Materials Chemistry and Physics 119 (2010) 330–336

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Corrosion inhibition of carbon steel and antibacterial properties of

aminotris-(methylenephosphonic) acid
Najoua Labjar a,b , Mounim Lebrini b , Fouad Bentiss c , Nour-Eddine Chihib d ,
Souad El Hajjaji a , Charafeddine Jama b,∗
a
Laboratoire d’Electrochimie – Corrosion, Faculté des Sciences, University Med V Agdal, Av. Ibn Battouta, B.P. 1014, M-10000 Rabat, Morocco
b
Laboratoire des Procédés d’Elaboration des Revêtements Fonctionnels, PERF-LSPES UMR-CNRS, 8008, ENSCL, B.P. 90108, F-59652 Villeneuve d’Ascq Cedex, France
c
Laboratoire de Chimie de Coordination et d’Analytique, Faculté des Sciences, Université Chouaib Doukkali, B.P. 20, M-24000 El Jadida, Morocco
d
Laboratoire de Procédés Biologiques, Génie Enzymatique et Microbien (ProBioGEM) Polytech’Lille, USTL, F-59652 Villeneuve d’Ascq Cedex, France

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

Article history: In this work, the corrosion inhibition property and the antibacterial activity of the aminotris-
Received 16 March 2009 (methylenephosphonic) acid (ATMP) have been studied. ATMP has been evaluated as a corrosion inhibitor
Received in revised form 3 September 2009 for carbon steel in 1 M HCl solution using weight loss, potentiodynamic polarization and electrochemical
Accepted 5 September 2009
impedance spectroscopy (EIS) techniques. According to the experimental results, the inhibition efficiency
increased with increasing inhibitor concentration. Tafel polarization study showed that the ATMP acts
Keywords:
as a mixed inhibitor. Data, obtained from EIS measurements, were analyzed to model the corrosion inhi-
Aminotris-(methylenephosphonic) acid
bition process through appropriate equivalent circuit models. Adsorption of ATMP on the carbon steel
Carbon steel
Hydrochloric acid
surface obeyed the Langmuir adsorption isotherm. The calculated Gads value showed that the corrosion
Corrosion inhibition inhibition of the carbon steel in 1 M HCl is mainly controlled by a physisorption process. In addition,
Antibacterial activity the effect of immersion time on the corrosion of carbon steel was also studied in this work using ac
impedance technique. The corrosion inhibition mechanism of ATMP was discussed. This inhibitor can be
also used as biocide in aqueous environments. Our results showed that ATMP have an antibacterial effect
against both Gram positive and Gram negative bacteria. The lowest MIC (0.2 mg l−1 ) was measured for
Pseudomonas fluorescens while the highest MIC was measured for Escherichia coli (3.1 mg l−1 ). In addition,
the results showed that the MIC of ATMP against Listeria innocua in a buffered medium (pH 6.5) was of ca.
4-fold higher than MIC measured in unbuffered medium. Thus, our findings showed that the antibacterial
activity of ATMP is a result of a combined effect of the pH solution and the chemical nature of the used
phosphonate molecule.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction with a phosphonic functional group are considered to be the most

The use of inhibitors is one of the most practical methods for
protection against metallic corrosion. Environmental restrictions
imposed on heavy-metal based corrosion inhibitors, oriented sci-
entific researches towards studying non-toxic and environmentally
friendly corrosion inhibitors [1]. In general, organic compounds,
such as amines, acetylenic alcohols, heterocyclic compounds,
phosphonates, etc., have been in use as inhibitors in industrial
applications [2–5]. The use of organic phosphonic acids to protect
carbon steel against corrosion has been the subject of various works
[6–15]. Indeed, they have been widely used as water treatment
agents because of their low toxicity, high stability and corrosion
inhibition activity in neutral aqueous media [16,17]. Compounds
∗ Corresponding author. Tel.: +33 320 336 311; fax: +33 320 436 584.
E-mail address: charafeddine.jama@ensc-lille.fr (C. Jama).
effective chemicals for inhibiting the corrosion process and it is well
known that short-chain-substituted phosphonic acids are good cor-
rosion inhibitors for iron and low alloyed steels [18,19].
Bacterial corrosion is a concern to many industrial sectors
such as oil industry, water distribution and treatment, geother-
mal plants, and also to several fields of the nuclear industry such
as waste management as well as the power plants or fuel repro-
cessing units [20]. Biocorrosion is a result of interactions, which
are often synergistic, between the metal surface, abiotic corro-
sion products, and bacterial cells and their metabolites [21]. These
bacteria typically coexist in naturally occurring biofilms, forming
complex consortia on corroding metal surfaces [22,23]. Thus, cor-
rosion inhibitors which possess an antimicrobial effect on microbial
corrosion inducers are of importance because they will reduce the
biological damage of equipments and service lines [24].
In the present study, the corrosion inhibition power and the
antibacterial activity of the aminotris-(methylenephosphonic) acid

