important of all, bamboo leaves extract is
in detail in our earlier reports [4750]. The immersion time
virtually nonpoisonous [45,46]. Recently, the bamboo leaves
of weight loss is 334 h, and the experimental tempera-
extracts have been reported as good inhibitors for steel in
ture is 2050 C. Electrochemical experiments were carried
HCl [47,48] and in H3 C6 H5 O7 [49] media. In continuation of
out using a PARSTAT 2273 advanced electrochemical system
our previous study, the present work rstly reports the inhi-
(Princeton Applied Research) with a conventional three-
bition effect of Dendrocalamus brandisii leaves extract (DBLE)
electrode system: counter electrode (platinum), reference
on the corrosion of cold rolled steel (CRS) in Cl3 CCOOH solu-
electrode (saturated calomel electrode (SCE)) coupled to a
tion by weight loss, polarization curves and electrochemical
ne Luggin capillary and working electrode (surface area is
impedance spectroscopy (EIS) methods. The steel surface
1.0 cm 1.0 cm).
was characterized by AFM technique. Meanwhile, molecu-
For the weight loss method, the corrosion rate (v) was cal-
lar dynamics (MD) was applied to theoretically elucidate the
culated from the following equation:
adsorption mode of major avonoid molecule (rutin, vientin,
isovientin, orientin) on Fe (001) surface. The electrochemical W
v= (1)
corrosion mechanism of steel in Cl3 CCOOH solution is pro- St
posed. Lastly, the inhibitive mechanism of DBLE is presented
according to the difference in inhibition performance between where W is the average weight loss of two parallel CRS sheets
DBLE and major avonoid. (g), S the total area of one CRS specimen (m2 ), and t is the
immersion time (h). With the calculated corrosion rate, the
inhibition efciency (w ) was calculated as follows:
2. Experimental
v0 v
w = 100 (2)
v0
2.1. Materials
where, v0 and v are the values of corrosion rate without and
Tests were conducted on CRS having composition (wt.%): with inhibitor, respectively.
0.07% C, 0.3% Mn, 0.022% P, 0.010% S, 0.01% Si, 0.030% Al and Before electrochemical measurements, the electrode was
the remainder Fe. Trichloroacetic acid (Cl3 CCOOH) is of ana- immersed in test solution at open circuit potential (OCP) for
lytical reagent (AR) grade, and four major compounds (rutin, 2 h at 20 C to reach a stable state. The potentiodynamic polar-
vientin, isovientin and orientin) are of pure standards. All of ization curves were carried out by polarizing to 250 mV vs.
160 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170
OCP at a sweep rate of 0.5 mV s1 . Inhibition efciency (p ) is
calculated through the corrosion current density (icorr ) values
[47]:
icorr icorr(inh)
p = 100%
icorr
where icorr and icorr(inh) represent corrosion current density
values without and with inhibitor, respectively.
Electrochemical impedance spectroscopy (EIS) was carried
out at stable OCP (no extra bias voltage, 2 h of immersion)
over a frequency range from 100 kHz to 10 mHz using a 10 mV
root mean square (r.m.s) voltage excitation. The total number
of points is 30. Inhibition efciency (R ) is estimated by the
relation below [47]:
Rt(inh) Rt(0)
R = 100%
Rt(inh)
where Rt(0) and Rt(inh) are charge transfer resistance values in
the absence and presence of the inhibitor, respectively.
2.3. Atomic force microscope (AFM)
The CRS specimens of 1.5 cm 1.0 cm 0.06 cm were prepared
as described above (Section 2.2). After immersion in 0.1 M
Cl3 CCOOH solutions without and with 200 mg l1 DBLE at 20 C
for 6 h, the specimens were cleaned with distilled water, dried
with a cold air blaster, and then used for a Japan instru-
ment model SPA-400 SPM Unit atomic force microscope (AFM)
examinations. The AFM images were measured in tapping
mode using Si3 N4 tips.
2.4. MD simulations
MD simulations were performed with Discover program in
Materials Studio 4.1 software from Accelrys Inc. [51]. Accord-
ing to many MD studies about the adsorption of inhibitor
on steel surface [52,53], there could be strong interaction
between organic inhibitor and Fe (001) surface, so Fe (001)
surface is chosen to study. Fe (001) plane was rstly cleaved
from pure Fe crystal, the surface was then optimized to
the energy minimum, and then was enlarged to fabricate
an appropriate supercell. After that, a vacuum slab with
1 A thickness was built above the Fe (001) supercell with
31.53 A 31.53 A 15.30 A of total 1331 Fe atoms. Meanwhile,
the optimized inhibitor molecules of rutin, vientin, isovi-
entin and orientin were done with DMol3 numerical based
density function theory (DFT) in Materials Studio 4.1 at
PW91/DNP/COSMO level [54,55], and then the inhibitor lay-
ers were built using the Amorphous cell program. Finally,
the adsorption system was built by layer builder to place the
inhibitor layer to Fe (001) supercell. All these slabs are sepa-
rated by a 10 A vacuum thickness to ensure that the interaction
between the periodically repeated slabs along the normal of
the surface is small enough. The adsorption system was opti-
mized using COMPASS force eld. The MD simulation was
performed under 298 K, NVT ensemble, with a time step of
1.0 fs and simulation time of 1000 ps.
Both adsorption energy (Eads ) and binding energy (Ebin )
could determine the stability of inhibitor on metal surface.
They have different view angles. Eads is mainly used to study
the adsorption of inhibitor on the metal surface, and it is cal-
culated as follows [56]:
(3)
Eads = (Einh + Esurf ) Etotal (5)
where Einh and Esurf are the energies of the free inhibitor
molecule and Fe (001) plane, respectively. Etotal is the total
energy of Fe (001) plane together with inhibitor molecule
adsorbed on the iron surface.
On the other hand, Ebin is mainly focused on the interaction
between inhibitor and metal surface, and it could be calculated
by means of the following relationship:
Ebin = Etotal (Einh + Esurf ) (6)
(4)
Comparing Eq. (5) with (6), it is evident that Ebin is the neg-
ative value of the Eads [57]:
Ebin = Eads (7)
3. Results and discussion
3.1. Weight loss measurements
The weight loss method is widely used to quantitatively deter-
mine corrosion rate (v) and inhibition efciency (w ) owing to
its good reliability. For the present study, the relative phase dif-
ference (RPD) v and w for two parallel specimens are less than
5%, which conrms that the reproducibility for the present
system is very precise.
3.1.1. Effect of DBLE concentration on inhibition efciency
The corrosion rates in 0.1 M Cl3 CCOOH solution with-
out inhibitor are 20.37 (RPD = 1.6%) g m2 h1 at 20 C; 40.90
(RPD = 1.9%) g m2 h1 at 30 C; 58.48 (RPD = 2.0%) g m2 h1 at
40 C; and 72.60 (RPD = 2.2%) g m2 h1 at 50 C, which indi-
cates that CRS is severely corroded by Cl3 CCOOH acid. When
DBLE is added to the Cl3 CCOOH media, the corrosion of CRS
is retarded prominently. Fig. 1 presents w for different DBLE
concentrations (10200 mg l1 ) in 0.1 M Cl3 CCOOH solutions
at 2050 C. Clearly, w increases with the inhibitor concen-
tration at all temperatures studied. w increases remarkably
with DBLE concentration from 10 to 100 mg l1 , but a further
raise in inhibitor concentration causes no appreciable change
in inhibitive performance. The maximum w at 200 mg l1 is
96.1% (RPD = 2.3%) at 20 C; 94.2% (RPD = 2.3%) at 30 C; 90.4%
(RPD = 2.4%) at 40 C; and 85.8% (RPD = 2.5%) at 50 C. Thus,
DBLE acts as a good inhibitor for CRS in Cl3 CCOOH media.
According to our recent work, bamboo leaves extract acts as
the good corrosion inhibitor for CRS in HCl [47,48], H2 SO4 [47]
and H3 C6 H5 O7 [49], which implies that the bamboo leaves
extract could be seemed as the good potential corrosion
inhibitor for steel in either inorganic acid or organic acid solu-
tion.
Also, Fig. 1 illustrates that w decreases to some extent
with the elevated temperature within whole inhibitor
 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170 161

