Corrosion Science 62 (2012) 163–175

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Inhibition of the corrosion of steel in HCl, H2SO4 solutions by bamboo leaf extract
Xianghong Li a,⇑, Shuduan Deng b, Hui Fu a
a
Faculty of Science, Southwest Forestry University, Kunming 650224, PR China
b
Faculty of Materials Engineering, Southwest Forestry University, Kunming 650224, PR China

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

Article history: The inhibition effect of the bamboo of Dendrocalmus sinicus Chia et J.L. Sun leaf extract (DSCLE) on the cor-
Received 31 December 2011 rosion of cold rolled steel (CRS) in 1.0–5.0 M HCl, 0.5–5.0 M H2SO4 solutions was studied by weight loss,
Accepted 17 May 2012 potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS) and atomic force
Available online 26 May 2012
microscope (AFM) methods. The results show that DSCLE is a good inhibitor in 1.0 M HCl and 0.5 M
H2SO4, and inhibition efficiency follows the order: HCl > H2SO4. The adsorption of DSCLE on CRS surface
Keywords: obeys Langmuir adsorption isotherm, and acts as a mixed-type inhibitor in both acids.
A. Steel
Ó 2012 Elsevier Ltd. All rights reserved.
B. AFM
B. EIS
B. Polarization
B. Weight loss
C. Acid inhibition

1. Introduction et al. [4,5] reported the inhibition effect of aqueous extracts of some
plant leaves (Opuntia, Aleo eru) and fruit peels (orange, mango) on
The use of inhibitors is one of the most practical methods for the corrosion of steel, aluminum, zinc and copper in acids and alu-
protecting metals against corrosion, especially in acidic media minum in NaOH solution. In 1990s, Azadirachta [6] and Vernonia
[1]. Acid solutions are widely used in industry; some of the impor- amygdalina (bitter leaf) [7] leaves extracts were reported as good
tant fields of application are acid pickling of steel, chemical clean- corrosion inhibitors for steel in HCl and H2SO4 solutions. Entering
ing and processing, ore production and oil well acidizing. As into the 21st century, along with people’s increasing awareness of
ordinary acids, HCl and H2SO4 are usually used as industrial acid protecting the environment, a large number of scientific manu-
cleaning and pickling acids. Because of the general aggression of scripts about plant leaves extracts as effective corrosion inhibitors
acid solutions, inhibitors are commonly used to retard the corro- of iron or steel in acidic media (HCl, H2SO4, HNO3, H3PO4, etc.) have
sive attack on metallic materials. During past decades, some com- been published; the studied plants such as henna [8–11], Nypa frut-
mercial inhibitors have been synthesized and used successfully to icans Wurmb [12,13], Azadirachta indica [14], Acalypha indica [15],
inhibit corrosion of steel in acidic media. However, the major prob- Zenthoxylum alatum [16,17], Damsissa [18], Mentha pulegium [19],
lem associated with most of these inhibitors is that they are not olive [20], Phyllanthus amarus [21,22], Occimum viridis [23,24], Car-
eco-friendly but toxic and expensive. Therefore, the study of new ica papaya [25], Murraya koenigii [26], Ocimum gratissimum [27], lu-
non-toxic or low-toxic corrosion inhibitors is essential to overcome pine [28], Palicourea guianensis [29], Ananas comosus [30],
this problem. The research in the field of eco-friendly corrosion Lasianthera africana [31], Strychnos nux-vomica [32,33], Rauvolfia
inhibitors has been addressed toward the goal of using cheap, serpentine [34], Justicia gendarussa [35], Oxandra asbeckii [36], Ferula
effective compounds at low or ‘‘zero’’ environmental impact. assa-foetida [37], coffee [38], fruit peel [39], Halfabar [40], Kopsia
Plant extracts are low-cost and biodegradable, and so the study Singapurenis [41], Jasminum nudiflorum [42] and ginkgo [43].
of plant extracts as corrosion inhibitors is an important scientific re- Through these studies, it is agreed that the inhibition performance
search field due to both economic and environmental benefits. As of plant extract is normally ascribed to the presence in their compo-
early as in 1930, plant extracts (dried stems, leaves and seeds) of sition of complex organic species such as tannins, alkaloids and
Chelidonium majus and other plants were used as corrosion inhibi- nitrogen bases, carbohydrates, amino acids and proteins as well
tors for steel in H2SO4 pickling baths [2]. In 1972, El Hosary et al. [3] as hydrolysis products. These organic compounds contain polar
studied the extract of Hibiscus subdariffa (Karkode) as the corrosion functions with N, S, O atoms as well as conjugated double bonds
inhibitor for Al and Zn in HCl and NaOH solutions. In 1980s, Saleh or aromatic rings in their molecular structures, which are the major
adsorption centers. However, confronting with the vast varieties of
⇑ Corresponding author. Tel.: +86 871 3863375; fax: +86 871 3863150. plant, the data regarding the use of plant leaves extract as the cor-
E-mail address: [email protected] (X. Li).

0010-938X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2012.05.008
164 X. Li et al. / Corrosion Science 62 (2012) 163–175

rosion inhibitor are still poor. In the present work, bamboo leaf ex- madzu Company, Japan). The absorption spectra of these solutions
tract is chosen to be the corrosion inhibitor. were determined with distilled water as reference.
Bamboo is a group of perennial evergreens in the Bambusoideae
subfamily, and features a short growth cycle, easy renewal, fast 2.3. Weight loss measurements
growth and strong regeneration capacity. There are about 1200
species and 70 genera of bamboo in the world. China is one of The cold rolled steel (CRS) sheets of 2.5  2.0  0.06 cm were
the richest countries in the world in terms of 500 bamboo species. abraded with a series of emery paper (grade 320-500-800) and
Bamboo leaf extract (BLE) is virtually nonpoisonous [44,45], and then washed thoroughly with distilled water and acetone. After
rich in flavonoids, amino acids, and active sugar [46]. In our labo- weighing accurately, the specimens were immersed in beakers
ratory, much work has been conducted to study the inhibition by which contained 250 ml acid solutions with different concentra-
BLE on the corrosion of metal in different media. Recently, Dendro- tions of DSCLE at a certain temperature remained by a water ther-
calamus brandisii leaves extract (DBLE) has been reported as a good mostat. All the aggressive acid solutions were open to air. After 6 h
inhibitor for steel in 1.0 M HCl solution [47]. However, in the ear- the specimens were taken out, washed, dried, and weighed accu-
lier work [47], the effects of acid concentration and immersion rately. Then the tests were repeated at different temperature and
time on inhibitive performance were still uncertain. In addition, immersion time. In order to get good reproducibility, experiments
the corrosion inhibition of BLE in H2SO4 media is little studied. were carried out in duplicate. The average weight loss of two par-
For these reasons, the present work is to investigate the corrosion allel CRS sheets was obtained. The corrosion rate (v) was calculated
inhibition of another bamboo, namely Dendrocalmus sinicus Chia et from the following equation:
J.L. Sun leaves extract (DSCLE) in HCl and H2SO4 solutions using
weight loss, polarization curves, impedance spectroscopy (EIS) W
v¼ ð1Þ
and atomic force microscope (AFM) methods. Effects of inhibitor St
concentration, temperature, immersion time and acid concentra- where W is the average weight loss of two parallel CRS sheets (g), S
tion on the corrosion inhibition were fully investigated and dis- the total area of one CRS specimen (m2), and t is the immersion
cussed. Furthermore, the comparison of inhibition performance time. With the calculated corrosion rate, the inhibition efficiency
in HCl and that in H2SO4 is discussed in detail. It is expected to (gw) was calculated as follows:
accumulate useful information about the inhibitive performance
of bamboo leaf extract for steel in HCl and H2SO4 media.
v0  v
gw ¼  100% ð2Þ
v0
2. Experimental where v0 and v are the values of corrosion rate without and with
inhibitor, respectively.
2.1. Materials
2.4. Electrochemical measurements
The experiments were performed with cold rolled steel (CRS)
with the following composition (wt%): C 0.07%, Mn 0.3%, P Electrochemical experiments were carried out in the conven-
0.022%, S 0.010%, Si 0.01%, Al 0.030% and Fe balance. The aggressive tional three-electrode cell with a platinum counter electrode (CE)
solutions of 1.0–7.0 M HCl and 0.5–7.0 M H2SO4 were prepared by and a saturated calomel electrode (SCE) coupled to a fine Luggin
dilution of AR grade 37% HCl and 98% H2SO4 with distilled water, capillary as the reference electrode. To minimise the ohmic contri-
respectively. bution, the Luggin capillary was kept close to the working electrode
Fresh Dendrocalmus sinicus Chia et J.L. Sun leaves were picked in (WE) which was in the form of a square CRS embedded in PVC
campus of Southwest Forestry University, and then cleaned with holder using epoxy resin so that the flat surface was the only sur-
tap water to eliminate ash of mud, dried for 2 days in an oven at face in the electrode. The working surface area was 1.0  1.0 cm,
60 °C, and ground to powder. Fifteen g sample of the powder was and prepared as described above (Section 2.3). Before measurement
refluxed in 450 ml 80% (percent by volume) C2H5OH at 75 °C for the electrode was immersed in test solution at open circuit poten-
2 h. The refluxed solution was filtered, and the filter liquor was tial (OCP) for 2 h to ensure OCP to reach steady state. All electro-
evaporated to 100 ml of dark brown residue, and then degreased chemical measurements were carried out using PARSTAT 2273
with petroleum ether (boiling bracket: 60–90 °C) using separating advanced electrochemical system (Princeton Applied Research).
funnel. Thereafter, the solution was evaporated to about 50 ml Each experiment was repeated at least three times to check the
dark brown residues using rotary evaporator, dried in vacuum dry- reproducibility.
ing oven at 60 °C until complete dryness (about 2 days). Then the The potential of potentiodynamic polarisation curves was in-
dark brown solid residue (about 1.6 g) of DSCLE was obtained creased at 0.5 mV s1 and started from a potential from 250 to
and preserved in a desicator. +250 mV vs. OCP. Inhibition efficiency (gp%) is defined as:
The stock solution (1000 mg l1) of DSCLE with dark yellow col-
icorr  icorrðinhÞ
or was prepared from distilled water, and then used to prepare the gp ¼  100% ð3Þ
icorr
desired concentration by dilution with distilled water. The concen-
tration range of DSCLE used was 5–200 mg l1. where icorr and icorr(inh) represent corrosion current density values
without and with inhibitor, respectively.
2.2. Characterization of DSCLE Electrochemical impedance spectroscopy (EIS) was carried out
at OCP in the frequency range of 0.01 Hz–100 kHz using a 10 mV
The solid plant extract of DSCLE was characterized by Fourier rms voltage excitation. Inhibition efficiency (gR%) is estimated
transform infrared (FTIR) spectroscopy. FTIR spectra was recorded using the following relation:
in an AVATAR-FTIR-360 spectrophotometer (Thermo Nicolet Com- RtðinhÞ  Rtð0Þ
pany, USA), which extended from 4000 to 400 cm1, using the KBr gR ¼  100% ð4Þ
RtðinhÞ
disk technique.
On the other hand, the solutions of DSCLE were analyzed by UV where Rt(0) and Rt(inh) are charge transfer resistance in the absence
spectral measurements using UV-2401PC spectrophotometer (Shi- and presence of the inhibitor, respectively.
 X. Li et al. / Corrosion Science 62 (2012) 163–175 165

