coatings

Article
Thiocarbohydrazones Based on Adamantane and
Ferrocene as Efficient Corrosion Inhibitors for
Hydrochloric Acid Pickling of C-Steel
Abdelwahed R. Sayed 1,2 and Hany M. Abd El-Lateef 1,3, *
1 Department of Chemistry, College of Science, King Faisal University, P.O. Box 400,
Al-Ahsa 31982, Saudi Arabia; arsayed@kfu.edu.sa
2 Chemistry Department, Faculty of Science, Beni-Suef University, Beni-Suef 62514, Egypt
3 Chemistry Department, Faculty of Science, Sohag University, Sohag 82524, Egypt
* Correspondence: hmahmed@kfu.edu.sa or hany_shubra@science.sohag.edu.eg




Received: 15 October 2020; Accepted: 3 November 2020; Published: 6 November 2020


Abstract: N0 -(adamantan-2-ylidene)hydrazinecarbothiohydrazide and 2-(ferrocenyl-1-ylidene)

hydrazinecarbothiohydrazide are used in coordination and organometallic complexes. The important
idea of the research in this paper is the principal to prepare thiocarbohydrazones from the reaction of
2-acetylferrocene (Fe-Th) or 2-adamantanone (Ad-Th) with carbonothioic dihydrazide. The materials
were elucidated by elemental analysis and spectral data. The as-prepared compounds were
applied as effective corrosion inhibitors for HCl pickling of C-steel. Detailed investigations
on electrochemical (open circuit potential (OCP) vs. time, potentiodynamic polarization (PDP),
and impedance spectroscopy (EIS)) techniques and surface morphology studies are introduced in this
work. Results indicated that Fe-Th could deliver greater inhibition performance than Ad-Th, and the
highest protection capacity values of 93.6% (Ad-Th) and 97.9% (Fe-Th) were accomplished at 200 ppm.
The adsorption of Ad-Th or Fe-Th additives followed the Langmuir isotherm with both the chemical
and the physical adsorption with chemisorption predominance. EIS measurements supported a
betterment in the capacitive behavior with the corrosion inhibitors. The inhibitors exhibited a
mixed-type behavior as observed from the PDP studies. Field emission scanning electron microscopy
(FESEM) and Fourier-transform infrared spectroscopy (FTIR) studies emphasize the occurrence of a
protective layer of the as-synthesized organic inhibitors on the C-steel interface. Theoretical studies
(density functional theory (DFT) calculations and Monte Carlo (MC) simulations) provide appropriate
support for the experimental findings. The existing report provides very significant consequences in
formulating and designing novel thiocarbohydrazone inhibitors with high protection efficacy.

Keywords: ferrocene; corrosion inhibition; surface morphology; EIS; thiocarbohydrazones;

DFT calculations

1. Introduction
Currently, carbon steel (C-steel) is applied in various manufacturing processes, including cooling
water systems, oil and gas processing industry, refining, water pipes, skyscrapers, and boilers. Its wide
applications are due to accessibility, low-cost, and simplicity of production. Nonetheless, C-steel remains
susceptible to various corrosion forms [1–3]. In numerous industrial procedures—like well acidizing,
acid pickling, and acid cleaning—contaminated and rust scales were usually extracted using acid
mediums. Furthermore, HCl can be produced as a by-product in the crude oil desalting process
and some oil refinery treatments [4]. HCl is the most extensively applied in the metals pickling
processes [5]. Actually, corrosion is a dangerous process that decreases material features and makes
them impracticable.

Coatings 2020, 10, 1068; doi:10.3390/coatings10111068 www.mdpi.com/journal/coatings

Coatings 2020, 10, 1068 2 of 20

In this regard, the application of organic additives is a practical alternative to protect alloys and
metals from corrosion in an aggressive medium [4]. The capacity of inhibitor molecules depends mainly
on the metal interface, the nature of the solution, and the inhibitor structure [6]. Indeed, the research in
the branch of corrosion protection by inhibitors is focused on the preparation of ecofriendly inhibitors.
The inhibitors having hetero-atoms (sulfur, nitrogen, phosphorus, oxygen, etc.), functional groups,
π-electrons, and benzene rings which not only have the capability to adsorb on a huge surface area but
could interact with the steel interface through physical or chemical adsorption [6]. The great molecular
weight compounds containing a high part of surface coverage are proven to be outstanding candidates
for corrosion inhibitors [7].
Recently, thiocarbohydrazones were obtained from the reaction of salicylaldehyde derivatives
with thiocarbohydrazide [8]. Synthesis of thiocarbonohydrazone containing tin for studying
biological and crystal structures was reported [9]. Preparation and quantum calculations
for bis-(isatincarbohydrazones or isatinthiocarbohydrazones) are described [10]. Mono- and
bis-(thiocarbohydrazones) based on 2-acetylpyridine have antioxidant activity are described [11].
Preparation of thiocarbohydrazones containing benzofuran heterocycles was reported [12].
Thiocarbohydrazone-1-(4-arylidene)-5-(2-oxoindolin-3-ylidene) having antidiabetic properties was
explained [13]. Schiff bases of thiocarbohydrazide are studied as chemical physio complexes [14].
Syntheses of isatin-β-thiocarbohydrazones based on the microwave-assisted are evaluated against
antiquorum-sensing, antimicrobial, and cytotoxic activities [15]. Thiocarbohydrazones based on
2-nitro benzaldehyde helped in the extraction for the determination of ruthenium (III) in catalysts
and alloy [16]. Thio-ligands are used in spectrophotometric in the detection of tellurium (IV) and
liquid–liquid extraction [17].
The reaction of malononitrile dimer with thiocarbohydrazones gave thiadiazine derivatives based
on the microwave-assisted as green chemistry [18]. Syntheses of coumarin by using simple and
efficient methods were prepared as fluorescent chemosensor for fluoride detection [19]. The reaction
of bisthiocarbohydrazones with cis-dioxomolybdenum (VI) gave complex for electrochemical
applications [20]. Enhanced corrosion inhibition of carbon steel in HCl solution by synthesized
hydrazine derivatives was reported [21–24].
The aim of this work is the examination of the corrosion protection performance of some
thiocarbohydrazones based on adamantane and ferrocene in the hydrochloric acid medium for
C-steel. Thiocarbohydrazones compounds are characterized through FTIR and nuclear magnetic
resonance (NMR) spectroscopies. Furthermore, the influence of the well-designed groups on the
protection action is experimentally inspected by the OCP vs. time, PDP, and EIS techniques as well
as the surface morphology (FESEM, FTIR). Moreover, the thermodynamic indices of the adsorption
isotherms were investigated to indicate the adsorption type of Ad-Th and Fe-Th on the metal surface.
Furthermore, the compositional support of the findings was carried out with density functional theory
(DFT) and Monte Carlo (MC) simulations to authenticate the experimentally obtained outcomes.

2. Experimental Part

2.1. Instrument, Solutions, and Materials

All required solvents and chemicals from Aldrich were analytical grade and were used without
additional purification. The melting points were determined on an Electro-thermal IA 9000 sequence
digital Device of melting point (Bibby Sci. Lim. Stone, Staffordshire, UK). FT-IR spectra were recorded
by using FT-IR 8101 PC spectrophotometers (Shimadzu, Tokyo, Japan). 1 H spectra were measured
at 300 MHz in deuterated dimethyl sulfoxide (DMSO-d6) (VX-300 NMR spectrometer; Varian, Inc.,
Karlsruhe, Germany). Mass spectra were measured on a GCMS-QP1000 EX mass spectrometer
(Shimadzu, Tokyo, Japan) at 70 eV. A German-made Elementarvario LIII CHNS analyzer (CKIC,
Frankfurt, Germany) determined elemental analyses.
Coatings 2020, 10, 1068 3 of 20

The
Coatings composition
2020, (wt%)
10, x FOR PEER of the designated C-steel sample applied as a working electrode in
REVIEW the
3 of 21
current study was carbon (0.19%), silicon (0.18%), manganese (0.05%), chromium (0.75%), nickel (0.18%),
and iron and
(0.18%), balance. The protective
iron balance. action of action
The protective the investigated inhibitorsinhibitors
of the investigated was considered at five different
was considered at five
concentrations quantifiedquantified
different concentrations by 20, 40, by
80,20,
150, and
40, 80,200
150,mg L−1
and . mg L−1.
200

2.2. Synthesis of
2.2. Synthesis N0 -(Adamantan-2-Ylidene)Hydrazinecarbothiohydrazide (4)
of N′-(Adamantan-2-Ylidene)Hydrazinecarbothiohydrazide (4) and
and 2-(Ferrocenyl-1-Ylidene)
2-(Ferrocenyl-1-Ylidene) Hydrazinecarbothiohydrazide (5)
Hydrazinecarbothiohydrazide (5)
Equimolar amounts of the appropriate carbonothioic dihydrazide 1 with 2-adamantanone 2 or
Equimolar amounts of the appropriate carbonothioic dihydrazide 1 with 2-adamantanone 2 or
2-acetylferrocene 3 in ethanol (40 mL) were heated for 4.5 h. The resulting solids were cooled and
2-acetylferrocene 3 in ethanol (40 mL) were heated for 4.5 h. The resulting solids were cooled and
crystallized from MeOH to provide 4 and 5, as shown in Scheme 1.
crystallized from MeOH to provide 4 and 5, as shown in Scheme 1.

