Applied Surface Science 476 (2019) 861–877

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Applied Surface Science

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Full length article

XPS and DFT investigations of corrosion inhibition of substituted T

benzylidene Schiff bases on mild steel in hydrochloric acid
Nor Zakiah Nor Hashima, , El Hassane Anouarb, , Karimah Kassimc,d, Hamizah Mohd Zakic,
⁎ ⁎

Abdulrahman I. Alharthib, Zaidi Embonge

a
Centre of Foundation, Universiti Teknologi MARA, Cawangan Selangor, Kampus Dengkil, 43800 Dengkil, Selangor, Malaysia
b
Chemistry Department, College of Science and Humanities Studies, Prince Sattam bin Abdulaziz University, P.O. Box 83, Al-Kharij 11942, Saudi Arabia
c
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
d
Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
e
Faculty of Applied Science and Technology (FAST), Universiti Tun Hussein Onn Malaysia (UTHM), Km 1, Jalan Panchor, Pagoh, 84600, Muar, Johor, Malaysia

ARTICLE INFO ABSTRACT

Keywords: A series of substituted benzylidene Schiff bases (2–4) were tested for their corrosion inhibition efficiency on mild
Schiff bases steel in 1 M HCl at 25 °C using electrochemical impedance spectroscopy, polarization and linear polarization
Corrosion inhibition resistance measurements. Experimental results demonstrated that the corrosion inhibition efficiency of the Schiff
Mild steel bases is more potent than their parent amine (1). XPS analysis proves the entire molecule of 3 ligand chemi-
Electrochemical measurements
sorbed through a covalent bond (π to π) interaction as found in C]C in the benzene ring and C]N. The
XPS
correlation between the corrosion inhibition efficiency and physicochemical and electronic properties of in-
DFT
hibitors (1–4) was investigated by using density functional theory method. Theoretical results clearly showed
that the corrosion inhibition efficiency mainly depends on the frontier orbitals parameters (e.g., ionization po-
tential, and electronic affinity).

1. Introduction medium [17,18]. The adsorption mechanism involved an electronic

Mild steel is one of the most frequently steels used in industry due to
its strength, low cost and simplicity in manufacturing. However, this
steel is highly corrodible when exposed to acid or basic solutions during
the diffusion-controlled processes. The use of corrosion inhibitors is one
of the most common methods applied for protecting metal or alloy
surfaces in acidic environment, since they can inhibit the corrosion rate
of mild steel, thus effectively lowering risks of material breakdown
[1–3]. Organic compounds possessing N, O and S heteroatoms and
multiple bonds have been extensively used as effective corrosion in-
hibitors [4,5]. Schiff bases, with a C]N azomethine functional group
resulting from the condensation between an amine and a ketone/al-
dehyde, have been shown to provide better inhibition performances
compared to corresponding amines [6–10]. They are widely reported as
effective corrosion inhibitors for steel [11,12], copper [13,14], and
aluminium [8,15] in acidic media [16] due to their simple and cost
effective preparation.
Generally, the corrosion inhibition by organic compounds is at-
tributed to their adsorption on the mild steel surface, thus forming an
adsorption layer (film) that reduces the corrosive attack in acidic
transfer from the inhibitor molecule to the metal surface, which leads to
the formation of coordinate covalent bonds between the inhibitor and
the metal [19]. The corrosion inhibition efficiency on the metal surface
depends on physicochemical properties of the adsorbed inhibitors. For
instance, the functional groups (e.g., C]O, C]N), π-electrons in mul-
tiple bonds, heteroatoms (e.g., N, O, S), aromaticity, steric effects,
electronic density and type of interaction between the inhibitor and the
metal surface may have different effects on the corrosion inhibition
efficiency. The protective ability of an inhibitor is strengthened by the
presence in its molecular structure of adsorption active sites such as
electronegative heteroatoms and aromatic electron clouds [20]. With
respect to Schiff bases, the C]N group is considered to be responsible
for the adsorption process and thus for their corrosion inhibition effi-
ciency [16,21,22].
Quantum chemical calculations have been widely used to model the
interaction mechanism between the corrosion inhibitor and metal sur-
face. As mentioned above, the corrosion inhibition efficiency is mainly
depending on the physicochemical, electronic properties of the organic
inhibitors, as well as the interaction between the inhibitor and the
metal surface. For instance, frontier orbitals and atomic charges are

⁎
Corresponding authors.
E-mail addresses: norzakiah21@gmail.com (N.Z.N. Hashim), anouarelhassane@yahoo.fr (E.H. Anouar).

https://doi.org/10.1016/j.apsusc.2019.01.149
Received 6 July 2018; Received in revised form 16 January 2019; Accepted 21 January 2019
Available online 23 January 2019
0169-4332/ © 2019 Elsevier B.V. All rights reserved.
N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

3 H 9
2 4 N 8 10
7
A B
1 11
5
NH2
6 12 14

(1): N-[(E)-11-benzylidene]-N’-phenyl-8,11-phenylenediamine

3 H 9
4 N 8
2 10
7
A B 15 17
1 11
5 13 18
N
16
6 12 14 C
19
21
20

(2): (E)-N8-benzylidene-N11-phenylbenzene-8,11-diamine

3 H 9
2 4 N 8 10
7
A B 15
1 11 17
5 13 18
N 16
6 12 14 C
19
21
Cl
20 22

(3): N-[(E)-11-chlorobenzylidene]-N’-phenylbenzene-8,11-diamine

3 H 9
2 4 N 8 10
7
A B 15
1 11 17
5 18
N 16
6 12 14 C
19 23

O
20 22

(4): N-[(E)-11-methoxybenzylidene]-N’-phenylbenzene-8,11-diamine
Fig. 1. Molecular and optimized structures of compounds 1–4.

largely used for determining the corrosion inhibitor active sites density functional theory (DFT) quantum chemical calculations.
[4,5,14,23].
We have synthesized aromatic Schiff bases 2–4 (Fig. 1) differing by
the nature of the substituent in the para position of the phenyl ring 2. Material and methods
[24,25]. The main objective of the present study was to investigate
their inhibition efficiency with respect to their parent amine (1) on mild 2.1. Schiff bases synthesis
steel in 1 M HCl at 25 °C via electrochemical impedance spectroscopy
(EIS), polarization and linear polarization resistance measurements. The Schiff bases (2–4) were synthesized from 1 (Fig. 1). The
The adsorption mechanism of the Schiff base (3) to the mild steel in- synthesis was achieved by reacting 5 mmol of N-phenyl-8,11-phenyle-
terface using X-ray photoelectron spectroscopy (XPS) in 1 M HCl was nediamine (1) in 10 mL of absolute ethanol with 5 mmol of benzalde-
explored. In addition, we aimed at determining (i) the relationships hyde, 4-chlorobenzaldehyde and 4-methoxybenzaldehyde, respectively.
between physicochemical, electronic properties and inhibition effi- The mixture solutions were refluxed for 30 min at 76 °C and left to cool
ciency, and (ii) the active binding sites of these Schiff bases by applying for 5 h. Precipitates formed, were collected and washed with cold
ethanol and dried in air [24]. The chemical structure of the Schiff bases

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N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

Fig. 2. Polarization curves for mild steel in 1 M HCl at 25 °C with and without the addition of inhibitors at different concentrations.