2.5. Atomic force microscope (AFM) bands in –CH2 and –CH3 are found to be at 1402 and 1338 cm1,
respectively. The absorption bands at 1501 and 1264 cm1 could be
The CRS specimens of size 1.5  1.0  0.06 cm were prepared as assigned to the framework vibration of aromatic ring. Besides these,
described above (Section 2.3). After immersion in 1.0 M HCl and there are absorption bands at 1113 and 1068 cm1, which can be as-
0.5 M H2SO4 solutions without and with addition of 200 mg l1 cribed to the C–N or C–O stretching vibration. The absorption bands
DSCLE at 20 °C for 6 h, the specimen was cleaned with distilled below 1000 cm1 correspond to aliphatic and aromatic C–H group.
water, dried with a cold air blaster, and then used for a Japan These results indicate that DSCLE contains O and N atoms in func-
instrument model SPA-400 SPM Unit atomic force microscope tional groups (O–H, N–H, C@C, C@O, C@N, CAN, CAO) and aromatic
(AFM) examinations. The AFM images were measured in tapping ring.
mode using Si3N4 tips. Fig. 2 shows the UV absorption spectra of 100 mg l1 DSCLE,
100 mg l1 DSCLE in 1.0 M HCl and 100 mg l1 DSCLE in 0.5 M
H2SO4. In all cases, UV exhibits almost the same absorption curve,
3. Results and discussion which indicates that chemical structures of the components in
DSCLE are not broken down in either HCl or H2SO4 medium. Gen-
3.1. FTIR and UV of DSCLE erally, UV of flavonoids has two characteristic absorption peaks at
300–400 nm (band I) and 240–280 nm (band II) [49]. From Fig. 2,
Fourier transform infrared (FTIR) spectroscopy of DSCLE is shown the absorption spectra appear three peaks at 197, 271 and
in Fig. 1. The strong absorption band at 3414 cm1 is attributed to N– 333 nm, respectively. The weak band at 333 nm (band I) is attrib-
H or O–H stretching vibration, and that at 2932 cm1 is related to C– uted to the electron transition of cinnamic acyl with B ring of flavo-
H stretching vibration. The strong band at 1621 cm1 is assigned to noids. The absorption band at 271 nm (band II) corresponds to the
C@C and C@O stretching vibration. Owing to the conjugation effect electron transition of benzoyl A ring of flavonoids. Noticeably, the
of flavonoids of DSCLE, the C@O peak shifts from about 1700 cm1 strong peak at 197 nm is caused by the electron transition of
to lower wavenumber (approximately 1620 cm1), C@C and C@O n ? r⁄ in N and O atoms. The result implies that the main consti-
stretching vibration bands are superposition [48]. The C–H bending tution compounds in DSCLE are flavonoids and other compounds
containing N or O atoms.
100
3.2. Weight loss measurements
80
3.2.1. Effect of DSCLE on corrosion rate
938 893

Figs. 3 and 4 show the logarithmic corrosion rate values (log v) of

Transmittance (%)

493
1338

60 CRS without and with different concentrations of DSCLE at 20–50 °C

615
2932

in 1.0 M HCl and 0.5 M H2SO4 solutions, respectively. Either in 1.0 M

1113
1402

HCl or 0.5 M H2SO4, along with the increase of DSCLE concentration,

1264
1068
1501

40 the values of log v decreases gradually, i.e. the corrosion of steel is

retarded by DSCLE, or the inhibition enhances with the inhibitor
1621

concentration. This behaviour is due to the fact that the adsorption

3414

20
coverage of inhibitor on steel surface increases with the inhibitor
concentration. But when the inhibitor concentration is up to
0 100 mg l1, the corrosion rates reach certain values either in 1.0 M
4000 3500 3000 2500 2000 1500 1000 500 HCl (0.50, 1.04, 2.06 and 5.24 g m2 h1 for 20, 30, 40 and 50 °C,
Wavenumbers (cm-1) respectively) or 0.5 M H2SO4 (1.87, 3.06, 5.29 and 8.34 g m2 h1
for 20, 30, 40 and 50 °C, respectively), and then do not vary remark-
Fig. 1. FTIR spectra of DSCLE. ably. At same temperature and inhibitor concentration, the corro-

3.0 3.0 3.0

a b c
2.5 2.5 2.5

2.0 2.0 2.0

Absorbance

1.5 1.5 1.5

1.0 1.0 1.0

0.5 0.5 0.5

0.0 0.0 0.0

200 300 400 200 300 400 200 300 400
Wavelength (nm)

Fig. 2. UV spectra of DSCLE (vs. distilled water). (a) 100 mg l1 DSCLE; (b) 1.0 M HCl + 100 mg l1 DSCLE; (c) 0.5 M H2SO4 + 100 mg l1 DSCLE.
166 X. Li et al. / Corrosion Science 62 (2012) 163–175

1.6 100
1.4 20 oC
30 oC 90
1.2 40 oC
1.0 50 oC 80

0.8
log v (g m-2 h-1)

70

ηw (%)
0.6
60 20 oC
0.4 30 oC
0.2 40 oC
50
50 oC
0.0
40
-0.2
-0.4 30
0 20 40 60 80 100 120 140 160 180 200 220 0 20 40 60 80 100 120 140 160 180 200 220
c (mg l-1) c (mg l-1)

Fig. 3. Relationship between logarithmic corrosion rate (log v) and concentration of Fig. 5. Relationship between inhibition efficiency (gw) and concentration of DSCLE
DSCLE (c) in 1.0 M HCl (weight loss method, immersion time is 6 h). (c) in 1.0 M HCl (weight loss method, immersion time is 6 h).

1.8
90
1.6 20 oC
30 oC 80
1.4 40 oC
50 oC
1.2 70
log v (g m-2 h-1)

1.0 20 oC
ηw (%)

60 30 oC
0.8
40 oC
0.6 50 50 oC

0.4
40
0.2
0 20 40 60 80 100 120 140 160 180 200 220 30
-1
0 20 40 60 80 100 120 140 160 180 200 220
c (mg l )
c (mg l-1)
Fig. 4. Relationship between logarithmic corrosion rate (log v) and concentration of
DSCLE (c) in 0.5 M H2SO4 (weight loss method, immersion time is 6 h). Fig. 6. Relationship between inhibition efficiency (gw) and concentration of DSCLE
(c) in 0.5 M H2SO4 (weight loss method, immersion time is 6 h).