O O
Fe H H
CH3
N N
3 H2N NH 2 2
S

S
NH 2 S
N N N
H H 2N N
H N N
Fe H H
CH3

5 4
Fe-Thiocarbohydrazon Ad-Thiocarbohydrazon

Scheme 1.
Scheme 1: Synthesis
Synthesis procedure of thiocarbohydrazones
procedure of thiocarbohydrazones Ad-Th
Ad-Th and
and Fe-Th.
Fe-Th.

N 0 -(Adamantan-2-ylidene)hydrazinecarbothiohydrazide (4):
N′-(Adamantan-2-ylidene)hydrazinecarbothiohydrazide (4): White
Whitesolid; Yield (88%); mp >
solid; Yield > 217 °C.◦ C.

IR (KBr):
(KBr): νmaxνmax3266,
3266, 3177 (NH,
3177 (NH,NHNH 2), 2986 (aliphatic),
2 ), 2986 1108 1108
(aliphatic), (C=S)(C=S)
cm−1. 1HcmNMR −1 . 1 H (DMSO-d 6): 1.08–1.88
NMR (DMSO-d 6 ):
(m, 6H, adam),
1.08–1.88 (m, 6H,2.10 (m, 8H,
adam), adam),
2.10 (m, 8H, 4.47adam),
(s, 2H, NH4.472),(s,7.72
2H,(s,NH1H,2 ),NH)
7.72and 8.96 NH)
(s, 1H, (s, 1H,andNH)
8.96ppm. MS
(s, 1H,
m/z (%):
NH) ppm. 238MS(Mm/z
+, 21). Anal.
(%): 238 (M + , 21).
Calcd for Anal.
C11H18Calcd
N4S (238.35):
for C11 H C,1855.43; H, 7.61; C,
N4 S (238.35): N, 55.43;
23.51. H,
Found: C, 55.41;
7.61; N, 23.51.
H, 7.63;C,
Found: N,55.41;
23.52%. H, 7.63; N, 23.52%.
2-(Ferrocenyl-1-ylidene) hydrazinecarbothiohydrazide
hydrazinecarbothiohydrazide(5): (5):Pale
Paleyellow
yellow solid; YieldYield
solid; (80%); mp:
(80%);
188 °C.
mp: 188IR◦ C.
(KBr): νmax 3265,
IR (KBr): νmax
3177, (NH,
3265, NH2),
3177, 2909,NH
(NH, 2884,2 ), 2849
2909, (aliphatic),
2884, 2849 1091 (C=S)
(aliphatic),cm −1. 1H (C=S)
1091 NMR
−1 . 1 H6):
(DMSO-d 2.19 (s, 3H, CH63):), 4.18–4.24 (m,CH5H,3 ),C4.18–4.24
5H4), 4.36–4.64 (m, C4H,
cm NMR (DMSO-d 2.19 (s, 3H, (m, 5H, 5 HC 5H
4 ), 4), 4.83 (s,(m,
4.36–4.64 2H,4H,
NHC 2),5 H
9.02
4 ),
(s, 1H,
4.83 (s, NH)
2H, NH and2 ),9.83
9.02(s,
(s,1H,
1H,NH)
NH)ppm.and 9.83MS (s,
m/z1H,
(%):NH)316ppm.(M+, 19);
MS Anal. Calcd
m/z (%): 316 for(M+C, 1319);
H16Anal.
FeN4SCalcd
(316.04):
for
C,1349.38;
C H16 FeN H,45.10; N, 17.72.
S (316.04): Found:
C, 49.38; H,C, 49.36;
5.10; H, 5.11;
N, 17.72. N, 17.70%
Found: C, 49.36; H, 5.11; N, 17.70%

2.3. Experimental Setup

2.3. Experimental Setup and
and Corrosion
Corrosion Measurements
Measurements
All
All the
the experimentations
experimentations were were accomplished
accomplished in in aa 1-L
1-L glass
glass cell
cell at
at atmospheric
atmospheric pressure.
pressure. The
The cell
cell
comprised
comprised ofof aa distinctive
distinctive three-electrode
three-electrode shape
shape where
where aa C-steel
C-steel was
was applied
applied as as aa working
working electrode,
electrode,
Ag/AgCl/KClsat
Ag/AgCl/KClsat electrode
electrode was
was utilized as aa reference
utilized as reference andand aa Pt
Pt sheet
sheet electrode
electrode served
served as
as aa counter.
counter.
Corrosion performance of the C-steel in molar hydrochloric acid solution with
Corrosion performance of the C-steel in molar hydrochloric acid solution with the occurrence the occurrence of organic
of
additives was analyzed
organic additives was by Gamry by
analyzed Potentiostat/Galvanostat/ZRA
Gamry Potentiostat/Galvanostat/ZRA (Gamry Instruments, Warminster,
(Gamry Instruments,
PA, USA). The
Warminster, PA, electrochemical determiningdetermining
USA). The electrochemical was documented after reaching
was documented equilibrium
after conditions
reaching equilibrium
at open circuit
conditions potential
at open circuit(Epotential
OCP ). EIS(Emeasuring was usedwas
OCP). EIS measuring a frequency break of 10
used a frequency mHz
break ofto
10100
mHzkHzto
100EOCP
at kHz over.
at EOCPInover.
addition, PDP evaluation
In addition, was measured
PDP evaluation was measured by altering the potential
by altering of theofC-steel
the potential the C-
from
steel from to +250
−250 −250 mV mV
to +250 based on E
based onOCP at at
EOCP a sweep
a sweep rate ofof0.2
rate 0.2mV/s
mV/s[25].
[25].Before
Beforeaccomplishing
accomplishing the
experiment, to obtain
obtain aa steady-state
steady-state open
open circuit
circuit potential
potential (E (EOCP
OCP),), the C-steel was exposed to molar molar
HCl medium at OCP for
medium at OCP for 50 min. 50 min. Gamry applications include software DC105 (version 4.35) for
corrosion, EIS300 (version 5.50) for EIS measurements,
measurements, and Echem Analyst 6.0 software package
software package
(Gamry Instruments, Warminster, PA, USA) for data fitting. It is well documented that the corrosion
rate of C-steel depends on the temperature, and the maximum corrosion rate is noticed at 50 °C, the
optimized corrosion temperature [26]. Consequently, to evaluate the protection capacity of the as-
prepared Fe-Th and Ad-Th additives on C-steel, all the measurements were accomplished at 50 °C.
Coatings 2020, 10, 1068 4 of 20

(Gamry Instruments, Warminster, PA, USA) for data fitting. It is well documented that the corrosion
rate of C-steel depends on the temperature, and the maximum corrosion rate is noticed at 50 ◦ C,
the optimized corrosion temperature [26]. Consequently, to evaluate the protection capacity of the
as-prepared Fe-Th and Ad-Th additives on C-steel, all the measurements were accomplished at 50 ◦ C.
Each measurement was duplicated at least three times and the values of corrosion parameters were
recorded as mean ± standard deviation.

2.4. Surface Characterization

The surface analysis by FE-SEM (JSM 5410 Model JEOL, Tokyo, Japan) of the C-steel electrode
was achieved after immersion of these samples for 48 h in 1.0 M HCl without and with 200 ppm of
Fe-Th. Experimental procedures of the FTIR of adsorbed films were similar, as designated in our
previous report [27].

2.5. Theoretical Studies (DFT Calculations and MC Simulation)

DFT calculations and MC simulation had been conducted using DMol3 and adsorption locator
modules in Materials Studio software V.7.0 from Accelrys Inc. (San Diego, CA, USA). For DFT
calculations, the investigated Ad-Th and Fe-Th molecules have been fully optimized using B3LYP
functional (Becke three-parameters Lee–Yang–Parr) with the double numeric plus polarization (DNP)
basis set and permitting the treating of solvation impacts utilizing COnductor-like Screening MOdel
(COSMO) controls, all these inputs are well-defined as in Eid et al. [28]. For MC simulation,
the adsorption locator reveals the potential adsorption configurations of the Ad-Th and Fe-Th
molecules with Monte Carlo searches on the Fe (110) surface to assess the inhibition capacity of
additives [29]. The interactions of Ad-Th and Fe-Th and Fe surface (110) accomplished in a simulation
box (32.27 Å × 32.27 Å × 50.18 Å) with periodic boundary conditions [29]. Forcite classical simulation
engine was utilized to optimize the energy of Ad-Th and Fe-Th molecules. To the establishment,
the Ad-Th and Fe-Th molecules/C-steel corrosion system in aqueous media the layer builder was
implemented, and this system includes the optimized Fe (110) surface, water, and the inhibitor
molecules. The universal simulation studies with force field were operated to simulate the adsorption
performance of Ad-Th and Fe-Th molecules on the surface of iron (110) [30].