0254-0584/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2009.09.006
 N. Labjar et al. / Materials Chemistry and Physics 119 (2010) 330–336
Fig. 1. Molecular structure of the aminotris-(methylenephosphonic) acid (ATMP).
(ATMP) were evaluated. The ATMP was investigated as an inhibitor
for the corrosion of carbon steel in 1 M hydrochloric acid (HCl)
using weight loss, potentiodynamic polarization and electrochem-
ical impendence spectroscopy (EIS). Electron probe microanalyses
(EPMA) were also carried out to establish the mechanism of corro-
sion inhibition. Moreover, the bacterial killing efficiency of ATMP
was investigated to evaluate the potential use of this compound as
antibiocorrosion agent.
2. Experimental method
2.1. Material
The molecular structure of the ATMP is shown in Fig. 1. The tested
compound, namely aminotris-(methylenephosphonic) acid (N[CH2 P(O)(OH)2 ]3 ),
(ATMP), obtained from Sigma–Aldrich (50 wt.% in H2 O), was tested without further
purification.
2.2. Material preparation for corrosion inhibition evaluation
The ATMP inhibitor was added to prepared acid solutions (1 M HCl) in the con-
centration range of 5 × 10−5 to 5 × 10−1 M. The material used in this study was a
carbon steel with chemical composition (in wt.%) of 0.370% C, 0.230% Si, 0.680% Mn,
0.016% S, 0.077% Cr, 0.011% Ti, 0.059% Ni, 0.009% Co, 0.160% Cu and the remain-
der iron (Fe). For all the experiments, the surface pre-treatment was carried out
by grinding with emery paper SiC (grades 120, 600 and 1200), rinsed with distilled
water, degreased in acetone in an ultrasonic bath immersion for 5 min and then
dried at room temperature before use. The acid solutions (1 M HCl) were prepared
by dilution of an analytical reagent grade 37% HCl with doubly distilled water.
2.2.1. Weight loss test
Gravimetric experiments were carried out in a double glass cell equipped with
a thermostated cooling condenser. The solution volume was 100 ml. The carbon
steel specimens used have a rectangular form (length = 2 cm, width = 1 cm, thick-
ness = 0.2 cm). The maximum duration of tests was 24 h at 30 ◦ C in non-de-aerated
solutions. At the end of the tests, the specimens were carefully washed in ace-
tone under ultrasound and then weighed. Duplicate experiments were performed
in each case and the mean value of the weight loss is reported. Weight loss allowed
calculation of the mean corrosion rate in mg cm−2 h−1 .
2.2.2. Electrochemical techniques
Further corrosion tests were performed electrochemically at room temperature
(30 ± 1 ◦ C) in a glass cell with a capacity of 500 ml for potentiodynamic polarization
experiment and a polymethyl methacrylate (PMMA) cell with a capacity of 1000 ml
for ac impedance technique. A saturated calomel electrode (SCE) was used as the
reference; a Pt electrode was used as the counter. All potentials are reported vs. SCE.
For polarization measurements, Tacussel-Radiometer model PGZ 301 poten-
tiostat monitored by a PC computer and Voltamaster 4.0 software were used for
run the tests, collect and evaluate the experimental data. A carbon steel cylinder
pressed into a Teflon holder acted as a working electrode (WE). Its working area
of 1 cm2 remained precisely fixed. A fine Luggin capillary was placed close to the
working electrode to minimize ohmic resistance. All test solutions were de-aerated
in the cell by using pure nitrogen for 30 min prior to the experiment. During each
experiment, the test solution was mixed with a magnetic stirrer and the gas bub-
bling was maintained. Before each Tafel experiment, the carbon steel electrode was
allowed to corrode freely and its open circuit potential (OCP) was recorded as a
function of time up to 30 min. After this time a steady-state OCP, corresponding to
the corrosion potential (Ecorr ) of the working electrode, was obtained. The potentio-
dynamic Tafel measurements were started from cathodic to the anodic direction,
E = Ecorr ± 250 mVSCE , with a scan rate of 0.5 mV s−1 .
331
Table 1
Corrosion parameters obtained from weight loss measurements of carbon steel in
1 M HCl containing various concentrations of ATMP at 30 ◦ C.
Inhibitor Concentration (M) Corrosion rate (mg cm−2 h−1 ) E (%)
Blank – 4.56 –
ATMP 5 × 10−5 3.81 16.44
1 × 10−4 3.26 28.51
5 × 10−4 2.77 39.25
1 × 10−3 2.20 51.75
5 × 10−3 1.03 77.41
1 × 10−2 0.71 84.43
5 × 10−2 0.25 94.52
1 × 10−1 0.18 96.05
5 × 10−1 0.15 96.71
Ac impedance measurements were performed using a Solartron 1255B fre-
quency response analyzer in a frequency range of 105 Hz to 10−3 Hz with ten points
per decade using 10 mV peak-to-peak sinusoidal voltage and a Solartron SI 1287