sion rate in 0.5 M H2SO4 is comparatively higher than that in 1.0 M

the series of bamboo leaf extract could be seemed as the good po-
HCl solution.
Also, the corrosion rate increases with temperature both in tential corrosion inhibitors for steel in acid solution.
At certain inhibitor concentration and temperature, gw follows
uninhibited and inhibited solutions, especially goes up more rap-
idly in the absence of inhibitor. These results confirm that DSCLE the order: 1.0 M HCl > 0.5 M H2SO4. Fig. 5 shows that gw decreases
with the experimental temperature within inhibitor concentra-
acts as an effective inhibitor in the range of temperature studied.
tions from 10 to 80 mg l1, but then gw increases slightly with an
increase of temperature. Similar results were reported for another
bamboo leaf extract of DBLE under same conditions [47]. For the
3.2.2. Effect of DSCLE on inhibition efficiency acid media of 0.5 M H2SO4, Fig. 6 illustrates that enhancing tem-
The values of gw for different DSCLE concentrations at 20–50 °C perature results in reducing inhibitive ability at 10–40 mg l1,
in 1.0 M HCl and 0.5 M H2SO4 solutions are presented in Figs. 5 and but in turn improves the inhibition performance at 70–200 mg l1.
6, respectively. In each acid medium, gw increases with the inhib-
itor concentration. Noticeably, when the concentration of DSCLE is 3.2.3. Adsorption isotherm
less than 100 mg l1, gw increases sharply with an increase in con- Organic compounds show inhibitive effect via adsorption on
centration, but a further raise inhibitor concentration causes no metal surface, and some adsorption isotherms have been widely
appreciable change in inhibitive performance. At the inhibitor con- used to study the mechanism of corrosion inhibition. Attempts
centration of 200 mg l1, the maximum gw in 1.0 M HCl is 89.0% at were made to fit the experimental data to various isotherms
20 °C; 90.2% at 30 °C; 91.2% at 40 °C; and 92.1% at 50 °C. In 0.5 M including Frumkin, Langmuir, Temkin, Freundlich, Bockris-Swin-
H2SO4, gw of 200 mg l1 DSCLE is 79.4% at 20 °C; 80.9% at 30 °C; kels and Flory-Huggins. In this study, Langmuir adsorption iso-
82.4% at 40 °C; and 86.5% at 50 °C. The results indicate DSCLE is a therm is applied to study the adsorption of inhibitor on steel
good inhibitor for steel in both 1.0 M HCl and 0.5 M H2SO4 solu- surface, and it has the following equation [50]:
tions. According to our recent work of the bamboo leaves extract
of DBLE [47], through comparison, the difference of inhibitive ac-
c 1
¼ þc ð5Þ
tion between two bamboo species is within 5%, which implies that h K
 X. Li et al. / Corrosion Science 62 (2012) 163–175 167

Table 1 where R is the gas constant (8.314 J K1 mol1), T the absolute tem-
Parameters of the linear regression between c/h and c in 1.0 M HCl. perature (K), and K is the adsorptive equilibrium constant (M1). Eq.
Acid solution Temperature (°C) r Slope K (l mg1) (7) can also be changed as follows [50]:
1.0 M HCl 20 0.9999 0.97 0.2395  DH 0
30 0.9999 0.97 0.1684 ln K ¼ þD ð8Þ
40 0.9999 0.95 0.1099 RT
50 0.9996 0.89 0.05246 where D is integration constant. Fig. 8 represents the straight lines
0.5 M H2SO4 20 0.9996 0.98 0.1824
30 0.9997 0.97 0.1363
of ln K versus 1/T with good linear relationship (the linear correla-
40 0.9999 0.93 0.08426 tion coefficients are 0.9684 and 0.9740 in HCl and H2SO4, respec-
50 0.9990 0.89 0.04529 tively). DH0 is calculated from the slope (DH0/R), and listed in
Table 2.
The adsorptive equilibrium constant (K) is related to the stan-
where c is the concentration of inhibitor, K the adsorptive equilib- dard adsorption free energy (DG0) obtained according to [52]:
rium constant, and h is the surface coverage, and calculated by 1 DG0
the Sekine and Hirakawa’s method [51]: K¼ expð Þ ð9Þ
csolvent RT
v0  v
h¼ ð6Þ where csolvent is the concentration of water in solution. It should
v0  vm
be noted that the unit of csolvent lies in that of K. As can be seen from
where vm is the smallest corrosion rate. Table 1, the unit of K is l mg-1, which results in that the unit
The linear regression parameters between c/h and c are listed in of csolvent is mg l-1 with the value of approximate 1.0  106.
Table 1, and the straight lines of c/h versus c in both acids at 20 °C is With the obtained both parameters of DG0 and DH0, the stan-
shown in Fig. 7. It is evident that all linear correlation coefficients dard adsorption entropy (DS0) can be calculated using the follow-
(r) are almost equal to 1, and the slope values are also close to 1, ing thermodynamic basic equation:
which indicates the adsorption of DSCLE on steel surface obeys
Langmuir adsorption isotherm. As shown in Table 1, the adsorptive DH0  DG0
DS0 ¼ ð10Þ
equilibrium constant (K) decreases with the temperature in either T
HCl or H2SO4 solution, which could be ascribed to that it is easy for All the standard thermodynamic parameters are listed in Table
inhibitor to adsorb on the steel surface at relatively lower temper- 2. In any case, the negative sign of DH0 suggests that the adsorption
ature. But when the temperature is gone up, the adsorbed inhibitor of inhibitor is an exothermic process, which means that inhibition
tends to desorb from the steel surface. At certain temperature, K efficiency decreases with rise in the temperature. The behavior
(1.0 M HCl) > K (0.5 M H2SO4), which means that DSCLE exhibits can be interpreted on the basis that increasing temperature leads
a stronger tendency to adsorb on steel surface in 1.0 M HCl com-
pared with that in 0.5 M H2SO4. Generally, large value of K is bound
up with better inhibition efficiency of a given inhibitor. This is in -1.0
good agreement with the values of gw obtained from Figs. 5 and 6.

-1.5
3.2.4. Thermodynamic parameters
Thermodynamic parameters are important to further under-
stand the adsorption process of inhibitor on steel/solution inter- -2.0
face. The standard adsorption enthalpy (DH0) could be calculated
ln K (l mg-1)

on the basis of Van’t Hoff equation:

-2.5
d ln K DH0
¼ ð7Þ
dT RT 2 1.0 M HCl
0.5 M H2SO4
-3.0

-3.5
220 0.0030 0.0031 0.0032 0.0033 0.0034 0.0035
200 1/T (K-1)
180
Fig. 8. Straight lines of ln K versus 1/T.
160
140
120
c/θ (mg l-1)

Table 2
100 Standard thermodynamic parameters of the adsorption of DSCLE on CRS surface in
acid solution.
80
1.0 M HCl Acid solution Temperature DG 0 D H0 DS 0
60
0.5 M H2SO4 (°C) (kJ mol1) (kJ mol1) (J mol1 K1)
40
1.0 M HCl 20 30.19 39.02 30.12
20 30 30.33 39.02 28.67
40 30.22 39.02 28.10
0
0 20 40 60 80 100 120 140 160 180 200 220 50 29.20 39.02 30.39
0.5 M H2SO4 20 29.52 36.52 23.88
c (mg l-1) 30 29.80 36.52 22.17
40 29.53 36.52 22.32
Fig. 7. Langmuir isotherm adsorption mode of DSCLE on the CRS surface in 1.0 M 50 28.80 36.52 23.89
HCl and 0.5 M H2SO4 at 20 °C from weight loss measurement.
168 X. Li et al. / Corrosion Science 62 (2012) 163–175

to the desorption amount of some adsorbed inhibitor molecules Table 3

from the steel surface rises as well. Generally, values of DG0 up to Parameters of the regression between ln v and 1/T.
20 kJ mol1 are consistent with the electrostatic interaction be- Acid c Ea A Linear regression
tween the charged molecules and the unlike charged metal (phys- solution (mg l1) (kJ mol1) (g m2 h1) coefficient (r)
ical adsorption) while those more negative than about 1.0 M HCl 0 57.36 6.74  1010 0.9983
40 kJ mol1 involve sharing or transfer of electrons from the 10 71.68 9.03  1012 0.9953
inhibitor molecules to the metal surface to form a co-ordinate bond 20 73.37 1.31  1013 0.9931
30 75.60 2.31  1013 0.9893
(chemisorption) [53]. Table 2 shows the values of DG0 in both acids 40 74.15 1.06  1013 0.9829
are with the range from 20 to 40 kJ mol1, probably means that 50 71.36 3.03  1012 0.9868
both physical adsorption and chemical adsorption (mixed adsorp- 60 69.81 1.46  1012 0.9897
tion) would take place. What’s more, the values of DG0 in 1.0 M 70 68.57 8.11  1011 0.9912
80 65.68 2.49  1011 0.9934
HCl is lower than that in 0.5 M H2SO4, demonstrating that it exhib-
90 63.57 1.00  1011 0.9938
its a stronger tendency for DSCLE adsorb on steel surface in HCl 100 60.74 3.14  1010 0.9928
solution. As for DS0 in Table 2, the sign is negative; means that 120 57.84 9.56  109 0.9946
the process of adsorption is accompanied by a decrease in entropy. 140 53.15 1.38  109 0.9965
It might be explained as follows: before the adsorption of inhibitor 160 54.31 2.07  109 0.9954
180 53.15 4.11  108 0.9963
onto the steel surface, the chaotic degree was high, but when inhib-
200 48.93 2.33  108 0.9977
itor molecules were orderly adsorbed onto the steel surface, as a re- 0.5 M 0 49.62 5.07  109 0.9962
sult, a decrease in entropy. H2SO4 10 60.74 2.12  1011 0.9971
20 62.77 3.70  1011 0.9919
30 60.57 1.35  1011 0.9908
3.2.5. Apparent activation energy (Ea) and pre-exponential factor (A) 40 61.11 1.50  1011 0.9921
On the basis of Arrhenius equation, the natural logarithm of the 50 58.09 4.13  1010 0.9892
corrosion rate (ln v) is a linear function with 1/T for the acid corro- 60 55.05 1.17  1010 0.9903
70 53.69 6.57  109 0.9875
sion of steel [47,50]:
80 51.69 2.87  109 0.9920
Ea 90 48.73 8.45  108 0.9951
ln v ¼ þ ln A ð11Þ 100 45.14 1.98  108 0.9962
RT 120 41.76 4.88  107 0.9970
140 41.14 3.57  107 0.9971
where Ea and A represent apparent activation energy and pre-expo-
160 41.23 3.57  107 0.9961
nential factor, respectively. 180 40.64 2.71  107 0.9959
Arrhenius plots of ln v vs. 1/T for the blank acid solutions and 200 39.25 2.54  107 0.9939
containing 200 mg l1 DSCLE are shown in Fig. 9, and the linear
regression parameters for all inhibitor concentrations are summa-
rized in Table 3. Through Fig. 9 and Table 3, all linear regression 200 mg l1. That is to say, in the present system there is a ‘‘peak-
coefficients (r) are very close to 1, which suggests that the corrosion like’’ value for Ea. The similar result was also reported for the bam-
of steel in HCl and H2SO4 solutions without and with inhibitor fol- boo leaves extract of DBLE in HCl [47]. It is noted that when the
lows the Arrhenius equation. Fig. 10 shows the relationship be- DSCLE concentration is 140–200 mg l1 in 1.0 M HCl as well as
tween Ea and inhibitor concentration in both media. Clearly, both 90–200 mg l1 in 0.5 M H2SO4, the apparent activation energy value
curves appear similar changing rule, and Ea in H2SO4 is higher than is lower than that of blank. The increase in the apparent activation
that in HCl at every inhibitor concentration. At relative lower con- energy Ea at low inhibitor concentrations may be interpreted as
centrations (0–30 mg l1 in 1.0 M HCl; 0–20 mg l1 in 0.5 M physical adsorption that occurs in the first stage [37,54–57].
H2SO4), Ea firstly increases with the concentration of inhibitor and Whereas a drop in Ea with respect to the blank solution, observed
reaches maximum values, then decreases sharply with increasing at the higher inhibitor concentration suggests chemisorption
concentration of inhibitor to about 140 mg l1, lastly remains al- [28,53,58–61]. This result may be considered in line with the sug-
most constant for the inhibitor concentration rises from 140 to gestion that the adsorption lies in the inhibitor concentration, and

