Materials Letters 61 (2007) 148 – 151

www.elsevier.com/locate/matlet

Copper corrosion inhibition by Azadirachta indica leaves extract

in 0.5 M sulphuric acid
L. Valek ⁎, S. Martinez
University of Zagreb, Faculty of Chemical Engineering and Technology, Marulićev trg 19, P.O. Box 177, HR-10000 Zagreb, Croatia
Received 5 July 2005; accepted 4 April 2006
Available online 5 May 2006

Abstract

Azadirachta indica leaves extract (AI) was investigated as a copper corrosion inhibitor in 0.5 M sulphuric acid. Inhibition efficiency of AI was
compared to that of the already proven good inhibitors 2-acetamino-5-mercapto-1,3,4-thiadiazole (AAMTDA) and 1,2,3-benzotriazole (BTAH).
The inhibition properties were studied using electrochemical polarization and weight loss techniques. In the region of active copper dissolution,
the highest inhibition efficiency was exhibited by AAMTDA (92.7%). AI exhibited somewhat higher efficiency (86.4%) than the widely used
BTAH (85.5%), showing that the extract could serve as a effective substitute for currently preferred copper corrosion inhibitors in sulphuric acid.
The weight loss results were interpreted by means of the Frumkin isotherm of adsorption on the metal surface. The values of ΔGads equal to
−41.96 kJ mol− 1 for AAMTDA and −35.22 kJ mol− 1 for BTAH indicate strong spontaneous adsorption while the surface coverage dependence
on the log c following the Frumkin isotherm is suggestive of chemisorption in case of all three tested inhibitors.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Copper corrosion; Inhibitor; Azadirachta indica leaves extract; Thiadiazole derivative; BTAH

1. Introduction sulphur have a tendency to act as good inhibitors in acid media

Due to the currently imposed environmental requirements for
eco-friendly corrosion inhibitors, there is a growing interest in the
use of natural products such as leaves or seeds extracts. Some
papers have reported the use of natural products for mild steel
corrosion inhibition in various corrosive media [1–8], but only few
examples of copper corrosion inhibition were reported [8,9]. It has
been found that AI is a very good inhibitor for mild steel corrosion
[1,2], but copper corrosion inhibition by AI has not been
investigated. AI extracts were reported to contain several
thousands of compounds, among which are: azadirachtin, azadi-
rone, gedunin, nimbin, nimbandiol, nimbinene, nimbolide, nimo-
nol, nimbolin, salannin, margolone, melianol, vilasanin, flavanoids
and structurally related compounds [10–14]. Most of the
compounds have complicated molecular structure, large molecular
weight and significant number of oxygen atoms incorporated in the
structure. Generally, compounds containing oxygen, nitrogen, or
⁎ Corresponding author. Tel.: +385 14597116; fax: +385 14597139.
E-mail address: lvalek@fkit.hr (L. Valek).
0167-577X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.04.024
[7,8,15,16], hence, the AI extract is expected to have great ability
for inhibitory action thorough oxygen active centres [6,8].
The aim of this work was to investigate the potential of the AI
extract to act as an inhibitor of copper corrosion in sulphuric acid.
AI, as a cheap, environmental friendly substance, was compared
to 2-acetamino-5-mercapto-1,3,4-thiadiazole (Scheme 1a) and
1,2,3-benzotriazole (Scheme 1b). BTAH is widely applied and
very efficient, but ecologically questionable inhibitor. AAMTDA
was chosen to be tested regarding that 2-methyl-5-mercapto-
1,3,4-thiadiazole and 2-amino-5-mercapto-1,3,4-thiadiazole have
been shown to have a significantly better inhibitive properties than
BTAH on copper in chloride medium [17].
2. Experimental
Investigation of copper corrosion inhibition by AI, AAMTDA
and BTAH in sulphuric acid was performed using electrochem-
ical polarization and gravimetric weight loss method.
Potentiodynamic polarization and linear polarization resis-
tance measurements were conducted on manually constructed
 L. Valek, S. Martinez / Materials Letters 61 (2007) 148–151 149