electrochemical interface. ZPlot 2.80 software was used to run the tests, collect and
evaluate the experimental data. Corrosion tests were performed in a polymethyl
methacrylate (PMMA) cell with a capacity of 1000 ml at 30 ± 1 ◦ C, using a thermo-
stat. A saturated calomel electrode (SCE) was used as the reference; a Pt electrode
was used as the counter. All potentials are reported vs. SCE. The working electrode
was prepared from a square sheet of carbon steel such that the area exposed to solu-
tion was 7.55 cm2 . The impedance spectra were recorded 24 h after the exposure of
the working electrode to the solution (no deaeration, no stirring). The impedance
data were analyzed and fitted with the simulation ZView 2.80, equivalent circuit
software.
2.2.3. Electron probe microanalyzer (EPMA)
The microstructural analysis was carried out using a Cameca SX100 Electron
Probe Microanalysis (EPMA). Phosphorus (P) X-ray quantification was carried out
at 10 kV, 400 nA. For quantification, a TAP crystal was used to detect the P K␣ X-
ray. Prior to analyze, the carbon steel substrates were carbon coated with a Bal-Tec
SCD005 sputter coater.
2.3. Antibacterial activity: bacteria and antimicrobial assays
The antibacterial activity of ATMP was studied against Aeromonas hydrophila
ATCC 7966, Bacillus subtilis ATCC 6633, Escherichia coli ATCC 11229, Listeria innocua
ATCC 51742, Pseudomonas aeruginosa MSH, Pseudomonas fluorescens ATCC 13525
and Staphylococcus aureus ATCC 6538. The bacterium was conserved at −24 ◦ C in
glycerol containing nutrient broth and was sub-cultured twice in Mueller-Hinton
(Biokar Diagnostics) at 30 ◦ C under agitation (60 rpm). The ATMP solution (500 g l−1 )
was filtered through 0.2 ␮m cellulose nitrate filter (Sartorius) before minimal inhi-
bition concentration (MIC) experiments. The MIC was measured using the serial
dilution methods [25]. These experiments were repeated at least three times. The
MIC was also determined against Listeria innocua ATCC 51742 in Mueller-Hinton
buffered with MOPS (3-(N-morpholino) propanesulfonic acid) 100 mM at pH 6.5.
The pH values of the solutions were then measured using an Inolab pH-meter
(Fisher).
3. Results and discussion
3.1. Corrosion inhibition evaluation
3.1.1. Weight loss Studies
Inhibition efficiency, E(%), and corrosion rate obtained from
weight loss method at different concentrations of inhibitor for the
corrosion of carbon steel in 1 M HCl for an immersion period of 24 h
at 30 ◦ C are given in Table 1. It is obvious from these results that
the ATMP inhibits the corrosion of carbon steel in 1 M HCl at all
concentrations used in this study. The corrosion rate (W) of car-
bon steel decreases with the increase of concentration. In the case
of gravimetric study, inhibition efficiency, E(%), is calculated by W
as described elsewhere [26]. It can be observed, from Table 1, that
the protection inhibition efficiency increases with increasing of the
concentration from 5 × 10−5 M to 5 × 10−2 M and the maximum of
E(%) was achieved at 1 × 10−1 M. Further increase in concentration
did not cause any appreciable change in the performance of the
inhibitor. This conclusion is also supported by the electrochemical
studies reported below.
332 N. Labjar et al. / Materials Chemistry and Physics 119 (2010) 330–336
Table 2
Polarization parameters and the corresponding inhibition efficiency for the corrosion of carbon steel in 1 M HCl containing different concentrations of ATMP at 30 ◦ C.
Inhibitor Concentration (M) Ecorr vs. SCE (mV)
Blank – −481.5
ATMP 5 × 10−5 −482.3
5 × 10−3 −473.2
5 × 10−2 −470.6
1 × 10−1 −463.9
3.1.2. Potentiodynamic tests
Polarization measurements have been carried out in order to
gain knowledge concerning the kinetics of the anodic and cathodic
reactions. The obtained polarization curves of carbon steel in 1 M
HCl solution without and with different ATMP concentrations are
shown in Fig. 2. The values of the electrochemical kinetic parame-
ters (corrosion potential (Ecorr ), corrosion current density (Icorr ) and
Tafel slopes (ba and bc )), determined from these experiments by
extrapolation method [27], are summarized in Table 2. They show
that the addition of the inhibitor hindered the acid attack of the
carbon steel electrode.
The corrosion potential (Ecorr ) in solutions containing inhibitor
is shifted towards more positive values with the increase of its
concentration (Table 2). Fig. 2 indicates that all the cathodic polar-
ization curves are parallel and cathodic Tafel slopes bc change
slightly with increase of ATMP concentration, which suggests that
the hydrogen evolution is activation controlled and the reduction
mechanism is not affected by the presence of the inhibitor [28,29].