100
Table 2 Parameters of the linear regression between c/
90 and c in 0.1 M Cl3 CCOOH solution.
80
Temperature ( C) r Slope K (l mg1 )
70
20 0.9999 1.01 0.15643
60
w , %

30 0.9994 0.98 0.06886

50
40
30
20
10
0 20 40 60 80 100 120 140 160 180 200 220
c (mg l1)
Fig. 1 Relationship between inhibition efciency (w ) and
concentration of DBLE (c) in 0.1 M Cl3 CCOOH (weight loss
method, immersion time is 6 h).
concentrations from 10 to 200 mg l1 , which would be
attributed to the DBLE desorption from the CRS surface due
to the higher temperatures.
3.1.2. Adsorption isotherm
Acid inhibitor generally exhibits inhibitive performance
through adsorption on metal surface, and some adsorption
isotherms have been widely used to study the adsorption
behavior. In previous studies of bamboo leaves extract as
corrosion inhibitors for steel in acids [4749], the adsorption
of bamboo leaves extract on steel surface follows Langmuir
adsorption isotherm. For the present study, Langmuir adsorp-
tion isotherm is also applied to study the adsorption of DBLE
on steel surface in CCl3 COOH solution [58]:
c 1
= +c
 K
where c is the concentration of inhibitor (mg l1 ), K the
adsorptive equilibrium constant (l mg1 ), and  is the surface
coverage with the value of inhibition efciency (w ) [58].
The straight lines of c/ vs. c at four temperatures are shown
in Fig. 2, and the corresponding linear regression parameters
are given in Table 2. All linear correlation coefcients (r) are
almost equal to 1, and the slope values are also close to 1,
20 C 40 0.9948 0.91 0.02936
30 C 50 0.9902 0.87 0.01883
40 C
50 C
so the adsorption of DBLE on CRS surface obeys the Lang-
muir adsorption isotherm. Larger value of K generally means
stronger adsorptive ability and hence better inhibitive ability
of a given inhibitor. As shown in Table 2, K decreases with
an increase of the temperature, which implies that it is easy
for DBLE to be adsorbed onto the steel surface in Cl3 CCOOH
solution at relatively low temperature. On the other hand, the
adsorbed inhibitor molecules tend to desorb from the metal
surface, giving rise to severe corrosive attack at high temper-
ature.
3.1.3. Effect of immersion time on corrosion inhibition
Fig. 3 shows the inhibition efciency (w ) values of 200 mg l1
DBLE for different immersion time (t) at 20 C in 0.1 M
Cl3 CCOOH using weight loss method. w increases with
immersion time from 3 to 6 h, thereafter remains almost sta-
ble from 6 to 24 h, and w is as high as 97.3% even when the
immersion is as long as 24 h. Similar results were also pre-
viously reported for bamboo leaves extract as the corrosion
inhibitor for HCl and H2 SO4 solutions [47]. This behavior could
be attributed to the adsorptive lm of inhibitor that rests upon
the immersion time [47]. The inhibitive lm on steel surface
rstly reaches a more compact and uniform condition during
prolonging immersion time (36 h), while the adsorptive lm
is in a saturated state within 624 h.
(8)
3.1.4. Effect of acid concentration on corrosion inhibition
Fig. 4 shows the relationship between corrosion rate (v) and
Cl3 CCOOH concentration (C) at 20 C (immersion time is 6 h).
It is of interest to note that the corrosion rate increases lin-
early with the increase of Cl3 CCOOH concentration from 0.05
to 0.5 M either in the absence or presence of 200 mg l1 DBLE.
This unique result of steel in Cl3 CCOOH is quite different from
that of steel in inorganic acids (HCl, H2 SO4 and H3 PO4 ) [59].

240 98
220
200 97

180
96
160
c/ (mg l1)

140 95
w , %

120
100 94
20 C
80
30 C 93
60
40 C
40 50 C 92
20
0 91
0 20 40 60 80 100 120 140 160 180 200 220 0 3 6 9 12 15 18 21 24 27
c (mg l1) t (h)

Fig. 2 Langmuir isotherm adsorption mode of DBLE on Fig. 3 Effect of immersion time (t) on inhibition efciency
CRS surface in 0.1 M Cl3 CCOOH solution. (w ) in 0.1 M Cl3 CCOOH at 20 C (weight loss method).
162 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170

130 0.390
120 Cl3CCOOH a--- 0.1 M CCl3COOH
110 Cl3CCOOH + 200 mg l1 DBLE 0.395
b--- 0.1 M CCl3COOH + 200 mg l1 DBLE
100 b
90

OCP (V vs. SCE)

2.0 0.400
80
v (g m2 h1)

70

v (g m2 h1)
60 1.5 0.405
50
a
40 1.0
0.410
30
20 0.5
0.0 0.1 0.2 0.3 0.4 0.5 0.6
0.415
10 C (M)
0
10 0.420
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0 30 60 90 120 150 180 210
C (M) t (min)

Fig. 4 Effect of acid concentration (C) on corrosion rate (v) Fig. 6 OCP time (t) curves for CRS in 0.1 M Cl3 CCOOH
of CRS in Cl3 CCOOH at 20 C (weight loss method). solutions at 20 C.

