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The inhibitive effect of hexamethylenetetramine on the acid corrosion of steel

Article  in  Materials Chemistry and Physics · July 2007

DOI: 10.1016/j.matchemphys.2007.02.073

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 Materials Chemistry and Physics 104 (2007) 74–82

The inhibitive effect of hexamethylenetetramine

on the acid corrosion of steel
E. Bayol a,∗ , K. Kayakırılmaz a , M. Erbil b
aDepartment of Chemistry, Faculty of Science and Art, Nigde University, 51200 Nigde, Turkey
b Department of Chemistry, Faculty of Science and Art, Cukurova University, 01330 Adana, Turkey
Received 10 February 2006; received in revised form 20 February 2007; accepted 22 February 2007

Abstract
The efficiency of hexamethylenetetramine (HMTA), as corrosion inhibitors for steel in de-aerated 0.3 M HCl, 0.1 M H2 SO4 and 0.1 M
H2 SO4 + 1.0 × 10−3 M HCl solutions have been determined by electrochemical studies. It was found that the HMTA acts a good corrosion inhibitor
for steel corrosion in acids solutions. Increase in inhibition efficiency with the increase of concentrations of HMTA shows that inhibition actions
are due to adsorption on the steel surface and adsorption follows the Langmuir isotherm. From the adsorption isotherms values of equilibrium
constant (Kads ), values of free energies of adsorption (G◦ads ), were calculated. The effect of temperature on the corrosion behaviour in the presence
of 1.0 × 10−1 M inhibitors was studied in the temperature range of 293–323 K. The inhibition efficiency of HMTA increased with increasing
temperature up to 323 K. Activation energies (Ea∗ ) were calculated from the obtained corrosion rates at different temperatures. Results obtained
from both potentiodynamic polarisation and AC impedance measurements reveal that the compound is an effective inhibitor for the corrosion of
steel and behave better in HCl than in H2 SO4 . Surface analyses were also carried out to establish the mechanism of corrosion inhibition of steel in
acidic media.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Steel; Corrosion; Hexamethylenetetramine; Electrochemical measurement

1. Introduction as functional group, steric factor, the electronic structure of the

Acid solutions are commonly used in industry, the most
imported field of practice being acid pickling, acid cleaning,
acid decaling and oil well acidizing [1–3]. Because of the gen-
eral aggressiveness of acid solutions, organic compound are
widely used as corrosion inhibitors that can be adsorbed on the
metal surface through donation of electrons such as ␲ electrons
in aromatic rings, or multiple bonds, or unpaired electrons in
the functional groups that contain atoms such as nitrogen, sul-
phur, and oxygen. Adsorption usually takes place through to the
vacant d-orbitals of the transition metals. Corrosion inhibitors
block the active sites and enhance the adsorption process, thus
decreasing the corrosion rate and extending the life of equipment
[4–6]. The nitrogen containing compounds are known to be effi-
cient inhibitors, forming covalent bonds with metal surfaces.
Their adsorption depends on physicochemical properties such
∗ Corresponding author. Tel.: +90 388 225 20 94; fax: +90 388 225 01 80.
E-mail address: emelbayol@nigde.edu.tr (E. Bayol).
molecule, etc. [7–16]. Lately, it has been found that low molec-
ular mass and high water solubility amines give rise to a better
adsorption and higher protection against corrosion. Physisorp-
tion and chemisorption are the two types of interaction between
organic inhibitors and the metal surface. The electrostatic attrac-
tion between the charge of hydrophilic groups and the charge
of active centres on the metal surface leads to physisorption.
However, the adsorption of some ions suggests that chemisorp-
tions involve not only an electrostatic interaction but also a
partial charge transfer leading to a covalent bond formation.
It is believed that the covalent bond would be formed and the
inhibitor chemisorbed on the surface if the adsorption process
include charge transfer from the inhibitor to the metal surface.
The adsorption of inhibitors is influenced by several factors such
as the nature and surface charge of the metal, on the type of acid,
the distribution of charge in the molecule, the type of interaction
between organic molecules and the metallic surface, which is
ruled by the dipole moment of inhibitors, and the chemical struc-
ture of organic inhibitors [17–24]. The study of HMTA as acid
inhibitors is particularly important since they are non-expensive,