3. Results and Discussions

3.1. Structure Configuration of the As-Prepared Compounds

Treatment carbonothioic dihydrazide 1 with 2-adamantanone 2 or acetylferrocene 3 in ethanol
under heating produced the final products N0 -(adamantan-2-ylidene)hydrazinecarbothiohydrazide
4 and 2-(ferrocenyl-1-ylidene) hydrazinecarbothiohydrazide 5, respectively. The compounds 4 or 5
have been synthesized in suitable yield (Scheme 1). The compounds 4 or 5 were elucidated by spectral
data and elemental analysis. The obtained data are compatible with the proposed structures for these
compounds as depicted in the experiment part, for instance, the IR spectrum 4 or 5 exhibited no
absorption bands at 1850–1650 cm−1 (Figure 1) which is belong to C=O group and this elucidated the
loss of water molecule to give thiocarbohydrazones 4 or 5.
Coatings 2020, 10, 1068 5 of 20
Coatings 2020, 10, x FOR PEER REVIEW 5 of 21

S
A Ad-Th H2N
N N
N

Transmittance/ %
H H

Coatings 2020, 10, x FOR PEER REVIEW 6 of 21

B I NH
where icor and icor are the icor in the blank
2
NH
and with the Ad-Th or Fe-Th inhibitors. It has been well-
C-H aliphatic
known in the literature [34] that if the Ecor value of displacementC=S in the presence of inhibitor is ≥85
mV with respect to Ecor in blank solution, the inhibitor is characterized as anodic or cathodic-type
4000 3500 3000 2500 2000 1500 1000 500
inhibitor according to the direction of the potential shift either -1
to the more positive or to the more
Wavenumber/ cm
negative direction, respectively [35]. If the shift is <85 mV then the inhibitor is categorized as a mixed
S
type of nature. In the present study,Bthe maximum Fe-Th change of EcorN is less
N
NH
than 0.038 and 0.026 V in the2
Transmittance/ %

N H
H
presence of Ad-Th and Fe-Th inhibitors, respectively. This suggests Fe
CH that the inhibitors display a
3

mixed nature [36]. The C-steel in blank HCl solutions (free inhibitor) presents an icor of 387.4 µA·cm−2.
The occurrence of additives declines remarkably icor to attain 24.8 and 8.1 µA·cm−2 with 200 ppm of
NH2 C-H aliphatic
Ad-Th and Fe-Th, respectively. The maximum protection power for corrosion comes out to be 93.6%
NH
and 97.9% in the presence of 200 ppm Ad-Th and Fe-Th, respectively. These findings approve that
the existence of either π-electrons or –NH, –C=S, –NH2 groups onC=S the inhibitor structure is promising
to increase protection efficiency in the HCl solution. It is obvious from Table 1 that the βc values in
the inhibited and uninhibited medium remain almost unchanged which indicated that the addition
4000 3500 3000 2500 2000 1500 1000 500
of as-prepared additives does not affect the hydrogen evolution mechanism, and the reduction of H+
ions predominantlyFigure 1. FTIR
Figureoccurs spectra
FTIRvia
spectra of
a chargeof the as-prepared
thetransfer
as-prepared (A) Ad-Th[37].
mechanism and (B) Fe-Th compounds.
Furthermore, it could be observed
from the anodic side of Figure 3A,B that the C-steel oxidation shrinkages regularly with the existence
3.2. OCP
3.2. OCP vs. Time
Time andand PDP
PDP Studies
of Ad-Th vs.and Fe-Th, at the Studies
applied anodic potentials.
The
The required time to extend
The required time to extenddose
influence of additive the values
the values
from 20of steady
of steady
to 200OCPOCP
mg L was
−1 on
was obtained from the
the protection
obtained from the capacity
test measuring
test measuring
has beenthe
the
values
examinedof OCP
as vs.
recordedimmersion
in Table time
1. for a
Generally,C-steel
it electrode
was remarkedin the existence
that all
values of OCP vs. immersion time for a C-steel electrode in the existence or lack of 200 ppm of Ad- the or lack
organic of 200 ppm
additives of Ad-Th
provided
andand
high
Th Fe-Th
Fe-Thinhibitors
protection powerineven
inhibitors molar atHCl
in molar a HCl
low solution.
dose. AsAs
The
solution. displayed
displayedinin
as-prepared Figure
Figure2,2,the
inhibitors, theEE
Ad-Th OCP
OCP
values
and obtained
Fe-Th,
values approve
obtained in
in
blank their
again
blank medium,
medium, changed
high changed
protection partially
capacity
partially towards the positive
which reaches
towards the positive
~93.6% direction,
and 97.9%,
direction, extended
extended steady-state
respectively, inmg
at 200in
steady-state theLclosest
the closest
−1. The

time, resulting
performance in the
time, resultingofinthese free E
additives
the free cor of the
could
Ecor of the C-steel. However,
be related
C-steel. However, to thein the presence
surface
in the presence coverage of 200
of 200andppm
ppm the Ad-Th and
stability
Ad-Th and ofFe-Th
the
Fe-Th
inhibitors,
protective the
inhibitors, layer E
the EOCP values
formed
OCP shifted
valuesonshifted
the steel slowly
slowly towards
interface
towards even the negative
theinnegative direction
small quantities.
direction and and stretched
The stretched a
additive speciesstable state
a stable were
state
after ~20
~20 min.
deposited
after min.
on the In the
In the case of
C-steel/HCl
case of the
the Fe-Th compound,
solution
Fe-Th compound,
surface to form the OCP
the OCP value shifted
a protective
value shifted towards
layer towards
by sharing aa more
more negative
the electrons
negative
value,
between this
value, this phenomena
thephenomena is related
π-electronsisorrelated
–NH, to to inhibitor
–C=S, adsorption
–NH2 adsorption
inhibitor groups andor/andor/and
the empty deposition of
d-orbital
deposition the
of the products
of iron atoms.
products ofThe
of the
the
corrosion
higher
corrosion reaction
reaction on
protection on the
theC-steel
capacity [25].
[25].The
is attributed
C-steel magnitude
Theto the additive
magnitude ofofthe OCP
OCPshift
structure
the indicates
and
shift that
the occurrence
indicates thatAd-Th
Ad-Th and
of Fe-Th
various
and Fe-
inhibitors
substituted at the
groups.same time affect the cathodic and anodic
Th inhibitors at the same time affect the cathodic and anodic reactions. reactions.
The information on the electrochemical kinetics of the inhibition performance and the
-0.505
adsorption of corrosion inhibitors 1could Blank
be achieved via PDP experiment measurements [31,32]. In
the current investigation,-0.510 2 200 ppm were
the PDP measurements Ad-Thcarried out in the blank and with the varying
3 200 ppm Fe-Th
EOCP / mV vs. (Ag/AgCl )

inhibitor concentrations and the outcomes are presented as the Tafel profiles in Figure 3. By
-0.515 2
inspections of Figure 3A,B, it is observed that the anodic and the cathodic current densities shifted to
lower values in the presence
-0.520of Ad-Th and Fe-Th inhibitors. This suggests that the addition of the
Ad-Th and Fe-Th inhibitors to the aggressive solution produces a barrier film, which lowers both the
-0.525
cathodic hydrogen evolution and the anodic C-steel dissolution reaction. From
1 the extrapolation of
the linear segments of the Tafel
-0.530 diagrams, the electrochemical parameters—i.e.,
3 corrosion potential
(Ecor), cathodic and anodic Tafel slopes (βc and βa), and corrosion current density (icor)—were
-0.535
computed and are documented in Table 1. The corrosion inhibition capacity ( ηP ) and the part of
surface coverage (θ) were-0.540
calculated using icor as shown below [33]
0 5 10 15 20 25 30 35 40 45 50
B I time/ min
i  i  cor cor
ηP / %   B  100%  θ 100% (1)
Figure
Figure 2.
2. Variation
Variation of
of the
theOCP
OCP of
ofC-steel
C-steelin
 inmolar
imolar
cor
◦
HCl
HClwith
 withimmersion
immersion time
time in
in the
thelack
lackand
andoccurrence
occurrence
of
of 200
200 ppm of Ad-Th and Fe-Th inhibitors at 50 °C.
C.
Coatings 2020, 10, 1068 6 of 20