5
80

4 75

70 1.0 M HCl
3 0.5 M H2SO4
65
ln v (g m-2 h-1)

2
Ea (kJ mol-1)

60

55
1
50

0 45

40
-1
0.0030 0.0031 0.0032 0.0033 0.0034 0.0035 35
0 20 40 60 80 100 120 140 160 180 200 220
1/T (K-1)
c (mg l-1)
Fig. 9. Arrhenius plots related to the corrosion rate of CRS in 1.0 M HCl and 0.5 M
H2SO4. –j– 1.0 M HCl; –d– 0.5 M H2SO4; –h– 1.0 M HCl + 200 mg l1 DSCLE; –s– Fig. 10. Relationship between apparent activation energy (Ea) and concentration of
0.5 M H2SO4 + 200 mg l-1 DSCLE. DSCLE (c) in 1.0 M HCl and 0.5 M H2SO4.
 X. Li et al. / Corrosion Science 62 (2012) 163–175 169

Table 4 100
Parameters of the linear regression between ln v and C for the corrosion of steel in HCl
and H2SO4 containing DSCLE at 20 °C (calculated from the data in Fig. 6 using Eq. (7)).

Acid solution c (mg l1) r k (g m2 h1) B (M1) 95

1.0 M HCl
HCl 0 0.9995 2.80 0.42 0.5 M H2SO4
200 0.9941 0.17 0.85
H2SO4 0 0.9964 6.28 0.51 90
200 0.9895 0.82 0.89

ηw (%)
85

manifests mainly physisorption at lower concentration while

chemisorption at higher concentration for a given inhibitor [62]. 80
From Table 4, it is also observed that the variance of A is similar
to that of Ea. Influenced by the altogether effect of the magnitudes
of Ea and A, the corrosion rate decreases with the inhibitor 75
0 12 24 36 48 60 72 84 96 108 120 132 144 156 168 180
concentration.
immersion time t (h)

Fig. 12. Effect of immersion time (t) on inhibition efficiency (gw) in 1.0 M HCl and
0.5 M H2SO4 at 20 °C (weight loss method).
3.2.6. Effect of immersion time on corrosion inhibition
The immersion time is another important parameter in assess-
ing the stability of inhibitive behaviour, so it is necessary to eval- 3.2.7. Effect of acid concentration on corrosion inhibition
uate the inhibition efficiency for a long immersion time. In the In order to study the effect of acid concentration on the corro-
present study, effect of immersion time (6–168 h) on corrosion sion of steel in the presence of 200 mg l1 DSCLE, dependence of
inhibition of 200 mg l1 DSCLE in 1.0 M HCl and 0.5 M H2SO4 at inhibition efficiency (gw) on the concentration of acid (1.0–5.0 M
20 °C was investigated using weight loss method. Fig. 11 shows HCl, 0.5–5.0 M H2SO4) at 20 °C is shown in Fig. 13. For either HCl
the corrosion rates obtained in the absence and presence of or H2SO4 media, increasing acid concentration resulted in decreas-
DSCLE act as a function of time. Without inhibitor, the corrosion ing gw gradually, and especially for H2SO4, gw decreases almost lin-
rates increases with the immersion time from 6 to 60 h, then re- early with the concentration of H2SO4. The minimum gw values are
mains at about 6.5 and 9.9 g m2 h1 in 1.0 M HCl and 0.5 M 55.6% and 26.3% in 5.0 M HCl and 5.0 M H2SO4 solutions, respec-
H2SO4, respectively. That is to say, it takes about 60 h for the cor- tively. At same acid concentration solution, inhibition performance
rosion rates in both acids reach certain values, and it is worth- follows the order: HCl > H2SO4.
while to study the effect of immersion time on the corrosion Assuming the corrosion rate (v) against the molar concentration
inhibition. Also through Fig. 11, it is found that the corrosion of acid (C) obeys the kinetic expression proposed by Mathur and
rates in the presence of DSCLE remain almost constant with the Vasudevan [63]:
immersion time studied, which may be ascribed to the adsorption
film formed on the steel surface. Dependence inhibition efficiency ln v ¼ ln k þ BC ð12Þ
(gw) on the concentration of DSCLE is shown in Fig. 12. It can be
seen that the changed rule of gw in both acids is similar. At first, where k is the rate constant, and B is the reaction constant. The
gw increases with immersion time from 6 to 36 h, while remains straight lines of ln v versus C are shown in Fig. 14, and the corre-
constant in 6–160 h (95% in 1.0 M HCl, 86% in 0.5 M H2SO4). The sponding kinetic parameters are listed in Table 4.
reasons could be attributed to the adsorptive film of inhibitor that As shown in Eq. (12), k can be deemed as a commencing rate at
rests upon the immersion time [50]. The adsorptive film reaches zero acid concentration, so k means the corrosion ability of acid for
more compact and uniform along with prolonging immersion metal [63]. Inspection of Table 4 reveals that in the presence of
time (6–36 h), and then the adsorptive film becomes saturated DSCLE, there is a drop of k to more extent, which indicates that
state within 36–160 h. the steel corrosion is retarded by the inhibitor of DSCLE. Further-

100
10
9 90

8 80
7
70
6
v (g m-2 h-1)

ηw (%)

5 0.5 M H2SO4 60
1.0 M HCl
4 50
0.5 M H2SO4 + 200 mg l-1 DSCLE
3 -1
1.0 M HCl
1.0 M HCl + 200 mg l DSCLE 40
2 0.5 M H2SO4
30
1
0 20
0 12 24 36 48 60 72 84 96 108 120 132 144 156 168 180 0 1 2 3 4 5 6
immersion time t (h) concentration of acid C (M)

Fig. 11. Effect of immersion time (t) on corrosion rate (v) of CRS in 1.0 M HCl and Fig. 13. The relationship between inhibition efficiency (gw) of 200 mg l-1 DSCLE and
0.5 M H2SO4 at 20 °C (weight loss method). acid concentration (C) at 20 °C (weight loss method).
170 X. Li et al. / Corrosion Science 62 (2012) 163–175

5 -0.2
blank
4 10 mg l
-1
-0.3 -1
50 mg l
3 100 mg l
-1

-0.4 200 mg l
-1
ln v (g m-2 h-1)

E (V vs. SCE)
1 -0.5

H2SO4
0 HCl -0.6
H2SO4 + 200 ppm DSCLE
-1 HCl + 200 ppm DSCLE
-0.7
-2
0 1 2 3 4 5 6
concentration of acid C (M) -0.8
-6 -5 -4 -3 -2 -1
-2
Fig. 14. The straight lines of ln v versus C at 20 °C. log i (A cm )