0254-0584/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2007.02.073
 E. Bayol et al. / Materials Chemistry and Physics 104 (2007) 74–82
soluble in water and contains a pair of unshared electrons for
donation. The aim of this work is to investigate the effect of hex-
amethylenetetramine on the corrosion of steel in various acids
solutions using polarisation and impedance techniques.
2. Experimental
Steel containing 0.097% C, 0.00321% Pb, 0.488% Cu, 0.117% Cr, 0.032% P,
0.099% Si, 0.012% V, 0.004% Nb, 0.054% Mo, 0.07% S, 0.018% Sn, 0.01% W,
0.0042% Co, 0.137% Ni, 0.459% Mn and the remainder iron was used for the
electrochemical measurements. The specimens were embedded in polyester,
with a surface area of 0.5 cm2 in contact with the corrosive media. Prior to
each experiment the surface of Fe specimens were mechanically polished with
different grades of emery paper (600–1200), degreased with acetone and rinsed
with distilled water and put into the cell. All the reagents used (HMTA, 37%
HCl and 98% H2 SO4 ) were of analytical grade acquired from Merck.
Polarisation experiments were carried out in a conventional three-electrode
cell. A platinum counter electrode with 1 cm2 surface area was also used. The
reference electrode was a Ag/AgCl with a Luggin probe positioned near the
electrode surface. The cell was wear-jacketed and connected to a constant
temperature circulator. The test solution is de-aerated with pure nitrogen. Gas
bubbling is maintained through the experiments. Electrochemical measurements
were carried out using an EG&G scanning potentiostat model 362 potentio-
stat/galvanostat. The steel electrode was immersed in the solution for 30 min and
the free corrosion potential, Ecorr , was recorded. The polarisation curves were
recorded using potentiodynamic technique with a constant scan rate of 1 mV s−1 .
The cathodic polarisation measurements were recorded first in a potential range
from Ecorr , to higher negative potentials. The anodic measurements were then
recorded. The current densities were calculated on the basis of the apparent
surface area of the electrode. Potentiostatic experiments were performed to test
the current response to different inhibitor injections. The corrosion rates (icorr )
before and after adding the HMTA were determined using the Tafel extrapolation
method.
Fig. 1. (a) Nyquist and (b) Bode plots for steel in 0.3 M HCl + X M HMTA at 298 K. X: 0 M (䊉), 1.0 × 10−3 M (), 1.0 × 10−2 M (), 4.0 × 10−2 M (), 7.0 × 10−2 M
(), 1.0 × 10−1 M (♦).
Fig. 2. (a) Nyquist and (b) Bode plots for steel in 0.1 M H2 SO4 + X M HMTA at 298 K. X: 0 (䊉), 1.0 × 10−3 M (), 1.0 × 10−2 M (), 4.0 × 10−2 M (), 7.0 × 10−2 M
(), 1.0 × 10−1 M (♦).
75
Electrochemical impedance measurements were obtained at instantaneously
measured open circuit potential (Ecorr ) applying 5 mV of amplitude, in frequency
range from 105 to 10−3 Hz. The electrochemical impedance measurements were
carried out with a CHI604A AC electrochemical analyser.
The morphology of the corroded surface of each specimen was studied using
a Leon 440 scanning electron microscope. All micrographs of the corroded
specimens were taken at a magnification of 1000.
3. Results and discussion
3.1. Electrochemical impedance spectroscopy
The corrosion behaviour of steel, in 0.3 M HCl, 0.1 M H2 SO4
and 0.1 M H2 SO4 + 1.0 × 10−3 M HCl solutions with and with-
out additives HMTA in the concentration range of 1.0 × 10−3 to
1.0 × 10−1 M, was investigated by EIS at 293 K. Nyquist plots
of steel in acidic solutions with and without of inhibitors dis-
played one capacitive arc which are given in Figs. 1–3 in different
solution, respectively.
In log f–log Z diagram (Figs. 1b–3b and 4b–6b), film resis-
tance (Rfilm ) and accumulation resistance (Ra ) value was
observed as plateau region, at low frequencies. This diagram
gave also another plateau region at highest frequency region,
which was related to pore resistance, Rpor . The sum of Rfilm
and Ra values was equal to polarisation resistance (Rp ) value
[25]. The Rpor , Rfilm , Ra and Rp values were determined from
log f–log Z diagrams and given in Tables 1 and 2.
To obtain the total capacitance of the circuit (C), the fre-
quency at which the imaginary component of the impedance is
76 E. Bayol et al. / Materials Chemistry and Physics 104 (2007) 74–82

