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Abstract—A comparative study of Fe and Cr complexes with a Schiff base ligand (1[(2hydroxy
ethyl)amino]2(5methoxysalicylideneamino)ethane) as inhibitors for mild steel corrosion in 0.5 M HCl
solution at 25°C was carried out. Electrochemical techniques were applied to study the metal corrosion
behavior of these inhibitors. EDX, SEM and ATRFTIR studies of the electrode surface confirmed existence
of a protective adsorbed film of the inhibitors on the electrode surface. The inhibition efficiency was increased
with the inhibitor concentration. The mechanism of adsorption is concluded that the adsorbed chloride ions
on the metal surface could be stabilized in their anionic form like a crabclaw.
DOI: 10.1134/S2070205115050135
1
1. INTRODUCTION rate [9–10]. Schiff base, an organic compound having
Mild steel is widely used in store tanks, petroleum general formula R–C=N–R' where R and R' are aryl,
refineries, and so on. The main problem of using mild alkyl or cycloalkyl or heterocyclic groups formed by
steel is its dissolution in acidic media. Acid solutions the condensation of an amine and a carbonyl group, is
are widely used for removal of undesirable scale and a potential inhibitor for different metallic surfaces.
rust in many industrial processes [1]. Several Schiff bases had been reported as effective cor
rosion inhibitors for mild steel in HCl media [11–13].
Inhibitor is a keyword in the case of corrosion pre
vention by changing the chemistry of corrosive media. The existing data show that these inhibitors act by
Many industrial divisions such as acid cleaning bath, adsorption on the metal/solution interface. This phe
water cooling system, various refinery units, pipelines, nomenon could take place via: i—electrostatic attrac
chemical operations, steam generators, ballast tanks, tion between the charged metal and the charged inhib
oil and gas production units are involved with inhibi itor molecules, ii—dipoletype interaction between
tors due to high corrosion rates in these parts [2]. unshared electron pairs in the inhibitor with the metal,
The use of inhibitors is one of the most practical iii—π electron interaction with the metal, and iv—
methods for protection against corrosion especially in combination of all of the above [14]. On the other
acidic conditions [3, 4]. Acid solutions are generally hand, some organic inhibitors could react with metal
used in several industrial processes. Severe corrosion ions resulting from corrosion process to form analo
problems arise due to the wide use of hydrochloric acid gous complexes spontaneously that may decrease the
for pickling, rescaling and cleaning processes of mild corrosion rate. However, studies about metal com
steel surfaces [5]. Because of their aggressiveness, the plexes as corrosion inhibitor for mild steel in acid solu
use of corrosion inhibitors is considered as the most tion appeared in the literature are extremely limited
effective method for protection of many metals and [15, 16].
alloys against such acid attack [6, 7]. Compound con Metal Schiff base complexes are widely used as cat
taining functional groups with heteroatoms, (N, O, S)
alyst of chemical reactions [17], biological [18], anti
which can donate one pair of electrons, are found to be
very effective as inhibitor against metal corrosion in fungal [19], anti tumor and anti HIV activities [20].
many environments. Many heterocyclic compounds Very few works have been performed to study anticor
with polar groups and/or π electrons are used as inhib rosive behaviour of metal Schiff base complexes.
itors in acidic solutions [8]. Organic molecules of this AbdelGaber et al. [21] proposed corrosion inhibition
type can adsorb on the metal surface and form a bond through a bulky Co (III) Schiff base complex molecule
between their heteroatoms and/or π molecular orbitals could cover more than one active site, where mild steel
and the metal surface, thereby reducing the corrosion was immersed in HCl solution. Some metal complexes
of Schiff base are suggested as an effective corrosion
1 The article is published in the original.
inhibitor for Cu and mild steel [22, 23].