Fig. 16. Potentiodynamic polarization curves for CRS in 0.5 M H2SO4 without and
more, the values of k in 1.0–5.0 M HCl uninhibited and inhibited with different concentrations of DSCLE at 20 °C (immersion time is 2 h).
solutions are respective lower than those in 0.5–5.0 M H2SO4 unin-
hibited and inhibited solutions, which confirms that the corrosion
both anodic and cathodic curves to lower current densities. In
of CRS in H2SO4 solution is stronger than that in HCl, and the inhi-
other words, DSCLE acts as a mixed-type inhibitor in HCl solution.
bition performance in 1.0–5.0 M HCl is more superior to that in
As for 0.5 M H2SO4 solution, DSCLE also inhibits both anodic and
0.5–5.0 M H2SO4. On the basis of Eq. (12), B is the slope of the line
cathodic reactions, while prominently inhibits the cathodic reac-
ln v-C, thus B implies the changed extent of v with the acid concen-
tion compared with the anodic reaction, especially for 10 and
tration [63]. It is observed that the values of B in the presence of
50 mg l1. The potentiodynamic polarization parameters including
inhibitor increase compared with those of blank HCl and H2SO4
corrosion current densities (icorr), corrosion potential (Ecorr), catho-
solutions, which suggests that the changed extent of corrosion rate
dic Tafel slope (bc), anodic Tafel slope (ba), and inhibition efficiency
with acid concentration in inhibited acid is larger than that in
(gP) are presented in Table 5.
uninhibited acid. In addition, the value of B in H2SO4 solution is
The corrosion current density (icorr) of uninhibited 0.5 M H2SO4
higher than that in corresponding HCl solution, which indicates
is higher than that of uninhibited 1.0 M HCl, and that the reason for
that the changed degree of corrosion rate with acid concentration
this is not yet known. The polarization curves show that the higher
in H2SO4 is greater than that in HCl.
current in H2SO4 is observed in the anodic branch, and not in the
cathodic branch, so the effect is in the kinetics of anodic dissolu-
3.3. Potentiodynamic polarization curves tion. The acid anions (Cl, SO42) are firstly adsorbed on the steel
surface to form the surface complexes in the anodic process, and
Figs. 15 and 16 show the potentiodynamic polarization curves the complexes desorbed from the surface [64].
for CRS in 1.0 M HCl and 0.5 M H2SO4 solutions without and with Table 5 shows that icorr decreases considerably in the presence
different concentrations of DSCLE at 20 °C (immersion time is of DSCLE in both acids, and decreases with the increase of inhibitor
2 h), respectively. In 1.0 M HCl solution, the presence of DSCLE concentration. In turn, inhibitive ability improves with the inhibi-
causes a remarkable decrease in the corrosion rate i.e., shifts the tor concentration. gp of 200 mg l1 DSCLE reaches up to a maxi-
mum of 90.3% in 1.0 M HCl; and 79.2% in 0.5 M H2SO4. In both
acids of HCl and H2SO4 solutions, Ecorr almost does not alter in
-0.2 the presence of DSCLE, which indicates DSCLE acts as a mixed-type
blank inhibitor. According to Cao [65], the inhibition category belongs to
-1
10 mg l geometric blocking effect. That is, the inhibition action manifests
-0.3 -1
50 mg l
-1
100 mg l
-1
-0.4 200 mg l
Table 5
E (V vs. SCE)

Potentiodynamic polarization parameters for the corrosion of CRS in 1.0 M HCl and
-0.5 0.5 M H2SO4 solutions containing different concentrations of DSCLE at 20 °C.

Acid solution Ecorr icorr bc ba gp

c (mg l1) (mV vs. (lA cm2) (mV dec1) (mV dec1) (%)
-0.6 SCE)
1.0 M HCl 0 453 152.5 123 66 –
-0.7 10 462 59.0 129 70 61.3
50 469 22.7 114 61 85.1
100 464 16.1 115 64 89.4
-0.8 0.5 M 200 461 14.8 119 72 90.3
-6 -5 -4 -3 -2 -1 H2SO4 0 481 481.4 140 41 –
-2 10 484 237.8 133 30 50.6
log i (A cm )
50 485 138.9 120 31 71.1
100 495 126.0 125 52 73.8
Fig. 15. Potentiodynamic polarization curves for CRS in 1.0 M HCl without and with 200 472 100.1 122 48 79.2
different concentrations of DSCLE at 20 °C (immersion time is 2 h).
 X. Li et al. / Corrosion Science 62 (2012) 163–175 171

through the reduction of the reaction area on the surface of the tive loop at low frequencies (LF). The capacitive loop at HF is gen-
corroding metal [65]. The slight vary of both bc and ba suggests that erally related to the charge transfer of the corrosion process and
the corrosion mechanism of steel does not change in the presence double layer behavior. In contrast, the inductive loop at LF may
of DSCLE. Table 5 again reveals that at same inhibitor concentra- be attributed to the relaxation process obtained by adsorption spe-
tion, icorr (1.0 M HCl) < icorr (0.5 M H2SO4); whereas gp (1.0 M cies like FeSO4 [67] or inhibitor species [68] on the electrode sur-
HCl) < gp (0.5 M H2SO4). face. In both acids, with respect to blank solution, the shape is
maintained throughout all tested concentrations, indicating that
there is almost no change in the corrosion mechanism occurs
3.4. Electrochemical impedance spectroscopy (EIS) regardless of the inhibitor addition [69].
It is noted that these capacitive loops in both acids are not per-
Figs. 17 and 18 show the Nyquist diagrams for CRS in 1.0 M HCl fect semicircles which can be attributed to the frequency disper-
and 0.5 M H2SO4 at 20 °C (immersion time is 2 h), respectively. sion effect as a result of the roughness and inhomogeneous of
Obviously, all impedance spectra have typical characteristics that electrode surface [70]. Furthermore, the diameter of the capacitive
have been widely reported for steel in strong acid media. As shown loop in the presence of inhibitor is larger than that in blank solu-
in Fig. 17, in uninhibited and inhibited 1.0 M HCl solutions, the tion, and enlarges with the inhibitor concentration. This indicates
impedance spectra exhibit one single capacitive loop, which indi- that the impedance of inhibited substrate increases with the inhib-
cates that the corrosion of steel is mainly controlled by the charge itor concentration, and leads to good inhibitive performance.
transfer process [66]. On the other hand, in 0.5 M H2SO4 solution, The EIS results of these capacitive loops are fitted using the
the impedance spectra shown in Fig. 18 consist of two loops, one equivalent circuit shown in Fig. 19 to pure electric models that
large capacitive loop at high frequencies (HF), and one small induc- could verify or rule out mechanistic models and enable the calcu-
lation of numerical values corresponding to the physical and/or
chemical properties of the electrochemical system under investiga-
550 70
tion [61]. The circuit employed allows the identification of both
10 mg l
-1 60 blank
500 solution resistance (Rs) and charge transfer resistance (Rt). It is
50 mg l
-1 50
450 worth mentioning that the double layer capacitance (Cdl) value is
-Zr (Ω cm )

40
2

-1
100 mg l affected by imperfections of the surface, and that this effect is sim-
400 -1 30
200 mg l ulated via a constant phase element (CPE) [71]. The CPE contains
20
350 10 the component Qdl and the coefficient a that quantifies different
300 0 physical phenomena like surface inhomogeneousness resulting
-Zi (Ω cm )
2

250 0 10 20 30 40 50 60 70 from surface roughness, inhibitor adsorption, porous layer forma-

Zr (Ω cm )
2 tion, etc. The double layer capacitance (Cdl) is accounted using
200
the following relation [72]:
150
100
C dl ¼ Q dl  ð2pfmax Þa1 ð13Þ

50 where fmax represents the frequency at which imaginary value

0 reaches a maximum on the Nyquist plot. The electrochemical
parameters of Rt, Cdl and gR are calculated by ZSimpWin software
0 50 100 150 200 250 300 350 400 450 500 550
and listed in Table 6.
2
Zr (Ω cm ) Clearly, Rt increases significantly whereas Cdl reduces with the
concentration of DSCLE in both acids. The greatest inhibitive effect
Fig. 17. Nyquist plots of the corrosion of CRS in 1.0 M HCl without and with
different concentrations of DSCLE at 20 °C (immersion time is 2 h).

CPE

Rs
240 50

10 mg l
-1 40 blank Rt
200 50 mg l
-1
30
-Zr (Ω cm )
2

-1
100 mg l 20 Fig. 19. Equivalent circuit used to fit the capacitive loop.
-1
160 200 mg l 10
0
-Zi (Ω cm )