Table 1
Corrosion parameters for mild steel in uninhibited and inhibited 1 M HCl solutions at 25 °C.
Cinh (mM) Parameter

-Ecorr (mV) icorr (μA cm−2) βa (mV dec−1) βc (mV dec−1) ηPol (%) θ

1 M HCl 385 706.1 89.2 97.8 – –

1
0.5 355 387.3 97.5 109.6 45.0 0.45
1.0 351 243.9 152.6 100.7 65.0 0.65
1.5 354 177.9 95.00 92.20 74.7 0.75
2.0 355 127.9 77.60 94.20 81.9 0.82

2
0.5 371 127.1 66.6 85.9 82.0 0.82
1.0 371 88.78 92.2 117.2 87.4 0.87
1.5 373 70.61 93.7 115.1 89.9 0.90
2.0 373 34.63 82.4 85.7 95.1 0.95

3
0.5 360 63.63 56.60 64.30 91.0 0.91
1.0 351 44.67 68.5 97.90 93.7 0.94
1.5 349 35.41 75.50 110.3 95.0 0.95
2.0 354 20.86 62.80 79.70 96.0 0.96

4
0.5 354 154.6 63.80 72.10 78.1 0.78
1.0 351 89.57 70.60 88.70 87.3 0.87
1.5 352 74.37 114.4 155.6 89.5 0.90
2.0 354 42.61 71.0 88.71 94.0 0.94

(2–4) were characterized by physical and spectroscopic analysis via 2.2. (E)-N8-benzylidene-N11-phenylbenzene-8,11-diamine (2)
elemental analysis, infrared (IR) and proton nuclear magnetic re-
sonance (1H NMR, 300 MHz, DMSO‑d6). Yield = 78%. Elemental analysis: Anal. calculated: C, 83.79; H,
5.92; N, 10.29. Found: C, 83.94; H, 5.88; N, 10.41. MP = 100 °C. IR

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N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

Table 2 Table 3
Polarization resistances and inhibition efficiencies for mild steel in 1 M HCl at Electrochemical parameters obtained from EIS plots for mild steel in 1 M HCl at
25 °C using different concentrations of compounds 1–4 from linear polarization 25 °C in the absence and presence of compounds 1–4.
measurements.
Cinh (mM) Rp (Ω cm2) Cdl (μF cm−2) ηEIS (%)
2
Cinh (mM) -Ecorr (mV) Rct (Ω cm ) ηEIS (%) CR (mm/year)
1 M HCl 14.0 138 –
1 M HCl 385 21.0 – 8.14 1
1 0.5 24.4 121 42.6
0.5 355 102 79.4 4.49 1.0 27.6 99.0 49.3
1.0 351 108 80.6 2.83 1.5 29.8 68.8 53.0
1.5 354 114 81.5 2.06 2.0 93.3 37.8 85.0
2.0 355 145 85.4 1.48
2
2 0.5 111 67.5 87.4
0.5 371 128 83.6 1.47 1.0 171 58.3 91.8
1.0 371 252 91.7 1.03 1.5 248 53.2 94.4
1.5 373 318 93.4 0.82 2.0 366 27.2 96.2
2.0 373 529 96.0 0.40
3
3 0.5 205 39.0 93.2
0.5 360 205 89.8 0.74 1.0 259 39.2 94.6
1.0 351 392 94.6 0.52 1.5 368 27.8 96.2
1.5 349 534 96.0 0.41 2.0 387 25.8 96.4
2.0 354 534 96.1 0.24
4
4 0.5 45.3 125 69.1
0.5 354 95.1 77.9 1.80 1.0 78.4 69.8 82.1
1.0 351 191 89.0 1.04 1.5 84.3 40.2 83.4
1.5 352 385 94.5 0.86 2.0 346 29.5 96.0
2.0 354 402 94.8 0.49

2.3. N-[(E)-11-chlorobenzylidene]-N′-phenylbenzene-8,11-diamine (3)

(KBr) vNH = 3409 cm−1, vC-C = 3043 cm−1, vC-N = 1080 cm−1,
vC=N = 1592 cm−1. 1H NMR (DMSO, 300 MHz, δ ppm) 8.32: singlet Yield = 72%. Anal. calculated: C, 74.38; H, 4.93; N, 9.13. Found: C,
(NH), 7.90–6.79: multiplets (aromatic protons), 8.63: singlet (imine 74.09; H, 4.91; N, 9.18. MP = 135 °C. IR (KBr) vNH = 3424 cm−1, vC-
proton).13C (DMSO, 300 MHz, δ ppm) 143.4 (C]N), 143.6 (CeN), C = 3018 cm
−1
, vC-N = 1082 cm−1,vC=N = 1603 cm−1 vC-
142.6–117.3 (AreC). Cl = 749 cm
−1 1
. H NMR (DMSO, 300 MHz, δ ppm) 8.41: singlet (NH),
7.91–6.80: multiplets (aromatic protons), 8.63: singlet (imine proton).

Fig. 3. Nyquist plots measured at Ecorr for mild steel in 1 M HCl at 25 °C in the absence and presence of various concentrations of 1 (a), 2 (b), 3 (c) and 4 (d).