When 200 mg l1 DBLE is added to Cl3 CCOOH solution, the cor- OCP values are 409 mV and 398 mV vs. SCE in the absence
rosion rate decreases sharply. This conrms that DBLE exhibits and presence of 200 mg l1 DBLE, respectively.
good inhibitive performance in the whole acid concentration
studied. In 0.5 M Cl3 CCOOH solution without inhibitor, the 3.3. Potentiodynamic polarization curves of DBLE
corrosion rate reaches as high as 118.56 g m2 h1 , while it is
decreased to 1.68 g m2 h1 in the presence of 200 mg l1 DBLE. Potentiodynamic polarization curves of CRS in 0.1 M
Fig. 5 illustrates the dependence of inhibition efciency Cl3 CCOOH containing 0, 10, 50, 100 and 200 mg l1 DBLE
(w ) on the concentration of Cl3 CCOOH (0.050.5 M) at 20 C. at 20 C (immersion time is 2 h) are shown in Fig. 7. As
Clearly, w increases slightly with the concentration of compared to that of the blank solution, the presence of
Cl3 CCOOH from 91.3% to 98.6% with respect to 0.05 M and DBLE causes the decrease in the corrosion rate of CRS in
0.5 M. The reason might be due to the more protective lm 0.1 M Cl3 CCOOH, i.e., shifts both cathodic curves and the
by the interaction of the inhibitor molecules with Fe2+ [60] or anodic curves toward lower current densities. The shift of
protonated inhibitor molecules with acid anion (Cl3 CCOO ) at polarization curves toward the lower current density region
higher acid concentration. is much more pronounced when the concentration of DBLE is
increased. The results indicate that both cathodic and anodic
3.2. Open circuit potential (OCP) time curves reactions of CRS electrode corrosion in Cl3 CCOOH solution
are retarded by DBLE. Namely, DBLE could be arranged as
Fig. 6 shows OCP as a function of time (0180 min) in 0.1 M a mixed-type inhibitor. The nature of polarization curves
Cl3 COOH solution without and with 200 mg l1 DBLE at 20 C. remains the same irrespective of different concentration
For both cases, OCP initially moves positive value along with of DBLE addition to acid solution, which suggests that the
time and reaches the peak at about 20 min, and then shifts mechanism for the corrosion of steel in CCl3 COOH solution
to negative and gradually reaches steady state from 60 to does not change by adding DBLE to the acid solution.
180 min. The potentiodynamic polarization curves and elec- Inspection of Fig. 7 reveals that the cathodic polarization
trochemical impedance spectroscopy (see later) were carried curves display three portions (I, II, and III), which indi-
out with OCP in a steady state with immersion time of 2 h, and cates that there are both activation controlled and diffusion

100 0.1
Blank
10 mg l1
0.2
98 50 mg l1
100 mg l1 V
E ( V vs. SCE)

0.3 200 mg l1
96
IV
w , %

0.4
94
0.5 III

92 II
0.6
I
90 0.7
0.0 0.1 0.2 0.3 0.4 0.5 0.6 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
C (M) log i (A cm2)

Fig. 5 Effect of Cl3 CCOOH concentration (C) on inhibition Fig. 7 Potentiodynamic polarization curves for CRS in
efciency (w ) at 20 C (weight loss method, immersion time 0.1 M Cl3 CCOOH without and with different concentrations
is 6 h). of DBLE at 20 C (immersion time is 2 h).
 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170 163

controlled regions for the cathodic polarization curves. Portion 300 25

10 mg l1 20 Blank
I might be related to the reduction of trichloroacetic acid in 250 50 mg l1 Fitting curve

Zim ( cm2)
15
strong cathodic polarization region (about 0.70 to 0.65 V 100 mg l1 10

vs. SCE). Portion II would be related to the reduction of O2 in

200 200 mg l1 5
____
Fitting Curves

Z im ( cm2)
diffusion region (about 0.65 to 0.55 V vs. SCE). Portion III 150 0

-5
represents the evolution of hydrogen in activation controlled 100
0 5 10
Zre ( cm2)
15 20 25

region (about 0.55 V vs. SCE to OCP). In a word, there are a

50
series of complex cathodic reduction reactions in Cl3 CCOOH
solution. Cl3 CCOOH would be dissociated to H+ and Cl3 CCOO 0

in water solution. According to the proposed mechanism of 50

steel in acid solution [61], the cathodic hydrogen evolution
100
reaction follows the steps (9)(12): 0 50 100 150 200 250 300
Zre ( cm2)
Fe + H+ (FeH+ )ads (9)
Fig. 8 Nyquist plots of the corrosion of CRS in 0.1 M
+
(FeH )ads + e (FeH)ads (10) Cl3 CCOOH without and with different concentrations of
DBLE at 20 C (immersion time is 2 h).
(FeH)ads + H+ + e Fe + H2 (11)

Two (FeH)ads may combine together to liberate hydrogen as
following [62]:
(FeH)ads + (FeH)ads 2Fe + H2
The anion of Cl3 CCOOH (Cl3 CCOO ) might also react with
H+ to produce HCl2 CCOO and H2 ClCCOO [63]:
Cl3 CCOO + H+ + 2e HCl2 CCOO + Cl
HCl2 CCOO + H+ + 2e H2 ClCCOO + Cl
For anodic polarization curves as shown in Fig. 7, it is
worth noting that two portions (IV and V) are observed, which
represent the weak polarization region (OCP to 0.35 V vs.
SCE) and strong polarization region (0.35 to 0.15 V vs. SCE),
respectively. According to the mechanism for the corrosion of
mild steel in aqueous solutions of formic acid (HCOOH) [62],
acetic acid (CH3 COOH) [64] and peracetic acid (CH3 COOOH)
[65], the anodic dissolution of CRS in Cl3 CCOOH solutions may
be assumed as follows:
Fe + Cl3 CCOO (FeCl3 CCOO )ads
(FeCl3 CCOO )ads (FeCl3 CCOO)ads + e
(FeCl3 CCOO)ads (FeCl3 CCOO+ ) + e
FeCl3 CCOO+ Fe2+ + Cl3 CCOO
Thus, the adsorption of Cl3 CCOO ions on the CRS surface
would be the prerequisite for the anodic dissolution to occur.
The electrochemical parameters of corrosion current den-
sities (icorr ), corrosion potential (Ecorr ), cathodic Tafel slope (bc )
and anodic Tafel slope (ba ) are obtained by using electrochem-
istry powersuite software to t weak polarization curves of
Tafel polarization in the optimum linear regions of III and IV.
Inhibition efciency (p ) values are calculated through icorr and
summarized in Table 3. The presence of DBLE shifts Ecorr to
positive to some extent, but the maximum change of Ecorr
is lower than 85 mV. Therefore, DBLE could be classied as
a mixed-type inhibitor [66,67]. Clearly, icorr decreases promi-
nently in the presence of DBLE, while p increases with the
inhibitor concentration, and the maximum p reaches as high
(12) as 97.2%, which indicates that DBLE acts as a good inhibitor in
Cl3 CCOOH. Tafel slopes of bc and ba change upon addition of
DBLE, which means that the inhibitor molecules are adsorbed
on both the anodic and cathodic sites resulting in the changing
rules of the potential with current densities.
(13)
3.4. Electrochemical impedance spectroscopy (EIS)
(14)
Fig. 8 shows the Nyquist diagrams of CRS obtained at OCP
(immersion time: 2 h) in 0.1 M Cl3 CCOOH without and with
different concentrations of DBLE at 20 C. It appears as a
large capacitive loop at high frequency (HF) followed also by
an inductive one at low frequency (LF) values. Comparing
with 0.1 M Cl3 CCOOH solution in the absence of inhibitor, the
general shape is maintained for all tested concentrations, indi-
cating that almost no change in the corrosion mechanism
occurs as a result of the inhibitor addition [68]. In addition, the
diameter of the capacitive loop in the presence of DBLE is big-
ger than that in blank solution and increases with the inhibitor
(15) concentration. This indicates that the impedance of inhibited
substrate increases with the concentration of inhibitor.
(16) The Bode modulus and phase angle plots for CRS in 0.1 M
Cl3 CCOOH containing different concentrations of DBLE are
(17) given in Fig. 9. As can be seen from Fig. 9(a), the increase
of absolute impedance at low frequencies in Bode modulus
(18) conrms the higher protection with increasing the concen-
tration of DBLE, which is related to the adsorption of the
inhibitor molecules on the CRS surface. Also from Fig. 9(b),
there are one phase peak at high frequency and one valley at
low frequency, which again conrms that there are two time
constants related to respective capacitive loop and inductive
loop.
The capacitive loop at HF is usually related to the charge
transfer of the corrosion process and double layer behavior.
These capacitive loops at HF are depressed semicircles shown
in Nyquist plots and the phase angle is lower than 90 in Bode
phase plots, which could be attributed to the frequency dis-
persion as a result of the roughness and inhomogeneous of
164 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170