The information on the electrochemical kinetics of the inhibition performance and the adsorption
of corrosion inhibitors could be achieved via PDP experiment measurements [31,32]. In the current
investigation, the PDP measurements were carried out in the blank and with the varying inhibitor
concentrations and the outcomes are presented as the Tafel profiles in Figure 3. By inspections of
Figure 3A,B, it is observed that the anodic and the cathodic current densities shifted to lower values in
the presence of Ad-Th and Fe-Th inhibitors. This suggests that the addition of the Ad-Th and Fe-Th
inhibitors to the aggressive solution produces a barrier film, which lowers both the cathodic hydrogen
evolution and the anodic C-steel dissolution reaction. From the extrapolation of the linear segments of
the Tafel diagrams, the electrochemical parameters—i.e., corrosion potential (Ecor ), cathodic and anodic
Tafel slopes (βc and βa ), and corrosion current density (icor )—were computed and are documented in
Table 1. The corrosion inhibition capacity (ηP ) and the part of surface coverage (θ) were calculated
using icor as shown below [33]

iBcor − iIcor
" #
ηP /% = × 100% = θ × 100% (1)
iBcor

where iBcor and iIcor are the icor in the blank and with the Ad-Th or Fe-Th inhibitors. It has been
well-known in the literature [34] that if the Ecor value of displacement in the presence of inhibitor is
≥85 mV with respect to Ecor in blank solution, the inhibitor is characterized as anodic or cathodic-type
inhibitor according to the direction of the potential shift either to the more positive or to the more
negative direction, respectively [35]. If the shift is <85 mV then the inhibitor is categorized as a mixed
type of nature. In the present study, the maximum change of Ecor is less than 0.038 and 0.026 V in
the presence of Ad-Th and Fe-Th inhibitors, respectively. This suggests that the inhibitors display a
mixed nature [36]. The C-steel in blank HCl solutions (free inhibitor) presents an icor of 387.4 µA·cm−2 .
The occurrence of additives declines remarkably icor to attain 24.8 and 8.1 µA·cm−2 with 200 ppm of
Ad-Th and Fe-Th, respectively. The maximum protection power for corrosion comes out to be 93.6%
and 97.9% in the presence of 200 ppm Ad-Th and Fe-Th, respectively. These findings approve that the
existence of either π-electrons or –NH, –C=S, –NH2 groups on the inhibitor structure is promising to
increase protection efficiency in the HCl solution. It is obvious from Table 1 that the βc values in the
inhibited and uninhibited medium remain almost unchanged which indicated that the addition of
as-prepared additives does not affect the hydrogen evolution mechanism, and the reduction of H+ ions
predominantly occurs via a charge transfer mechanism [37]. Furthermore, it could be observed from
the anodic side of Figure 3A,B that the C-steel oxidation shrinkages regularly with the existence of
Ad-Th and Fe-Th, at the applied anodic potentials.
The influence of additive dose from 20 to 200 mg L−1 on the protection capacity has been examined
as recorded in Table 1. Generally, it was remarked that all the organic additives provided high protection
power even at a low dose. The as-prepared inhibitors, Ad-Th and Fe-Th, approve again their high
protection capacity which reaches ~93.6% and 97.9%, respectively, at 200 mg L−1 . The performance of
these additives could be related to the surface coverage and the stability of the protective layer formed
on the steel interface even in small quantities. The additive species were deposited on the C-steel/HCl
solution surface to form a protective layer by sharing the electrons between the π-electrons or –NH,
–C=S, –NH2 groups and the empty d-orbital of iron atoms. The higher protection capacity is attributed
to the additive structure and the occurrence of various substituted groups.
Coatings 2020, 10, 1068 7 of 20
Coatings 2020, 10, x FOR PEER REVIEW 7 of 21

-2.0
Blank 1.0 M HCl (free inhibitor)
-2.5 20 mg/L
-3.0

-3.5

-2
log i, A cm
-4.0
-4.5
40 mg/L
-5.0
80 mg/L
-5.5 150 mg/L
200 mg/L
-6.0

-6.5
A
-7.0
-0.75 -0.70 -0.65 -0.60 -0.55 -0.50 -0.45 -0.40 -0.35 -0.30
E, V vs. (Ag/AgCl)

Figure 3.
3. Polarization
Polarizationprofiles
profilesfor
forC-steel
C-steelinin
molar HCl
molar containing
HCl various
containing doses
various of (A)
doses Ad-Th
of (A) andand
Ad-Th (B)
Fe-Th at 50at°C.
(B) Fe-Th ◦
50 C.

Table 1. PDP parameters and the inhibition capacitates derived for C-steel in molar HCl medium as
Table 1. PDP parameters and the inhibition capacitates derived for C-steel in molar HCl medium as
function of inhibitor dose at 50 ◦ C
function of inhibitor dose at 50 °C
Inhibitor Cinh / Cinh/ icor i±corSD/
±−2SD/ −Ecor
−E±corSD/
± SD/ βa /βa/ c / c/
−β−β
θ η /%
P
Inhibitor
Code Code
mg L−1 µA·cm V (Ag/AgCl) mV dec−1 mV dec −1 θ ηP/%
mg L
−1 −2 µA·cm V (Ag/AgCl) mV dec −1 mV dec −1
387.4 ± 26
Blank
Blank 0.0
0.0 387.4 ± 26−0.523 ± 0.035
−0.523 ± 0.035 91
91 145
145 –
– ––
20 20 267.7 ± 17 −0.537 ± 0.051
267.7 ± 17 −0.537 ± 0.051 94 94 145
145 0.309
0.309 30.9
30.9
40 211.5 ± 14 −0.552 ± 0.043 96 154 0.454 45.4
40 211.5 ± 14 −0.552 ± 0.043 96 154 0.454 45.4
Ad-Th 80 156.9 ± 9 −0.561 ± 0.053 92 157 0.595 59.5
Ad-Th 150 80 156.9
96.4 ± 7 ± 9 −0.529
−0.561 ± 0.053
± 0.047 95 92 157
139 0.595
0.751 59.5
75.1
200 150 24.896.4
± 3 ± 7 −0.514
−0.529 ± 0.047
± 0.049 93 95 139
144 0.751
0.936 75.1
93.6
20 200 237.124.8
± 21± 3 −0.530
−0.514 ± 0.049
± 0.056 96 93 144
157 0.936
0.388 93.6
38.8
40 20 237.1
180.1 ± 17± 21−0.542
−0.530 ± 0.056
± 0.040 98 96 157
153 0.388
0.535 38.8
53.5
Fe-Th 80 40 117.8 ± 10 −0.524 ± 0.039
180.1 ± 17 −0.542 ± 0.040 94 98 147
153 0.696
0.535 69.6
53.5
150 53.1 ± 5 −0.549 ± 0.051 98 148 0.863 86.3
Fe-Th 80 117.8 ± 10 −0.524 ± 0.039 94 147 0.696 69.6
200 8.1 ± 2 −0.544 ± 0.046 100 144 0.979 97.9
150 53.1 ± 5 −0.549 ± 0.051 98 148 0.863 86.3
200 8.1 ± 2 −0.544 ± 0.046 100 144 0.979 97.9
3.3. EIS Studies
TheStudies
3.3. EIS EIS experiments provided an appropriate and non-destructive means to examine the interfaces
of solid metallic substrates exposed to an electrolytic solution [38]. The corrosion inhibition performance
The EIS experiments provided an appropriate and non-destructive means to examine the
of the Ad-Th and Fe-Th molecules was investigated using the impedance investigations and the
interfaces of solid metallic substrates exposed to an electrolytic solution [38]. The corrosion inhibition
achieved findings are graphically presented in the form of the Nyquist, Bode module, and bode
performance of the Ad-Th and Fe-Th molecules was investigated using the impedance investigations
phase profiles in Figure 4A–C. Both in the uninhibited (free inhibitor) as well as in inhibited systems,
and the achieved findings are graphically presented in the form of the Nyquist, Bode module, and
bode phase profiles in Figure 4A–C. Both in the uninhibited (free inhibitor) as well as in inhibited
systems, only one depressed semicircle was detected having their center below the real x-axis (Figure
4(I-A,I-B)). This kind of performance is characteristic of the metallic surfaces suffering the corrosive
attack of the acidic medium [39]. The semicircle diameters in the Nyquist diagrams are showed to
rise with increasing the inhibitor concentration, which designates the formation of a protective layer
between the10,aggressive
Coatings 2020, 1068 solution and the pristine metal [40]. Furthermore, the shape of these profiles 8 of 20
for the inhibited systems is the same as the blank ones, indicating that the occurrence of Ad-Th or Fe-
Th additives improve the impedance but does not modify the other electrochemical features [39,40].
onlyacquired
The one depressed
Nyquist semicircle
diagrams wasare
detected having
not perfect their center
semicircles butbelow the real x-axis
are depressed (Figure
loops 4(I-A,I-B)).
(Figure 4(I-A,I-
This kind of performance is characteristic of the metallic surfaces suffering
B)). These deviation types are frequently encountered due to the inhomogeneity and/or surface the corrosive attack of
the acidic medium
roughness [39]. substrates
of the C-steel The semicircle
[41]. diameters in the Nyquist diagrams are showed to rise with
increasing the inhibitor concentration,
The Bode and the phase angle modules whichfordesignates
the blankthe formation
and of a protective
the inhibited systems are layer between
depicted in
the aggressive solution and the pristine metal [40]. Furthermore, the shape of
Figure 4(II-A,II-B,III-A,III-B). The diagrams obtained for all specimens (uninhibited and inhibited) these profiles for the
inhibitedthe
confirm systems
presence is the same
of one as the blankroute.
time-constant ones,Theindicating
aberrationthatfrom
the the
occurrence of Ad-Th behavior
perfect capacitive or Fe-Th
additives improve the impedance but does not modify the other electrochemical
(phase angle −90° and slope −1) could be related to the inhomogeneity of interface resulting owing features [39,40].
to
Thecorrosion
the acquired development
Nyquist diagrams of theare not perfect
surface semicircles
of C-steel but are depressed
[42]. Nevertheless, loops (Figure
in the presence 4(I-A,I-B)).
of as-prepared
These deviation
Ad-Th and Fe-Thtypes are frequently
molecules, encountered
the approach due to
of the phase the inhomogeneity
angle and/or the
and the slope towards surface
idealroughness
behavior
of the C-steel substrates [41].
could be ascribed to the corrosion protection performance of Ad-Th and Fe-Th inhibitors [43].

