Corrosion Science 69 (2013) 292301

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

Neolamarckia cadamba alkaloids as eco-friendly corrosion inhibitors for mild steel

in 1 M HCl media
Pandian Bothi Raja a, Ahmad Kaleem Qureshi b, Adah Abdul Rahim a,, Hasnah Osman a, Khalijah Awang b
a
b

School of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, P. Pinang, Malaysia
Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia

a r t i c l e

i n f o

Article history:
Received 7 August 2012
Accepted 28 November 2012
Available online 29 December 2012
Keywords:
A. Mild steel
B. EIS
B. Polarization
B. SEM
B. IR spectroscopy
C. Acid corrosion

a b s t r a c t
The inhibition effect of Neolamarckia cadamba crude extract (bark, leaves) and pure alkaloid (3b-isodihydrocadambine) were investigated for mild steel corrosion in 1 M HCl medium. Potentiodynamic polarization, electrochemical impedance, scanning electron microscopy, FTIR spectroscopy and molecular
modelling were employed for this study. Results showed that crude extracts and 3b-isodihydrocadambine reduced the corrosion rate signicantly at all concentrations. Polarization measurements indicated
that these green inhibitors acted through mixed type inhibition. SEM studies evidenced the formation of
a protective lm over metal surface while FTIR, supported by molecular modelling proved that this
shielding effect was caused by alkaloids, particularly 3b-isodihydrocadambine.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
In recent days, studies on steel corrosion phenomena have become an industrial and academic topic, especially in acid media
[1]. This is because of the increasing industrial applications of acid
solutions. The most important elds of applications are acid pickling, industrial cleaning, acid descaling, oil-well acidizing in oil
recovery and the petrochemical processes. Aqueous solutions of
acids are among the most corrosive media. So, the rate of corrosion
at which metals are destroyed in acidic media is very high, especially when soluble corrosion products are formed. Therefore,
investigating and exploring corrosion inhibitors for steel corrosion
in acid solutions are not only important from an academic point of
view but also for its practical applications [2,3].
Most of the reported acid corrosion inhibitors are synthetic organic compounds containing heterocyclic atoms (nitrogen, sulfur,
oxygen and phosphorous), aromatic rings or triple bonds [46].
Even though, these synthesized molecules have shown high corrosion inhibitive effect, they pollute the environment during the process of their synthesis and applications [7].
Currently, research in corrosion is focused on green corrosion
inhibitors, that show good inhibition efciency with low risk of
environmental pollution [8]. The term green inhibitor or ecofriendly inhibitor refers to substances that are biocompatible such
as plant extracts since they are of biological origin [9]. Thus natural
Corresponding author. Tel./fax: +60 46574854.
E-mail address: adah@usm.my (A. Abdul Rahim).
0010-938X/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2012.11.042

products (derived from plant materials) are being studied for their
corrosion inhibition potential as they are showing good corrosion
protection and are more environment friendly [1014]. We have
successfully reported many green corrosion inhibitors for metals
in acid media from various plant sources like mangrove tannins
[15], Kopsia singapurensis [16], Xylopia ferruginea [17] and catechins
[18].
Although, there are numerous successful reports on plant extracts as corrosion inhibitors [7], the phytochemical investigation
is rarely carried out on the extract and efforts are seldom made
on the pure compounds present in the plant extract. The aim of
the present work is to evaluate the corrosion inhibition effect of
Neolamarckia cadamba (bark and leaves) crude alkaloid extracts
and also that of the major compound from both extracts; 3bisodihydrocadambine. The crude extracts and 3b-isodihydrocadambine were tested for MS corrosion in 1 M HCl medium by using
the following techniques; potentiodynamic polarization, electrochemical impedance spectroscopy, scanning electron microscopy
(SEM) and FTIR analysis.
N. cadamba species belongs to Rubiaceae family which is known
as Laran in Malaysia and reported to have various medicinal properties such as antidiuretic [19], astringent and antihepatotoxic
[20]. Previous phytochemical studies of this plant by various investigations have led to the isolation and identication of indole
alkaloids; aminocadambines A and B [21], cadamine, cadambine,
isocadambine [22] while neolamarckines A and B [23] have been
reported from our laboratory. In continuation of alkaloid isolation
from N. cadamba species, we have isolated and structurally