Compared to the blank sample, the anodic curves of the carbon steel
electrode in the acid solution shift obviously to the direction of cur-
rent reduction as adding the ATMP, which implies that the organic
compounds can also suppress the anodic reaction (steel dissolu-
tion) and the variation in the anodic Tafel slope ba may be due
to the chloride ions/or inhibitor molecules adsorption onto carbon
steel surface [30]. Based on the marked decrease of the cathodic
and anodic current densities upon introducing the inhibitor in the
aggressive solution, this inhibitor is considered as a mixed-type
inhibitor. This means that the addition of ATMP reduces the anodic
dissolution and also retards the cathodic hydrogen evolution reac-
tion.
Differently, for anodic polarization curves with ATMP (Fig. 2), it
seems that when the carbon steel electrode potential is higher than
about −300 mVSCE , the presence of the ATMP does not change the
Fig. 2. Polarization curves for carbon steel in 1 M HCl containing different concen-
trations of ATMP.
Icorr (␮A cm−2 ) ba (mV dec−1 ) bc (mV dec−1 ) E (%)
569.8 92 188 –
477.8 91 186 16.15
175.4 84 146 69.22
109.3 87 128 80.82
76.7 78 122 86.54
current vs. potential characteristics. Such potential can be defined
as desorption potential [31,32]. This phenomenon may be due to
desorption of the ATMP molecules from the electrode surface lead-
ing to the metal dissolution. In this case, the desorption rate of the
inhibitor is higher than its adsorption rate, so the corrosion current
increases more obviously with rising potential [32,33]. This result
shows that the inhibition effect of this compound depends on the
electrode potential.
The inhibitor efficiency values, E(%), are calculated from the
Icorr values, as previously described [26], and are presented in
Table 2. Inspection of these data shows that the addition of
ATMP inhibits the corrosion process in a wide range of con-
centrations, 5 × 10−5 M ≤ Cinh ≤ 10−1 M. The inhibition efficiency
increases with Cinh reaching its maximum value, 86.54%, at 10−1 M.
The potentiodynamic data confirm the main gravimetric results.
ATMP has pronounced inhibition efficiency which depends on the
concentration. The differences observed between the two types of
experiments are probably due to a greater extent to the different
exposure time in the corrosive solution (40 min for the potentio-
dynamic and 24 h for the gravimetric measurements). Hence these
factors do not affect the inhibition mechanism and influence only
the kinetics of the processes.
3.1.3. Ac impedance studies
3.1.3.1. Effect of ATMP concentration. Impedance measurements of
the carbon steel electrode at its open circuit potential after 24 h
of immersion in 1 M HCl solutions alone and in the presence of
ATMP are performed over the frequency range from 100 KHz to
1 mHz. Fig. 3 shows the obtained Nyquist diagrams of carbon
steel in 1 M HCl solution in the absence and presence of different
concentrations of ATMP. These diagrams have similar shape; the
shape is maintained throughout all tested concentrations, indicat-
ing that almost no change in the corrosion mechanism occurs due
to the inhibitor addition. The Nyquist diagrams show one capac-
itive loop at high frequencies with one capacitive time constant
in the Bode-phase plots (Fig. 4, representative example) and one
inductive loop at low-frequency values (i.e. two time constants).
The first capacitive loop, at high frequencies (HF), represents the
phenomenon associated with the double electric layer. A capaci-
tive loop arises from the time constant of the electric double layer
and charge-transfer resistance, and an inductive loop appeared at
low-frequency (LF) values in the presence of ATMP. The presence
of the LF inductive loop may be attributed to the relaxation process
obtained by adsorption species like Clads − and Hads + on the elec-
trode surface [34–37]. It may also be attributed to the adsorption
of inhibitor on the electrode surface [38] or to the re-dissolution
of the passivated surface at low frequencies [39]. In other words,
the inductive behaviour at low frequency is probably due to the
consequence of the layer stabilization by products of the corro-
sion reaction on the electrode surface (for example, [FeOH]ads and
[FeH]ads ) involving inhibitor molecules and their reactive products
[40]. Also, a small inductive loop is observed at very high frequen-
cies (Fig. 3). The inductance in the high frequency region can be
attributed to the actual physical inductance of wires and, possibly,
of the electrode itself [41].
 N. Labjar et al. / Materials Chemistry and Physics 119 (2010) 330–336 333