Scheme 1. Structural formula of (a) 2-acetamino-5-mercapto-1,3,4-thiadiazole

and (b) 1,2,3-benzotriazole.

copper electrode (d = 7 mm). Electrode was first mechanically

abraded on 1200 grade emery paper and polished on 1, 0.3 and
0.05 μm Al2O3, then degreased with ethanol and rinsed in
redistilled water. Counter electrode was Pt-foil and reference
electrode was saturated calomel electrode (SCE). All potentials
reported refer to SCE. Experiments were performed in 0.5 M
H2SO4 without or with addition of the inhibitors in the fol-
lowing concentrations: 10− 3 M BTAH, 5 · 10− 4 M AAMTDA
and 1 g L− 1 AI. The inhibitor concentrations for potentiody-
namic measurements were chosen based on the results of the
surface coverage dependence on the inhibitor concentrations
obtained from gravimetric experiments. Commercial Azadir-
achta indica leaves extract powder supplied by Rym Exports
has been used. All the measurements were performed after half
an hour immersion with scan rate 1 mV s− 1 for the poten-
tiodynamic polarization and 2 mV min− 1 for the linear polariza-
tion resistance measurements.
Weight loss measurements were carried out on the copper plate
specimens (40 × 50 × 3 mm). Plates were first mechanically
cleaned with 600 grade emery paper, degreased with ethanol,
rinsed with redistilled water and then dipped in 7 M HNO3 for
30 s, rinsed in redistilled water and dried. The specimens were
immersed in the test solution and left to stand for the 24 h at the
room temperature under the air atmosphere. Concentration ranges
−6 −4
of the test solutions were 2.5 · 10 –5 · 10 M for AAMTDA,
−6 −4 −1
2.5 · 10 –0.05 M for BTAH and 8.5 · 10 –8.5 g L for AI.
Fig. 2. Potentiodynamic polarization curves (scan rate 1 mV s−1) of copper in 0.5 M
H2SO4 solution without and with addition of the BTAH, AAMTDA and AI.
range is presented in Fig. 1. Curves exhibit a potential range of active
copper dissolution ending with a current peak and followed by a
current plateau that is indicative of a film formation process at the
electrode surface, i.e. formation of the layer containing copper(I) oxide
(Cu2O) [18].
Addition of the inhibitors to the corrosive medium shifted the
polarization curve towards lower current density values, i.e. lower peak
current density and lower plateau current density pointing to the
inhibitors' promotion of the passive behaviour of copper. The most
pronounced passivating activity exhibited BTAH, which is known as a
very good inhibitor in neutral media due to its pronounced ability to
form a polymer film in the presence of the oxide layer at the copper
surface [18,19].
Polarization curves in the polarization range of Ecorr ±150 mV
obtained with and without the addition of inhibitors are presented in
Fig. 2. A positive shift of the Ecorr by the AAMTDA can be observed,
while AI and BTAH shifted Ecorr to the negative values. The presence
of inhibitors suppressed the cathodic and especially the anodic current
densities. During the cathodic polarization, oxygen reduction reaction
expressed in Eq. (1), occurs at the electrode surface [20,21]:

3. Results and discussion O2 þ 4Hþ þ 4e− ⇄ 2H2 O ð1Þ

Anodic polarization behaviour of copper in sulphuric acid with and At highly cathodic polarization potentials, a behaviour charac-
without the addition of the inhibitors obtained in a wide polarization teristic of a diffusion limited process can be observed, indicating

Table 1
Corrosion parameters obtained from the Tafel analysis of the polarization curves
bC / bA / Ecorr / jcorr / r/ IE /
mV dec− 1 mV dec− 1 mV μA cm− 2 μg cm− 2 h− 1 %
0.5 M H2SO4 − 2198 38.6 −30 11.0 13.0 –
BTAH − 240.3 59.9 −85 1.6 1.9 85.5
AAMTDA − 532.1 68.0 25 0.8 0.9 92.7
AI − 181.4 59.7 −104 1.5 1.8 86.4