P.B. Raja et al. / Corrosion Science 69 (2013) 292301

identied 3-b-isodihydrocadambine as a major compound and

tested this compound for its corrosion inhibitive potential.
2. Experimental

293

All the isolated green inhibitors (crude bark, leaf extracts and
3-b-isodihydrocadambine) were dried separately and prepared in
different concentrations (mg L1) by using AR grade HCl and
double distilled water for the corrosion analysis.
2.3. Characterization of 3b-isodihydrocadambine (Supporting
information)

2.1. Material
The leaves and bark of N. cadamba were collected at Sg. Suda
Dam, Jeli, Kelantan in 2008. The botanical identication was made
by Mr. Teo Leong Eng., Faculty of Science, University of Malaya. The
voucher specimen (Herbarium No.: KL5604) was deposited at
the Herbarium of the Department of Chemistry, University of
Malaya, Kuala Lumpur, Malaysia.
2.2. Extraction and isolation of inhibitor
Dried and ground leaves/bark of N. cadamba (2.0 kg) were separately extracted with hexane. Defatted plant material was dried
and then moistened in 25% NH4OH for 2 h. They were then soaked
and macerated with CH2Cl2 (15 L and 17 L respectively) twice over
a period of 3 days. The supernatant obtained were concentrated to
give dichloromethane crudes from leaves (30.5 g) and from bark
(38.7 g). These crudes were further subjected to acidbase treatment by using 5% HCl and 25% NH4OH to give the crude alkaloid
extracts from the leaves (3.5 g) and the bark (4.8 g). The presence
of alkaloids were tested by using TLC (Thin Layer Chromatography)
technique and Dragendoffs staining reagent giving orange spot on
aluminum TLC plate and by Mayer reagent giving cloudy precipitates [24].
The crude alkaloid (3.0 g each) of leaves/bark extract was subjected to column chromatography over silica gel using dichloromethane:methanol solvent system (100:0 ? 4:1) and nally
ushed with methanol. Further purication of the 7th and 8th fractions (CH2Cl2:MeOH; 92:08 and 90:10, respectively) of leaves and
6th fraction (CH2Cl2:MeOH; 90:10) of bark were done by Preparative Thin Layer Chromatography. The solvent systems used were
CH2Cl2:MeOH, 92:08 saturated with NH4OH for leaves while CH2Cl2:MeOH, 90:10 saturated with NH4OH for bark. The resultant
compound was a brown amorphous solid with yield of 69.6 mg
from leaves while 29.9 mg from bark which showed an orange spot
on TLC upon spraying with Dragendorff reagent. Structural elucidation of this compound, 3b-isodihydrocadambine (Fig. 1) was established by systematic spectral analysis of 1H and 13C NMR, 2D NMR,
FTIR, UV and MS data values and comparison with the literature
values [2527].