Fig. 3. (a) Nyquist and (b) Bode plots for steel in 0.1 M H2 SO4 + 1.0 × 10−3 M HCl + X M HMTA at 298 K. X: 0 M (䊉), 1.0 × 10−3 M (), 1.0 × 10−2 M (),
4.0 × 10−2 M (), 7.0 × 10−2 M (), 1.0 × 10−1 M (♦).

maximum (−Zmax  ) is calculated and C values are obtained from It is apparent from these figures that the impedance responses
the following equation [26]: for steel in acidic solutions change significantly with increas-
ing inhibitor concentration. The great effect was observed at
 1 a concentration of 1.0 × 10−1 M, which produce Rp values
f (−Zmax )= (1)
2πCRp of 1342, 1401 and 1307  in 0.3 M HCl, 0.1 M H2 SO4 and
0.1 M H2 SO4 + 1 × 10−3 M HCl, respectively (Figs. 1–3). As
The percent inhibition efficiency, IE% is calculated by polar- the inhibitor concentration increased, the Rp values increased,
isation resistance that is obtained from Nyquist plots, according but the C values tended to decrease. The decrease in C value is
to the equation below: due to the adsorption of inhibitor of the metal surface, which
  led to an increase in IE% [27–29]. The decrease in the C values
Rp − Rpo can result from a decrease in local dielectric constant and/or an
IE% = × 100 (2)
Rp increase in the thickness of the electrical double layer, which
cause the HMTA molecules adsorption on the steel surface.
where Rp and Rpo are the values of the polarisation resistance Figs. 4–6 show Nyquist diagrams for steel at the rest potential
with and without inhibitor, respectively. in the de-aerated test solutions containing 1.0 × 10−1 M HMTA

Fig. 4. (a) Nyquist and (b) Bode plots for steel in 0.3 M HCl and 0.3 M HCl + 1.0 × 10−1 M HMTA. 293 K (䊉), 303 K (), 313 K (), 323 K ().

Fig. 5. Nyquist and (b) Bode plots for steel in 0.1 M H2 SO4 and 0.1 M H2 SO4 + 1.0 × 10−1 M HMTA. 293 K (䊉), 303 K (), 313 K (), 323 K ().
 E. Bayol et al. / Materials Chemistry and Physics 104 (2007) 74–82 77

Table 1
Impedance parameters and inhibition efficiency for the corrosion of the steel in 0.3 M HCl, 0.1 M H2 SO4 and 0.1 M H2 SO4 + 1.0 × 10−3 M HCl without and with
addition of various concentrations of HMTA at 293 K
Medium X:[HMTA] (M) C (␮F) Rpor () Rfilm () Ra () Rp () IE%

0.0 100 5 147 89 236 –

1.0 × 10−3 130 4 497 84 581 59.4
1.0 × 10−2 80 4 789 157 946 75.1
0.3 M HCl + X M HMTA
4.0 × 10−2 64 4 994 198 1192 80.2
7.0 × 10−2 60 5 1251 – 1251 81.1
1.0 × 10−1 56 5 1168 174 1342 82.4
0.0 70 6 142 43 185 –
1.0 × 10−3 54 6 483 154 637 70.9
1.0 × 10−2 51 5 624 163 787 76.5
0.1 M H2 SO4 + X M HMTA
4.0 × 10−2 42 6 653 597 1250 85.2
7.0 × 10−2 40 7 785 493 1278 85.5
1.0 × 10−1 36 9 821 580 1401 86.8
0.0 100 13 142 45 187 –
1.0 × 10−3 68 10 436 184 620 69.8
0.1 M H2 SO4 + 1.0 × 10−3 M 1.0 × 10−2 54 7 529 257 786 76.2
HCl + X M HMTA 4.0 × 10−2 42 7 637 583 1220 84.8
7.0 × 10−2 42 10 783 464 1247 85.0
1.0 × 10−1 40 9 989 318 1307 85.7