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N.Z.N. Hashim et al.
Fig. 4. Langmuir's adsorption isotherm for compounds 1–4 on mild steel surface in stagnant condition of 1 M HCl at 25 °C.
Table 4
Adsorption equilibrium constants (Kads) and free Gibbs energies of compounds
1–4 on mild steel in 1 M HCl at 25 °C.
Inhibitor Kads ΔGads (kJ/mol)
1 1.51 × 103 −28.11
2 7.63 × 103 −32.12
3 25.6 × 103 −35.12
4 6.62 × 103 −31.77
13
C (DMSO, 300 MHz, δ ppm) 155.8 (C]N), 143.5 (CeN), 142.9
(CeN), 135.7 (CeCl), 142.9–117.3 (AreC).
2.4. N-[(E)-11-methoxybenzylidene]-N′-phenylbenzene-8,11-diamine (4)
Yield = 80%. Anal. calculated: C, 79.44; H, 6.00; N, 9.26; O, 5.29.
Found: C, 79.31; H, 5.58; N, 9.42; O, 5.47. MP = 116 °C. IR (KBr)
vNH = 3397 cm−1, vC-C = 3043 cm−1, vC-N = 1091 cm−1,vC=N = 1604
cm−1, vC-O = 1280 cm−1, vCH3 = 1375 cm−1, 1H NMR (δ ppm) 8.21:
singlet (NH), 7.78–6.78: multiplets (aromatic protons), 8.51: singlet
(imine proton) 3.42 ppm; triplet (methyl proton). 13C (DMSO, 300 MHz,
δ ppm) 157.2 (C]N), 143.7 (CeN), 143.9 (CeN), 129.7–117.7 (AreC),
55.7 (OCH3).
2.5. Test solutions
For corrosion measurements, 1 M HCl solutions were used to test the
uninhibited and inhibited solutions containing test compounds, with
concentration ranges 0.5–2.0 mM. The acidic solutions were prepared
by dilution of analytical grade conc. HCl (37%) with distilled water.
2.6. Electrochemical experiments
Electrodes for electrochemical measurements were square-shaped
mild steel XC48 specimens with the following chemical composition
(wt%): C = 0.418, Mn = 0.730, Mo = 0.012, P = 0.016, S = 0.019,
Si = 0.245, Ni = 0.079, F = 0.777 and Fe = 98.0 were embedded in an
epoxy resin having an exposed surface area of 0.049 cm2. The speci-
mens were mechanically polished using different grades of silica car-
bide paper, then polished to mirror finish using diamond paste. They
were degreased with ethanol, rinsed with distilled water and lastly
dried before introduction into the acidic solution. The tests were carried
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Applied Surface Science 476 (2019) 861–877
out at 25 °C in stagnant condition in a 100-mL cell. For the conventional
three-electrode cell system, a platinum rod was used as counter elec-
trode, a Gamry Instruments silver‑silver chloride electrode
(Ag|AgCl|Cl−) as reference, and mild steel as working electrode.
The measurements were performed using a Gamry Reference 600™
potentiostat/galvanostat connected to a personal computer. The
working electrode was immersed completely in the acidic solution at
open circuit potential (Eocp) for 30 min. In polarization method, the
curves were obtained with a potential scan rate of 1 mV/s from the
corrosion potential (Ecorr) in the cathodic followed by anodic direction.
The inhibition efficiencies ηpol (%) were calculated by using the fol-
lowing equation [26]:
icorr icorr
pol (%) = 100
icorr (1)
where icorr and i'corr are the corrosion current densities without and
with addition of inhibitors, respectively.
The polarization resistance (Rp) values were calculated using the
slope of the potential to current lines using the following equation [27]:
dE
Rp = A
di (2)
where A refers to the surface area of the electrode, while dE and di are
the potential and current variations, respectively.
The Rp values were adopted to determine the inhibition efficiencies
(ηRp) by the following equation [16]:
Rp (inh) Rp
Rp (%) = 100
Rp (inh) (3)
where Rp(inh) is the polarization resistance in inhibited solution, while
Rp is polarization resistance in uninhibited solution.
The corrosion rates (CR) in millimeter per year were calculated
using the following equation [28]:
i corr (µA/cm2) EW
Corrosion rate (mm/year) = 0.00327
density (g/cm3) (4)
where 0.00327 is a constant factor used for dimension and time con-
version factor, and EW is the equivalent weight in grams.
Electrochemical impedance spectroscopy (EIS) measurements were
performed by applying frequency range 100,000–0.1 Hz with a signal
amplitude perturbation of 10 mV by employing AC signals at Eocp.
N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

Fig. 5. SEM micrographs (1000×) of mild steel surface after 24 h immersion at 25 °C 1 M HCl in the absence (a) and presence of 2.0 mM of 1 (b), 2 (c), 3 (d) and 4
(e).

2.7. Surface analyses analyses were performed at the same level of theory. The absence of
imaginary frequencies confirmed that the structures were true minima
The mild steel specimens with surface area of 1 cm2 were analyzed of the potential energy surface. A triple-ζ Pople-type basis set 6-311+G
after immersion in 1 M HCl with and without addition of 2.0 mM in- (d,p) was used, in which polarized and diffuse functions are taken into
hibitors for 24 h at 25 °C. They were taken out from the solution, rinsed consideration. To explain the interactions between the title compounds
with acetone and dried. The surface analysis of the specimens was and the mild steel metal surface, a set of electronic properties such as
carried out using Field Emission Scanning Electron Microscopy HOMO and LUMO energies, ionization potential (IP), electronic affinity
(FESEM) and Atomic Force Microscopy (AFM). The surface area ana- (EA), energy gap, electronegativity (χ), chemical hardness (η), softness
lyzed by AFM for roughness quantification was set at 10 × 10 μm. (S), electrophilicity (ω) and dipole moment (μ) were calculated at the
X-ray photoelectron spectroscopy (XPS) spectra were recorded with same level of theory (B3LYP/6-311+G(d,p)). The electronic para-
Omicron Nanotechnology (ELS5000) spectrometer with the mono- meters EA, IP, χ and η were calculated using Koopman's theorem, in
chromatized Al Kα radiation source of 1486.6 eV and the binding energy which IP = −EHOMO and EA = −ELUMO χ, η and ω were calculated by
of C 1s (285.0 eV) as the internal reference. Quantification and simu- the following formula:
lation of the experimental photopeaks were done using CasaXPS soft-
ware. The mild steel (1 cm2) was immersed in 1 M HCl with and without IP + EA
= = µ (µ is the chemical potential)
addition of 2.0 mM inhibitor 3 for 24 h. After removal from the test 2 (5)
solution, specimen was lightly rinsed with distilled water and dried
before introducing it into the XPS chamber. 1 µ 1 2E (IP EA)
= = =
2 N 2 N2 2 (6)
2.8. Theoretical calculations
1
The ground states of the studied compounds (1–4) were optimized S=
(7)
by using B3LYP/DFT hybrid functional method [29]. The frequency

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N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

Fig. 6. AFM three-dimensional images of mild steel surfaces: (a) after 24 h of immersion at 25 °C in 1 M HCl, (b) after 24 h of immersion in 1 M HCl + 2.0 mM 1, (c)
after 24 h of immersion in 1 M HCl + 2.0 mM 2, (d) after 24 h of immersion in 1 M HCl + 2.0 mM 3, (e) after 24 h of immersion in 1 M HCl + 2.0 mM 4.