UV (MeOH) kmax (log e) 201 (4.40), 225 (4.51), and 275 (3.84)
nm; IR (KBr) mmax 3418, 2917, 1666, 1620, 1582, 1487, 1460 and
1161 cm1. HRESITOFMS gave a psuedo-molecular ion peak at
m/z 547 (M+H)+,1H NMR (500 MHz, CDCl3/CD3OD) d: 7.45 (1H, s,
H-17), 7.37 (1H, d, J = 7.8 Hz, H-9), 7.25 (1H, d, J = 7.8 Hz, H-12),
7.04 (1H, t, J = 7.8 Hz, H-11), 6.97 (1H, t, J = 7.8 Hz, H-10), 5.38
(1H, d, J = 9.1 Hz, H-21), 4.74 (1H, d, J = 7.9 Hz, H-10 ), 4.254.31
(1H, m, H-19), 3.753.87 (1H, m, H-3), 3.73 (3H, s, OMe), 3.62
3.71 (2H, m, H-60 ), 3.353.45 (2H, m, H-30 and H-40 ), 3.32 (1H. t,
J = 7.9 Hz, H-20 ), 3.153.24 (2H, m, H-18 and H-50 ), 3.023.10 (2H,
m, H-5 and H-18), 2.953.02 (2H, m, H-5 and H-15), 2.822.91
(1H, m, H-6), 2.68 (1H, br d, J = 14.9 Hz, H-6), 2.18 (1H, d,
J = 14.4 Hz, H-14), 1.912.00 (1H, m, H-20), 1.641.74 (1H, m, H14). 13C NMR (125 MHz, CDCl3/CD3OD) d: 168.9 (22-C = O), 153.2
(C-17), 136.9 (C-13), 134.8 (C-2), 127 (C-8), 121.7 (C-11), 119.3
(C-10), 118.2 (C-9), 111.4 (C-12), 109.7 (C-16), 108.3 (C-7), 100.1
(C-10 ), 96.5 (C-21), 77 (C-50 ), 76.8 (C-30 ), 73.2 (C-20 ), 69.4 (C-40 ),
64.9 (C-19), 63.6 (C-3), 61 (C-60 ), 58.7 (C-18), 55.4 (C-5), 51.8
(22-OCH3), 43.4 (C-20), 36.8 (C-14), 33.3 (C-15), 22.9 (C-6).
2.4. Specimen preparation
Mild steel (MS) specimens (C = 0.205 wt%, Si = 0.06 wt%,
Mn = 0.55 wt%, S = 0.047 wt%, P = 0.039 wt% and Fe remaining)
with an exposed area of 3.14 cm2 were used for the electrochemical study and specimens of size 2.3  0.2  2.3 cm were used for
the SEM analysis. The surface preparation of the mechanically
abraded specimens was carried out using different grades (350,
500, 800, 1000, 1200 and 1500) of emery papers.
2.5. Electrochemical studies
Electrochemical studies were carried out using Gamry Instruments reference 600 (potentiostat/galvanostat/ZRA). A conventional three electrode system was used for this purpose. MS
specimen was used as a working electrode. Pt electrode and saturated calomel electrode (SCE) served as auxillary and reference

Fig. 1. Structure of 3b-isodihydrocadambine.

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P.B. Raja et al. / Corrosion Science 69 (2013) 292301

Table 1
Corrosion inhibition effect of N. cadamba extract on MS in HCl medium (impedance
studies).
S.
Inhibitor Concentration of Rct
CPE
n
no.
inhibitor
(X cm2) (lF cm2)
1
(mg L )

Chi
Square

g
(%)

1.

5.85

513.7

0.906 0.000076

2.

Bark
extract

1
2
3
4
5

14.53
20.66
38.04
45.84
47.90

283.7
214.6
167.5
141.9
139.6

0.917
0.917
0.916
0.915
0.914

0.00008
0.00011
0.00022
0.00024
0.00026

64
76
79
81
82

3.

Leaves
extract

1
2
3
4
5

17.66
25.94
31.30
35.07
36.42

253.3
204.9
176.9
164.5
156.2

0.918
0.917
0.921
0.919
0.918

0.00017
0.00015
0.00017
0.00021
0.00021

67
77
81
83
84

4.

Pure
alkaloid

1
2
3
4
5

8.74
15.85
28.80
29.88
34.47

381.3
278.6
229.1
183.7
180.1

0.916
0.916
0.921
0.917
0.917

0.00092
0.00011
0.00015
0.00016
0.00018

33
63
80
81
83

2.6. Electrochemical impedance study (EIS)

AC impedance measurements were carried out at potential
amplitude of 10 mV, peak-to-peak (AC signal) in open-circuit, with
10 points per decade and the frequency ranging from 10,000 Hz to
0.1 Hz. The impedance results obtained are represented as Nyquist
plots. Inhibition efciency g (%) is calculated from the charge
transfer resistance (Rct) values by using the following equation:

g % 1 

Rcto
Rcti


 100

where Rct(o) is the charge transfer resistance of MS without inhibitor, Rct(i) is the charge transfer resistance of MS with inhibitor.

2.7. Potentiodynamic polarization study

Fig. 2. Nyquist plots for MS in 1 M HCl medium in the presence and absence of N.
cadamba, (a) bark extract, (b) leaves extract, and (c) 3b-isodihydrocadambine.