Fig. 3. Nyquist diagrams for carbon steel in 1 M HCl containing different concentra-
tions of ATMP at 30 ◦ C.

The capacitive loop corresponds to the charge-transfer reaction,

which depends either on direct electron transfer at the metal sur-
face or on the electron conduction through the film surface. The
depressed form of the HF loop reflects the surface inhomogeneity
of structural or interfacial origin, such as those found in adsorp-
tion processes [42]. In this case, the constant phase element, CPE, is
introduced in the circuit instead of a pure double layer capacitor to
give a more accurate fit [43,44]. The impedance function of a CPE
has the following equation [45]:
−n
ZCPE = A−1 (iω)
where A is the CPE constant, ω is the angular frequency (in rad s−1 ),
i2 = −1 is the imaginary number and n is a CPE exponent which can
be used as a gauge of the heterogeneity or roughness of the surface
[46]. Depending on the value of n, CPE can represent resistance
(n = 0, A = R), capacitance (n = 1, A = C), inductance (n = −1, A = L) or
Warburg impedance (n = 0.5, A = W).
In the studied frequency range, the system could be described
by the corresponding structural model of the interface with ATPM,
as shown in Fig. 5a. In this equivalent circuit, Rs is the solution
resistance, R1 refers to the polarization resistance, L the inductance,
and R1 + R2 present the charge-transfer resistance (Rct ). R2 and L
Fig. 4. EIS Nyquist and Bode diagrams for carbon steel/1 M HCl + 1 × 10−1 M ATMP
interface: (· · ·) experimental data and (—) calculated.
represent the inductive elements. For 1 M HCl without inhibitor,
the equivalent circuit of Fig. 5b is adopted to fit the EIS data. Fig. 4
reports an example (Nyquist and Bode formats) of the relative fit
obtained with the circuit model of Fig. 5a. One can observe that the
proposed model is well representative of the phenomena which
(1) may occur in the investigated system, both in the HF and in the LF
parts of the spectra. The corresponding fitted parameters are listed
in Table 3. The data are found to be sufficiently well fitted within the
limits of experimental error and reproducibility of data. In Table 3
are shown also the calculated “double layer capacitance” values,
Cdl , derived from the CPE parameters according to [47]:
1−n 1/n
Cdl = (A · Rct ) (2)
and the time constant of the charge-transfer process ( d ), it is
defined [48,49] as
d = Cdl Rct (3)

Fig. 5. Equivalent circuits used to fit the EIS data of carbon steel in 1 M HCl + xM ATMP, without (a) and with (b) inductive loop.
334 N. Labjar et al. / Materials Chemistry and Physics 119 (2010) 330–336

Table 3
Impedance parameters and inhibition efficiency values for carbon steel after 24 h immersion period in 1 M HCl without and with different concentrations of ATMP at 30 ◦ C.

Inhibitor Conc. (M) Rs ( cm2 ) 104 A (sn −1 cm−2 ) n R1 ( cm2 ) R2 ( cm2 ) L (H cm−2 ) Rct ( cm2 ) Cdl (␮F cm−2 )  d (s) E (%)

Blank 0 5.70 ± 0.02 8.444 ± 0.05 0.879 ± 0.001 37.05 ± 0.13 – – 37.05 524.11 0.0194 –

−5
ATMP 5 × 10 5.56 ± 0.02 7.182 ± 0.02 0.896 ± 0.003 39.50 ± 0.28 4.37 ± 0.30 83.45 ± 2.12 43.87 480.79 0.0211 15.54
1 × 10−3 6.27 ± 0.02 4.063 ± 0.04 0.889 ± 0.002 119.20 ± 0.46 9.27 ± 0.53 94.73 ± 2.81 128.47 281.01 0.0361 71.16
5 × 10−3 4.79 ± 0.03 3.994 ± 0.02 0.902 ± 0.005 126.80 ± 1.73 13.46 ± 1.09 196.50 ± 4.51 140.26 292.02 0.0409 73.58
5 × 10−2 6.19 ± 0.05 2.007 ± 0.04 0.889 ± 0.005 231.90 ± 2.57 28.77 ± 2.14 234.10 ± 5.23 260.67 138.86 0.0362 85.79
1 × 10−1 6.21 ± 0.06 1.459 ± 0.03 0.897 ± 0.003 371.30 ± 3.61 36.50 ± 3.01 285.06 ± 6.08 407.80 105.52 0.0430 90.91