918
INHIBITION OF MILD STEEL CORROSION IN HYDROCHLORIC ACID SOLUTION 919
(a)
The aim of the present investigation is to examine
the inhibitory action of two novel Schiff base com MeO N N OH
plexes of Iron and Chromium with unique steric H
molecular structure with two OH bonding tail, O
absorbed at the interface of the metal and two hydro Fe O
phobic tail at the opposite side of the metal, namely:
Bis[N(2(2hydroxyethylamino)ethyl)5methox NH N OMe
ysalicylideneimine) For the corrosion of mild steel in HO
0.5 M HCl on the basis of weight loss, potentiody (b)
namic polarization and impedance measurements. MeO N N OH
H
2. EXPERIMENTAL O Cr O
2.1. Synthesis of Schiffbase Metal Complexes
The Schiffbase Fe complex (SBIC) was synthe NH N OMe
sized by reaction of precursor compound N(2(2 HO
hydroxyethylamino)ethyl) 5methoxysalicylidene
imine (L) with FeCl3 ⋅ 6H2O. The precursor com Fig. 1. Chemical structures of Schiff base metal com
pound L was synthesized by reaction of equimolar sal plexes, (a) SBIC and (b) SBCC.
icylaldehyde (0.84 mmol, 103 mg) and 2(2aminoet
hylamino)ethanol (1.2 mmol, 122 mg) in anhydrous
ethanol (5 ml). FeCl3 ⋅ 6H2O (0.12 mmol, 33 mg) in brief, mild steel specimens in triplicate were immersed
anhydrous ethanol (5 ml) was added to previous solu for a period of 4 h in 50 mL HCl 0.5 M containing var
tion. After keeping the solution in air to evaporate ious concentrations of studied inhibitors. After
about half of the solvent, dark brown prisms of the immersion, the surface of the specimen was cleaned by
complex compound were formed. The crystals were double distilled water followed by rinsing with ace
isolated, washed with ethanol three times and dried in tone. The mass of the specimens before and after
a vacuum desiccator using silica gel. The Schiffbase immersion was determined using an analytical bal
Cr complex (SBCC) was synthesized in the same pro anced accurate to 0.1 mg. In the present study, for the
cedure. All the chemicals chosen for our study were of specified experimental conditions, relative differences
analytical grade and double distilled water was used between replicate experiments were found to be less
throughout the experiment. The chemical structure of than 6% indicating good reproducibility. For further
synthesized inhibitors (SBIC and SBCC) has shown in data processing, the average of the three replicate val
Fig. 1. ues was used. For each experiment, a freshly prepared
solution was used and the solution temperature was
controlled at a desired value thermostatically.
2.2. Electrodes
Prior to all measurements, the mild steel speci 2.3.2 Electrochemical techniques. Electrochemical
mens, having composition (in wt%) 0.099 C, 0.166 Si, impedance measurements (EIS) and potentiody
0.346 Mn, 0.131 Cr, 0.040 Mo and the remainder iron, namic polarization studies were carried out using an
were abraded successively with fine grade emery electrochemical unit (model PARstat 2273). A three
papers (600–1200 grade). The specimens were washed electrode setup was employed using a graphite of con
thoroughly with double distilled water and finally venient area as counter electrode and a SCE electrode
degreased with acetone and dried at room tempera (Radiometer Copenhague) as reference electrode.
ture. For weight loss measurements, mild steel speci The working electrode mild steel (7.5 cm long stem)
mens dimensions 26 mm diameter and 2 mm thick with the exposed surface of 1.0 cm2 was immersed into
ness were used. For polarization and electrochemical aggressive solutions with and without inhibitor and the
impedance studies, the metal was embedded in epoxy open circuit potential was measured after 30 min, (the
resin, to expose a geometrical surface area of 1 cm2 to stable potential time). EIS measurements were per
the electrolyte. The aggressive solution 0.5 M HCl was formed at corrosion potentials, Ecorr, over a frequency
prepared by dilution of analytical grade HCl (37%) range of 100 kHz to 10 mHz with an AC signal ampli
with double distilled water and all experiments were tude perturbation of 10 mV peak to peak. Potentiody
carried out in unstirred solutions. namic polarization studies were performed with a scan
rate of 1 mVs–1 in the potential range from 250 mV
below the corrosion potential to 250 mV above the
2.3. Corrosion Tests corrosion potential. All potentials were recorded with
2.3.1 Weight loss measurements. Gravimetric cor respect to SCE. All measurements were done at 25 ±
rosion measurements were carried out according to 0.1°C. Impedance fitting was performed using Zview
the ASTM standard procedure described in [24]. In software.