120
2

0 10 20 30 40 50 Table 6
2 EIS parameters for the corrosion of CRS in 1.0 M HCl and 0.5 M H2SO4 solutions
Zr (Ω cm ) containing DSCLE at 20 °C.
80
Acid solution c (mg l1) Rt (X cm2) Cdl (lF cm2) gR (%)
40 1.0 M HCl 0 64.8 95.3 –
10 149.8 74.5 56.7
50 369.3 65.3 82.4
0 100 484.2 57.2 86.6
200 513.6 39.3 87.4
0 40 80 120 160 200 240 0.5 M H2SO4 0 46.3 103.5 –
2 10 96.55 86.8 52.0
Zr (Ω cm )
50 149.2 72.6 69.0
100 188.3 67.1 75.4
Fig. 18. Nyquist plots of the corrosion of CRS in 0.5 M H2SO4 without and with 200 218.6 66.7 78.8
different concentrations of DSCLE at 20 °C (immersion time is 2 h).
172 X. Li et al. / Corrosion Science 62 (2012) 163–175

is observed at 200 mg l1 of DSCLE which presents Rt value of DSCLE exhibits good inhibitive performance for CRS in both acid
513.6 X cm2 in 1.0 M HCl, and 218.6 X cm2 in 0.5 M H2SO4; Cdl va- solutions, and it is more efficient to inhibit the corrosion of steel
lue of 39.3 lF cm2 in 1.0 M HCl, and 66.7 lF cm2 in 0.5 M H2SO4. in 1.0 M HCl than 0.5 M H2SO4.
A large charge transfer resistance is associated with a less corrod- Inhibition efficiencies obtained from weight loss (gw), potentio-
ing system. On the contrary, better protection provided by an dynamic polarization curves (gp) and EIS (gR) are in good reason-
inhibitor can be associated with a decrease in capacitance of the ably agreement.
metal. According to Helmholtz model [73]:

e0 e 3.5. Atomic force microscope (AFM) surface examination

C dl ¼ A ð14Þ
d
The atomic force microscope (AFM) provides a powerful tool of
where e0 is the permittivity of air, e the local dielectric constant, d characterizing the microstructure [74]. Fig. 20 shows that the
the thickness of the film and A is the surface area of the electrode. three-dimensional AFM images of steel surface in both 1.0 M
Accordingly, the small in Cdl in comparing with that in blank solu- HCl and 0.5 M H2SO4 solutions without and with DSCLE at 20 °C
tion (without inhibitor), which can result from a decrease in local (immersion time is 6 h). Fig. 20(a) and (c) reveal that the steel
dielectric constant and/or an increase in the thickness of the electri- surfaces after immersion in uninhibited 1.0 M HCl and 0.5 M
cal double layer, suggests that the inhibitor molecules function by H2SO4 solutions appear an aggressive attack on steel surface by
adsorption at the metal/solution interface [67]. gR increases with the corroding medium. There are no evident black holes or cre-
the concentration of DSCLE, and follows the order: gR (HCl) > gR vices on the surface owing to general uniform corrosion of steel
(H2SO4). The maximum gR values are 87.4% and 78.8% in 1.0 M in strong acid media. Clearly, the corrosion of steel in 0.5 M
HCl and 0.5 M H2SO4, respectively. These results again confirm that H2SO4 is stronger than that in 1.0 M HCl. In the experiment, a

Fig. 20. AFM three-dimensional images of CRS surface: (a) after 6 h of immersion at 20 °C in 1.0 M HCl; (b) after 6 h of immersion at 20 °C in 200 mg l1 DSCLE + 1.0 M HCl; (c)
after 6 h of immersion at 20 °C in 0.5 M H2SO4; (d) after 6 h of immersion at 20 °C in 200 mg l-1 DSCLE + 0.5 M H2SO4.
 X. Li et al. / Corrosion Science 62 (2012) 163–175 173

slight yellow film was observed on CRS surface in the presence of It should be noted that AFM has examined only the microstruc-
200 mg l1 DSCLE. AFM microstructures of Fig. 20(b) as well as (d) ture; we focus on only the comparison of the steel surface corro-
shows that there is a wrapping zonal film adsorbed on CRS sur- sion before and after adding inhibitor. Some limitations of this
face in either 1.0 M HCl or 0.5 M H2SO4 with addition of study are that it could not provide the chemical composition of
200 mg l1 DSCLE, which does not exist in corresponding adsorption film. Despite its limitation, this study can clearly indi-
Fig. 20(a) and (c). In accordance, it could be concluded that the cate that the steel corrosion is retarded after adding inhibitor in
adsorption film can efficiently protect the steel from corrosion. both acids.

OH O
a OH b
glu OH
OH

OH
OH
HO O
O
HO

glu O xyl

OH O OH O
c d
OH OH

OCH3 glu
OH
O O
HO O
glu

e OH O f OH
HO
H2N
OH O

NH2 HO OH

O O
H
N
O

O O O

O O
O

Fig. 21. The chemical structures of (a) orientiu-xyloside; (b) lsoorient; (c) vitexin-40 -OCH3; (d) luteolin-7-O-glucosioe; (e) d–hydroxyl lysine; (f) xylose; (g) galactose.
174 X. Li et al. / Corrosion Science 62 (2012) 163–175

3.6. Explanation for inhibition (4) The corrosion rate of steel in HCl and H2SO4 solutions with-
out and with DSCLE acts as a function of immersion time.
Bamboo leaf extract (BLE) is composed of numerous naturally gw increases with immersion time from 6 to 36 h, and then
occurring organic compounds. Accordingly, the inhibitive action remains constant (95% in 1.0 M HCl, 86% in 0.5 M H2SO4)
of BLE could be attributed to the adsorption of its components on prolonging to 160 h.
the steel surface. The ethanol/water extract of bamboo leaf mainly (5) Inhibition efficiency decreases gradually with acid concen-
contains flavonoids, amino acid and amalose that have been well tration (1.0–5.0 M HCl; 0.5–5.0 M H2SO4). The corrosion of
characterized [75,76], and the chemical structures is shown in CRS in HCl and H2SO4 solutions without and with inhibitor
Fig. 21. Inspection of Fig. 21 reveals that these compounds contain supports the kinetic equation proposed by Mathur and
many O, N atoms in functional groups (O–H, C@O, C–O, N–H) and Vasudevan. The rate constant (k) decreases markedly after
O–herterocyclic rings, which meets the general characteristics of adding DSCLE, while the reaction constant (B) increases.
typical corrosion inhibitors. Thus, it is reasonable to deduce that (6) ]DSCLE acts as a mixed-type inhibitor in 1.0 M HCl and
the flavonoids, amino acid and amalose in DSCLE exhibit the inhibi- 0.5 M H2SO4 solutions. The inhibition efficiency values
tion performance. In the present study, our results are lack of isolat- obtained from weight loss, polarization curves and EIS are
ing these compounds, thus it is not possible to determine what in good agreement.
components present in BLF created their relatively high ability to (7) The introduction of DSCLE into HCl and H2SO4 solutions
inhibit corrosion. results in the formation of a film on the CRS surface, which
These main chemical compounds as shown in Fig. 21 might be pro- effectively protects steel from corrosion.
tonated in acid media. The charge of the metal surface is determined
by the minus value of Ecorr – Eq=0 (zero charge potential) [73]. The Eq=0 Acknowledgement
of iron is 530 mV vs. SCE in HCl [77]; and 550 mV vs. SCE in H2SO4
[78]. In the present system, the values of Ecorr in 1.0 M HCl and 0.5 M This work was carried out in the frame of research projects
H2SO4 are 455 mV and 481 mV vs. SCE, respectively. The steel sur- funded by Chinese Natural Science Foundation under the grant
face charges positive in both 1.0 M HCl and 0.5 M H2SO4 solutions be- No. 51161023. The electrochemical measurements were carried
cause of Ecorr – Eq=0 > 0. The acid anions of Cl– and SO42 could be out using PARSTAT 2273 advanced electrochemical system (Prince-
firstly adsorbed; they create excess negative charge toward the solu- ton Applied Research) provided by Advanced Science Instrument
tion, and favor more adsorption of the cations [79]. Then the proton- Sharing Center of Southwest Forestry University.
ated inhibitor may adsorb on the negatively charged metal surface
through electrostatic interactions. In other words, there could be a References
synergism between anions (Cl, SO42) and protonated inhibitor.
The inhibitive ability of DSCLE in HCl is greater than that in H2SO4, [1] G. Trabanelli, Inhibitors an old remedy for a new challenge, Corrosion 47
which implies that the adsorption of inhibitor could be influenced (1991) 410–419.
[2] P.B. Raja, M.G. Sethuraman, Natural products as corrosion inhibitor for metals
by the nature of anions in acidic solutions. It is well known that Cl in corrosive media – a review, Mater. Lett. 62 (2008) 113–116.
ions have stronger tendency to adsorb than do SO42 ions [58], and [3] A.A. El Hosary, R.M. Saleh, A.M. Shams El Din, Corrosion inhibition by naturally
the electrostatic influence on the inhibitor adsorption may be the rea- occurring substances. I. Effect of Hibiscus subdariffa (karkade) extract on the
dissolution of aluminum and zinc, Corros. Sci. 12 (1972) 897–904.
son for an increased protective effect in halide-containing solution [4] R.M. Saleh, A.A. Ismail, A.A. El Hosary, Corrosion inhibition by naturally
[59]. Moreover, the lesser interference of SO42 ions with the adsorbed occurring substances. VII. The effect of aqueous extracts of some leaves and
protonated cations may lead to lower adsorption [60]. So, the adsorp- fruit peels on the corrosion of steel, aluminum, zinc and copper in acids, Br.
Corros. J. 17 (1982) 131–135.
tion of DSCLE on steel surface in HCl solution is stronger than that in [5] R.M. Saleh, A.A. Ismail, A.A. El Hosary, Corrosion inhibition by naturally
H2SO4 solution, which leads to higher inhibition performance in HCl occurring substances. IX. The effect of the aqueous extracts of some seeds,
than that in H2SO4. When protonated chemical molecules in DSCLE leaves, fruits, and fruit peels on the corrosion of aluminum in sodium
hydroxide, Corros. Sci. 23 (1983) 1239–1241.
are adsorbed on steel surface, a coordinate bond may be formed by [6] U.J. Ekpe, E.E. Ebenso, U.J. Ibok, Inhibitory action of Azadirachta leaves extract
partial transference of electrons from O, N atoms to vacant d orbits on corrosion of mild steel in tetraoxosulphate (VI) acid, J. West African Assoc.
of Fe. Owing to lone-pair electrons of O, N atoms in DSCLE, DSCLE 37 (1994) 13–30.
[7] C.A. Loto, The effect of Vernonia amygdalina (bitter leaf) solution extract on the
may combine with freshly generated Fe2+ ions on steel surface to form
corrosion inhibition of mild steel, Nig. Cor. J. 19 (1998) 20–28.
the metal inhibitor complexes. These complexes might get adsorbed [8] H. Al-Sehaibani, Evaluation of extracts of henna leaves as environmentally
onto steel surface by van der Waals force to form a protective film friendly corrosion inhibitors for metals, Mater Wissen Werkst. Tech. 31 (2000)
which keeps CRS from corrosion. 1060–1063.
[9] A. Chetouani, B. Hammouti, Corrosion inhibition of iron in hydrochloric acid
solutions by naturally henna, Bull. Electrochem. 19 (2001) 23–25.
[10] A. Ostovari, S.M. Hoseinieh, M. Peikari, S.R. Shadizadeh, S.J. Hashemi, Corrosion
4. Conclusions 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. 51 (2009) 1935–1949.
(1) DSCLE acts as a good inhibitor for the corrosion of CRS in [11] A.Y. El-Etre, M. Abdallah, Z.E. El-Tantawy, Corrosion inhibition of some metals
1.0 M HCl and 0.5 M H2SO4 solutions. Inhibition efficiency using lawsonia extract, Corros. Sci. 47 (2005) 385–395.
(gw) increases with the inhibitor concentration, and the [12] K.O. Orubite, N.C. Oforka, Inhibition of the corrosion of mild steel in
hydrochloric acid solutions by the extracts of leaves of Nypa fruticans
maximum gw of 200 mg l1 DSCLE are higher than 89%
Wurmb, Mater. Lett. 58 (2004) 1768–1772.
and 79% at 20–50 °C, respectively. [13] K. Orubit-Okorosaye, I.R. Jack, M. Ochei, O. Akaranta, Synergistic effect of
(2) The adsorption of DSCLE on CRS surface obeys Langmuir potassium iodide on corrosion inhibition of mild steel in HCl medium by
extracts of Nypa fruticans’ Wurmb, J. Appl. Sci. Environ. Manage 11 (2007) 27–
adsorption isotherm. The adsorption process is an exother-
31.
mic process accompanied by a decrease in entropy, [14] S.K. Sharma, A. Mudhoo, G. Tain, T. Sharma, Corrosion inhibition and
involves in both physisorption and chemisorption. adsorption properties of Azadirachta indica mature leaves extract as green
(3) There was a ‘‘peak-like’’ changed rule for Ea changing with inhibitor for mild steel in HNO3, Green Chem. Lett. Rev. 3 (2010) 7–15.
[15] M. Sivaraju, K. Kannan, Inhibitive properties of plant extract (Acalypha indica
the concentration in both HCl and H2SO4 solutions. The L.) on mild steel corrosion in 1 N phosphoric acid, Inter. J. Chem. Tech.
parameter of Ea indicates that the adsorption of DSCLE Research 2 (2010) 1243–1253.
manifests mainly physisorption at 10–80 mg l1 while [16] G. Gunasekaran, L.R. Chauhan, Eco friendly inhibitor for corrosion
inhibition of mild steel in phosphoric acid medium, Electrochim. Acta 49
chemisorption at 90–200 mg l1. (2004) 4387–4395.
 X. Li et al. / Corrosion Science 62 (2012) 163–175 175