Inspection of data in Table 3 clearly shows that Rct and Cdl values
have opposite trend at the whole concentration range (Rct increases
and Cdl decreases with ATMP concentration). Also, the value of
the proportional factor A of CPE varies in a regular manner with
inhibitor concentration. It can be supposed that a protective layer
covers the carbon steel surface. Indeed, the increase of the values
of n, when compared to the blank, vs. ATMP concentration can be
explained by some decrease of the surface heterogeneity, due to
the adsorption of the inhibitor on the most active adsorption sites
[50]. On the other hand, the calculated value of the time constant
( d ) obtained in the absence of ATMP was found to be 0.0194 s.
The addition of AMPT in acid solution results in an increase in 
value at 5 × 10−3 M ( d = 0.0409 s) which remains approximately
unchanged. Upon increasing the concentration of ATMP, the time
of adsorption process becomes much higher which means slow
adsorption process [51,52]. The double layer between the charged
metal surface and the solution is considered as an electrical capac-
itor. The adsorption of ATMP on the carbon steel surface decreases
its electrical capacity because they displace the water molecules
and other ions originally adsorbed on the surface. The decrease
in this capacity with increase in ATMP concentrations may be
attributed to the formation of a protective layer on the electrode
surface [53]. The thickness of this protective layer increases with
increase in inhibitor concentration, since more ATMP will electro-
statically adsorb on the electrode surface, resulting in a noticeable
decrease in Cdl . This trend is in accordance with Helmholtz model,
given by the following equation [54]:
ε0 ε
Cdl = S (4)
e
where e is the thickness of the protective layer, ε is the dielectric
constant of the medium, ε0 is the vacuum permittivity and S is the
effective surface area of the electrode.
In the case of impedance study, the inhibition efficiency,
E(%), is calculated from Rct as previously described [52]. The
calculated E(%) values are listed in Table 3. The E(%) values indi-
cate that by the increase of inhibitor concentrations induces
an increase in corrosion inhibition too. The inhibition effi-
ciency values, calculated from ac impedance study, show the
same trend as those obtained from weight loss measurements
and Tafel polarization techniques. Comparison of the E(%) val-
ues obtained using these methods show acceptable agreement
(Tables 1–3).
3.1.3.2. Effect of immersion time. Ac impedance measurements are
particularly useful in long time tests because they do not perturb
the system dramatically and it is possible to follow the evolution
of the inhibitor–metal system over time. The time dependency of
carbon steel in 1 M HCl is studied in the case of 5 × 10−2 M ATMP.
The analysis of the EIS data obtained at different times of immersion
revealed that the Nyquist plots showed a capacitive loop in the high
frequency (HF) range and an inductive loop in the low-frequency
(LF) range. As previously described in Section 3.1.3, the capacitive
loop was related to charge-transfer in corrosion process, whereas,
the inductive loop might correlate to the adsorption–desorption
process of the inhibitive particle on the electrode surface [38,39].
The equivalent circuit employed to fit the experimental data is
the same as shown in Fig. 5a. The main fitted parameter results
are given in Table 4. It is shown that when the immersion time
increases, the Rct values increase and Cdl values decrease, which
indicates the higher protection efficiency as a result of adsorption
of ATMP molecules at surface carbon steel. This is also confirmed
by the fact that the time constant of the charge-transfer process
( d ) value increases vs. time. Indeed, the n factor values also gen-
erally present an increasing trend with time, which corroborates
the decrease of the surface inhomogeneity due to adsorption of
ATMP molecules. It is also shown that the carbon steel electrode
with longer immersion time (48 h) has a larger Rct value and has
better protection ability. However, when the immersion time was
prolonged beyond 48 h, a sudden decrease in Rct and n, and an
increase in Cdl values were observed. This behaviour can be due
to the decrease of the stability of the protective layer as result of
desorption of the ATMP molecules and/or diffusion process through
the interface protective layer/electrolyte [55]. Moreover, the sud-
den decrease in  d values beyond 48 h confirms the desorption of
ATMP molecules. Therefore, based on the present EIS results, one
can suggests that the ATMP adsorption on the carbon steel surface
in the experimental conditions used is more a physisorption than
a chemisorption. Therefore, a thermodynamic study is carried out
and discussed below in order to support such hypothesis.
3.1.4. Adsorption isotherm and surface analysis
Corrosion inhibition by organic compounds is, mainly, due to
their ability to adsorb onto a metal surface to form a protective
film. The establishment of isotherms that describe the adsorp-
tion behaviour of corrosion inhibitor is important as they provide

Table 4
Impedance parameters values for carbon steel in 1 M HCl with 5 × 10−2 M ATMP at different immersion times.