250 500
20
20
Blank 1.0 M HCl Blank 1.0 M HCl Blank 1.0 M HCl Blank 1.0 M HCl
16 20 mg/L 16 20 mg/L
200 12 40 mg/L 400 12 40 mg/L
8 80 mg/L 8 80 mg/L
150 mg/L 150 mg/L

2
4 4

-Z Imag/  cm
2

300
-Z Imag/  cm

150 200 mg/L 0

200 mg/L
0
0 4 8 12 16 20 0 4 8 12 16 20

25 Hz I-A 200
25 Hz
I-B
100 100 kHz 100 kHz
//
//

1.99 Hz 1.99 Hz
10 Hz
50 100
0.1 Hz 0.1 Hz
10 Hz
0 0
0 50 100 150 200 250 0 100 200 300 400 500
/ 2 / 2
Z Real/  cm Z Real/  cm
2.5 3.0
Blank 1.0 M HCl Blank 1.0 M HCl
20 mg/L 2.5 20 mg/L
2.0
40 mg/L 40 mg/L
80 mg/L 2.0 80 mg/L
1.5
2

2
log |Z|/  cm

log |Z|/  cm

1.5
1.0
1.0
0.5 150 mg/L 150 mg/L
200 mg/L 0.5 200 mg/L
0.0
0.0
-0.5 -0.5
II-A II-B
-1.0 -1.0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
log frequency/ Hz log frequency/ Hz
0
Blank 1.0 M HCl
-10 20 mg/L
40 mg/L
80 mg/L
-20
Phase angle/ degree

-30

-40

-50

-60

-70 150 mg/L

III-A 200 mg/L
-80
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
log frequency/ Hz

Figure 4.
4. Nyquist
Nyquist profiles
profiles (I)
(I) for
for C-steel
C-steel in
in molar
molar HCl
HCl in
in the
the lack
lackand
and in
inthe
theoccurrence
occurrence of
of the
thedifferent
different
doses (A) Ad-Th and (B) Fe-Th at 50 °C. ◦ C. (II) Bode module and (III) bode phase diagrams.

The Bode
The and the were
EIS findings phasefitted
angleto
modules for the blank
the equivalent and
circuit the inhibited
diagram systems
to obtain are depicted in
the electrochemical
Figure 4(II-A,II-B,III-A,III-B).
parameters, which are recorded The
in diagrams obtained
Table 2 with for all specimens
the protection (uninhibited
capacity. The and inhibited)
fitted Nyquist diagrams
confirm
in theand
the lack presence of one
with the time-constant
Ad-Th route. Theare
and Fe-Th inhibitors aberration
presentedfrom the perfect
in Figure 5A,B.capacitive
A worthybehavior
fit with
◦
(phase angle −90 and slope −1) could be related to the inhomogeneity of interface resulting owing to
the corrosion development of the surface of C-steel [42]. Nevertheless, in the presence of as-prepared
Ad-Th and Fe-Th molecules, the approach of the phase angle and the slope towards the ideal behavior
could be ascribed to the corrosion protection performance of Ad-Th and Fe-Th inhibitors [43].
Coatings 2020, 10, 1068 9 of 20

The EIS findings were fitted to the equivalent circuit diagram to obtain the electrochemical
parameters, which are recorded in Table 2 with the protection capacity. The fitted Nyquist diagrams in
the lack and with the Ad-Th and Fe-Th inhibitors are presented in Figure 5A,B. A worthy fit with the
equivalent circuit diagram was achieved for all experimental findings. The equivalent circuit model
using Echem Analyst software supported by Gamry electrochemical is displayed in Figure 5 (inset),
in which the resistance of electrolyte (Rs ) is shorted by a constant phase element (CPE) that is in parallel
to the polarization resistance (Rp ). The reason for using Rp rather than the resistance of charge transfer
(Rct ) is formerly discussed in detail [44]. In the case of the inhibited system, the Rp is the collective
contribution of the resistance from the Rct + Rf (the film resistance formed on the C-steel surface) [45].
The CPE is frequently utilized to substitute the capacitance of double-layer (Cdl ) to provide a more
precise fit of the experimental EIS findings. The impedance of CPE (ZCPE ) is given by [45]

ZCPE = Y0−1 ( jω)−n (2)

where Y0 symbolizes a proportionality coefficient, j is the imaginary digit, ω represents the angular
frequency, n characterizes CPE exponent with values between 0 and 1, and delivers a measure for
the surface inhomogeneity. The increase in the n value (0.861–0.898) in the case of inhibited system,
in comparison with the n value obtained in the blank aggressive medium (0.724), could be attributed
to a lessening of surface heterogeneities produced by Ad-Th and Fe-Th molecules adsorption at
C-steel/medium interface. The protection capacity (ηE ) was calculated as [46]
 i
 Rp − R0p 

ηE /% =   × 100% = θ × 100% (3)
Rip 


where R0p and Rip denote the polarizations resistances without and containing inhibitor, respectively.
It is observed from Table 2 that the Rp values can be ranked in the following sequence:
Fe-Th > Ad-Th, while the Cdl values follow the opposite order, leading to the protection capacity order
as follows: Fe-Th > Ad-Th. The highest protection capacity values are 91.8% and 95.9% for Ad-Th and
Fe-Th, respectively. Moreover, a significant decrease in the Cdl values against inhibitor concentration is
demonstrated. The values of Cdl decrease from 336.1 µF cm−2 for the C-steel in uninhibited medium to
54.0 and 39.6 µF cm−2 in the case of 200 ppm Ad-Th and Fe-Th, respectively. The organic additive
species adsorb at the C-steel/HCl interface by substituting the pre-adsorbed H2 O with inhibitor
molecules leading to the development of a defensive film on the metal interface. This causes a lowering
of the local dielectric constant and also a thickening of the double layer. These two aspects cause an
enhancement in the capacitive performance and the part of surface coverage (θ) by effective adsorption
of inhibitor molecules, which led to improving the protection capacity.

Table 2. EIS parameters and protection capacity of C-steel in 1.0 M HCl in the lack and existence of
various concentrations of thiocarbohydrazones derivatives at 50 ◦ C

ZCPE
Inhibitor Code Cinh /mg L−1 Rs /Ω cm2 Rp /Ω cm2 Cdl /µF cm−2 θ ηE /%
Y0 /µΩ−1 sn cm−2 n
Blank 0.0 0.12 152.5 0.724 18.7 ± 2 336.1 – –
20 0.18 87.1 0.873 33.5 ± 3 206.9 0.441 44.1
40 0.21 75.4 0.871 53.4 ± 5 148.8 0.649 64.9
Ad-Th 80 0.23 53.2 0.861 92.8 ± 8 113.3 0.798 79.8
150 0.26 40.3 0.882 169.7 ± 12 97.1 0.889 88.9
200 0.34 30.7 0.875 230.3 ± 18 54.0 0.918 91.8
20 0.36 75.6 0.867 43.8 ± 4 163.2 0.573 57.3
40 0.45 65.6 0.886 75.1 ± 6 134.8 0.751 75.1
Fe-Th 80 0.54 46.2 0.878 221.2 ± 15 104.1 0.915 91.5
150 0.61 34.9 0.898 297.9 ± 23 85.6 0.937 93.7
200 0.74 26.7 0.894 464.1 ± 34 39.6 0.959 95.9
Coatings 2020, 10, 1068 10 of 20

Coatings 2020, 10, x FOR PEER REVIEW 10 of 21

20

15

2
/  cm
10 A1

Imag
//
-Z
5
Uninhibited system
Fit data
A
0
0 5 10 15 20
/ 2
Z Real/  cm
500

400
2
-Z Imag/  cm

300
B1
200
//

100
Inhibited system
Fit data B
0
0 100 200 300 400 500
/ 2
Z Real/  cm

Figure
Figure 5. Experimental
Experimentaland andfitted
fitted Nyquist
Nyquist results
results of C-steel
of C-steel in thein the uninhibited
uninhibited system system
(A) and (A) and
inhibited
inhibited system
system (B). Inset(B). Inset equivalent
equivalent circuits
circuits model formodel for the phenomena
the phenomena (A1,B1). (A1,B1).