Table 3 Potentiodynamic polarization parameters for the corrosion of CRS in 0.1 M Cl3 CCOOH solution containing
different concentrations of DBLE at 20 C (immersion time is 6 h).
c (mg l1 ) Ecorr (mV vs. SCE) icorr (A cm2 ) bc (mV dec1 ) ba (mV dec1 ) p (%)

0 418.1 2.9 1386.8 19 181 4 51 6

10 385.3 2.5 628.2 12 178 3 31 7 54.7
50 398.5 2.1 222.7 13 152 4 30 6 83.9
100 388.7 3.4 108.6 8 138 3 27 4 92.2
200 389.5 2.6 38.3 10 119 3 24 4 97.2

electrode surface [68]. On the other hand, the cause of the
inductive loop is still uncertain. The relaxation of adsorbed
charged intermediates may result in the inductive loop [69].
This is more pronounced when the intermediates are strongly
adsorbed. The relaxations of adsorbed species include Hads +
[70], acid anions [71] or inhibitor species [30] on the electrode
surface.
The EIS results in Cl3 CCOOH solutions are simulated by
the equivalent circuits shown in Fig. 10. Rs , Rt and RL are the
solution resistance, charge transfer resistance and inductive
resistance, respectively. CPE is a constant phase element. L
is the inductance, which is intimately associated with the
inductive loop. The solid lines in Figs. 8 and 9 correspond
to the tted plots for EIS experiment data using the elec-
tric circuit of Fig. 10, which indicates that the experimental
a 103
Blank
10 mg l1
50 mg l1
100 mg l1
102
200 mg l1
Z ( cm2)
data could be simulated using this equivalent circuit. The
impedance parameters of CRS in Cl3 CCOOH solution are listed
in Table 4. The chi-squared (2 ) is used to evaluate the preci-
sion of the tted data [72,73]. Table 4 reveals that 2 values
are low, which indicates that the tted data have good agree-
ment with the experimental data. It is observed that Rs is
about 610  cm2 in 0.1 M Cl3 CCOOH, while the Rs is less than
0.5  cm2 for steel in 1.0 M HCl and 0.5 M H2 SO4 solutions
[47,48]. This implies that 0.1 M Cl3 CCOOH water solution is
not very conductive. Rt is increased to more extent when DBLE
is added to the 0.1 M Cl3 CCOOH solution, which indicates the
electrode exhibits slower corrosion in the presence of the plant
inhibitor of DBLE. In contrast, the decrease of CPE in the pres-
ence of DBLE comparing with that in blank Cl3 CCOOH solution
(without inhibitor) results from a decrease in local dielectric
constant and/or an increase in the thickness of the electrical
double layer. In other words, the inhibitor molecules func-
tion by adsorption at the metal/solution interface [67]. The
exponent n of CPE is usually used to study the change in
interfacial surface condition of steel/solution. Inspection of
Table 4 reveals that n is around 0.8, which might be resulted
from irregular surface of electrode or arbitrary distribution of
current on electrode surface causing frequency dispersion.

Fitting Curves
L is as low as 84 H cm2 in blank solution (without inhibitor),
which is increased with increase of concentration of DBLE.
101 L values are especially as high as 4666 and 4607 H cm2
with the addition of 100 and 200 mg l1 DBLE, respectively.
Accordingly, it is presumed that the adsorption/desorption
process might mainly be the adsorbed intermediates of Hads +
100
102 101 100 101 102 103 104 105 and CCl3 COO at low L (Cl3 CCOOH, Cl3 CCOOH + 10 mg l1
(Hz) DBLE), while the composition of Hads + , CCl3 COO and DBLE
b 60 inhibitor at moderate L (Cl3 CCOOH + 50 mg l1 DBLE), and
Blank mainly the DBLE inhibitor at high L (Cl3 CCOOH + 100 mg l1
50
10 mg l1 DBLE, Cl3 CCOOH + 200 mg l1 DBLE).
50 mg l1
40
100 mg l1 From Table 4, R increases with the concentration of DBLE,
Phase angle ()

30 200 mg l1 and the maximum R value could also reach the high value
Fitting Curves
of 94.0%. These results again conrm that DBLE exhibits good
20
inhibitive performance for CRS in 0.1 M Cl3 CCOOH solution.
10

10
CPE
20
102 101 100 101 102 103 104 105
(Hz) Rs Rt

Fig. 9 Bode plots of the corrosion of CRS in 0.1 M

Cl3 CCOOH without and with different concentrations of L RL

DBLE at 20 C (immersion time is 2 h): (a) Bode modulus;

and (b) Bode phase angle plots. Fig. 10 Equivalent circuit used to t the EIS.
 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170 165

Table 4 EIS parameters for the corrosion of CRS in 0.1 M Cl3 CCOOH containing DBLE at 20 C.
c (mg l1 ) Rs ( cm2 ) Rt ( cm2 ) RL ( cm2 ) CPE (F cm2 ) n L (H cm2 ) 2 R (%)
3
0 6.18 0.06 15.14 0.50 29.82 0.80 433.2 3.0 0.8401 0.02 84 4 5.09 10
10 6.15 0.09 30.91 0.80 67.96 0.90 233.3 5.0 0.8251 0.02 121 6 6.41 103 51.0
50 7.63 0.12 83.01 1.20 148.01 0.95 179.5 6.7 0.8021 0.02 1203 9 9.32 103 81.8
100 8.14 0.16 180.50 1.30 290.40 1.20 96.6 8.2 0.8187 0.03 4666 12 2.25 102 91.6
200 9.97 0.23 253.02 1.80 272.20 2.30 73.6 8.4 0.7977 0.03 4607 13 5.79 102 94.0

1
[deg]

2
150

1 4
2
3
4

[m]

b c

0 0

1
[deg]

1
[deg]

2 2
200

140

3 3

1 4 1 4
2 2
3 3
4 4

[m] [m]

Fig. 11 AFM three-dimensional images of CRS surface: (a) before immersion; (b) after 6 h of immersion at 20 C in 0.1 M
Cl3 CCOOH; and (c) after 6 h of immersion at 20 C in 200 mg l1 DBLE + 0.1 M Cl3 CCOOH.