µ2 1
= = ( + + yy ).
2 (8) 3
xx yy
(10)

In the hardness formula (Eq. (6)), N is the number of electrons, υ the

µ= µ 2x + µ 2y + µ 2z (9) external potential, and E the electronic energy.

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N.Z.N. Hashim et al.
Fig. 7. Height profiles of the mild steel surfaces: (a) after 24 h of immersion at 25 °C in 1 M HCl, (b) after 24 h of immersion in 1 M HCl + 2.0 mM 1, (c) after 24 h of
immersion in 1 M HCl + 2.0 mM 2, (d) after 24 h of immersion in 1 M HCl + 2.0 mM 3, (e) after 24 h of immersion in 1 M HCl + 2.0 mM 4.
The fraction of the transferred electrons (∆N) was calculated by
using Pearson's theory [30]:
Fe inh
N=
2( Fe + inh )
where χ is the electronegativity, η the hardness, Fe the iron atom, and
inh the inhibitor.
To determine the most likely reactive atoms allowing the title in-
hibitors to react with mild steel, Mulliken atomic charges were calcu-
lated. The solvent effects were taken into account implicitly using the
polarizable continuum model (PCM). In this model, the solute is em-
bedded into a cavity surrounded by solvent described by its dielectric
constant ε (e.g., for water ε = 78.3553) [31].
All theoretical calculations including ground state geometry opti-
mization and frequency analysis were performed with Gaussian 09
package [32]. The molecular orbitals were visualized using Molden
Applied Surface Science 476 (2019) 861–877
software (http://www.cmbi.ru.nl/molden/).
3. Results and discussion
(11)
3.1. Electrochemical experiments
3.1.1. Polarization and linear polarization resistance measurements
The inhibitor concentrations were chosen in the range 0.5–2.0 mM.
The lower limit was selected from poor inhibition performance, while
the upper one corresponds to the corrosion inhibition reaching a pla-
teau and essentially unaffected by further concentration increase [33].
The common polarization curves for mild steel in 1 M HCl in the
presence and absence of inhibitors at different concentrations for 1 and
Schiff bases 2–4 are shown in Fig. 2. Corrosion parameters including
corrosion potential (Ecorr), corrosion current densities (icorr), anodic and
cathodic slopes (βa and βc), surface coverage (θ), polarization resistance
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N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

(a) C 1s

Intensity (a.u.)
C-C

C-O
C(-COO-)

292 290 288 286 284 282 280

Binding energy (eV)

(b) C 1s
Intensity (a.u.)

C=C

Shake up
satellite C-NH
C(-COO-) C=N+
C=N C-Cl
C-C

294 289 284 279

Binding energy (eV)

Fig. 8. High-resolution spectra of C 1s mild steel immersed for 24 h in 1 M HCl in the (a) absence of inhibitor, (b) 1 M HCl + 2.0 mM of 3 analyzed at photoemission
angle of 0°.

Table 5
Binding energies (eV), relative intensity and their assignment for C 1 s peak observed for 1 M HCl in an optimum concentration of 3 at 0° photoemission angle.
Sample Chemical species Photoemission angle (°) Assignment BE (eV) Relative intensities (%)

1 M HCl + 2.0 mM 3 C 1s 0 C]C 284.2 61.72

CeC 285.0 3.24
CeCl 286.0 3.24
CeNH 286.2 9.73
C]N 286.5 3.24
CeO 287.0 1.23
C]N+ 288.4 3.99
C(eCOO−) 290.2 3.06
Shake up satellite 292.8 10.53

(Rp), and percentage of inhibition efficiencies (ηPol%) for each inhibitor
are shown in Table 1. From these data, it is obvious that current den-
sities decrease inversely with inhibitor concentrations. This may in-
dicate that the adsorption of the inhibitor molecules takes place on the
mild steel surface. The corrosion rates of mild steel are much reduced in
inhibited solutions compared to uninhibited solutions, especially at
higher concentrations.
The polarization curves in Fig. 2 clearly demonstrate that the ad-
dition of 0.5 mM inhibitors to the 1 M HCl solution affects both βa and
βc parameters, due to the decrease in both anodic and cathodic pro-
cesses. The corrosion inhibition improves significantly until their con-
centration reaches a maximum of 2.0 mM. This implies an alteration of

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(a) O 1s

Intensity (a.u.)
Fe-Ox
C(-COO-)

H2O

538 536 534 532 530 528 526 524

Binding energy (eV)

(b) O 1s
Intensity (a.u.)

C(-COO-)

H2O
Fe-Ox

543 538 533 528 523

Binding energy (eV)

Fig. 9. High-resolution spectra of O 1 s mild steel immersed for 24 h in 1 M HCl in the (a) absence, (b) 1 M HCl + 2.0 mM of 3 analyzed at photoemission angle of 0°.

Table 6
Binding energies (eV), relative intensity and their assignment for O 1 s peak observed for 1 M HCl in an optimum concentration of 3 at 0° photoemission angle.
Sample Chemical species Photoemission Assignment BE (eV) Relative intensities (%)
angle (°)

1 M HCl + 2.0 mM 3 O 1s 0 Fe-Ox 531.3 27.53

C(eCOO−) 532.7 52.40
H2O 535.7 20.07

the mechanism in the cathodic hydrogen reaction and blocking of the
active sites on the iron surface [34,35].
In presence of the parent amine and Schiff base inhibitors, the Ecorr
was greatly shifted to noble (active) direction indicating a greater
number of inhibitors being adsorbed on the metal-solution interface,
thus decreasing the rate of anodic reaction of the metal compared to the
blank solution. These results suggest that these inhibitors are of mixed
type and able to retard both anodic and cathodic reactions of iron in
1 M HCl.
From the polarization measurement results, it is clear that the in-
hibition efficiency increases with the inhibitor concentration. The
above suggests that Schiff bases were initially adsorbed on the surface
of mild steel, thus covering the electrode surface. Subsequently, the
formation of coordination bonds with the metal leads to the formation
of a film on the mild steel surface. This film preserves the metal un-
derneath from attack of chloride ions, since chloride from the bulk
solution control the anion movement into crevices. The chloride mi-
gration is faster in comparison to other anions in the bulk solution. If
the chloride ions fail to reach the metal surface, the cascade of events
associated with crevice corrosion (such as complex formation with Fe,
hydrolysis of these complexes, pH increase and mild steel in active
dissolution) is therefore prevented [36,37].
The inhibition efficiency values of studied amine 1 and its Schiff
bases 2–4 in 1 M HCl rank as follows:
•C inh = 0.5 mM: 3 (91.0%) > 2 (82.0%) > 4 (78.1%) > 1 (45.0%)