Table 1. Weight loss results of mild steel corrosion in 0.5 M HCl with addition of various concentrations of inhibitor at 25°C
CrSchiff base complex (SBCC) FeSchiff bae complex (SBIC)
C/(mg/L) weight corrosion weight corrosion
θ IEw (%) θ IEw (%)
loss (mgr) rate (mpy) loss (gr) rate (mpy)
0 8.3 – – 75 8.3 – – 75
100 2.1 0.74 74 19 3.3 0.60 60 30
200 1.6 0.81 81 14.5 2.4 0.71 71 21.7
2.4. Surface Examination SBIC was investigated by the corrosion weight loss
and Analysis of Corrosion Products measurements in 0.5 M HCl solution is shown in Table 1.
2.4.1 Scanning electron microscope (SEM). The Weight loss, surface coverage (θ) and inhibition effi
morphology and inhibition effect of the surface of ciency (IEW(%)) for different SBCC and SBIC con
mild steel in 0.5 m HCl solution in absence and pres centrations were reported. Inhibition efficiency with
ence of 400 ppm of Schiff base complexes for 4 h was 200 ppm of inhibitor concentration for SBCC and
also tested by SEM examinations. SBIC inhibitors at room temperature was obtained
respectively to 82 and 73%. By increscent of SBCC
2.4.2 UVreflectance spectral studies. Spectropho and SBIC concentration, the surface coverage and
tometer technique was employed in this study to inves inhibition efficiency were improved. Corrosion rate in
tigate the stability of the complexes under study. Spec different concentrations of the inhibitors are shown in
tra were achieved using UVvisible double beam ratio Table 1. Average corrosion rate of steel in 0.5 M HCl is
recording, spectrophotometer JASCO model V670. 169 mpy but in present of 200 ppm of SBCC and SBIC
the corrosion rate slow down respectively to 29.8 and
3. RESULTS AND DISCUSSION 46.8 mpy.
3.1. Weight Loss Measurements
The weight loss method of monitoring corrosion 3.2. Polarization Measurements
rate is useful because of its simple application and reli Potentiodynamic polarization plots for mild steel
ability [25]. Therefore, a series of weight loss measure specimens in 0.5M HCl solution and at room temper
ments were carried out in the absence and presence of ature in the absence and presence of different concen
various concentrations of the inhibitors. The behavior trations of SBIC and SBCC are shown in Fig. 2. The
of corrosion inhibition for mild steel by SBCC and results of polarization measurements are given in Table 2.
(a) (b)
1 3 1 1
1 1–4
2 4 2
–2 3 –2
3
4
4
Current density, i/Acm–2
–3 2 –3
Eb
Eb
–4 –4
1 – 0 ppm 1 – 0 ppm
2 – 100 ppm 2 – 100 ppm
–5 3 – 200 ppm –5 3 – 200 ppm
4 – 400 ppm 4 – 400 ppm
–6 –6
–0.8 –0.6 –0.4 –0.2 –0.8 –0.6 –0.4 –0.2
E (vs. SCE)/V
Fig. 2. Polarization curves of mild steel in 0.5 M HCl in the absence and presence of various concentrations of inhibitors; SBIC
(a), SBC (b).
Table 2. Kinetic parameters of mild steel in 0.5 M HCl at 25 ± 1°C containing different concentrations of SBIC and SBCC
–Ecorr Icorr βc βa
Inhibitor C (mg/L) θ IE (%) mpy
(mV SCE–1) (μAcm–2) (mV dec–1) (mV dec–1)
Blank 0 343 230 97 72.9 0 – 108
SBIC 100 306 79 97 78 0.65 65.5 36
200 302 37 98 78 0.83 83.9 17
400 294 33 94 69 0.85 85.6 15
SBCC 100 284 34 97 42 0.85 85.2 16
200 290 26 101 65 0.88 88.7 12
400 294 24 90 61 0.89 89.5 11
The respective kinetic parameters including corrosion inhibitor concentration reflect the formation of anodic
current density (icorr), corrosion potential (Ecorr), protective films on the electrode surface.