3.5. Atomic force microscope (AFM) surface
examination
AFM provides a powerful means of characterizing the
microstructure [74], and is generally used in the eld of metal
corrosion. The three-dimensional AFM images of CRS surface
are shown Fig. 11. The CRS surface before immersion seems
smooth as shown in Fig. 11(a). However, it is not absolute
smooth and uniform, and small precipitates appear on the
steel surface, which could be attributed to some contaminates
formed on AFM tip during the examination process. As for
Fig. 11(b), the CRS surface after immersion in uninhibited 0.1 M
Cl3 CCOOH for 6 h exhibits a very rough surface owing to cor-
rosive attack by CCl3 COOH acid, and covered with the uneven
and potholed corrosion products layer upon layer. On contrast,
in the presence of 200 mg l1 DBLE, Fig. 11(c) shows that the
steel surface appears the more at, homogeneous and uni-
form, and even some original abrading scratches are seen on
the steel surface, which indicates that DBLE retards efciently
the corrosion the steel in 0.1 M Cl3 CCOOH solution.
3.6. Corrosion inhibition of the major avonoids
Bamboo leaves extract is composed of numerous chemical
compounds, and then the inhibitive action of bamboo leaves
extract would be due to the adsorption of its components on
the steel surface. However, it is rather difcult to assign the
inhibitive effective to a particular constituent owing to the
complex chemical composition of the bamboo leaves extract.
The ethanol/water extract of bamboo leaf is mainly com-
posed of the bamboo leaf avonoids (BLF) [75]. According to
our recent work [55], there is a relation between the content
166 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170

a OH b OH
OH O
HO OH
HO O HO

OH HO O
OH
O O OH
O CH3
OH O OH
OH OH OH OH O
OH

d
OH
OH
O
c OH
HO
OH O HO
OH
HO HO O
O
HO
HO HO O
HO
HO O

OH
e OH f

OH O OH O
OH

HO O HO O

Fig. 12 Chemical molecular structures of major components in BLE: (a) rutin; (b) orientin; (c) isovientin; (d) vientin; (e)
avones backbone structure (FBS); and (f) avones backbone structure (FBS) of isovientin and vientin.

of total avonoids and inhibition efciency, and it might be
deduced that the avonoids would be one of the contribu-
tors to the inhibitive activity. On the other hand, the major
avonoids in bamboo leaves extract are rutin, orientin, isovi-
entin and vientin [76,77], and their molecular structures are
shown in Fig. 12. In our recent work [49,54], rutin, orientin,
vientin and isovientin are conrmed in the presence of bam-
boo leaves extract through analyzing high performance liquid
inhibition efciency values range from 70% to 85%, which indi-
cates that these avonoids could also retard to more extent the
corrosion of steel in Cl3 CCOOH solution. Also, the inhibition
efciency decreases with the temperature.
MD simulations have been done to further study the
adsorption behavior of the four avonoids molecules of
84

chromatography (HPLC). According to the quantum chemical 82

calculations of rutin, orientin, vientin and isovientin in our
recent work [54,55], the adsorption of avonoids is mainly 80

through the avones backbone structure (FBS) whose molec- 78

w , %

ular structure is shown in Figs. 12(e) and (f). Noticeably, a

number of avonoids have similar chemical molecular skele- 76

ton structure of FBS, which implies that the series of avonoids 74 Rutin
could be seemed as the potential contributors for the inhibi- Orientin
Isovientin
tion performance [49]. 72 Vientin
In the present study, the inhibition action of four 70
major components of rutin, isovientin, vientin and orientin 15 20 25 30 35 40 45 50 55

with 200 mg l1 in 0.1 M Cl3 CCOOH solution at 20 C are Temperature (C)