Immersion time (h) Rs ( cm2 ) 10−4 A (sn −1 cm−2 ) n Rct ( cm2 ) Cdl (␮F cm−2 )  d (s)

2 5.71 ± 0.04 3.31 ± 0.03 0.806 ± 0.002 124.40 ± 077 153.93 0.0191
4 5.38 ± 0.05 2.352 ± 0.03 0.847 ± 0.002 185.60 ± 1.68 149.79 0.0278
8 4.94 ± 0.05 2.259 ± 0.03 0.874 ± 0.002 191.20 ± 2.05 143.38 0.0274
24 6.19 ± 0.05 2.007 ± 0.04 0.889 ± 0.005 260.67 ± 4.71 138.86 0.0362
48 5.34 ± 0.04 1.523 ± 0.03 0.850 ± 0.004 281.43 ± 5.35 119.44 0.0336
72 5.58 ± 0.03 4.693 ± 0.04 0.806 ± 0.002 51.64 ± 0.62 191.26 0.0099
96 6.77 ± 0.02 5.234 ± 0.02 0.808 ± 0.002 38.14 ± 0.25 206.77 0.0079
102 6.64 ± 0.03 6.280 ± 0.05 0.802 ± 0.002 17.95 ± 0.34 207.52 0.0037
120 6.04 ± 0.02 8.470 ± 0.02 0.760 ± 0.003 14.18 ± 0.12 209.62 0.0030
 N. Labjar et al. / Materials Chemistry and Physics 119 (2010) 330–336
Fig. 6. Langmuir’s isotherm adsorption of ATMP on the carbon steel surface in 1 M
HCl.
important clues about the nature of metal–inhibitor interaction.
Values of degree of surface coverage () corresponding to different
ATMP concentrations at 30 ◦ C after 24 h of immersion were used
to determine which isotherm best described the adsorption pro-
cess. In the present study, values of  were calculated using the
impedance results according to the equation [51]:
0 − 1/R
1/Rct ct
= 0
(5)
1/Rct
0 and R are the charge-transfer resistance values without
where Rct ct
and with inhibitor, respectively. The results obtained for ATMP in
1 M HCl solution fit well Langmuir adsorption isotherm (Fig. 6),
given by Eq. (6) [32]:
Cinh 1 mainly responsible for the good protective properties of this com-
= + Cinh (6)
 Kads
where  is the degree of surface coverage, Cinh is the inhibitor con-
centration in the electrolyte and Kads the equilibrium constant of
the adsorption process. From Fig. 6 it can be seen that the linear
correlation coefficient (R) is close to 1 and the slope of straight line
is also close to 1, which suggests that the adsorption of ATMP from
1 M HCl solution on the carbon steel obeys the Langmuir model
and exhibit single-layer adsorption characteristic. From the inter-
cept of the straight line Cinh /-axis, Kads value can be calculated.
The equilibrium constant of the adsorption process Kads , is related
to the standard free energy of adsorption, Gads0 , with the following
equation [56]:
 0