cathodic Tafel slope (βc) and anodic Tafel slope (βa)
are listed in Table 2. The degree of surface coverage (θ)
and the percentage of inhibition efficiency (IE%) were 3.4. Electrochemical Impedance Measurements
calculated using the following equations [26]: Impedance measurements of steel electrode at its
0
i corr– i corr open circuit potential after 0.5 h of immersion in
θ =
0
. (1) 0.5 M HCl solution alone and in the presence of vari
i corr ous inhibitors concentrations were performed over the
IE% = θ × 100, (2)
0 (a)
where i corrand i corr are corrosion current densities in
90
the absence and presence of inhibitors, respectively. It
is illustrated from the data of Table 2 that the addition
of SBIC and SBCC decrease corrosion current den 80
sity. It can be clearly seen that the inhibition efficiency SBIC
of SBIC and SBCC increase with inhibitor concentra SBCC
IE, %
60
the cathodic branches and to a lesser extent in the
anodic branches of the polarization curves. Moreover,
in the presence of SBIC and SBCC the values of cor 40
rosion potential Ecorr are nearly constant; therefore,
SBIC could be classified as a mixedtype inhibitor 20
with predominant anodic effectiveness and SBCC
could be classified as a mixed type inhibitor with pre
dominant cathodic effectiveness. On the other hand, the 0 100 200 300 400
recorded polarization curves in the presence of inhibitors Concentration, ppm
are characterized by the presence of anodic breakdown
potential, Eb. The noble shift of Eb and the decrease of the Fig. 3. Plots of inhibition efficiency and mpy vs. concen
corresponding current densities with increasing the tration of inhibitor.
–40 Rs
Zim/Ω cm2
–30
–20 Rct
–10 Fig. 5. Equivalent circuits used to fit the EIS data of steel
in 0.5 M HC1 + xM inhibitor.
0
10 process are also given in Fig. 4a. The intersection of
0 20 40 60 80 100 120 the capacitive loop with the real axis represents the
Zre/Ω cm2 ohmic resistance of the corrosion product films and
(b) the solution enclosed between the working electrode
–250 and the reference electrode, Rs [27, 28]. Rct represents
0 ppm
100 ppm
the chargetransfer resistance whose value is a mea
–200 sure of electron transfer across the surface and is
200 ppm
400 ppm inversely proportional to corrosion rate [29]. The con
–150 randelz fit
stant phase element, CPE, is introduced in the circuit
Zim/Ω cm2
randelz fit
– +
specis like Cl ads. and H ads. on the electrode surface
–150
[33]. It may also attribute to the redissolution of the
–100 passivated surface at low frequencies [34].
–50 The effect of addition of increasing concentrations
of the investigated compounds on the EIS of steel in
0 0.5 M HCl solution has been studied at the respective
open circuit potentials; some of the obtained results
50 are shown in Figs. 4b and 4c. The electrochemical
0 100 200 300 400 500 600 700
parameters obtained from fitting the recorded EIS
Zre/Ω cm2 data using equivalent circuit of Fig. 5 are listed in Table 3.
The inhibition efficiencies, IE%, of the tested inhibi
Fig. 4. Nyquist plot of the steel electrode in 0.5 M HC1 tors were calculated from the Rct values at different
without (a) and with different concentrations of (b) SBIC concentrations using the following equation [35]:
and (c) SBCC after immersing the electrode in the working
solutions for 1 h under open circuit conditions. –1 –1
R ct ( free ) – R ct ( inh )
–1
× 100,
IE% = (3)
R ct ( free )
frequency range from 100 KHz to 10 MHz. The
recorded EIS spectrum for steel in 0.5 M HCl, Fig. 4a, where Rct(free) and Rct(inh) are the chargetransfer resis
shows one depressed capacitive loop at higher fre tance values in the absence and presence of inhibitor,
quency range (HF) followed by an inductive loop that respectively. Increasing the concentration of either
is observed in the lower frequency region (LF). The SBIC or SBCC increases the corresponding IE% val
equivalent circuit of Fig. 5, fits well our experimental ues till Cinh =400 ppm without passing through a max
results, simulated points originated from the fitting imum, Figs. 4b and 4c and Table 3. We can note from
Table 3. Electrochemical impedance parameters for mild steel corrosion in 5.0 M HCl solution in the absence and presence
various concentrations of inhibitors