Potentiodynamic polarization measurements were carried out

by scanning the electrode potential from 800 mV to 200 mV
(vs SCE) with a scan rate of 0.5 mV s1. The linear Tafel segments
were chosen (approximately 50100 mV from the corrosion potential, Ecorr, of the anodic and cathodic curves) and were extrapolated
to Ecorr several times to obtain reproducible corrosion current density (icorr) values. Eq. (2) shows the calculation of g (%) from the icorr
values:

g % 1 

icorri
icorro

 100

where icorr(o) is the corrosion current density of MS without inhibitor, icorr(i) is the corrosion current density of MS with inhibitor.
Fig. 3. The electrical equivalent circuit for AC impedance measurement.

electrodes, respectively. All polarization and impedance curves

were recorded at room temperature (30 2 C) at pH range of
0.70.8. The working electrode was immersed in the test solution
for 30 min until a steady state open-circuit potential was attained.
GAMRY Echem Analyst software package 5.50 was used for tting
impedance data in an equivalent circuit as well as for extrapolating
Tafel slopes. Experiments were carried out in duplicate to ensure
reproducibility of results.

2.8. Scanning Electron Microscope (SEM) analysis

SEM LEO SUPRA 50VP Scanning Electron Microscope was used
at an accelerating voltage of 15 keV for monitoring the surface
morphological changes. For this study, MS plates were carefully
polished to a 2500 grit surface nish using silicon carbide paper
and immersed in 1 M HCl medium in the presence and absence
of 5 mg L1 of inhibitors for 6 h. Then the specimens were cleaned
with distilled water, dried in cold air blaster and used for the SEM
analysis.

P.B. Raja et al. / Corrosion Science 69 (2013) 292301

295

Occupied Molecular Orbital (HOMO) and Lowest Unoccupied

Molecular Orbital (LUMO) was performed using Gaussian 03 program [28]. The global minimum energy structure of inhibitor was
obtained by using density functional theory (DFT) with Becke 3Parameter combined with Lee, Yang and Parr functional (B3LYP)
method with 6-31G(d,p) basis set. The same level of theory
(B3LYP/6-31G(d,p)) was used to compute the molecular orbitals
of different oxidation states of Fe (0, +2 and +3). The molecular
orbitals were visualized using Gassview (4.2) program.

3. Results and discussion

3.1. Electrochemical impedance study (EIS)

Fig. 4. Tafel plots for MS in 1 M HCl medium in presence and absence of N.

cadamba, (a) bark extract, (b) leaves extract, and (c) 3b-isodihydrocadambine.

2.9. FTIR analysis

The isolated inhibitor (3b-isodihydrocadambine), as well as the
protective lm formed over the MS surface by the inhibitor molecule was analyzed separately by FTIR spectroscopy using the KBr
pellet method. For this purpose, MS specimens were immersed in
the corrosive medium consisting of 5 mg L1 of 3b-isodihydrocadambine for 120 h which resulted in the formation of a ne protective
lm over the MS surface. Further, the lm was carefully scratched
out from the MS surface and analyzed. The study was carried out
by using the Perkin Elmer System 2000 FTIR instrument.
2.10. Molecular modelling
The structure optimization of pure alkaloid (3b-isodihydrocadambine) as well as the molecular orbitals calculations viz., Highest