870
N.Z.N. Hashim et al.
Intensity (a.u.)
C=N+
410 405 400
Binding energy (eV)
Fig. 10. High-resolution spectra of N 1 s mild steel immersed for 24 h in 1 M HCl + 2.0 mM of 3 analyzed at photoemission angle of 0°.
Table 7
Binding energies (eV), relative intensity and their assignment for N 1 s peak observed for 1 M HCl in an optimum concentration of 3 at 0° photoemission angle.
Sample Chemical species Photoemission
angle (o)
1 M HCl + 2.0 mM 3 N 1s 0 NeH
•C inh = 1.0 mM: 3 (93.7%) > 2 (87.4%) > 4 (87.3%) > 1 (65.0%)
•C inh = 1.5 mM: 3 (95.0%) > 2 (89.9%) > 4 (89.5%) > 1 (74.7%)
•C inh = 2.0 mM: 3 (96.0%) > 2 (94.8%) > 4 (94.0%) > 1
(81.9%).
At all concentrations, the ranking remains consistent with Schiff
base 3 showing the best inhibition performance.
From the linear polarization resistance measurements (Table 2), it
was found that inhibition efficiency values at maximum concentration
of 2.0 mM decrease in the following order, 3 (96.1%) > 2
(96.0%) > 4 (94.8%) > 1 (85.4%). With this technique, it is possible
to determine the absolute corrosion rates in millimeter per year (mm/
year). Thus, corrosion rates at 2.0 mM rank as follows: 1 (1.48 mm/
year) > 4 (0.49 mm/year) > 2 (0.40 mm/year) > 3 (0.24 mm/year).
From these results, it is obvious that dissolution rates of the mild steel
are effectively improved in the presence of Schiff base inhibitors (2–4)
compared to the parent amine (4) even at similar concentration of
additives. These results are in good agreement with the above ones of
polarization measurements in terms of their inhibition corrosion effi-
ciencies.
3.1.2. Electrochemical impedance spectroscopy (EIS)
Fig. 3 presents Nyquist plots of mild steel in 1 M HCl solution in the
absence and presence of 1–4 inhibitors at various concentrations. The
Nyquist plot measured in uninhibited solution appears as one depressed
capacitive loop while the semicircle diameter increases with the in-
hibitor concentration. This indicates the formation of a thin film on the
metal surface, which becomes strengthened in the presence of in-
hibitors. All EIS spectra are shaped as semicircle and fit Randles cir-
cuits, where elements involved are solution resistance component (Rs),
capacitance (Cdl) and charge-transfer resistance component (Rct). Im-
pedance parameters containing inhibition efficiencies and polarization
resistance values are shown in Table 3. The double layer capacitance
was calculated using the following equation [38]:
1 1
Cdl =
2 fmax Rct (12)
871
Applied Surface Science 476 (2019) 861–877
N 1s
N-Fe
N-H
395 390
Assignment BE (eV) Relative intensities (%)
397.03 3.27
NeFe 398.73 80.08
C]N+ 399.73 16.65
where fmax is the maximum frequency at which the imaginary compo-
nent of the Nyquist plot is maximum. Since Rct is inversely proportional
to the corrosion current densities, inhibition efficiency (ηEIS %) can be
calculated using the following equation [4]:
Rct (inh) Rct
EIS % = 100
Rct(inh) (13)
where Rct(inh) and Rct are the charge-transfer resistance in the presence
and absence of inhibitor, respectively.
From Table 3, when the concentration of inhibitors increases, Rct
values are increased while Cdl values are decreased. These results sug-
gest that adsorption takes place on the mild steel surface leading to the
formation of a protective thin film that inhibits metal dissolution in
acidic solution. At the highest concentration of 2.0 mM, the inhibitive
action can be ranked as follows: 3 > 2 > 4 > 1 (96.4, 96.2, 96.0 and
85.0%, respectively). The EIS results are in good agreement with po-
larization and linear polarization resistance measurements.
3.1.3. Influence of the molecular structure on the inhibition efficiencies
The three Schiff bases have similar basic structures with no sub-
stituent (2), a chlorine (3) or a methoxy (4) group at para position of
the benzylidene ring. The corrosion inhibition efficiency values showed
that 3 is more protective than 2, which is more protective than 4. As
mentioned above, the parent amine (1) has least protective properties
compared to Schiff bases. The differences in inhibition properties are
mainly due to the presence of the azomethine (C]N) group that is
attached to the aryl group with a different substituent for each in-
vestigated Schiff base. Chemisorption interaction is due to the inter-
action of the C]N group, π electrons of the aromatic ring along with
free electron pair of the N heteroatom with mild steel surface [21,39].
This type of adsorption occurs via π back bonding (π back donation), in
which it involves synergic interaction by donation of electrons from the
filled π orbitals of the benzene ring, C]N group and lone pair of n
orbitals of the Schiff bases. These orbitals overlap with the empty or-
bitals of the iron atom and simultaneously a back donation of electrons
takes place from the d orbital of iron into the unfilled π⁎ antibonding
orbital of the Schiff bases [40,41].
N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

improve its inhibition efficiency. The substitution of chlorine at the

Cl 2p
para position in the aromatic ring 3 increases the inhibition perfor-
(a) mance compared to unsubstituted 2 and methoxylated 4. The chlorine
atom increases the tendency for anchoring by helping the coordination
bond to the surface and therefore further strengthening the adsorption
1 M HCl +2.0 mM of 3 of 3.
Intensity (a.u.)