3.4.Adsorption
3.4. AdsorptionConsiderations
Considerations
Theinhibitor
The inhibitormolecule
moleculeadsorption
adsorptionon onthe
themetallic
metallicsurface
surfacecould
couldbe beclarified
clarifiedwith
withthe
thehelp
helpof
ofan
an
appropriateadsorption
appropriate adsorption isotherm
isotherm [47].
[47]. The
Theadsorption
adsorptionofofthe
thecorrosion
corrosioninhibitor
inhibitormolecules
moleculesAd-Th
Ad-Thand
and
Fe-Th was studied by fitting the experimentally obtained data to several isotherms
Fe-Th was studied by fitting the experimentally obtained data to several isotherms including including Frumkin,
Temkin, Langmuir,
Frumkin, and Freundlich
Temkin, Langmuir, and [48,49]. Amongst
Freundlich the examined
[48,49]. Amongst isotherms,
the examined the Langmuir model
isotherms, the
exhibited the most suitable fit. The isotherm model can be given as [50]
Langmuir model exhibited the most suitable fit. The isotherm model can be given as [50]
Cinh
Cinh = C + 1 1
inh (4)
θ  Cinh Kads (4)
θ K ads
Herein, the symbols Cinh and Kads signify the inhibitor dose and equilibrium constant for
Herein, the symbols Cinh and Kads signify the inhibitor dose and equilibrium constant for the
the adsorption, respectively. The curve of Cinh /θ versus Cinh generated straight lines as given in
adsorption, respectively. The curve of Cinh/θ versus Cinh2generated straight lines as given in Figure 6.
Figure 6. The slope and the regression coefficient (R ) are close to unity, which authenticates the
The slope and the regression coefficient (R2) are close to unity, which authenticates the successful
successful fitting of the Langmuir model. Based on these explanations it may be conserved that a
fitting of the Langmuir model. Based on these explanations it may be conserved that a monolayer of
monolayer of Ad-Th or Fe-Th inhibitors is designed on the metal surface and thus hinders corrosion.
Ad-Th or Fe-Th inhibitors is designed on the metal surface and thus hinders corrosion. The Kads values
The Kads values were calculated from the intercepts of the obtained straight lines (Figure 6) and are
were calculated from the intercepts of the obtained straight lines (Figure 6) and are as follows: 4.3 ×
as follows: 4.3 × 104 L mol−1 for Ad-Th and 7.8 × 104 L mol−1 for Fe-Th. This consequence could be
104 L mol−1 for Ad-Th and 7.8 × 104 L mol−1 for Fe-Th. This consequence could be understood as the
understood as the Fe-Th adsorption was more efficient due to the increasing adsorption capability at
Fe-Th adsorption was more efficient due to the increasing adsorption capability at the C-
the C-steel/solution interface and hence, the protection capacity was improved. Using the Kads values,
steel/solution interface and hence, the protection capacity was improved. Using the Kads values, the
0 ) was
the standard free energy of adsorption (∆G 0 ads
computed using the equation [51]
standard free energy of adsorption (  G ads ) was computed using the equation [51]
 −∆G0 0ads 
 
1
Kads = 1 expGads   (5)
K ads  55.5exp  RT  (5)
55.5  RT 
where the term 55.5 denotes the H2 O concentration in mol/L and the other symbols have their normal
where the term
meanings. The 55.5 denotes
negative thevalues
∆G0ads H2O concentration in mol/L
indicate a strong and the
inhibitors other symbols
adsorption on thehave theirinterface
metallic normal
meanings. The negative G ads 0 values indicate a strong inhibitors adsorption on the metallic interface

as well as the spontaneity of the adsorption route. Generally, if Gads 0 values are around −20 kJ mol−1
Coatings 2020, 10, 1068 11 of 20

Coatings 2020, 10, x FOR PEER REVIEW 11 of 21

as well as the spontaneity of the adsorption route. Generally, if ∆G0ads values are around −20 kJ mol−1
or lesser is associated with an electrostatic interaction between the charged metal surface and charged
inhibitor
inhibitor molecules,
molecules, i.e.,
i.e., physical
physicaladsorption;
adsorption;those
thoseofof−40.0
−40.0 kJ mol−1
kJ mol or higher
−1 or higher involve
involve charge sharing
or transfer
transfer from
fromthe
theinhibitor
inhibitormolecules
moleculestoto the
the electrode
electrode interface
interface to form
to form a coordinate
a coordinate typetype
bond,bond,
i.e.,
i.e., chemical adsorption [44]. The calculated ∆G
chemical adsorption [44]. The calculated Gads values
0 0 values were −39.41 and −41.03 kJ −1
ads
mol −1 for Ad-Th
were −39.41 and −41.03 kJ mol for Ad-Th and
and Fe-Th, respectively. This suggests that Ad-Th
Fe-Th, respectively. This suggests that Ad-Th and Fe-Th and Fe-Thinhibitors
inhibitorsundergo
undergoboth
boththe
the chemical
chemical and
and
the physical adsorption on the metal surface with a predominance of
the physical adsorption on the metal surface with a predominance of chemisorption.chemisorption.

1.0
2
R =0.989
Cinh./ (mmol L )
-1 0.8

0.6
0.4

0.2
A Ad-Th
0.0
0.0 0.2 0.4 0.6 0.8 1.0
-1
Cinh./ mmol L
0.8 2
R =0.995
Cinh./ (mmol L )

0.6
-1

0.4

0.2
B Fe-Th
0.0
0.0 0.2 0.4 0.6 0.8

Figure 6.
Figure 6. Langmuir
Langmuir adsorption
adsorption diagram for (A)
diagram for (A) Ad-Th and (B)
Ad-Th and (B) Fe-Th
Fe-Th on
on C-steel
C-steel in
in molar
molar HCl
HCl medium
medium
at 50
at 50 ◦°C.
C.

3.5. Surface Analysis

3.5. Surface Analysis (FESEM
(FESEM and
and FTIR)
FTIR)
To
To approve
approvethethecorrosion
corrosionprotection findings
protection of the as-prepared
findings inhibitors, inhibitors,
of the as-prepared the surface morphology
the surface
with and without Ad-Th and Fe-Th inhibitors were detected after 48
morphology with and without Ad-Th and Fe-Th inhibitors were detected after 48 h of immersion h of immersion in the corrosive in
HCl medium by FE-SEM investigations. Figure 7A,B display the comparison
the corrosive HCl medium by FE-SEM investigations. Figures 7A,B display the comparison between between the surface
morphologies of the C-steelofspecimen
the surface morphologies the C-steel before and after
specimen 48 h of
before and exposure
after 48toh1.0ofMexposure
hydrochloric to 1.0acid.
M
It could be displayed the scraping owing to the mechanical preparation
hydrochloric acid. It could be displayed the scraping owing to the mechanical preparation of of electrode by emery-papers
before
electrode experiments (Figure 7A).
by emery-papers beforeIn experiments
the uninhibited system,
(Figure 7A).theIn C-steel surface issystem,
the uninhibited severelythe scratched
C-steel
after
surfaceimmersion with
is severely the presence
scratched after of distortions
immersion at the
with the metal
presencesurface (Figure 7B).
of distortions atIn
thethe existence
metal surfaceof
an inhibited medium, the C-steel surface is devoid of pit formation or any
(Figure 7B). In the existence of an inhibited medium, the C-steel surface is devoid of pit formation orroughness and very clean
(Figure 7C,D). This
any roughness andconfirms
very clean the development
(Figure 7C,D). of This
adsorption
confirmsfilmtheof Ad-Th and Fe-Th
development of molecules
adsorptioncovering
film of
the C-steel surface, which performances as a barrier towards the overall
Ad-Th and Fe-Th molecules covering the C-steel surface, which performances as a barrier towards corrosion process. In the case of
the Ad-Th molecule, the C-steel surface was not completely shielded
the overall corrosion process. In the case of the Ad-Th molecule, the C-steel surface was not and the protective layer presents
some deformities
completely which
shielded andexplain the low protection
the protective capacitysome
layer presents of thisdeformities
compound. which Certainly, the protection
explain the low
capacity of the Ad-Th compound is between 30.9% and 93.6%, and
protection capacity of this compound. Certainly, the protection capacity of the Ad-Th compoundlower than that obtained for theis
Fe-Th compound (between 38.8% and 97.9%).
between 30.9% and 93.6%, and lower than that obtained for the Fe-Th compound (between 38.8% and
The bonding data of crude Ad-Th, as well as the adsorption surface film on the C-steel substrate
97.9%).
after The
exposure to 1.0
bonding M HCl
data containing
of crude Ad-Th,200 as ppm
well ofas Ad-Th for 48 h, surface
the adsorption was inspected
film onby FTIR
the investigation,
C-steel substrate
as exemplified
after exposure intoFigure
1.0 M8.HCl The spectrum
containingof200 crudeppm Ad-Th is presented
of Ad-Th for 48inh,Figure
was 8inspected
line A. The bybands
FTIR
at 3265 and 3177 cm −1 (peaks 1 and 2) are related to the –NH and–NH, respectively. The peak at
investigation, as exemplified in Figure 8. The spectrum of crude Ad-Th is presented in Figure 8 line
2
2909 −1 (peak 3) is attributed to the
cmbands C–H aliphatic cm−1respectively.
A. The at 3265 and 3177 cm−1 (peaks 1 and 2)asymmetric.
are related to Thetheband
–NHat2 1108
and–NH, (peak 4) can
be
Theassigned
peak at to thecm
2909 C=S. By comparing
−1 (peak the bands
3) is attributed to theinC–HFigure 8B, it is
aliphatic observed that
asymmetric. Thethebandcommon
at 1108ofcm the
−1