[17] L.R. Chuanhan, G. Gunasekaran, Corrosion inhibition of mild steel by plant [48] Q.Y. Deng, L. Liu, H.M. Deng, Principles of Spectrometric Identification,2nd
extract in dilute HCl medium, Corros. Sci. 49 (2007) 1143–1161. Edition, Science Press, Beijing, 2007, p. 37 (in Chinese).
[18] A.M. Abdel-Gaber, B.A. Abd-El Nabey, I.M. Sidahmed, A.M. El-Zayady, M. [49] H.X. Kuang, Traditional Chinese Medicine Chemistry, Traditional Chinese
Saadawy, Effect of temperature on inhibitive action of Damsissa extract on the Medicine Press, Beijing, 2003, p. 155 (in Chinese).
corrosion on steel in acidic media, Corrosion 62 (2006) 293–299. [50] X.H. Li, S.D. Deng, H. Fu, G.N. Mu, Inhibition effect of 6-benzylaminopurine on the
[19] A. Bouyanzer, B. Hammouti, L. Majidi, Pennyroyal oil from Mentha pulegium as corrosion of cold rolled steel in H2SO4 solution, Corros. Sci. 51 (2009) 620–634.
corrosion inhibitor for steel in 1 M HCl, Mater. Lett. 60 (2006) 2840–2843. [51] I. Sekine, Y. Hirakawa, Effect of 1-hydroxyethlidene-1,1-diphosphonic acid on
[20] A.Y. El-Etre, Inhibition of acid corrosion of carbon steel using aqueous extract the corrosion of SS41 steel (1) in 0.3% sodium chloride solution, Corrosion 42
of olive leaves, J. Colloid Interface Sci. 314 (2007) 578–583. (1986) 272–277.
[21] P.C. Okafor, M.E. Ikpi, I.E. Uwah, E.E. Ebenso, U.J. Ekpe, S.A. Umoren, Inhibitory [52] R. Fuchs-Godec, V. Doleček, A effect of sodium dodecylsufate on the corrosion
action of Phyllanthus amarus extracts on the corrosion of mild steel in acidic of copper in sulphuric acid media, Colloids Surf. A 244 (2004) 73–76.
media, Corros. Sci. 50 (2008) 2310–2317. [53] F. Bentiss, M. Lebrini, M. Lagrenée, Thermodynamic characterization of metal
[22] N.O. Eddy, Ethanol extract of Phyllanthus amarus as a green inhibitor for the dissolution and inhibitor adsorption processes in mild steel/2,5-bis(n-thienyl)-
corrosion of mild steel in H2SO4, Portugaliae Electrochim. Acta 27 (2009) 579– 1,3,4-thiadiazoles/hydrochloric acid system, Corros. Sci. 47 (2005) 2915–2931.
589. [54] S. Martinez, I. Stern, Thermodynamic characterization of metal dissolution and
[23] E.E. Oguzie, Evaluation of the inhibitive effect of some plant extracts on the inhibitor adsorption processes in the low carbon steel/mimosa tannin/sulfuric
acid corrosion of mild steel, Corros. Sci. 50 (2008) 2993–2998. acid system, Appl. Surf. Sci. 199 (2002) 83–89.
[24] E.E. Oguzie, Studies on the inhibitive effect of Occimum viridis extract on the [55] J. Yu, F. Gan, L. Jiang, Inhibition effect of 2-amino-5-mercapto-1,2,4-triazole on
acid corrosion of mild steel, Mater. Chem. Phys. 99 (2006) 441–446. copper corrosion, Corrosion 64 (2008) 900–904.
[25] P.C. Okafor, E.E. Ebenso, Inhibitive action of Carica papaya extracts on the [56] S.M.A. Hosseini, M. Salari, E. Jamalizadeh, S. Khezripoor, M. Seifi, Inhibition of
corrosion of mild steel in acidic media and their adsorption characteristics, Pig. mild steel corrosion in sulfuric acid by some newly synthesized organic
Resin Tech. 36 (2007) 134–140. compounds, Mater. Chem. Phys. 119 (2010) 100–105.
[26] M.A. Quraishi, A. Singh, V.K. Singh, D.K. Yadav, A.S. Singh, Green approach to [57] M. Behpour, S.M. Ghoreishi, N. Soltani, M. Salavati-Niasari, The inhibitive effect
corrosion inhibition of mild steel in hydrochloric acid and sulphuric acid of some bis-N, S-bidentate Schiff bases on corrosion behaviour of 304 stainless
solutions by the extract of Murraya koenigii leaves, Mater. Chem. Phys. 122 steel in hydrochloric acid solution, Corros. Sci. 51 (2009) 1073–1082.
(2010) 114–122. [58] Q.H. Cai, Y.K. Shan, B. Lu, X.H. Yuan, Inhibitive behavior of cadmium sulfate on
[27] N.O. Eddy, S.A. Odoemelam, I.N. Ama, Ethanol extract of Ocimum gratissimum corrosion of aluminum in hydrochloric acid, Corrosion 49 (1993) 486–490.
as a green corrosion inhibitor for the corrosion of mild steel in H2SO4, Green [59] F. Bentiss, M. Traisnel, N. Chaibi, B. Mernari, H. Vezin, M. Lagrenée, 2, 2,5-
Chem. Lett. Rev. 3 (2010) 7–15. Bis(n-methoxyphenyl)-1,3,4-oxadiazoles used as corrosion inhibitors in acidic
[28] A.M. Abdel-Gaber, B.A. Abd-El-Nabey, M. Saadawy, The role of acid anion on media: correlation between inhibition efficiency and chemical structure,
the inhibition of the acidic corrosion of steel by lupine extract, Corros. Sci. 51 Corros. Sci. 44 (2002) 2271–2289.
(2009) 1038–1042. [60] S.A. Umoren, O. Ogbobe, I.O. Igwe, E.E. Ebenso, Inhibition of mild steel
[29] M. Lebrini, F. Robert, C. Roos, Alkaloids extract from Palicourea guianensis plant corrosion in acidic medium using synthetic and naturally occurring polymers
as corrosion inhibitor for C38 steel in 1 M hydrochloric acid medium, Int. J. and synergistic halide additives, Corros. Sci. 50 (2008) 1998–2006.
Electrochem. Sci. 6 (2011) 847–859. [61] A.R.S. Priya, V.S. Muralidharam, A. Subramania, Development of novel
[30] U.F. Ekanem, S.A. Umoren, I.I. Udousoro, A.P. Udoh, Inhibition of mild steel acidizing inhibitors for carbon steel corrosion in 15% boiling hydrochloric
corrosion in HCl using pineapple leaves (Ananas comosus L.) extract, J. Mater. acid, Corrosion 64 (2008) 541–552.
Sci. 45 (2010) 5558–5566. [62] E.E. Oguzie, G.N. Onuoha, A.I. Onuchukwu, Inhibitory mechanism of mild steel
[31] N.O. Eddy, S.A. Odoemelam, A.O. Odiongenyi, Joint effect of halides and ethanol corrosion in 2 M sulphuric acid solution by methylene blue dye, Mater. Chem.
extract of Lasianthera africana on corrosion of mild steel in H2SO4, J. Appl. Phys. 89 (2005) 305–311.
Electrochem. 39 (2009) 849–857. [63] P.B. Mathur, T. Vasudevan, Reaction rate studies for the corrosion of metals in
[32] P.B. Raja, M.G. Sethuraman, Strychnos nux-vomica an eco-friendly corrosion acids-I, Iron in Mineral Acids, Corrosion 38 (1982) 171–178.