3.1.4. Adsorption isotherm

The adsorption of inhibitors on the metal surface can be analyzed
using adsorption isotherm. The degree of surface coverage (θ) at dif-
1 M HCl + 0 mM Schiff base ferent inhibitor concentrations (Table 1) is calculated using the fol-
lowing equation [45]:
pol
= .
100 (14)
207 202 197 192 Langmuir's adsorption isotherm is obtained using the following
Binding energy (eV) formula [46]:
Cinh 1
= + Cinh.
K ads (15)
Cl 2p where Kads is the adsorption equilibrium constant and Cinh the inhibitor
(b) concentration.
Langmuir's adsorption isotherms were interpreted by using linear
regression plots of Cinh/θ vs Cinh displayed in Fig. 4. The correlation
coefficients (R2) and slopes are very close to 1, which means that the
adsorption of inhibitors at the metal-solution interface abides by this
Intensity (a.u.)

Cl 2p3/2
Cl 2p1/2
205 203 201 199
Binding energy (eV)
Fig. 11. High resolution of Cl 2p spectra for (a) untreated mild steel sample in
1 M HCl, (b) treated mild steel sample in the presence of an optimum con-
centration of 3 in 1 M HCl.
Other factors contribute in increasing the efficiencies of the Schiff
bases over amines. As one of them, the planarity of the structure assists
in the orientation arrangement into the thin film on the exposed surface
of mild steel [42,43]. The structures of the title Schiff bases are not
totally planar. For instance, the calculated torsion angles in solution
(PCM) of the central aromatic ring with phenyl and chlorophenyl rings
in Schiff base 3 are 19° and 30°, respectively, while X-ray analysis
showed torsion angles of 12° and 44° between the same groups in solid
state [24]. The higher surface area of Schiff bases compared to the
amine is another reason for the increase in inhibition efficiencies due to
the additional delocalized π electron density on the benzene ring [44].
On the other hand, Schiff base 4 with a p-methoxy group has a
surprisingly lower inhibition efficiency compared to 2. Generally, an
increase in the π electron density on the phenyl ring resulting from the
presence of a methoxy group (electron-donating group) should enhance
the adsorption of the molecule onto the mild steel surface and thus
type of adsorption isotherm. These isotherms show that the adsorption
of organic molecules on the metal surface is monolayer [38]. The Kads
was calculated using the intercept of 1/K (M−1) from the straight line.
The Kads was linked to the energy of adsorption (ΔGads) using the re-
lation [47]:
Gads = RTln (55.5K ads ) (16)
where R is the universal gas constant, T the absolute temperature and
197 195 55.5 the value for molar concentration of water in solution (mol/L).
The measured ΔGads and Kads values are shown in Table 4. The high
ΔGads values indicate a strong adsorption of the inhibitor molecules
onto the metal surface.
Generally, for ΔGads values below than or equal to −20 kJ/mol the
adsorption is due to physisorption electrostatic interaction between the
charges at metal surface and inhibitor. For ΔGads around −40 kJ/mol,
the adsorption is of chemisorption type, due to the formation of co-
ordinate bonds by charge sharing or electron transfer from the neutral
organic compound to the metal surface. Based on the ΔGads values for
the studied inhibitors in Table 4, the adsorption for 1 is governed by
physisorption, while for Schiff base derivatives it is not typical chemi-
sorptions or physisorption but rather a combination of both (compre-
hensive adsorption) [48,49].
3.2. Surface analyses
3.2.1. Scanning electron microscopy
The SEM images of mild steel immersed in 1 M HCl for 24 h at 25 °C
in absence and presence of inhibitors are shown in Fig. 5. Without
addition of inhibitors (Fig. 5a), the mild steel surface was heavily da-
maged due to high metal dissolution in the corrosive solution. In con-
trast, the surface in the presence of Schiff bases (Fig. 5c-e) was greatly
improved compared to the solution containing parent amine 1 (Fig. 5b).

Table 8
Binding energies (eV), relative intensity and their assignment for Cl 2p peak observed for 1 M HCl in an optimum concentration of 3 at 0° photoemission angle.
Sample Chemical species Photoemission Assignment BE (eV) Relative
angle (o) intensities (%)

1 M HCl + 2.0 mM 3 Cl 2p 0 Cl 2p3/2 199.50 66.69

Cl 2p1/2 201.11 33.31

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N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

Fe 2p1/2 Fe 2p3/2 Fe 2p
(a)

Fe2+
satellite

Fe3+

Intensity (a.u.)
satellite
Fe3+
Fe2+

745 740 735 730 725 720 715 710 705 700
Binding energy (eV)

Fe 2p3/2 Fe 2p
Fe 2p1/2
(b)

Fe2+
Fe3+
Intensity (a.u.)

Fe3+

Fe2+

Fe0

745 740 735 730 725 720 715 710 705 700
Binding energy (eV)

Fig. 12. High-resolution spectra of Fe 2p mild steel immersed for 24 h in (a) untreated mild steel sample in 1 M HCl, (b) 1 M HCl + 2.0 mM of 3 analyzed at
photoemission angle of 0°.

Table 9
Binding energies (eV), relative intensity and their assignment for Fe 2p peak observed for 1 M HCl in an optimum concentration of 3 at 0° photoemission angle.
Sample Chemical species Photoemission angle (°) Assignment BE (eV) Relative intensities (%)

0
1 M HCl + 2.0 mM 3 Fe 2p 0 Fe 2p3/2 Fe 707.0 7.31
Fe2+ 711.3 31.30
Fe3+ 713.7 20.82
Fe 2p3/2 satellites Fe2+ 719.3 10.71
Fe3+ 721.7 7.12
Fe 2p1/2 Fe0 723.7 7.18
Fe2+ 725.5 5.90
Fe3+ 727.9 3.92
Fe 2p1/2 satellites Fe2+ 733.5 3.75
Fe3+ 735.9 1.99

3.2.2. Atomic force microscopy absence and presence of inhibitor at optimum concentration of 2.0 mM
The SEM results were further confirmed using AFM techniques. The in 1 M HCl are shown as in Fig. 6. The surface of mild steel in solution of
three-dimensional images of mild steel surfaces immersed in the Schiff bases (Fig. 6c-d) showed less surface damages than in solution

873
N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

Table 10
Electronic properties (eV if no unit mentioned) of the compounds 1–4 calculated at the B3LYP/6–311 + G (d, p) level of theory.
Inhibitor εHOMO εLUMO IP EA εGap χ η ∆Ν μ (D) ηpol (%)

1 −5.27 −0.67 5.27 0.67 4.60 2.97 2.30 0.88 2.77 81.9
2 −5.40 −2.04 5.40 2.04 3.36 3.72 1.68 0.97 2.91 95.1
3 −5.42 −2.15 5.42 2.15 3.28 3.78 1.64 0.98 4.31 96
4 −5.34 −1.88 5.34 1.88 3.46 3.61 1.73 0.98 1.96 94