peaks of crude Ad-Th are detected in the spectra of the surface layer on
(peak 4) can be assigned to the C=S. By comparing the bands in Figure 8B, it is observed that the C-steel samples immersed in
1.0 M HClofcontaining
common the peaks200 of ppm
crudeofAd-Th
Ad-Th,are which approves
detected thespectra
in the existence of of
theAd-Th in the
surface layersurface films.
on C-steel
samples immersed in 1.0 M HCl containing 200 ppm of Ad-Th, which approves the existence of Ad-
Th in the surface films. Nonetheless, it is noteworthy that there are some characteristic changes in
spectra between the crude Ad-Th and surface film. In the specimen spectrum immersed 1.0 M HCl
Coatings 2020, 10, 1068 12 of 20

Nonetheless, it is noteworthy that there are some characteristic changes in spectra between the crude
Coatings 2020, 10, x FOR PEER REVIEW 12 of 21
Ad-Th and surface film. In the specimen spectrum immersed 1.0 M HCl containing 200 ppm of Ad-Th
Coatings 2020, 10, x FOR PEER REVIEW
(Figure 8B), the characteristic bands of –NH , –NH, and C=S shifted to 3241, 3150, and 1108 12 cmof−1
21
,
containing 200 ppm of Ad-Th (Figure 8B), the2 characteristic bands of –NH2, –NH, and C=S shifted to
which is different from Figure 8A, which illustrations a probable interaction of the functional groups
3241, 3150,200
containing and ppm1108 cm−1, which
of Ad-Th (Figureis8B),
different from Figure
the characteristic 8A,ofwhich
bands –NH2, illustrations
–NH, and C=S a shifted
probable to
(–NH2 , –NH, and C=S) of Ad-Th inhibitor with the steel surface.
interaction
3241, 3150,ofand the functional
1108 cm−1,groups
which (–NH 2, –NH, and
is different fromC=S) of Ad-Th
Figure inhibitor
8A, which with the steel
illustrations surface.
a probable
interaction of the functional groups (–NH2, –NH, and C=S) of Ad-Th inhibitor with the steel surface.

Figure 7.
Figure 7. SEM
SEMpicture
pictureofofC-steel
C-steelspecimens
specimensbefore and
before after
and 48 48
after h immersion
h immersion in 1.0 M HCl
in 1.0 at 50at°C.
M HCl 50 (A)
◦ C.
before
Figure
(A) immersion,
7. SEM
before (B) of
picture
immersion, after exposure
(B)C-steel
after to blank
specimens
exposure medium
tobefore
blank and (free(free
after
medium 48inhibitor), (C) after
h immersion
inhibitor), in 1.0
(C) immersion
M HCl
after with
at 50
immersion 200
°C.with
(A)
ppm of
before Ad-Th and
immersion, (D)
(B) After
after immersion
exposure to with
blank 200 ppm
medium of Fe-Th.
(free
200 ppm of Ad-Th and (D) After immersion with 200 ppm of Fe-Th. inhibitor), (C) after immersion with 200
ppm of Ad-Th and (D) After immersion with 200 ppm of Fe-Th.

B
% %

B
Transmittance/
Transmittance/

A
A

1 2 3 4
1
4 0 0 0 3 5 0 0 320 0 03 2 5 0 0 2 0 0 0 1 5 0 0 41 0 0 0 5 0 0
-1
4 0 0 0 3 5 0 0 3 0 0W0 a2v5en
0 0u m2 0b0er/
0 1cm500 1000 500
-1
Figure 8. FTIR analysis in a range of 400–4000W a vcmen−1uofm(A)
b er/ cm Ad-Th and (B) surface film of C-steel
crude
sample
Figure after
Figure 8.
8. FTIR
FTIRimmersion
analysis inaa1.0
in
analysis in M HCl
range
range of containing
of 400–4000
400–4000 cm200
cm −1 ofppm
−1 of (A) of Ad-Th
(A) crude
crude for and
Ad-Th
Ad-Th 48 h(B)
and at 50
(B) °C. film
surface
surface of C-steel
film of C-steel
sample after immersion in in 1.0 M HCl
HCl containing
containing 200
200 ppm
ppm of of Ad-Th
Ad-Th for
for 48
48 hh at
at 50 ◦
50 °C.
C.
3.6. Corrosion Mitigation Mechanism
3.6. Corrosion Mitigation
3.6. Corrosion Mitigation Mechanism
Mechanism
The effectiveness of inhibitor additives to diminish corrosion mainly depends on their
The
The effectiveness
adsorption of of
inhibitor
capacity. Inhibitor
effectiveness additives
adsorption
inhibitor to
at diminish
additives corrosion
thetometal/solution
diminish mainly depends
interface
corrosion on their by
was affected
mainly depends adsorption
onvarious
their
capacity.
factors
adsorption Inhibitor
such capacity. adsorption
as molecular at
structure,
Inhibitor the
themetal/solution
existence
adsorption interface
at theofmetal/solution
donor atoms,was
theaffected bymedium
corrosive
interface was various factors
affectedtype, such
nature,
by various
as
andmolecular
thesuch
factors asstructure,
charge existing on
molecular the existence
the metalthe
structure, ofexistence
donor
surface. atoms,
Fe-Th ofand theatoms,
Ad-Th
donor corrosive medium type,
(thiocarbohydrazones
the corrosive nature,
medium type,and
derivatives) the
are
nature,
charge existing
nitrogen-containingon
and the charge existing the metal
organic surface.
on the molecules Fe-Th and
(seeFe-Th
metal surface. Scheme Ad-Th
and 1).
Ad-Th (thiocarbohydrazones
In HCl derivatives)
solution, the Fe-Th
(thiocarbohydrazones and Ad-Th
derivatives) are
are
inhibitors can occur in
nitrogen-containing protonated
organic and neutral
molecules forms as1).
(see Scheme [25]In HCl solution, the Fe-Th and Ad-Th
inhibitors can occur in protonated
Fe-Th or and neutral
Ad-Th + nHforms as [25]n or Ad-ThHn]n+
+ ↔ [Fe-ThH (6)
Fe-Th or Ad-Th + nH ↔ [Fe-ThHn or Ad-ThHn]
+ n+ (6)
Furthermore, in HCl solution the potential of zero charge (EPZC = 0) for Fe is −0.59 V [52]. In the
current study, Ecor for
Furthermore, C-steel
in HCl in 1.0 HCl
solution solution was
the potential −0.523
of zero V. Accordingly,
charge (EPZC = 0) forthe
FeC-steel
is −0.59surface
V [52].carries
In the
current study, Ecor for C-steel in 1.0 HCl solution was −0.523 V. Accordingly, the C-steel surface carries
Coatings 2020, 10, 1068 13 of 20

nitrogen-containing organic molecules (see Scheme 1). In HCl solution, the Fe-Th and Ad-Th inhibitors
can occur in protonated and neutral forms as [25]

Fe-Th or Ad-Th + nH+ ↔ [Fe-ThHn or Ad-ThHn ]n+ (6)

Furthermore, in HCl solution the potential of zero charge (EPZC = 0) for Fe is −0.59 V [52]. In the
current study, Ecor for C-steel in 1.0 HCl solution was −0.523 V. Accordingly, the C-steel surface carries
a positive charge because of the Ecor − EPZC = +0.067 > 0 [52]. Consequently, Fe-Th or Ad-Th may be
adsorbed on the C-steel surface by the following pathways [52]:
(a) The protonated Fe-Th or Ad-Th molecules might be adsorbed via its electrostatic interactions
with the positive charge of the C-steel surface by using Cl− ions attached to the electrode surface as a
negative embankment. Then, the donor–acceptor interaction is accomplished between the nitrogen
atom of thiocarbohydrazones derivatives and the empty d-orbital of the Fe atoms (or may be connected
with the newly produced Fe2+ ions at the metal surface) forming Fe-inhibitor complexes as follows:

Fe → Fe2+ + 2e− (7)