1 −Gads
Kads = exp (7)
55.5 RT
where R is the universal gas constant and T is the absolute tem-
perature. The value 55.5 in the above equation is the concentration
of water in solution in mol l−1 . At 30 ◦ C, the calculated Gads
0 of
−1 0 the highest MIC is measured for E. coli (3.1 mg l−1 ). The results in
ATMP was −27.52 kJ mol . The negative value of Gads suggests
that the adsorption of ATMP is a spontaneous process [26]. Gen-
erally speaking, the adsorption type is regarded as physisorption
if the absolute value of Gads0 was lower than 20 kJ mol−1 . The
inhibition behaviour is attributed to the electrostatic interaction
between the organic molecules and iron atom. When the absolute
0
value of Gads is higher than 40 kJ mol−1 , the adsorption could
be seen as chemisorption. In this process, the covalent bond is
formed by the charge sharing or transferring from the inhibitor
molecules to the metal surface [57,58]. Based on the literature
[59], the obtained Gads0 in this work indicates that the adsorp-
tion mechanism of ATMP on carbon steel surface involves two
types of interactions, predominant physisorption (ionic) and weak
chemisorption (molecular).
335
Fig. 7. Variation of percentage of phosphorus and inhibition efficiency with ATMP
concentration.
It was reported that the surface charge of steel at Ecorr in
HCl solution is expected to be positive. Thus, the anions are first
adsorbed on the steel surface creating an excess negative charge,
which in turn, facilitates physical adsorption of the inhibitor cations
[60]. Accordingly, the Cl− and phosphonate ions adsorb and the
surface becomes negatively charged. Due to the electrostatic attrac-
tion, the protonated ATMP molecules are adsorbed on carbon steel
0 = −27.52 kJ mol−1 ). The adsorption
surface (physisorption, Gads
of free molecules could take place via interaction of the unshared
pairs of electrons of nitrogen atoms and the vacant d-orbitals of
iron atoms (chemisorption). However, this mode of adsorption has
no substantial contribution. Indeed, the AMPT molecules are eas-
ily protonated to form ionic forms in acid solution. It is logical
to assume that in this case the electrostatic cations adsorption is
pound.
In order to gain more information about the ATMP inhibi-
tion mechanism, the surface analysis (EMPA) study is given and
discussed below. The EPMA chemical analysis of carbon steel
immersed in the 1 M HCl solution—ATMP shows the presence of
phosphorus, which could be attributed to the adsorption of the
organic ATMP molecules. On the other hand, in the presence of
ATMP, only the elements which come from the inhibitor constitute
the protective film. Fig. 7 shows the found percentage of phos-
phorus and E(%) according to inhibitor concentration. It is obvious
from this figure that both P(%) and E(%) follow the same pattern
and increase continuously with increasing additive concentration
of ATMP.
3.2. Antibacterial activity of the ATMP
The results of Table 5 show that ATMP have an antibacterial
effect against both Gram positive and Gram negative bacteria.
The lowest MIC (0.2 mg l−1 ) is measured for P. fluorescens while
Table 5 show also that the phosphonates MIC against L. innocua
Table 5
The minimal inhibition concentration (MIC) of ATMP and the pH-medium corre-
sponding to the MIC of each bacterium. The pH was measured in Mueller-Hinton
medium with the corresponding ATMP concentration without the bacterium.
Bacteria MIC (␮g ml−1 ) pH
Aeromonas hydrophila ATCC 7966 0.8 4.7
Bacillus subtilis ATCC 6633 0.8 4.7
Escherichia coli ATCC 11229 3.1 3.3
Listeria innocua ATCC 51742 1.6 4.0
Pseudomonas aeruginosa MSH 1.6 4.0
Pseudomonas fluorescens ATCC 13525 0.2 6.3
Staphylococcus aureus ATCC 6538 0.8 4.7
336 N. Labjar et al. / Materials Chemistry and Physics 119 (2010) 330–336
Table 6
Minimal inhibition concentration (MIC) measurement of ATMP against Listeria
innocua in buffered Mueller-Hinton (pH 6.5). The medium was buffered with MOPS
100 mM.
Bacterium ATMP concentration
(␮g ml−1 )
Listeria innocua ATCC 51742 1.6 3.1
+ +
and P. aeruginosa is 2-fold higher (1.6 mg l−1 ) than that of the
ATMP MIC of A. hydrophila, B. subtilis, and S. aureus (0.8 mg l−1 ).
The pH corresponding to the MIC of each bacterium is measured in
Mueller-Hinton medium with the corresponding ATMP concentra-
tion without the bacterium (Table 5). This result shows that these
pH values are lower than pH 5 except for P. fluorescens, for which
the pH was 6.3. Such pH values may not support the growth of
the bacteria tested as reported for Listeria for which the minimum
growth pH is pH 4.0–4.4 [61,62].
From these results raise the question about the inhibitory activ-
ity of ATMP which may be due to the pH of the solutions used rather
than to its chemical nature. To assess if there are other inhibitory
mechanisms of the ATMP, the MIC against L. innocua was performed
in a buffered medium (Table 6). The results show that the MIC
of ATMP against L. innocua in a buffered medium is of ca. 4-fold
higher than MIC measured in unbuffered medium. These findings
show that the antibacterial activity of ATMP is results of a com-
bined effect of the pH of the solution and of the chemical nature
of the phosphonate molecule. Thus, the activity of ATMP appears
to be both direct and indirect. Part of the direct effect results from
the fact that the pH of the culture medium decreases when the
ATMP is added. However, another mechanism must be active since
the ATMP shows antibacterial activity in buffered medium. Such
results are in agreement with those reported by Chase in the case
of Fosetyl-Al (aluminium tris-o-ethyl phosphonate) [63].
4. Conclusion
The corrosion inhibition power and the antibacterial activity
of the aminotris-(methylenephosphonic) acid (ATMP) have been
evaluated. The ATMP has been investigated as a corrosion inhibitor
for carbon steel in 1 M HCl solution using weight loss, potentiody-
namic polarization and electrochemical impedance spectroscopy
(EIS) techniques. The results show that ATMP is effective inhibitor
for the carbon steel corrosion in 1 M HCl solutions and its inhibi-
tion efficiency increases with the increase in ATMP concentration.
Tafel polarization data show that ATMP acts as mixed-type inhibitor
in 1 M HCl. Impedance measurements show a high frequency
capacitive loop related to the charge-transfer process of the metal
corrosion and the double layer behaviour and a low-frequency
inductive part attributed to the relaxation of adsorbed species and
metal dissolution. The EIS spectra are described well by the pro-
posed structural models. The corrosion process is inhibited by the
adsorption of ATMP on carbon steel surface and the adsorption of
the inhibitor fits a Langmuir isotherm model. Moreover, the calcu-
0 and the EIS immersion time effect reveal that
lated value of Gads
the adsorption mechanism of ATMP on steel surface in 1 M HCl
solution is mainly due to physisorption. The antibacterial activ-
ity investigations show that the ATMP has an antibacterial effect
against both Gram positive and Gram negative bacteria. In addi-
tion, our findings show that the antibacterial activity of ATMP is a
result of a combined effect of the pH solution and of the chemical
nature of the used phosphonate molecule.
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