Table 2
Corrosion parameters obtained by linear polarization resistance measurements
Rp / jcorr / r/ IE /
Ω cm2 μA cm−2 μg cm−2 h−1 %
0.5 M H2SO4 1357 12.0 14.2 –
BTAH 9934 2.1 2.5 82.5
AAMTDA 16,702 1.6 1.9 86.7
Fig. 1. Anodic potentiodynamic polarization curves (scan rate 1 mV s−1) of copper
AI 10,623 1.8 2.1 85.0
in 0.5 M H2SO4 without and with addition of the BTAH, AAMTDA and AI.
150 L. Valek, S. Martinez / Materials Letters 61 (2007) 148–151

that the transport of oxygen from the solution to the electrode

surface is controlling the reaction rate. Consequently, high values of
cathodic Tafel slopes are obtained. Corrosion parameters calculated
from the data in Fig. 2 are presented in Table 1. The presence of
inhibitors lowers the cathodic Tafel slope values, implying the
influence of the inhibitors on the cathodic reaction, probably by
blocking the metal surface and slowing the oxygen reduction
reaction [15,21].
During anodic polarization of the electrode, dissolution of copper
takes place by the following two continuous steps [15,18,20]:

k1
CuðsÞ − e− ⇄ Cuþ
ðadsÞ ðfast stepÞ ð2Þ
k−1

k2
Cuþ −
ðadsÞ − e Y CuðsolnÞ
2þ
ðslow stepÞ ð3Þ

Fig. 3. The Frumkin isotherms for adsorption of BTAH, AAMTDA and AI on

where Eq. (3) is the rate-determining step. Anodic Tafel slope value of
38.6 mV dec− 1 confirms that diffusion of Cu2+ ions from the metal
surface has a little influence on anodic current [15]. Presence of the
inhibitors increases the anodic Tafel slope value yielding the corrosion
rate decrease probably due to blocking of the active sites at the metal
surface by the inhibitor molecules [7,21].
The best inhibitory efficiency was obtained by AAMTDA (92.7%).
AI exhibited better efficiency than BTAH, exerting very good copper
corrosion protection in the active region. The results show a dual nature
of the BTAH inhibition mechanism. BTAH inhibits active copper
corrosion, but its inhibitory action is more pronounced in the passive
region, as it was shown by the anodic polarization measurements (Fig.
1). Inhibitory action of the AATDA and AI is, on the other hand, more
marked in the range of active corrosion, while promotion of the pas-
sivation is less pronounced.
Corrosion parameters obtained from the linear polarization
resistance measurements (data not shown in figures) are presented in
Table 2. The results are in very good agreement with those obtained
from potentiodynamic polarization measurements.
Performance of the tested inhibitors has been evaluated by the
weight loss measurements in a wide range of concentrations. Since the
inhibition works though the mechanism of adsorption of the inhibitor
molecules on the metal surface, the use of adsorption isotherms pro-
vides useful insight into the corrosion inhibition mechanism. The
Frumkin adsorption isotherm [7,18]:
h −2ah
Bc ¼ e ð4Þ
1−h
has been found to give the best fit to the weight loss results of the three
tested inhibitors (Fig. 3). Where, c denotes the inhibitor concentration,
θ the surface coverage, a the attraction constant and B the adsorption–
desorption equilibrium constant linked to the free energy of adsorption,
ΔGads by the equation:
 