CPET
Inhibitor Cinh (ppm) CPEP fmax (μF cm–2) Rs (Ω) Rct (Ω) θ IE %
(μF cm–2)
Blank 0 140 0.93 13.9 140 1.62 110 – –
SBIC 100 90 0.91 5.17 69 0.071 455 0.75 75
200 83 0.90 5.18 51 2.74 599 0.81 81
400 68 0.90 5.18 48 2.52 630 0.83 83
SBCC 100 140 0.92 7.2 140 3.01 210 0.48 48
200 120 0.92 7.2 76 2.48 290 0.62 62
400 90 0.92 5.18 65 2.71 470 0.77 77
Figs. 4b and 4c that the characteristic frequencies of organic adsorbate at metalsolution interface can be
the inductive loop diminish with increasing the mag presented as a substitution adsorption process between
nitude of the electrode impedance whatever the inhib the organic molecules in aqueous solution, (Org
itor concentration is. In the high impedance Nyquist (sol)), and the water molecules on metallic surface,
plots, the growing up inhibiting film delays the charge (H2O (ads)) [42]:
transfer processes to lower frequencies. The high Org ( sol ) + xH 2 O ads ⇔ Org ( ads ) + H 2 O ( sol ) , (6)
impedance EIS curves were fitted to the one time con
stant equivalent circuit shown in Fig. 5 where the where Org(sol) and Org(ads) are the organic specie dis
induction loops shifted below the studied low fre solved in the aqueous solution and adsorbed onto the
quency limit. The protection layer resistance and the metallic surface, respectively, H2O(ads) is the water
diffuse charge capacitance in it are not separated in molecule adsorbed on the metallic surface and x is the
this approximation, rather they are conceived to be size ratio representing the number of water molecules
included in the elements of the used circuits. replaced by one organic adsorbate. For the studied
Inspection of the data reveals that its addition of inhibitors, it was found that the experimental data
the inhibitors increases the capacitive loop diameter of obtained from polarization readings could be fitted by
the Nyquist plots without affecting their characteristic Langmuir’s adsorption isotherm.
features. This means that the inhibition action of this According to this isotherm, the surface coverage (θ) is
inhibitor is due to its adsorption on the metal surface related to inhibitor concentration (C) by [43, 40]:
without altering the corrosion mechanism. In addi θ
tion, the double layer capacitances, Cdl, for a circuit = K ads C. (7)
including a CPE were calculated from the following 1–θ
equation [36, 37]: Rearranging Eq. 7 gives:
n–1
C dl = Y 0 ( ω max ) , (4) C 1
= + C, (8)
where ωmax = 2πfmax, fmax is the frequency at which the θ K ads
imaginary component of the impedance is maximal. where Kads is the equilibrium constant of the inhibitor
The data of Table 3 show that the magnitude of Cdl adsorption process, C is the inhibitor concentration
decreases with increasing Cinh. The decrease in Cdl and θ is the surface coverage that was calculated by Eq. 1.
could be attributed to the adsorption of the inhibitors This model for Langmuir’s adsorption isotherm has
forming protective adsorption layers [38]. The thick been used extensively in the literatures for various
ness of the protective layer (d) is related to Cdl accord metal/inhibitor/acid solution systems [41]. A fitted
ing to the following equation [39]: straight line is obtained for the plot of C/θ versus C
εε with slopes close to 1 as seen in Fig. 6a and Fig. 6b.
C dl = 0 , (5) The strong correlation (R2 > 0.99) suggests that the
d adsorption of inhibitor on the mild steel surface
where ε is the dielectric constant of the protective layer and obeyed this isotherm. This isotherm assumes that the
ε0 is the permittivity of free space (8.854 × 10–14 F cm–1). adsorbed molecules occupy only one site and there are
no interactions with other adsorbed species [41].
3.5. Adsorption Isotherms The Kads values can be calculated from the intercept
lines on the C/θaxis. This is related to the standard
Adsorption isotherms provide information about 0
the interaction of the adsorbed molecules with the free energy of adsorption ( ΔG ads ) with the following
electrode surface [40, 41]. The adsorption of an equation [41]:
0
0.6 [41]. In some literatures, the values of ΔG ads are
0.5 reported less negative than –40 kJ/mol for physical
adsorption commonly interpreted as the formation of
0.4 an adsorptive film with an electrostatic character [41].