at different temperatures. In all cases, we note a decrease of Rp
with increasing temperature, but the values of Rp in the presence
of inhibitor are less compared to those obtained with blank assay.
This result confirmed that HMTA acted as an efficient inhibitor
in the range of temperature studied.
3.2. Polarisation measurements
Anodic and cathodic potentiodynamic polarisation curves
for steel in de-aerated 0.3 M HCl, 0.1 M H2 SO4 and 0.1 M
H2 SO4 + 1.0 × 10−3 M HCl in absence and presence of HMTA
under investigation were studied at 293 K. Fig. 7 shows that
the potentiodynamic polarisation curves of steel in 0.3 M HCl
in the absence and presence of different amounts (1.0 × 10−3
to 1.0 × 10−1 M) of HMTA. It is seen in Fig. 7 that the cor-
rosion current density in the region of corrosion potential and
in the range of −0.800 to −0.100 V potential, decreases as the
inhibitor concentration increases. Polarisation curves obtained
in 0.3 M HCl in the absence and presence of different con-
centration of HMTA have showed similarity with the curves

Table 2
The influence of temperature on the impedance parameters and inhibition efficiency for the corrosion of the steel electrode immersed in 0.3 M HCl (A), 0.1 M H2 SO4
(B) and 0.1 M H2 SO4 + 1.0 × 10−3 M HCl (C) without and with addition of 1.0 × 10−1 M of HMTA
T (K) A A + 0.1 M HMTA

C (␮F) Rpor () Rfilm () Ra () Rp () C (␮F) Rpor () Rfilm () Ra () Rp () IE%

293 100 5 147 89 236 56 5 1168 174 1342 82.4

303 104 3 57 – 57 86 4 597 – 597 90.4
313 148 4 48 – 48 60 4 265 129 394 87.8
323 226 6 22 – 22 76 4 259 – 259 91.5

T (K) B B + 0.1 M HMTA

C (␮F) Rpor () Rfilm () Ra () Rp () C (␮F) Rpor () Rfilm () Ra () Rp () IE%

293 70 6 142 43 185 36 9 821 580 1401 86.8

303 130 6 74 6 80 46 10 353 268 621 87.1
313 142 5 60 – 60 78 9 300 – 300 80.0
323 116 6 48 – 48 66 11 193 – 193 75.1

T (K) C C + 0.1 M HMTA

C (␮F) Rpor () Rfilm () Ra () Rp () C (␮F) Rpor () Rfilm () Ra () Rp () IE%

293 100 13 142 45 187 40 9 989 318 1307 85.7

303 120 5 73 16 89 54 10 479 304 783 88.6
313 138 6 60 – 60 76 10 370 – 370 83.8
323 122 5 30 – 30 80 10 194 – 194 84.5
78 E. Bayol et al. / Materials Chemistry and Physics 104 (2007) 74–82
Fig. 6. (a) Nyquist and (b) Bode plots for steel in 0.1 M H2 SO4 + 1.0 × 10−3 M HCl and 0.1 M H2 SO4 + 1.0 × 10−3 M HCl + 1.0 × 10−1 M HMTA. 293 K (䊉), 303 K
(), 313 K (), 323 K ().
obtained in 0.1 M H2 SO4 and 0.1 M H2 SO4 + 1.0 × 10−3 M
HCl.
The inhibition efficiency (IE%) of corrosion of steel is cal-
culated by using the following equation:
 