EIS measurements were carried out to study the concentration

effect on MS in 1 M HCl in the absence and presence of N. cadamba
barks, leaves extracts and 3b-isodihydrocadambine; results obtained are depicted as Nyquist plots in Fig. 2ac respectively. An
equivalent circuit (Fig. 3) was used to consider all the processes involved in the electrical response of the system. The rst element in
the circuit is a resistance (Rs) which corresponds to the ohmic
resistance of the system. A constant phase element (CPE) represents the double layer capacity. A resistance Rct represents the
inhibitors resistance to the charge transfer upon oxidation of the
metal. The different elements were evaluated by a tting procedure. The data obtained after the tting procedure are shown in
Table 1.
Analysis of the Nyquist plots (Fig. 2) showed a depressed capacitive loop which arises from the time constant of the electrical double layer and charge transfer resistance. This could be attributed to
different physical phenomena such as roughness and inhomogeneities of the solid surfaces, impurities, grain boundaries and distribution of the surface active sites [29]. All the curves obtained are
approximated by a single capacitive semicircle, showing that the
corrosion process was mainly charge-transfer controlled [30]. The
general shape of the curves is very similar for all samples; the
shape is maintained throughout the whole test period, indicating
that almost no change in the corrosion mechanism occurred either
due to the immersion time or to the inhibitor addition [31].
The various impedance parameters such as charge transfer
resistance (Rct), CPE, n, goodness of t (chi square) and g (%) calculated are depicted in Table 1. The value of n seems to be associated with the non-uniform distribution of current as a result of
roughness and possible oxide surface defects. When n = 1, CPE is
an ideal capacitor. A true capacitive behavior is rarely obtained.
The n values close to 1 (Table 1) represent the deviation from
the ideal capacitor. A constant phase element (CPE) is utilized for
data tting instead of an ideal capacitor, since the n values obtained were in the range of 0.9, the value obtained from the data
tting was taken as the capacitance. The quality of tting to the
equivalent circuit was judged by chi square value [32]. The obtained chi square values (0.000070.00011) in Table 1 indicate a
good tting to the proposed circuit.
From Table 1, it is observed that addition of inhibitors increases
Rct values (5.8547.90 X cm2) while decreases CPE values (513.7
141.9 lF cm2); which indicated reduction in corrosion rate. Correspondingly, all studied inhibitors showed good g (%) with similar
trend and reached maximum of above 80% at concentration level
of 45 mg L1. Bark and leaf extracts showed similar g (%) values
since both extracts contain similar types of alkaloid phytoconstituents that has enabled us to isolate the pure alkaloid (3b-isodihydrocadambine) as a major compound.
At lower concentrations (1 and 2 mg L1), 3b-isodihydrocadambine showed less g (%) values compared with that of the bark and
leaf extracts. The presence of other alkaloid constituents (besides

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P.B. Raja et al. / Corrosion Science 69 (2013) 292301

Table 2
Corrosion inhibition effect of N. cadamba extract on MS in HCl medium (polarization studies).
Inhibitor

Concentration of inhibitor (mg L1)

ba (mV dec1)

bc (mV dec1)

Ecorr (mV) (vs SCE)

icorr (lA cm2) (0.5  104)

g (%)

Bark extract

0
1
2
3
4
5

94
65
63
60
61
60

112
114
117
130
124
125

457
460
465
452
460
445

1930
350
263
221
193
169

81
86
88
90
91

Leaves extract

1
2
3
4
5

60
70
70
70
70

125
128
130
135
135

445
456
458
458
450

604
406
284
236
229

69
79
85
87
88

Pure alkaloid

1
2
3
4
5

75
65
65
60
60

107
104
104
106
112

472
461
453
474
469

850
413
227
216
204

55
78
87
88
89

the pure alkaloid) in the crude extracts, may have been involved in
the corrosion inhibition process or synergistically enhance the
adsorption of crude alkaloids over the MS surface.
3.2. Potentiodynamic polarization study
Fig. 4ac displays the potentiodynamic polarization curves of
MS in 1 M HCl medium which were obtained before and after
the introduction of various doses of N. cadamba inhibitors (bark,
leave extracts and 3b-isodihydrocadambine). Various corrosion
parameters viz., corrosion current density (icorr), corrosion potential (Ecorr) and Tafel slope values (ba and bc) derived from these gures are given in Table 2.
Precise evaluation of Tafel slopes by Tafel extrapolation is often
impossible, simply because an experimental polarization curve
does not exhibit linear Tafel regions [3337]. Most of the polarization curves obtained in our studies, especially the blank sample, do
not display the expected log/linear Tafel behavior but both anodic
and cathodic branches exhibited curvature over the complete applied potential range. Bandy and Jones [36] attributed this to a
number of aspects including a change in the nature of the metal
surface as liberated corrosion products or impurities in the steel
(e.g., Fe3C) deposit to form a non-passivating, conducting surface
lm [33]. At both cathodic and anodic branches, since the solution
is stationary, diffusion of H+ ions and Fe ions will be slow, and concentration polarization can act to shorten the cathodic and anodic
linear Tafel regions.