inhibitor for mild steel in 1 M sulfuric acid medium, Mater. Corros. 60 (2009) 22–28. [64] A.M. Abdel-Gaber, N. Khalil, A. Abou El-Fetou, The dissolution mechanism of
[33] A. Singh, V.K. Singh, M.A. Quraiki, Inhibition effect of environmentally being steel in inorganic acid, Anti-Corros. Meth. Mater. 50 (2003) 442–447.
kuchla (Strychnos nuxvomica) seed extract on corrosion of mild steel in [65] C. Cao, On electrochemical techniques for interface inhibitor research, Corros.
hydrochloric acid solution, Rasayan J. Chem. 3 (2010) 811–824. Sci. 38 (1996) 2073–2082.
[34] P.B. Raja, M.G. Sethuraman, Studies on inhibition of mild steel corrosion by [66] M. Behpour, S.M. Ghoreishi, N. Mohammadi, N. Soltani, M. Salavati-Niasari,
Rauvolfia serpentine in acid media, J. Mater. Eng. Perform. 19 (2010) 761–766. Investigation some Schiff base compounds containing disulfide bond as HCl
[35] A.K. Satapathy, G. Gunasekaran, S.C. Sahoo, K. Amit, R.V. Rodrigues, Corrosion corrosion inhibitors for mild steel, Corros. Sci. 52 (2010) 4046–4057.
inhibition by Justicia gendarussa plant extract in hydrochloric acid solution, [67] M. Lagrenée, B. Mernari, M. Bouanis, M. Traisnel, F. Bentiss, Study of the
Corros. Sci. 51 (2009) 2848–2856. mechanism and inhibiting efficiency of 3,5-bis(4-metylthiophenyl)-4H-1,2,4-
[36] M. Lebrini, F. Robert, A. Lecante, C. Roos, Corrosion inhibition of C38 steel in triazole on mild steel corrosion in acidic media, Corros. Sci. 44 (2002) 573–588.
1 M hydrochloric acid medium by alkaloids extract from Oxandra asbeckii [68] A.K. Singh, M.A. Quraishi, Effect of cafazolin on the corrosion of mild steel in
plant, Corros. Sci. 53 (2011) 687–695. HCl solution, Corros. Sci. 52 (2010) 152–160.
[37] M. Behpour, S.M. Ghoreishi, M. Khayatkashani, N. Soltani, The effect of two [69] N. Labjar, M. Lebrini, F. Bentiss, N.E. Chihib, S. El Hajjaji, C. Jama, Corrosion
oleo-gum resin exudates from Ferula assa-foetida and Dorema ammoniacum on inhibition of carbon steel and antibacterial properties of aminotris-
mild steel corrosion in acidic media, Corros. Sci. 53 (2011) 2489–2501. (methylnephosnic) acid, Mater. Chem. Phys. 119 (2010) 330–336.
[38] V.V. Torres, R.S. Amado, C. Faia de Sá, T.L. Fernandez, C.A.S. Riehl, A.G. Torres, E. [70] M. Lebrini, M. Lagrenée, H. Vezin, M. Traisnel, F. Bentiss, Experimental and
D’Elia, Inhibitory action of aqueous coffee ground extracts on the corrosion of theoretical study for corrosion inhibition of mild steel in normal hydrochloric
carbon steel in HCl solution, Corros. Sci. 53 (2011) 2385–2392. acid solution by some new macrocyclic polyether compounds, Corros. Sci. 49
[39] J.C. Rocha, J.A.C.P. Gomes, E. D’Elia, Corrosion inhibition of carbon steel in (2007) 2254–2269.
hydrochloric acid solution by fruit peel aqueous extracts, Corros. Sci. 52 (2010) [71] P. Bommersbach, C. Alemany-Dumont, J.P. Millet, B. Normand, Hydrodynamic
2341–2348. effect on the behaviour of a corrosion inhibitor film: characterization by
[40] A.M. Abdel-Gaber, B.A. Abd-El-Nabey, I.M. Sidahmed, A.M. El-Zayady, M. electrochemical impedance spectroscopy, Electrochim. Acta 51 (2006) 4011–4018.
Saadawy, Inhibitive action of some plant extracts on the corrosion of steel [72] C.S. Hsu, F. Mansfeld, Concerning the conversion of the constant phase element
in acidic media, Corros. Sci. 48 (2006) 2765–2779. parameter Yo into a capacitance, Corrosion 57 (2001) 747–748.
[41] R.P. Bothi, R.A. Abdul, O. Hasnah, A. Khalijah, Inhibition effect of Kopsia [73] D.P. Schweinsberg, V. Ashworth, The inhibition of the corrosion of pure iron in
Singapurenis extract on the corrosion behavior of mild steel in acid media, 0.5 M sulphuric acid by n-alkyl quaternary ammonium iodides, Corros. Sci. 28
Acta Phys. -Chim. Sin. 26 (2010) 2171–2176. (1988) 539–545.
[42] X.H. Li, S.D. Deng, H. Fu, Inhibition by Jasminum nudiflorum Lindl. leaves extract [74] A.A. Gewirth, B.K. Niece, Electrochemical applications of in-situ scanning
of the corrosion of cold rolled steel in hydrochloric acid solution, J. Appl. probe microscopy, Chem. Rev. 97 (1997) 1129–1162.
Electrochem. 40 (2010) 1641–1649. [75] Z.X. Zhou, The studies on the chemical constituents of bamboo leaves, Resear.
[43] S.D. Deng, X.H. Li, Inhibition by Ginkgo leaves extract of the corrosion of Develop. Natur. Prod. 4 (1992) 44–51.
steel in HCl and H2SO4 solution, Corros. Sci. 55 (2012) 407–415. [76] H.Y. Li, J.W. Sun, S.W. Dai, Study on chemical components of bamboo leaf, Chin.
[44] B.Y. Lu, X.Q. Wu, X.W. Tie, Y. Zhang, Y. Zhang, Toxicology and safety of Med. Mater. 26 (2003) 562–563.
anti-oxidant of bamboo leaves. Part 1: acute and subchronic toxicity [77] G. Banerjee, S.N. Malhotra, Contribution to adsorption of aromatic amines on
studies on anti-oxidant of bamboo leaves, Food Chem. Toxicol. 43 (2005) mild steel surface from HCl solutions by impedance, UV, and Raman
783–792. spectroscopy, Corrosion 48 (1992) 10–15.
[45] B.Y. Lu, X.Q. Wu, J.Y. Shi, Y.J. Dong, Y. Zhang, Toxicology and safety of anti- [78] S.C. Roy, S.K. Roy, S.C. Sircar, Critique of inhibitor evaluation by polarization
oxidant of bamboo leaves. Part 2: Developmental toxicity test in rats with measurement, Br. Corro. J. 32 (1988) 102–104.
antioxidant of bamboo leaves, Food Chem. Toxicol. 44 (2006) 1739–1743. [79] F. Bentiss, M. Traisnel, M. Lagrenée, The substituted 1,3,4-oxadiazoles: a new
[46] Y.D. Yue, H.Q. Cao, F. Tang, Advance in bamboo chemical ingredients and its class of corrosion inhibitors of mild steel in acidic media, Corros. Sci. 42 (2000)
utilizations, J. Anhui Agri. Univ. 34 (2007) 328–333 (in Chinese). 127–146.
[47] X.H. Li, H. Fu, S.D. Deng, Inhibition effect of Dendrocalamus brandisii leaves
extract on steel in hydrochloric acid solution, J. Chin. Soc. Corros. Prot. 21
(2011) 149–154 (in Chinese).