icorr − icorr(inh)
IE% = × 100 (3)
icorr
where icorr(inh) and icorr are the corrosion current density values
with and without inhibitor, respectively, determined by extrapo-
lation of the cathodic Tafel lines to the respective free corrosion
potential. The values of the corrosion current density (icorr ), the
corrosion potential (Ecorr ), cathodic Tafel slopes (βc ) and the
percentage inhibition efficient (IE%) obtained as a function of
HMTA concentrations are given in Table 3.
It is seen in Table 3 that the increase in the concentration
of HMTA slightly shifts the corrosion potential (Ecorr ) to pos-
itive direction and the cathodic Tafel lines (βc ) values show a
light modification when compared with those values obtained
in the reference solutions. This result suggests that the mech-
anism of hydrogen reduction on the surface of steel is not
modified by the addition of HMTA [30]. As the concentration of
HMTA has increased, the value of corrosion current density has
decreased too and hence the inhibition efficiency has increased,
with inhibitor concentration reaching a maximum value at
Fig. 7. Polarisation curves for steel in 0.3 M HCl and 0.3 M HCl + X M HMTA
at 298 K.
1.0 × 10−1 M of HMTA. The corresponding efficiency values in
0.3 M HCl, 0.1 M H2 SO4 and 0.1 M H2 SO4 + 1 × 10−3 M HCl
are 88.8%, 82.7% and 87.3%, respectively.
In anodic field, we notice that in the presence of HMTA
in 0.3 M HCl, there is a reduction of anodic current density
(Fig. 7). It is important to note that in anodic domain, for poten-
tial higher than −0.390 V, the presence of HMTA did not change
the current versus potential characteristic. The potential can be
defined as the desorption potential. The behaviour of HMTA
at potentials greater than −0.390 V could be associated to the
significant steel dissolution leading to desorption of inhibiting
film. This dissolution results in the desorption of the adsorbed
film of inhibitor on the surface of the electrode in 0.3 M HCl
media. In this case the desorption rate of HMTA is raised more
than its adsorption. However, HMTA influences anodic reac-
tion at potentials lower than −0.390 V. This fact means that
the inhibition mode of the studied HMTA depends on electrode
potential.
The HMTA is weakly adsorbed on steel, since the metal
surface in sulphuric acid is positively charged.
The polarisation curves for steel in 0.3 M HCl in the
absence and presence of 1.0 × 10−1 M HMTA and at various
temperatures (293–323 K) are shown in Fig. 8a and b. How-
ever similar results were obtained in 0.1 M H2 SO4 and 0.1 M
H2 SO4 + 1.0 × 10−3 M HCl, their electrochemical parameters
are given in Table 4.
In all cases, we note an increase of corrosion current density
with increasing temperature, but the values of corrosion current
density in the presence of inhibitor are less compared to those
obtained with blank assay. The IE% value in 0.3 M HCl increases
with increasing temperature and reaches 95.2% at 323 K.
The values of activation energies (Ea∗ ) for the dissolution
of steel in all the acids studied, in the absence and presence
of the inhibitors were calculated from the Arrhenius type plot
according to the following equation:
 
E∗
icorr = A exp − a (4)
RT
where icorr is the corrosion rate in the absence and presence of
inhibitors, A the Arrhenius constant, Ea∗ the apparent activation
energy, R the gas constant and T is the absolute temperature.
 E. Bayol et al. / Materials Chemistry and Physics 104 (2007) 74–82 79

Table 3
Electrochemical polarisation parameters for the steel in 0.3 M HCl, 0.1 M H2 SO4 and 0.1 M H2 SO4 + 1.0 × 10−3 M HCl various concentrations of HMTA at 293 K
Medium X:[HMTA] (M) −Ecorr (mV) −βc (mV dec−1 ) icorr (␮A cm−2 ) IE%

0 505 106 98 –
1.0 × 10−3 495 94 24 75.5
0.3 M
1.0 × 10−2 490 96 19 80.6
HCl + X M
4.0 × 10−2 492 99 15 84.7
HMTA
7.0 × 10−2 493 97 13 86.7
1.0 × 10−1 485 100 11 88.8
0 505 117 98 –
1.0 × 10−3 495 109 27 72.4
0.1 M
1.0 × 10−2 495 98 26 73.5
H2 SO4 + X M
4.0 × 10−2 505 106 24 75.5
HMTA
7.0 × 10−2 510 102 19 80.6
1.0 × 10−1 510 107 17 82.7
0 499 111 110 –
0.1 M 1.0 × 10−3 505 111 29 73.6
H2 SO4 + 1.0 × 10−3 M 1.0 × 10−2 500 98 22 80.0
HCl + X M 4.0 × 10−2 485 106 20 81.8
HMTA 7.0 × 10−2 477 104 17 84.5
1.0 × 10−1 495 107 14 87.3

Table 4
The influence of temperature on the electrochemical parameters for steel electrode immersed in 0.3 M HCl (A), 0.1 M H2 SO4 (B) and 0.1 M H2 SO4 + 1.0 × 10−3 M
HCl (C) without and with addition of 1.0 × 10−1 M of HMTA
T (K) A A + 1.0 × 10−1 M HMTA

−Ecorr (mV) −βc (mV dec−1 ) icorr (␮A cm−2 ) −Ecorr (mV) −βc (mV dec−1 ) icorr (␮A cm−2 ) IE%

293 505 106 98 485 98 11 88.5

303 505 123 277 485 104 26 90.4
313 500 145 446 480 120 35 92.3
323 500 191 1114 545 180 54 95.2