In aerated acidic solution, along with dissolved oxygen, only

one anodic (metal dissolution) and two cathodic (hydrogen evolution and dissolved oxygen reduction) reactions are expected. Thus,
the composite cathodic branch may also exhibit no linearity or a
short Tafel region [33]. In the extreme case, linearity may disappear altogether such as in ours, with the cathodic and anodic reactions now under combined activation and diffusion control at Ecorr.
Therefore, at cathodic and anodic overpotentials, the marked curvature in the experimental Tafel plot is roughly mimicked by the
calculated plots (Fig. 5) and extrapolated by using Gamry Echem
Analyst software version 5.50, according to the procedure described in Section 2.7. Lack of linear Tafel regions has given rise
to an uncertainty and source error in the numerical values of icorr
as shown in Table 2.
From Table 2, it could be observed that the presence of different
concentrations of green inhibitors molecules cause a decrease of
the current density (icorr) when the concentration of the inhibitor
is increased. It is also observed that addition of N. cadamba leaves
and bark extract slightly shifted Ecorr values (10 mV) in both anodic and cathodic directions while the pure alkaloid showed Ecorr
shift (15 mV) in the cathodic direction.
But, analysis of both anodic (ba) and cathodic (bc) Tafel slope
values indicated that both anodic and cathodic reactions were suppressed during the addition of all green inhibitors, which suggested that all inhibitors reduced anodic dissolution and also
retarded the hydrogen evolution reaction [38]. Thus, Tafel slope
values conrmed that N. cadamba leaves and bark extract as well

Fig. 5. Tafel extrapolation method for the calculation of Tafel parameters for blank (MS in 1 M HCl).

P.B. Raja et al. / Corrosion Science 69 (2013) 292301

297

Fig. 6. Langmuir plot of N. cadamba, (a) bark extract, (b) leaves extract, and (c) 3bisodihydrocadambine on MS corrosion in 1 M HCl medium.

as pure alkaloid reduced corrosion rate through mixed type of inhibition. The obtained g (%) values showed similar trend with the
impedance results and reached maximum of above 87% at concentrations of 45 mg L1 but were slightly deviated at lower concentrations (12 mg L1). The shorter experimental duration for the
impedance study in comparison with the polarization measurement may reduce the adsorption of inhibitor molecules at lower
concentrations. Consequently, less inhibitor molecules were adsorbed onto the MS surface and were not sufcient to form a
time-resistant layer [39], leading to low Rct values which caused
a decrease in g (%) values at low concentrations of inhibitors.
3.3. Adsorption isotherm
It is generally assumed that the adsorption of the inhibitors on
the metal surface is the essential step in the inhibition mechanism
[40]. To establish the adsorption mode, the fraction of the surface

Fig. 7. SEM images of, (a) abraded MS, (b) MS immersed in 1 M HCl medium, (c) MS
immersed in 1 M HCl medium containing 5 mg L1 of N. cadamba bark extract, (d)
MS immersed in 1 M HCl medium containing 5 mg L1 of N. cadamba leaves extract,
(e) MS immersed in 1 M HCl medium containing 5 mg L1 of 3bisodihydrocadambine.

covered by adsorbed molecules (h) was calculated from Eqs. (3)

and (4) for impedance and polarization studies respectively [41]:

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P.B. Raja et al. / Corrosion Science 69 (2013) 292301

Fig. 8. IR absorption spectra of, (a) 3b-isodihydrocadambine, and (b) protective lm formed by 3b-isodihydrocadambine.



Rcti  Rcto
Rcti



icorro  icorri
icorro

Data were tested graphically by tting to various isotherms. The

plot of concentration (C) against C/h resulted in a straight line
(Fig. 6ac) accordingly with Langmuir adsorption isotherm, which
can be expressed as:

C
1
C

h K ads

Fig. 9. Optimized structure of 3b-isodihydrocadambine.

where Kads is the adsorption equilibrium constant which can be calculated from the intercept of the straight line on the C/h-axis. In all
3 cases, the linear regression coefcients (R2) are almost equal to 1
and the slopes are very close to 1, indicating that these green inhibitors were adsorbed on the MS surface according to Langmuir
adsorption isotherm [42]. Kads values found for leaves extract are

Fig. 10. Electron density distribution on 3b-isodihydrocadambine molecule, (a) HOMO, (b) LUMO.