studied, and the results are given in Fig. 13. The inhibi-
Fig. 13 Relationship between inhibition efciency (w ) of
tion efciency of these avonoids follows the sequence:
major avonoids with 200 mg l1 and temperature in 0.1 M
rutin > orientin > isovientin > vientin. At all temperatures, the
CCl3 COOH.
 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170
Fig. 14 Equilibrium adsorption conguration of inhibitors
on Fe (001) planes obtained by MD simulations: (a) rutin; (b)
orientin; (c) isovientin; and (d) vientin.
rutin, orientin, isovientin and vientin on the Fe (001) surface.
Through the analysis of the temperature and energy, it takes
about 250 ps for the adsorption system containing both Fe (001)
surface and the studied inhibitor molecule to reach equilib-
rium. The adsorption system is at steady state and uctuates
slightly from 500 ps to 1000 ps. Fig. 14 shows the adsorption
congurations on Fe (001) surface for inhibitor molecules, and
the corresponding Eads and Ebin values are listed in Table 5.
As can be seen from Fig. 14, these avonoids are adsorbed
on Fe (001) surface through FBS with a nearby at orienta-
tion. In other words, the adsorption center is FBS, which is
in accordance with the previous result of quantum chemical
calculations [54,55]. Moreover, the values of Eads in Table 5
reveal the sequence of rutin > orientin > isovientin > vientin,
meaning that the adsorptive ability on steel surface fol-
lows the expected trend: rutin > orientin > isovientin > vientin.
167
Table 5 Values of adsorption energy (Eads ) and binding
energy (Ebin ) between the molecules and Fe (001) plane.
Molecule Eads (kJ mol1 ) Ebin (kJ mol1 )
Rutin 1104.35 1104.35
Orientin 890.01 890.01
Isovientin 831.83 831.83
Vientin 830.95 830.95
On the other hand, magnitude of Ebin is indicative of sta-
bility of adsorptive system, and Ebin follows the order:
rutin < vientin < isovientin < orientin. More negative value
of Ebin suggests a more stable adsorption system and
leads to the higher inhibitive action. Accordingly, inhi-
bition efciency for four studied inhibitors is ranked as
rutin > orientin > isovientin > vientin based on the parameters
of Eads and Ebin . Thus, the theoretical inference is in good
agreement with experimental data.
The difference in their inhibitive action can be explained
on the basis of their molecular structure. The FBS of rutin and
orientin as shown in Fig. 12(e) has one additional hydroxyl
group (OH) than the FBS of isovientin and vientin as shown
in Fig. 12(f). The substitution OH is the additional center
of adsorption, which causes more adsorption centers and
corresponding better inhibition performance. Consequently,
rutin and orientin give better inhibitive performance than
isovientin and vientin. Besides the FBS, this classication
of inhibition efciency could be attributed to the difference
in sugar substitute to the FBS. Rutin has the disaccharide
substituents to FBS, while orientin has the monosaccharide
substituent. The disaccharide substituents have more oxy-
gen atoms, thus rutin has higher inhibitive performance than
orientin. It should be noted that the substitutional group of
both isovientin and vientin are the same. However, Fig. 13
shows that isovientin gives slightly better inhibitive perfor-
mance than vientin. This difference in inhibition efciency
could be explained on the basis of substitution group posi-
tion.
Noticeably, the inhibitory value of each avonoid is lower
than the crude extract of DBLE, which may suggest that
other composition compounds have additional contribution
to the inhibitive performance. The same conclusion was also
reported for bamboo leaves extract as the corrosion inhibitor
for steel in H3 PO4 solution [54]. Similar comparative results
between plant extract and its major component have also been
reported for the coffee extract [20] and A. pallens [26]. Besides
the avonoids, the ethanol/water extract of bamboo leaf con-
tains amino acid, chlorophyll and amylose [78], and these
compounds contain many O, N atoms in functional groups
(OH, C O, CO, NH) and O-heterocyclic rings. Thus, it is rea-
sonable to deduce that these compounds get to be protonated
in the acid solution. In Cl3 CCOOH solution, Cl3 CCOO could
be adsorbed onto the steel surface, then the protonated com-
pounds approach the steel surface due to the electrostatic
attraction. In addition, O, N atoms with plentiful lone electrons
could be considered responsible for the adsorption centers
on steel surface. Coordinate bond could be formed by par-
tial transference of electrons from the N atoms to the metal
surface.
168 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170
4. Conclusions
(1) DBLE acts as a good inhibitor for the corrosion of CRS
in 0.1 M Cl3 CCOOH solution, and w value of 120 mg l1
DBLE is higher than 94% at 20 C. Inhibition efciency
(w ) increases with the inhibitor concentration, immersion
time and acid concentration, but decreases with the tem-
perature. The adsorption of DBLE on steel surface obeys
Langmuir adsorption isotherm.
(2) The cathodic reductions of CRS in CH3 COOH involve
hydrogen evolution, H+ reaction with dissolved O2 , and
the dechlorination of Cl3 CCOO . For the anodic dissolu-
tion, the adsorption of Cl3 CCOO ions on the CRS surface
would be the prerequisite to occur, and both Fe2+ and Fe3+
ions are the dominant products.
(3) DBLE acts as a mixed-type inhibitor for CRS in 0.1 M
Cl3 CCOOH solution. EIS spectra exhibit a large capacitive
loop at high frequencies followed by an inductive one at
low frequency values. Comparing with blank solution, the
presence of DBLE enhances Rt while reduces CPE.
(4) AFM clearly shows that CRS suffers severe corrosive attack
by Cl3 CCOOH, and the presence of DBLE could drastically
retard the corrosion of steel in CCl3 COOH media.
(5) MD simulations reveal that the major avonoids in DBLE
are adsorbed on Fe (001) surface through FBS with a
nearby at orientation. The sequence of either Eads or
Ebin is in accordance with that of inhibition efciency:
rutin > orientin > isovientin > vientin.
(6) The crude extract of DBLE exhibits better inhibition
performance than the major avonoids. Other compo-
sition compounds could have additional contribution to
inhibitive performance.
Conicts of interest
The authors declare no conicts of interest.
Acknowledgements
This work was carried out in the frame of research projects
funded by the National Natural Science Foundation of China
(51161023) and Training Program of Young and Middle Aged
Academic and Technological Leaders in Yunnan Province
(2015HB049).
references
[1] Trabanelli G. Inhibitors an old remedy for a new challenge.