100 98
98 R2 = 95% 96 R2 = 99.35%
Inhibition Efficiency (%)

Inhibition Efficiency (%)

96 94
94 92
92 90
90
88
88
86
86
84 84
82 82
80 80
5.26 5.28 5.30 5.32 5.34 5.36 0.50 1.00 1.50 2.00 2.50
IP (eV) EA (eV)

(a) (b)

98 98
96 R2 = 99.47% 96 R2 = 98.92%
Inhibition Efficiency (%)
Inhibition Efficiency (%)

94 94
92 92
90 90
88 88
86 86
84 84
82 82
80 80
3.00 3.50 4.00 4.50 5.00 0.85 0.90 0.95 1.00
Gap (eV) ∆N

(c) (d)
Fig. 13. Correlation curves between inhibition efficiencies and electronic parameters for compounds 1–4.

containing parent amine 1 (Fig. 6b). The mild steel in the absence of of 285.0 eV. Thus the adsorbed CeC on mild steel surface in the
inhibitor in 1 M HCl as shown in Fig. 6a is highly cracked due to the solution containing 3 inhibitor is due to the adsorbed Schiff base
attack of acid on the metal surface. This was quantified by the average molecules and not the non-oxidized carbon rich contaminants as in
surface roughness of mild steel calculated at 196 nm using height pro- untreated sample immersed in 1 M HCl (Fig. 8a). Due to the presence of
files as in Fig.7. However, this value was reduced to 46 nm with ad- chlorine at para position of the benzylidene proves to increase the
ditive 1 while in the presence of 2, 3 and 4 the values further decreased adsorption by aiding the conjugated double bond of C]C and also C]
to 12, 8.4 and 19 nm, respectively. N to adsorb on the surface of metal. This is confirmed by the assigned
CeCl in the 3 (Fig. 8b) which appeared at 286.0 eV (Table 5). The
presence of carboxylic group contaminations (C(eCOO−)) also
3.2.3. XPS analysis in the absence and presence of 2.0 mM 3 inhibitor on expected to be present at higher BE, at round 290.2 eV for treated
mild steel in 1 M HCl samples with addition of 3 corrosion inhibitor. The adsorbed gaseous
3.2.3.1. C 1 s spectra. The entire molecules are chemisorbed through a organic species are possibly found precisely on top of the adsorbed
covalent bond (π to π) interaction as found in C]C in the benzene ring inhibitors film. Schiff base molecules under study are bind to the metal
and C]N while the orientation of this 3 ligand on the metal surface is surface of iron mostly via C atoms.
almost flat in the acidic solution. Separated at 7.8 eV from the main
peak of C 1s, “shake up” excitations occurred in the π orbitals of the aryl
groups (C]C) at 292.8 eV for the 3 treated mild steel. During 3.2.3.2. O 1s spectra. The first deconvoluted peak is assigned to iron
photoemission, an electron is transferred from an occupied π bonding oxides (Fe-Ox) (Fig. 9) which appeared at 531.3 eV (Table 6). As
orbital on the C]C to an unoccupied π⁎ antibonding orbital. The justified previously in C 1s signal, the adsorbed oxidized
energy loss from this excitation reduces the kinetic energy of electron carbonaceous species can be found on top of the adsorbed film of
thus appeared at higher binding energy from the main C 1 s peak. The inhibitors molecules and allocated at 532.7 eV in O 1 s spectrum. The
investigated 3 Schiff base (Fig. 1) also have a CeC (alkyl group) in its molecular water usually appeared at higher BE compared to formation
structure as found in C15–C16 which appeared at binding energy (BE) of hydroxyl group on iron (FeOH). As an instance, the hydroxyl group is

874
N.Z.N. Hashim et al. Applied Surface Science 476 (2019) 861–877

Table 11
Mulliken atomic charges for compounds 1–4 calculated at the B3LYP/6-311+G
(d, p) level of theory.
1 Inhibitor

1 2 3 4

1 −0.167 −0.196 −0.192 −0.205

2 −0.257 −0.332 −0.342 −0.300
3 −0.728 −0.686 −0.583 −0.634
4 −0.109 0.073 0.097 0.059
5 0.593 0.627 0.531 0.513
6 −0.360 −0.257 −0.290 −0.246
7 −0.016 −0.002 −0.001 −0.008
2
8 0.103 −0.128 0.002 0.047
9 −0.557 −0.866 −1.026 −1.011
10 −0.116 −0.118 −0.009 0.001
11 −0.270 −0.153 −0.166 −0.204
12 −0.053 −0.021 0.033 0.003
13 0.303 0.562 0.498 0.520
14 −0.427 0.071 0.076 0.067
15 – −0.297 −0.107 −0.112
16 – 0.738 0.205 0.648
17 – −0.504 −0.543 −0.543
18 – −0.451 −0.924 −0.531
19 – −0.135 0.853 −0.427
3 20 – −0.462 −0.681 0.310
21 – 0.063 −0.170 −0.319
22 – – 0.357 −0.208
23 – – – −0.235

in treated sample containing inhibitors in acidic and near neutral

solutions has been reported by several authors [52–54]. They have
proposed that chlorine is involved in electrostatic interaction between
the chloride with the positively charged surface to form surface
complex (Fe(Cl−)ads) followed by physical adsorption occur due to
4 attraction of Fe(Cl−)ads and cationic form of Schiff base (C]N+).
Hence, the contribution of chloride by forming a surface complex can't
be ignored. Therefore, based on this reason with addition of 2.0 mM of
3 to the corrosive medium it may confirmed that the Cl 2p signal is the
result of chloro substituent in the benzylidene and not due to chloride
that is presence in the testing solution (Fig. 11a) in which two peaks
HOMO LUMO
were deconvoluted (Fig. 11b) at BE of 199.50 eV and 201.11 eV
Fig. 14. Frontier molecular orbitals of compounds 1–4. (Table 8) which assigned for Cl 2p3/2 and Cl 2p1/2, respectively.