T (K) B B + 1.0 × 10−1 M HMTA

−Ecorr (mV) −βc (mV dec−1 ) icorr (␮A cm−2 ) −Ecorr (mV) −βc (mV dec−1 ) icorr (␮A cm−2 ) IE%

293 505 117 98 500 107 17 84.5

303 512 134 184 505 115 30 84.2
313 509 149 336 540 122 38 88.8
323 505 160 735 595 149 91 92.1

T (K) C C + 1.0 × 10−1 M HMTA

−Ecorr (mV) −βc (mV dec−1 ) icorr (␮A cm−2 ) −Ecorr (mV) −βc (mV dec−1 ) icorr (␮A cm−2 ) IE%

293 499 117 110 495 105 13 86.5

303 510 131 238 520 109 30 86.8
313 510 133 538 560 124 40 90.3
323 510 192 1151 590 185 86 92.7

The plot of ln(icorr ) for steel obtained from the polarisation Table 5
curves as a function of (1/T) gives straight lines with a slope The values of activation parameters Ea∗ for steel in 0.3 M HCl (A), 0.1 M H2 SO4
of −Ea∗ /R (Fig. 9) and the Ea∗ obtained from these graphs are (B) and 0.1 M H2 SO4 + 1.0 × 10−3 M HCl (C) without and with addition of
1.0 × 10−1 M of HMTA
given in Table 5.
The inhibition efficiency of HMTA increases with increas- Compound Ea∗ (kJ mol−1 )
ing temperature and its increase leads to a decrease in the A 61.21
apparent activation energy. The results show that presence of B 52.24
HMTA, gives maximum efficiency, by lowering the activation C 61.87
energy. It is considered to chemisorption on the steel sur- A + 1.0 × 10−1 M HMTA 40.13
B + 1.0 × 10−1 M HMTA 41.32
face [31,32]. The value of apparent activation energy Ea∗ of C + 1.0 × 10−1 M HMTA 46.92
hydrogen evolution reaction in 0.3 M HCl without an inhibitor
80 E. Bayol et al. / Materials Chemistry and Physics 104 (2007) 74–82
Fig. 8. Effect of temperature on polarisation curves for steel in (a) 0.3 M HCl
and (b) 0.3 M HCl + 1.0 × 10−1 M HMTA.
(61.21 kJ mol−1 ) (Table 5) agrees well with the literature data
on Ea∗ for steel and steel in hydrochloric acid, which are in the
range 58–100 kJ mol−1 [33,34].
It was found that, the inhibition efficiency of this compound
depends on its concentration. The inhibitive action of this com-
Fig. 9. The relation between ln icorr vs. 1/T for steel in 0.3 M HCl and 0.3 M
HCl solution containing 1.0 × 10−1 M HMTA.
pound was discussed in terms of blocking the electrode surface
by adsorption of the molecules through the active centres con-
tained in its structure. The values of surface coverage θ for
different concentrations at 293 K have been used to explain the
best isotherm that determines the adsorption process.
Attempts were made to fit these θ values to various
isotherms including Langmuir, Frumkin, Freundlich and Temkin
isotherms. However the best fit was obtained from the Langmuir
isotherm. This has been also used for other inhibitor systems
[35]. Langmuir isotherm is as follows:
C 1
= +C (5)
θ K
where θ is the degree of coverage on the metal surface, K the
equilibrium constant of the adsorption reaction and C is the
concentration of inhibitor.
The plots of Cinh /θ versus Cinh yield a straight line with corre-
lation coefficient higher than 0.95, showing that the adsorption
of this inhibitor can be fitted to a Langmuir adsorption isotherm
(Fig. 10). This indicates that the inhibitor molecules are adsorbed
on the metal surface and form a barrier, which isolated the metal
surface from the electrolyte. Langmuir adsorption isotherm may
be explained on the basis of interaction between the adsorbed
species on the metal surface [2,36].
The value of the adsorption coefficient (Kads ) for steel in pres-
ence of HMTA is calculated as 909, 556 and 769 in 0.3 M HCl,
0.1 M H2 SO4 and 0.1 M H2 SO4 + 1.0 × 10−3 M HCl, respec-
tively. Results show that HMTA give high values of K in 0.3 M
HCl, indicating that it was adsorbed strongly on the steel sur-
face, thus, the inhibition efficiency increased with increasing
adsorption coefficient.
The equilibrium constant for adsorption process is related
to the free energy of adsorption, Gads , and is expressed by
following equation:
 