Corrosion 1991;47:4109.
[2] Ostovari A, Hoseinieh SM, Peikari M, Shadizadeh SR,
Hashemi SJ. Corrosion inhibition of mild steel in 1 M HCl
solution by henna extract: a comparative study of the
inhibition by henna and its constituents (lawsone, Gallic
acid, a-d-Glucose and Tannic acid). Corros Sci
2009;51:193549.
[3] El-Etre AY, Abdallah M, El-Tantawy ZE. Corrosion inhibition
of some metals using lawsonia extract. Corros Sci
2005;47:38595.
[4] Orubite KO, Oforka NC. Inhibition of the corrosion of mild
steel in hydrochloric acid solutions by the extracts of leaves
of Nypa fruticans Wurmb. Mater Lett 2004;58:176872.
[5] Chuanhan LR, Gunasekaran G. Corrosion inhibition of mild
steel by plant extract in dilute HCl medium. Corros Sci
2007;49:114361.
[6] Bouyanzer A, Hammouti B, Majidi L. Pennyroyal oil from
Mentha pulegium as corrosion inhibitor for steel in 1 M HCl.
Mater Lett 2006;60:28403.
[7] El-Etre AY. Inhibition of acid corrosion of carbon steel using
aqueous extract of olive leaves. J Colloid Interface Sci
2007;314:57883.
[8] Okafor PC, Ikpi ME, Uwah IE, Ebenso EE, Ekpe UJ, Umoren SA.
Inhibitory action of Phyllanthus amarus extracts on the
corrosion of mild steel in acidic media. Corros Sci
2008;50:23107.
[9] Abdel-Gaber AM, Abd-El Nabey BA, Sidahmed IM, El-Zayady
AM, Saadawy M. Effect of temperature on inhibitive action of
Damsissa extract on the corrosion on steel in acidic media.
Corrosion 2006;62:2939.
[10] Oguzie EE. Evaluation of the inhibitive effect of some plant
extracts on the acid corrosion of mild steel. Corros Sci
2008;50:29938.
[11] Oguzie EE. Studies on the inhibitive effect of Occimum viridis
extract on the acid corrosion of mild steel. Mater Chem Phys
2006;99:4416.
[12] Quraishi MA, Singh A, Singh VK, Yadav DK, Singh AS. Green
approach to corrosion inhibition of mild steel in
hydrochloric acid and sulphuric acid solutions by the extract
of Murraya koenigii leaves. Mater Chem Phys 2010;
122:11422.
[13] Abdel-Gaber AM, Abd-El-Nabey BA, Saadawy M. The role of
acid anion on the inhibition of the acidic corrosion of steel
by lupine extract. Corros Sci 2009;51:103842.
[14] Ekanem UF, Umoren SA, Udousoro II, Udoh AP. Inhibition of
mild steel corrosion in HCl using pineapple leaves (Ananas
comosus L.) extract. J Mater Sci 2010;45:555866.
[15] Eddy NO, Odoemelam SA, Odiongenyi AO. Joint effect of
halides and ethanol extract of Lasianthera africana on
corrosion of mild steel in H2 SO4 . J Appl Electrochem
2009;39:84957.
[16] Raja PB, Sethuraman MG. Strychnos nux-vomica an
eco-friendly corrosion inhibitor for mild steel in 1 M sulfuric
acid medium. Mater Corros 2009;60:228.
[17] Satapathy AK, Gunasekaran G, Sahoo SC, Amit K, Rodrigues
RV. Corrosion inhibition by Justicia gendarussa plant extract in
hydrochloric acid solution. Corros Sci 2009;51:284856.
[18] Lebrini M, Robert F, Lecante A, Roos C. Corrosion inhibition
of C38 steel in 1 M hydrochloric acid medium by alkaloids
extract from Oxandra asbeckii plant. Corros Sci
2011;53:68795.
[19] Behpour M, Ghoreishi SM, Khayatkashani M, Soltani N. The
effect of two oleo-gum resin exudates from Ferula
assa-foetida and Dorema ammoniacum on mild steel corrosion
in acidic media. Corros Sci 2011;53:2489501.
[20] Torres VV, Amado RS, Faia de S C, Fernandez TL, Riehl CAS,
Torres AG, et al. Inhibitory action of aqueous coffee ground
extracts on the corrosion of carbon steel in HCl solution.
Corros Sci 2011;53:238592.
[21] Rocha JC, Gomes JACP, DElia E. Corrosion inhibition of
carbon steel in hydrochloric acid solution by fruit peel
aqueous extracts. Corros Sci 2010;52:23418.
[22] Abdel-Gaber AM, Abd-El-Nabey BA, Sidahmed IM, El-Zayady
AM, Saadawy M. Inhibitive action of some plant extracts on
the corrosion of steel in acidic media. Corros Sci
2006;48:276579.
[23] Bothi RP, Abdul RA, Hasnah O, Khalijah A. Inhibition effect of
Kopsia Singapurenis extract on the corrosion behavior of mild
steel in acid media. Acta Phys Chim Sin 2010;26:21716.
 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170
[24] Li XH, Deng SD, Fu H. Inhibition by Jasminum nudiorum Lindl.
leaves extract of the corrosion of cold rolled steel in
hydrochloric acid solution. J Appl Electrochem
2010;40:16419.
[25] Deng SD, Li XH. Inhibition by Ginkgo leaves extract of the
corrosion of steel in HCl and H2 SO4 solution. Corros Sci
2012;55:40715.
[26] Garai S, Garai S, Jaisankar P, Singh JK, Elango A. A
comprehensive study on crude methanolic extract of
Artemisia pallens (Asteraceae) and its active component as
effective corrosion inhibitors of mild steel in acid solution.
Corros Sci 2012;60:193204.
[27] Soltani N, Tavakkoli N, Khayatkashani M, Jalali MR,
Mosavizade A. Green approach to corrosion inhibition of 304
stainless steel in hydrochloric acid solution by the extract of
Salvia ofcinalis leaves. Corros Sci 2012;62:12235.
[28] Li LG, Zhang XP, Lei JL, He JX, Zhang ST, Pan FS. Adsorption
and corrosion inhibition of Osmanthus fragran leaves extract
on carbon steel. Corros Sci 2012;63:8290.
[29] Tan KW, Kassim MJ, Oo CW. Possible improvement of
catechin as corrosion inhibitor in acidic medium. Corros Sci
2012;65:15262.
[30] de Assunco Araujo Pereira SS, Pgas MM, Fernndez TL,
Magalhaes M, Schntag TG, Lago DC, et al. Inhibitory action
of aqueous garlic peel extract on the corrosion of carbon
steel in HCl solution. Corros Sci 2012;65:3606.
[31] Raja PB, Qureshi AK, Rahim AA, Osman H, Awang K.
Neolamarckia cadamba alkaloids as eco-friendly corrosion
inhibitors for mild steel in 1 M HCl media. Corros Sci
2013;69:292301.
[32] Gunasekaran G, Chauhan LR. Eco friendly inhibitor for
corrosion inhibition of mild steel in phosphoric acid
medium. Electrochim Acta 2004;49:438795.
[33] Sivaraju M, Kannan K. Inhibitive properties of plant extract
(Acalypha indica L.) on mild steel corrosion in 1 N phosphoric
acid. Inter J Chem Tech Res 2010;2:124353.
[34] Li XH, Fu H, Zhang J, Liu XY. Corrosion inhibition of Acer
truncatum leaves extractive for steel in sulfuric acid solution.
Corros Sci Prot Tech 2011;23:614 [in Chinese].
[35] Li XH, Deng SD, Fu H, Liu XY. Corrosion inhibition of Acer
buergerianum leave extractive for steel in HCl solution. Corros
Prot 2010;21:28790 [in Chinese].
[36] Mourya P, Banerjee S, Singh MM. Corrosion inhibition of mild
steel in acidic solution by Tagetes erecta (Marigold ower)
extract as a green inhibitor. Corros Sci 2014;85:35263.
[37] Ji G, Anjum S, Sundaram S, Prakash R. Musa paradisica peel
extract as green corrosion inhibitor for mild steel in HCl
solution. Corros Sci 2015;90:10717.
[38] Faustin M, Maciuk A, Salvin P, Roos C, Lebrini M. Corrosion
inhibition of C38 steel by alkaloids extract of Geissospermum