characterized by O 1s at around 531.0 eV while from the results, the
peaks found to be at 535.7 eV. This suggests the appearance of water
molecules can be distinguished from the FeOH, thus conclude no OH−
group that is adsorbed on the metal surface. Furthermore, the same
findings for water peaks were reported at around 532.8 eV to 538.0 eV
[51]. In our case, the adsorbed water appeared at somewhat higher BE
due to the existence of water film in multilayer in comparison to the
monolayer film.
3.2.3.3. N 1s spectra. The adsorption of inhibitors may occur in
multilayer form, in which the first or most inner layer might
chemisorbed to the iron substrate. This adsorption is assisted by the
presence of surface oxide (FeOx) via nitrogen atom assigned as NeFe
(Fig. 10), appeared at 398.73 eV as presented in Table 7.
The subsequent layer (one or more) of inhibitors are physisorbed on
that inner most layer via intermolecular hydrogen bonding. It is verified
by the X-ray crystallography 3 data [24] which found that in the crystal
structure, there is a weak intermolecular hydrogen bonding of CeHeπ
(CeH groups interact with π-bases). This bond can be described by
hydrogen bonding between one carbon atom (CeH) in the aromatic
ring bonded to another nitrogen atom in C]N from different molecule.
The peak appeared at 399.73 eV indicated for C]N+ in 3.
3.2.3.5. Fe 2p spectra. Fe 2p signal comprises of a doublet nature (2
peaks) as a result of multiplets splitting as in Fe 2p3/2 and Fe 2p1/2
which arises due to existence of unpaired valence electrons (Fig. 12).
With the addition of 2.0 mM of 3 inhibitor in 1 M HCl, the deconvoluted
iron peak found in the high resolution spectrum comprises of Fes (iron
substrate), Fe3O4 or FeO (Fe2+), Fe2O3 (Fe3+) and the presence of
satellite peaks at the higher BE side of the main peaks (Fe 2p3/2 and Fe
2p1/2) which are due to the characteristics of Fe2+ and Fe3+ as shown
in Fig. 12b. The most prominent difference can be seen at BE in the
treated samples containing 2.0 mM of 3 inhibitor at 707.0 eV (Fe 2p3/2)
and 723.7 eV (Fe 2p1/2) in the Table 9 which allocated for metallic iron
(Fe°) and is absence for untreated mild steel as presented in Fig. 12a.
In the analysis of Fe 2p spectra, both of the iron high spin (Fe 2p3/2)
and iron low spin Fe (2p1/2) was fitted accordingly to the relevant peak
height ratio while the Fe2+ and Fe3+ species were modelled using 2 GL
functions respectively with two broader GL functions for the Fe2+ and
Fe3+ shake-up satellites peaks. Even though it may feasible to acquire
better curve fitting when extra peaks are used [55], trouble in classi-
fying these peaks due to the position of the peak is too close to each
other is the purpose we prefer not to use additional peaks.
3.3. Theoretical calculations

3.2.3.4. Cl 2p spectra. The presence of chlorine peak on metal surface The corrosion inhibition efficiencies (ηPol %) and the electronic

875
N.Z.N. Hashim et al.
properties of the 1–4 inhibitors are shown in Table 10. To determine
the relationship between each parameter and the inhibition efficiency
of the compounds (1–4), corresponding correlation curves were plotted
(Fig. 13). As can be seen in Fig. 13, the inhibition efficiency increases
with the ionization potential (IP) and electronic affinity (EA), while it
decreases with the energy gap.
Inhibitors with a high IP value have an increased tendency of of-
fering electrons to the d orbitals of the metal, and thus increased ad-
sorption strength. In addition, the higher is the EA value, the easier the
inhibitor is accepting electrons from the metal surface. The above re-
lationship was confirmed by the values of the HOMO-LUMO energy
gap. The lower is the energy gap, the higher is the corrosion inhibition
efficiency. HOMO and LUMO frontier molecule orbitals are displayed in
Fig. 14. HOMO electronic densities are mainly located on the C1-N14
chain, while LUMO densities are mainly found around the aniline ring
A. HOMO and LUMO orbitals are useful for predicting the sites of ad-
sorption of the inhibitors onto the metal surface [50,51]. Efficient in-
hibitors are those able to donate electrons (nucleophilic attack) to the d
orbital of the metal, and accept electrons from the metals (electrophilic
attack) [14]. Mulliken atomic charges were calculated for C, N, O and
Cl atoms of the title compounds (Table 11). As can be seen in Table 11,
some atomic centers present small charge electronic densities (e.g., N7
and N14) susceptible to nucleophilic attack, while others present large
electronic densities (e.g., C3 and N14) and therefore prone to electro-
philic attack. The number of electrons transferred from inhibitor to
metal (∆N) was also calculated (Table 10). The inhibition efficiency and
∆N (i.e., electrons donation) show a positive correlation (Fig. 8d). These
results agree with a previous study that reported an inhibition effi-
ciency increasing with the electron-donating ability of the inhibitor
[14]. The dipole moment (μ) values of the compounds 1–4 are shown in
Table 10. A correlation coefficient of 97% was obtained between the
inhibition efficiency and the dipole moment when only the Schiff bases
2–4 (with a similar backbone) are considered. However, the correlation
becomes less significant when parent amine 1 was taken into con-
sideration (R2 = 71%).
4. Conclusion
The Schiff base derivatives, namely 2, 3 and 4 are efficient in-
hibitors on mild steel in 1 M HCl solution at 25 °C.
1. The results acquired from polarization measurement show that these
inhibitors adsorb on mild steel surface. A dose-dependent reduction
of anodic & cathodic current densities is observed together with a
shift of the corrosion potential to the noble direction, thus sug-
gesting and inhibition of the metal dissolution process.
2. The inhibition efficiencies of 1–4 as determined through EIS, po-
larization and linear polarization resistance measurements ranked
as 3 > 2 > 4 > 1.
3. The adsorption follows Langmuir adsorption isotherm and ΔGads
rank exactly as above.
4. SEM and AFM analyses confirmed the protective effect of inhibited
solutions.
5. The relationships between the corrosion inhibition efficiency and
electronic properties of 1–4 inhibitors were determined by DFT
calculations. The inhibition efficiency increases along with IP and
EA, and decreases with gap energy. The atomic charges and frontier
molecular orbitals analysis showed that the Schiff bases could act as
donor/acceptor of electrons to/from metal surface of the mild steel.
Acknowledgement
The authors are grateful to the Ministry of Higher Education,
Malaysia for the FRGS grant no. 600-IRMI/FRGS 5/3 (030/2017) and to
Mr. Mohamad Safwan bin Jusof (Universiti Malaya, Kuala Lumpur,
Malaysia) for granting access to his institution supercomputer
876
Applied Surface Science 476 (2019) 861–877
PTMLXSMP.
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