1 Gads
Kads = exp − (6)
55.5 RT
where 55.5 is the molar concentration of water in the solu-
tion. The value of free energy of adsorption, Gads , for steel
Fig. 10. Langmuir adsorption isotherm of HMTA on steel in 0.3 M HCl, 0.1 M
H2 SO4 , 0.1 M H2 SO4 + 1.0 × 10−3 M HCl solutions.
 E. Bayol et al. / Materials Chemistry and Physics 104 (2007) 74–82 81

Fig. 11. SEM photograph of the surface for steel after 24 h of immersion period (a) before corrosion, (b) 0.3 M HCl, (c) 0.3 M HCl + 1.0 × 10−1 M HMTA, (d) 0.1 M
H2 SO4 , (e) 0.1 M H2 SO4 + 1.0 × 10−1 M HMTA, (f) 0.1 M H2 SO4 + 1.0 × 10−3 M HCl and (g) 0.1 M H2 SO4 + 1.0 × 10−3 M HCl + 1.0 × 10−1 M HMTA.

in presence of HMTA in 0.3 M HCl, 0.1 M H2 SO4 and 0.1 M
H2 SO4 + 1 × 10−3 M HCl was calculated as −26.39, −25.19
and −25.99 kJ mol−1 , respectively.
The low and negative value of Gads indicates the spon-
taneous adsorption of inhibitors on the surface of steel and
Gads also suggest the monolayer adsorption of the inhibitor
molecules with the steel surface [37]. Generally, G◦ads val-
ues up to −20 kJ mol−1 are consistent with the electrostatic
interaction between the charged molecules and the charged
metal (physical adsorption), while those that are more nega-
82 E. Bayol et al. / Materials Chemistry and Physics 104 (2007) 74–82
tive than −40 kJ mol−1 involve charge sharing or transfer from
the inhibitor molecules to the metal surface to form a coordinate
type of bond (chemisorption) [38,39].
In the present study, HMTA was found to be effective for
the inhibition of steel corrosion in 0.3 M HCl. It is well known
that chloride ions have a smaller degree of hydration; they
could bring excess negative charges in the vicinity of the inter-
face, which facilitates positively charged ions adsorption onto
the surface. HMTA might be protonated in the acid solution
and the protonated HMTA are attached to the steel surface by
means of electrostatic interaction between Cl− and the proto-
nated HMTA. When HMTA molecules are adsorbed onto the
metal surface, coordinate bonds have formed by partial transfer
of electrons from the polar atom of HMTA to the metal surface.
HMTA is more effective in HCl than in H2 SO4 media, this can
be explained by the fact that chloride ions being less hydrated
than sulphate ions and therefore more strongly adsorbed on the
metal surface by creating an excess negative charge towards the
solution phase, which favours inhibitor adsorption on the steel
surface.
3.3. Morphological examination
A SEM image of polished steel sample is shown in Fig. 11a.
The micrograph shows a characteristic inclusion, which was
probably an oxide inclusion. Fig. 11b, d and f shows SEM image
of the surface of the steel specimens after immersion in acidic
solutions for 24 h. The micrograph reveals that, the surface was
strongly damaged in absence of inhibitors. Fig. 11c, e and g
shows SEM image of the surface of another steels specimen
after immersion for the same time interval in all acidic solu-
tions containing 1.0 × 10−1 M HMTA. The micrograph reveals
that, there is a good protective film present on the steel surface.
This confirms the highest inhibition efficiency of the HMTA at
1.0 × 10−1 M concentration.
4. Conclusions
The main conclusions of this study are given below:
1. The HMTA actually inhibits steel corrosion in the tested acid
media.
2. Inhibition efficiency increases with an increase in inhibitor
concentration and rise in temperature.
3. The HMTA inhibit the corrosion by controlling both the
anodic and cathodic in 0.1 M H2 SO4 and by controlling
anodic in 0.3 M HCl.
4. The adsorption of the investigated compound from 0.3 M
HCl, 0.1 M H2 SO4 and 0.1 M H2 SO4 + 1 × 10−3 M HCl on
the steel surface obeys a Langmuir adsorption isotherm.
5. The negative values of free energy of adsorption, G◦ads indi-
cate the spontaneous adsorption of HMTA on the surface of
steel.
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6. The investigated compound was more effective in HCl than
in H2 SO4 .
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