P.B. Raja et al. / Corrosion Science 69 (2013) 292301

299

Fig. 11. Electron density distribution on Iron, (a) Fe (HOMO and LUMO together), (b) Fe2+ (HOMO), (c) Fe2+ (LUMO), (d) Fe3+ (HOMO), (e) Fe3+ (LUMO).

Table 3
Calculated quantum chemical parameters for pure alkaloid (3b-isodihydrocadambine) and iron (Fe, Fe2+ and Fe3+).
Compound

EHOMO (eV)

ELUMO (eV)

DE (eV) (EHOMO  ELUMO)

Pure alkaloid
Fe
Fe2+
Fe3+

0.188
0.201
1.001
1.765

0.033
0.123
0.705
1.124

0.155
0.078
0.296
0.641

2500 L g1 for both impedance and polarization studies; bark extract showed 2500 L g1 for impedance and 5000 L g1 for polarization studies while 3b-isodihydrocadambine showed 527 L g1 for
impedance and 1360 L g1 for polarization studies. Higher values
of Kads showed that the inhibitor adsorbed more strongly on MS surface [43].
3.4. SEM analysis
To establish whether corrosion inhibition is due to the formation of green inhibitors protective lm on the metal surface, SEM
images were taken. Fig. 7 shows the results of the surface morphology of SEM analysis of the samples (MS) examined. Fig. 7b presents
the micrograph of MS obtained after exposure to 1 M HCl medium
while Fig. 7ce represents the surface morphology of MS
specimens immersed in 1 M HCl medium containing 5 mg L1 of
corrosion inhibitors viz., N. cadamba bark, leaves and 3b-isodihyd-

rocadambine respectively. Parallel features on the polished MS surface before exposure to the corrosive solution, which are
associated with polishing scratches (Fig. 7a) were observed.
Fig. 7b shows the SEM image after immersion, which revealed a
severe damage on the MS surface due to metal dissolution. It appeared that material dissolution began on grain boundaries between ferrite and perlite. It is well known that grain boundaries
are active sites where dislocations and other lattice defects are
accumulated, so that iron oxide/oxyhydroxide deposition is likely
to be initiated on grain boundaries to be later spread to the whole
surface. Fig. 7ce shows the protected MS surface after addition of
green inhibitors, whereby the surface damage has diminished in
comparison to the blank material. This is attributed to the formation of a good protective lm on the MS surface.
3.5. FTIR studies
The FTIR spectra were taken for the characterization of the pure
alkaloid, 3b-isodihydrocadambine as well as the scratched protective lm formed over the MS surface and are given in Fig. 8a and b,
respectively. FTIR spectra (Fig. 8a) of 3b-isodihydrocadambine
showed peaks which may be assignable to OAH, NAH stretches
(3418 cm1), NAH bending (1620 cm1), carbonyl of a methyl ester
(1666 cm1) and aromatic C@C stretches (indole moiety) at
1582 cm1, 1487 cm1 and 1460 cm1 [27]. In Fig. 8b, the carbonyl
peak (1666 cm1 Fig. 8a) that has shifted and merged with the
NAH bending peak (1620 cm1 Fig. 8a) and with aromatic C@C

Fig. 12. Possible mode of interaction of 3b-isodihydrocadambine on MS surface in 1 M HCl medium.