1 −DGads
B¼ exp ð5Þ
55:5 RT
Application of a nonlinear fitting procedure to the weight loss
results yielded ΔGads and a values for AAMTDA and BTAH. It was
not possible to calculate those parameters for AI since the average
molar mass of extract is unknown. The values of ΔGads for the
AAMTDA − 41.96 kJ mol− 1 and for the BTAH −35.22 kJ mol− 1
indicate strong spontaneous adsorption of the inhibitor molecules on
the metal surface. Attraction constants were −1.620 for the AAMTDA
and −0.898 for the BTAH. Negative values are pointing to the presence
copper in 0.5 M H2SO4.
of the repulsive forces between the inhibitor molecules adsorbed on the
surface of the metal [7,18].
Surface coverage dependence on the log c following Frumkin
adsorption isotherm is suggestive of chemisorption of the tested inhibitors
on copper surface [22]. Since there is high possibility for the chemisorption
to take place at the metal surface in the presence of organic compounds
containing O, S, and N active centers. Due to the structural nature of the
oxygen compounds in the AI extract, adsorption of these constituents may
occur through their oxygen active centres [7,8,16].
4. Conclusions
A. indica leaves extract was proven as an excellent inhibitor
of active copper corrosion in sulphuric acid. While AAMTDA
revealed even better inhibitory properties, its ecological aspects
and costs are of question. BTAH exhibited better inhibitory
properties at high anodic polarization potentials, proving his
passivating ability, while gravimetric measurements and polari-
zation in the Tafel region revealed somewhat lesser inhibition
efficiency of the active copper dissolution. The adsorptive
behaviour of investigated inhibitors was approximated by
Frumkin adsorption isotherm suggesting the chemisorption
mechanism of inhibition. The results obtained on the inhibitory
action of the A. indica leaves extract show that AI can be proposed
as good, ecologically acceptable candidate for acid copper corro-
sion inhibition.
References
[1] M.A. Quraishi, I.H. Farooqi, P.A. Saini, Corrosion 55 (1999) 493.
[2] U.J. Ekpe, E.E. Ebenso, U.J. Ibok, J.W., Afr. Sci. Assoc. 37 (1994) 13.
[3] K.O. Orubite, N.C. Oforka, Mater. Lett. 58 (2004) 1768.
[4] F. Zucchi, I.H. Omar, Surf. Technol. 24 (1985) 391.
[5] E.E. Ebenso, U.J. Ekpe, W.A.J., Biol. Appl. Chem. 41 (1996) 21.
[6] I.H. Farooqui, A. Hussain, M.A. Quarishi, P.A. Saini, Anti-Corros. 46
(1999) 328.
[7] S. Martinez, I. Štern, J. Appl. Electrochem. 31 (2001) 973.
[8] R.M. Saleh, A.A. Ismail, A.A. El Hosary, Br. Corros. J. 17 (1982) 131.
[9] J. Mabriur, M. Akssira, M. Azzi, M. Zertoubi, N. Saib, A. Messaoudi, A.
Albizane, S. Tahiri, Corros. Sci. 46 (2004) 1833.
[10] O.P. Sidhu, V. Kumar, H.M. Behl, Ind. Crops Prod. 19 (2004) 69–75.
 L. Valek, S. Martinez / Materials Letters 61 (2007) 148–151 151

[11] B.S. Siddiqui, F. Afshan, S. Faizi, Tetrahedron 57 (2001) 10281–10286.
[12] M.S Nair, S. Gopal, D. Issac, Phytochemistry 46 (1997) 1177–1178.
[13] G. Suresh, N.S. Narasimhan, N. Palani, Phytochemistry 45 (1997)
807–810.
[14] G. Brahmachari, ChemBioChem 5 (2004) 408–421.
[15] G. Quartarone, T. Bellomi, A. Zingales, Corros. Sci. 45 (2003) 715.
[16] S.A. Abd El-Maksoud, Electrochim. Acta 49 (2004) 4205.
[17] O. Blajiev, A. Hubin, Electrochim. Acta 49 (2004) 2761.
[18] J.M. Bastidas, P. Pinilla, E. Cano, J.L. Polo, S. Miguel, Corros. Sci. 45
(2003) 427.
[19] D. Tromans, J.C. Silva, Corros. Sci. 53 (1997) 16.
[20] H. Ma, S. Chen, B. Yin, S. Zhao, X. Liu, Corros. Sci. 45 (2003) 867.
[21] S. Sankarapapavinasam, F. Pushpanaden, M.F. Ahmed, Corros. Sci. 32
(1991) 193.
[22] I.L. Rozenfeld, Corrosion Inhibitors, McGraw-Hill, New York, 1981.