laeve in 1 M hydrochloric acid: electrochemical and
phytochemical studies. Corros Sci 2015;92:287300.
[39] Matheswaran P, Ramasamy AK. Corrosion inhibition of mild
steel in citric acid by aqueous extract of Piper nigrum L. E-J
Chem 2012;9:758.
[40] Desai PS, Vashi RT. Inhibitive efciency of xylenol orange as
corrosion inhibitors for aluminum in trichloroacetic acid.
Indian J Chem Tech 2010;17:505.
[41] Sampat SS, Vora JC. Corrosion inhibition of 3s aluminium in
trichloroacetic acid by methyl pyridines. Corros Sci
1974;14:58195.
[42] Vashi RT, Desai PS. Amino acetanilides as corrosion
inhibitors for aluminum in trichloroacetic acid. Bull
Electrochem 2007;23:8793.
[43] Desai PS, Vashi RT. Inhibitive efciency of sulphathiazole for
aluminum corrosion in trichloroacetic acid. Anti-Corros
Methods Mater 2011;58:705.
169
[44] Ebenso EE, Okafor PC, Ekpe UJ. Studies on the inhibition of
aluminium corrosion by 2-acetylphenothiazine in
chloroacetic acids. Anti-Corros Methods Mater
2003;50:41421.
[45] Lu BY, Wu XQ, Tie XW, Zhang Y, Zhang Y. Toxicology and
safety of anti-oxidant of bamboo leaves. Part 1: Acute and
subchronic toxicity studies on anti-oxidant of bamboo
leaves. Food Chem Toxicol 2005;43:78392.
[46] Lu BY, Wu XQ, Shi JY, Dong YJ, Zhang Y. Toxicology and
safety of anti-oxidant of bamboo leaves. Part 2:
Developmental toxicity test in rats with antioxidant of
bamboo leaves. Food Chem Toxicol 2006;44:173943.
[47] Li XH, Deng SD, Fu H. Inhibition of the corrosion of steel in
HCl, H2 SO4 solutions by bamboo leaf extract. Corros Sci
2012;62:16375.
[48] Li XH, Fu H, Deng SD. Inhibition effect of Dendrocalamus
brandisii leaves extract on steel in hydrochloric acid solution.
J Chin Soc Corros Prot 2011;21:14954 [in Chinese].
[49] Li XH, Deng SD, Xie XG, Fu H. Inhibition effect of bamboo
leaves extract on steel and zinc in citric acid solution. Corros
Sci 2014;87:1526.
[50] Li XH, Deng SD. Inhibition effect of Dendrocalamus brandisii
leaves extract on aluminum in HCl, H3 PO4 solutions. Corros
Sci 2012;65:299308.
[51] Materials Studio 4.1. San Diego, CA: Accelrys Inc.; 2006.
[52] Liu X, Chen S, Ma H, Lin G, Shen L. Protection of iron
protection by stearic acid and steric imidazoline
self-assembled monolayers. Appl Surf Sci 2006;253:81420.
[53] Zhang J, Hu SQ, Wang Y, Guo WY, Liu JX, You L. Theoretical
investigation on inhibition mechanism of
1-(2-hydroxyethyl)-2-alkyl-imidazoline corrosion inhibitors.
Acta Chim Sin 2008;66:246975.
[54] Li XH, Deng SD, Fu H, Xie XG. Synergistic inhibition effects of
bamboo leaf extract/major components and iodide ion on
the corrosion of steel in H3 PO4 solution. Corros Sci
2014;78:2942.
[55] Li XH, Deng SD, Xie XG, Du GB. Inhibition effect of bamboo
leaf extract on the corrosion of aluminum in HCl solution.
Acta Phys Chim Sin 2014;30:188394.
[56] Zhang J, Zhao WM, Guo WY, Wang Y, Li ZP. Theoretical
evaluation of corrosion inhibition performance of
benzimidazole corrosion inhibitors. Acta Phys Chim Sin
2008;24:123944.
[57] Xu B, Liu Y, Yin XS, Yang WZ, Chen YZ. Experimental and
theoretical study of corrosion inhibition of
3-pyridinecarbozalde thiosemicarbazone for mild steel in
hydrochloric acid. Corros Sci 2013;74:20613.
[58] Li XH, Xie XG, Deng SD, Du GB. Inhibition effect of two
mercaptopyrimidine derivatives on cold rolled steel in HCl
solution. Corros Sci 2015;92:13647.
[59] Mathur PB, Vasudevan T. Reaction rate studies for the
corrosion of metals in acids I, iron in mineral acids.
Corrosion 1982;38:1718.
[60] Li XH, Deng SD, Fu H. Corrosion inhibition of red tetrazolium
for cold rolled steel in hydrochloric acid. Chin J Appl Chem
2009;26:10759.
[61] Bereket G, Yurt A, Trk H. Inhibition of the corrosion of low
carbon steel in acidic solution by selected polyelectrolytes
and polymers. Anti-Corros Methods Mater 2003;50:
42235.
[62] Singh MM, Gupta A. Corrosion behavior of mild steel in
formic acid solutions. Mater Chem Phys 1996;46:1522.
[63] Esclapez MD, Dez-Garca MI, Sez V, Tudela I, Prez JM,
Garca JG, et al. Spectroelectrochemical study of
trichloroacetic acid reduction at copper electrodes in an
aqueous sodium sulfate medium. Electrochim Acta
2011;56:813846.
170 j m a t e r r e s t e c h n o l . 2 0 1 7;6(2):158170
[64] Gao YM, Wang SM, Xu YX, Wu WT. Corrosion behavior and
mechanism of A3 steel in acetic acid. Corros Prot
2006;27:113.
[65] Qu Q, Jiang S, Li L, Bai W, Zhou J. Corrosion behavior of cold
rolled steel in peracetic acid solutions. Corros Sci
2008;50:3540.
[66] Mourya P, Singh P, Tewari AK, Rastogi RB, Singh MM.
Relationship between structure and inhibition behavior of
quinolinium salts for mild steel corrosion: experimental and
theoretical approach. Corros Sci 2015;95:7187.
[67] Hegazy MA, Ali M, Emara MM, Bakr MF, Youssef AH.
Evaluating four synthesized Schiff bases as corrosion
inhibitors on the carbon steel in 1 M hydrochloric acid.
Corros Sci 2012;65:6776.
[68] Deng SD, Li XH, Fu H. Nitrotetrazolium blue chloride as a
novel corrosion inhibition of steel in sulfuric acid solution.
Corros Sci 2010;52:38406.
[69] Amin MA, Mohsen Q, Hazzai OA. Synergistic effect of I ions
on the corrosion inhibition of Al in 1.0 M phosphoric acid
solutions by purine. Mater Chem Phys 2009;114:90814.
[70] Amin MA, Abd El-Rehim SS, El-Sherbini EEF, Bayyomi RS. The
inhibition of low carbon steel corrosion in hydrochloric acid
solutions by succinic acid: Part I. Weight loss, polarization,
EIS, PZC, EDX and SEM studies. Electrochim Acta
2007;52:3588600.
[71] Lagrene M, Mernari B, Bouanis M, Traisnel M, Bentiss F.
Study of the mechanism and inhibiting efciency of
3,5-bis(4-methylethiophenyl)-4H-1,2,4-triazole on mild steel
corrosion in acidic media. Corros Sci 2002;44:57388.
[72] Jingling MA, Wen J, Gengxin LI, Chunhua XV. The corrosion
behaviour of AlZnInMgTi alloy in NaCl solution. Corros
Sci 2010;52:5349.
[73] Osrio WR, Peixoto LC, Goulart PR, Garcia A. Electrochemical
corrosion parameters of as-cast AlFe alloys in a NaCl
solution. Corros Sci 2010;52:297993.
[74] Gewirth AA, Niece BK. Electrochemical applications of in-situ
scanning probe microscopy. Chem Rev 1997;97:112962.
[75] Jing WJ. Research progress of avonoids in bamboo leaf (FBL).
Sci-Tech Inf Dev Econ 2009;19:13941.
[76] Tang HG, Zheng WD, Chen ZD. Component study on
avonoids from leaves of Dendrocalamus latiorus. Chin Agric
Sci Bull 2005;21:1148.
[77] Li HY, Sun JY, Zhang JM, Shou D. Determination of orientin,
isoorientin, isovitexin in Bamboo leaf from different sources
by HPLC. Chin Tradit Pat Med 2004;26:20810.
[78] Yue YD, Cao HQ, Tang F. Advance in bamboo chemical
ingredients and its utilizations. J Anhui Agric Univ
2007;34:32833.