300

P.B. Raja et al. / Corrosion Science 69 (2013) 292301

peak (1582 cm1 Fig. 8a) to give a broad absorption band centred
at 1628 cm1 (Fig. 8b) is observed. Further, aromatic C@C peaks
at 1460 cm1 and 1487 cm1 were merged, broadened and shifted
to 1455 cm1 (Fig. 8b). These observations suggested that aromatic
indole moiety and carbonyl groups of 3b-isodihydrocadambine
may be involved in the corrosion inhibition process by coordinating with the iron metal.
3.6. Molecular modelling studies
Molecular modelling study was carried out to determine the
electron rich groups/atoms in a molecule as well as calculation of
the highest molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) will give further insights on the possibility of electron transfer between the inhibitor and metal.
The optimized geometry of 3b-isodihydrocadambine is given in
Fig. 9 and their corresponding Frontier molecular orbitals (HOMO
and LUMO) are shown in Fig. 10a and b respectively. Fig. 11 shows
the molecular orbitals of iron (Fe, Fe2+ and Fe3+) while the energy
levels viz., EHOMO, ELUMO and DE calculated are depicted in Table 3.
From Fig. 10, it is evident that electron density (HOMO) is located
within the vicinity of the aromatic indole moiety while that of
LUMO is located on carbonyl group (C@O). An ideal corrosion
inhibitor has a greater tendency to donate electrons, receive electrons or bind strongly to the metal surface [44] which suggests that
3b-isodihydrocadambine may donate electrons to the metal surface through HOMO (indole moiety) and accept electrons from
the metal surface through LUMO (carbonyl group). These observations are in agreement with the FTIR results that suggested these
two groups (aromatic indole moiety and carbonyl group) are involved in coordination with the MS surface. Further, EHOMO value
for 3b-isodihydrocadambine was found to be 0.188 eV, which
was higher (less negative) than that of iron values (0.201,
1.001 and 1.765 eV). The literature shows that EHOMO is often
associated with the electron donating ability of the molecule and
the g (%) increases with increase in the values of EHOMO [45]. A
higher value of EHOMO for 3b-isodihydrocadambine than of iron
[45] clearly suggests that it has a greater potential to donate electrons. Moreover, higher energy gap values (DE) will prevent the inter electron transfer and prefer the electron donation to MS.
From Table 3, it is clear that the energy gap values follow the
order, Fe > 3b-isodihydrocadambine > Fe2+ > Fe3+; which suggested
that 3b-isodihydrocadambine has an ability to donate electrons
preferably to Fe3+ and Fe2+. Thus, molecular modelling studies supported well the corrosion inhibition potential of 3b-isodihydrocadambine while its possible mode of interaction with metal surface is
given in Fig. 12.

4. Conclusion
In this study, corrosion inhibition efciency of N. cadamba
leaves and bark extract, 3b-isodihydrocadambine on MS in 1 M
HCl medium was determined by polarization, impedance and
SEM analysis. Results evidenced that all these green inhibitors
showed excellent performance (more than 80% at 5 mg L1) as corrosion inhibitors. They inhibit corrosion through adsorption process and were found to follow Langmuir adsorption isotherm.
Impedance studies revealed that the inhibitors reduced the corrosion rate by increasing the resistance of the system, and the equivalent circuit was found to t well with CPE. Potentiodynamic
polarization studies conrmed that all the inhibitors acted through
mixed type of corrosion inhibition mechanism. SEM studies supported that green inhibitors formed protective layer on MS surface
during the inhibition process. FTIR analysis suggested that aromatic indole ring and carbonyl group of 3b-isodihydrocadambine
are involved in coordination with the MS surface. Molecular modelling studies supported well the FTIR ndings and evidenced the
possibility of electron transfer from inhibitor to metal surface.
The ndings from this study suggest that the alkaloids of N. cadamba, in particular 3b-isodihydrocadambine, are potential ecofriendly corrosion inhibitors which may be benecial to related
industries.
Acknowledgments
The authors gratefully acknowledged the nancial support provided by University Sains Malaysia (RU-1001/229/PKIMIA/811006
and FRGS-203/PKMIA/671030), University of Malaya Research
Grants (UMRG RG011/09BIO and UMRP 001-2012) and Centre National de la Recherche Scientique (CNRS-Grant 57-02-03-1007).
We are thankful to Prof. Hiroshi Morita from Hoshi University,
Ebara 2-4-41 Shinagawa-ku, Tokyo 142-8501, Japan, for collecting
the NMR data. Authors also thank Dr. K. Thirumoorthy, Research
Associate, Department of Radiation and Oncology, The Ohio State
University, Columbus, USA and Assoc. Prof. Dr. Rohana Adnan,
School of Chemical Sciences, Universiti Sains Malaysia, Penang,
Malaysia, for their technical assistance in molecular modelling
studies.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.corsci.2012.11.
042.
References

3.7. Mechanism of corrosion inhibition

The inhibition of MS corrosion in acidic solutions by crude alkaloid extracts and 3b-isodihydrocadambine can be explained on the
basis of an adsorption process. From the polarization results, it is
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that 3b-isodihydrocadambine is the major contributor to the activity. However its inhibitory value is slightly lower than the crude
which may suggest that other alkaloids in the crude extract may
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