0
0.3 Regarding the present work, the calculated ΔG ads val
0.2 ues for SBIC and SBCC show that an electrostatic
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 interaction, i.e., physisorption, is presented between
C (mM) the inhibitors and charged metal surface. The higher
(b) 0
values of Kads and ΔG ads refer to higher adsorption and
0.9
y = 1.134x + 0.018 higher inhibiting effect. The higher inhibition effects
0.8 R2 = 0.999 of SBCC in comparison with the SBIC may be attrib
0.7 uted to the deposition of trivalent chromium on the
surface. In physisorption process, it can be assumed
0.6 that acid anions such as Cl– ions are specifically
C/θ (mM)
(a)
Cl1
H3A H6A Mild Steel
O3 O6
Mild Steel in HCl
H2A H4A
Reflectance
N2 N4
Fig. 7. Hydrogen bondings in the crabclaw site of the Mild Steel in HCl
complexs.
(a)
1.2
SBIC in Ethanol
SBIC in acid
1.0
0.8
Absorbance
0.2
0
250 350 450 550 650
Wavelength, nm
2.0 (c) 20 µm (d) 20 µm
(b) SBCC in Ethanol
SBCC in Acid
Fig. 10. SEM micrographs of mild steel after immersion in
1.5 0.5 M HCl (a) Blank; (b) 400 mg/L SBIC; (c) 400 mg/L
SBCC after potentiodynamic tests.
Absorbance
1.0
of inhibitormetal interaction can be identified. First
the electrostatic force between the cationic molecules
0.5 (followed by protonation of its basic functionalities in
acidic media with excess positive charge of Iron and
0 Chromium on their molecules structure) and the neg
250 350 450 550 650 ative charged of the metal surface (especially in acidic
Wavelength, nm media which may be brought about by specific adsorp
tion of chloride anions) leading the SBCC and SBIC
Fig. 9. UVvisible absorption spectra for synthesized com molecules coming toward the water interface of the
plexes; SBIC(a), SBCC(b) in alcoholic and acidic solu
tions. metal, then there are the free electron pair on OH den
tate capable of forming a coordinate bond with dtype
orbitals of the metal [48]. Further, the double bonds in
the oxidation and corrosion of mild steel is lightly in the molecules allow back donation of metal delec
comparison with that in blank.
trons to the π*orbitals. Thirdly, π electrons from the
As shown in Fig. 10d, after addition of SBCC in the aromatic rings may interact with metal surface.
acid, the surface morphology of mild steel is smoother
than that in SBIC case, and some mechanically pol
ishing nicks can still be found. Chloride hydrate was 4. CONCLUSION
detected lower than that in SBIC case, and the oxida
tion degree is lower than that in SBIC reflected by the Two novel synthesized Schiff base of iron and chro
oxygen content. mium complexes are found to inhibit the corrosion of
It can be concluded that, the inhibition ability is in mild steel in 0.5 M HCl solution and the extent of
descent order as SBCC > SBIC from the evidence of inhibition is concentration dependent. Inhibition effi
surface corrosion and oxidation degree after immer ciency increases with increasing inhibitor concentra
sion in acid and drying in air. It is in good accordance
with the results obtained from potentiodynamic and tion. The value of Gibbs free energy of adsorption
impedance measurement. indicates that SBIC and SBCC is more physically
adsorbed onto the surface of the metal and the nega
Comparing the EDX results (Table 5) one could 0
hypothesize the process of inhibition. The results tive values of ΔG ads show the spontaneity of the
demonstrate formation of a layer on the sample adsorption. The results of potentiodynamic polariza
immersed in SBCC electrolyte composed of Cr 1.08% tion measurements point to SBIC and SBCC func
atm. In other words, SBCC and SBIC form a layer on
the mild steel surface. A schematic interaction mech tioning as a mixed type (cathodic/anodic) inhibitors.
anism of metal Schiff base complexes with mild steel The adsorption characteristics of SBIC and SBCC
surface is displayed in Fig. 9. To consider the structure were approximated by Langmuir’s adsorption iso
of the investigated inhibitors, several potential source therm.