[Fe-ThHn or Ad-ThHn ]n+ + Fe2+ → [Fe-ThHn -Fe or Ad-ThHn -Fe](2 + n)+ (8)

(b) The neutral Fe-Th or Ad-Th molecules may be adsorbed at metal/solution interface through the
chemisorption route, involving the replacing of H2 O molecules from the electrode surface, where the
Fe-Th or Ad-Th additives could be adsorbed at the C-steel interface according to donor–acceptor
interactions between π-electrons and/or nitrogen and unoccupied d-orbitals of iron [53] as

Fe(H2 O)ads + Fe-Th(aq) or Ad-Th(aq) → Fe-(Fe-Th)ads or Fe-(Ad-Th)ads + H2 O (9)

Meanwhile, the existence of iron bonded two cyclopentadienyl rings in Fe-Th compared to Ad-Th
made the compound more adsorbed to the C-steel surface and so achievement more protection capacity.
Moreover, the Fe-Th compound has an electron donor-acceptor conjugated structure and is an effective
redox couple of the Fe2+ /Fe3+ forms [54]. The surface measurements by FE-SEM showed a quantitative
improvement in the surface smoothness in the occurrence of the corrosion inhibitor, which supported
the adsorption and the inhibition performance. FT-IR studies also supported the presence of the
adsorbed inhibitor on the C-steel surface. The above discussion is also consistent with calculated ∆G0ads
values, i.e., mixed adsorption type.

3.7. DFT Calculations

DFT calculations are an appreciated routine to examine the relationship between the structures
of prepared additives and their protection feature. The lowest unoccupied molecular orbital energy
(ELUMO ) and the highest occupied molecular orbital energy (EHOMO ) of the neutral and protonated
Ad-Th and Fe-Th molecules using the DMol3 module are presented in Figure 9. The intended quantum
chemical parameters of the studied additives are recorded in Table 3. These parameters were found to
be very significant to elucidate the chemical reactivity of Ad-Th and Fe-Th additives and its protonated
(Ad-ThH and Fe-ThH) form with the metal interface [55]. The energy gap (∆E) characterizes the
reactive inclination of an inhibitor species [55]. Consequently, as the ∆E becomes lower, the protection
capacity would be higher. Fe-Th has a lower ∆E value. Inhibitor with higher ∆E values provides lower
protection capacity because the energy necessary to eliminate an electron from unavailable orbital
will be very high [56]. The trend for ∆E values have the order Ad-Th > Ad-ThH or Fe-Th > Fe-ThH
(Table 3). These findings indicating that the protonated species have a greater tendency to adsorb on
the C-steel surface than the non-protonated molecules. The dipole moment (µ) provides an appropriate
analysis for the molecule’s polarity and also related to the electron distribution in a molecule Inhibitor
with a high µ value interact powerfully with the C-steel interface through dipole–dipole interaction
and so measured a respectable corrosion inhibitor. There is no straight relative between µ of inhibitor
Coatings 2020, 10, 1068 14 of 20

and its protection action [57]. The values of µ are higher for the protonated molecules than for the
non-protonated molecules indicating that dipole–dipole interactions are more predominant in the
interaction between the C-steel interface and the protonated form than in the interaction between the
C-steel surface and the non-protonated form [58].
In this report, the intended µ values are well-coordinated with other quantum parameters—i.e., EHOMO,
ELUMO , ∆E—and the protection capacity increase in the order (Fe-Th > Ad-Th). The number of
electrons transferred (∆N) from compound to C-steel interface is an additional routine to compare
quantum indices with the protection capacity [59]. In addition, the values of ∆N < 3.6 suggest that the
protection capacity increases as the electron-donating capability of the inhibitor molecules increases [60].
From the findings in Table 3, the values of ∆N are in the sequence (Ad-ThH < Fe-ThH < Ad-Th < Fe-Th).
Herein, Ad-Th and Fe-Th compounds are the donors of electrons, and the C-steel surface is the acceptor.
This result supports the emphasis that the adsorption of Ad-Th and Fe-Th additives on the steel
interface could take place by donor–acceptor interactions between π-electrons and/or nonbonding
electron pairs of the nitrogen atom and unoccupied d-orbitals of iron. According to the above-calculated
quantum parameters, it can be established that the protonated Ad-ThH and Fe-ThH forms are more
anti-corrosion effective than non-protonated Ad-Th and Fe-Th forms.
Coatings 2020, 10, x FOR PEER REVIEW 15 of 21

Figure
Figure 9. HOMO
9. HOMO andand LUMO
LUMO of the
of the protonated
protonated andand non-protonated
non-protonated Ad-Th
Ad-Th andand Ad-Fe
Ad-Fe molecules
molecules using
using DMol3 module.
DMol3 module.

3.8. MC Simulations
MC simulation has been a favored route to investigate the adsorption shape, and the protective
power of corrosion additives adsorbed on a C-steel interface [61]. In order to expect the most
promising conformation of the adsorbed inhibitor species on the metal interface and to acquire more
understanding into the processes of adsorption, MC simulations were performed for Fe-Th and Ad-
Th compounds. The top and side visions of the final adsorption of the Ad-Th and Ad-Fe on the Fe
Coatings 2020, 10, 1068 15 of 20

Table 3. DFT parameters of the non-protonated and protonated Ad-Th and Fe-Th molecules.

Non-Protonated Form Protonated Form

Parameters
Ad-Th Fe-Th Ad-ThH Fe-ThH
EHOMO (eV) −3.758 −3.822 −3.693 −3.923
ELUMO (eV) −2.012 −3.020 −2.047 −3.128
∆E= ELUMO − EHOMO (eV) 1.746 0.802 1.646 0.795
Dipole moments (µ) debye 7.246 5.849 13.13 22.57
The number of electrons transferred (∆N) 1.215 1.786 0.976 1.453

3.8. MC Simulations
MC simulation has been a favored route to investigate the adsorption shape, and the protective
power of corrosion additives adsorbed on a C-steel interface [61]. In order to expect the most
promising conformation of the adsorbed inhibitor species on the metal interface and to acquire more
understanding into the processes of adsorption, MC simulations were performed for Fe-Th and
Ad-Th compounds. The top and side visions of the final adsorption of the Ad-Th and Ad-Fe on the
Fe (110) interface in the solution are displayed in Figure 10. The intended binding and interaction
energies for both Fe-Th and Ad-Th are recorded in Table 4. As exemplified in Table 4, the interaction
energies are negative and of substantial extent, indicating the robust attraction strength between
Fe surface and Fe-Th and Ad-Th molecules [62]. Moreover, the higher extent of binding energies
designates the greater steadiness of the adsorption route, and convenient adsorption of the as-prepared
compounds on the Fe-surface [61,62]. Furthermore, the adsorption energy of Fe-Th is higher than Ad-Th.
This indicates that the Fe-Th molecule adsorbs better than the Ad-Th molecule at C-steel/solution
interface. Interestingly, these findings are matched with the above DFT and empirical outcomes.
Coatings 2020, 10, x FOR PEER REVIEW 16 of 21

Figure 10.
Figure 10. Top
Topand
andside
sidevisions
visions
of of
thethe final
final adsorption
adsorption ofAd-Th
of the the Ad-Th and Ad-Fe
and Ad-Fe on the on
ironthe iron
(110) (110)
surface
surface in solution.
in solution.

Table 4. Selected energy indices acquired from MC simulations for the adsorption of Ad-Th and Fe-
Th molecules on Fe (110) surface.

Adsorption Rigid Adsorption Deformation Energy dEads/dNi: dEads/dNi:

System
Energy/kJ mol−1 Energy/kJ mol−1 /kJ mol−1 kJ mol−1 Water kJ mol−1
Fe (110)
Ad-Th −2160.84 −2185.42 −526.99 −751.11 −75.48
H2O
Fe (110)
Coatings 2020, 10, 1068 16 of 20

Table 4. Selected energy indices acquired from MC simulations for the adsorption of Ad-Th and Fe-Th
molecules on Fe (110) surface.

Adsorption Rigid Adsorption Deformation Energy dEads /dN i : kJ dEads /dN i :

System
Energy/kJ mol−1 Energy/kJ mol−1 /kJ mol−1 mol−1 Water kJ mol−1
Fe (110)
Ad-Th −2160.84 −2185.42 −526.99 −751.11 −75.48
H2 O
Fe (110)
Fe-Th −3719.59 −2437.30 −1282.29 −1414.63 −77.87
H2 O

3.9. Comparison of the Protection Capacity of Ad-Th and Fe-Th Inhibitors with Earlier Reports
The comparison of the protection capacity of the prepared thiocarbohydrazones (Ad-Th and Fe-Th)
for the steel corrosion in acidic medium with some selected hydrazone derivatives, previously designated
in the same conditions, is given in Table 5 [21–23,63,64]. The list of earlier reports from the
naproxen-based hydrazones, dinitrophenyl hydrazone derivatives, propanehydrazide derivatives,
benzohydrazide derivatives, and methoxynaphthalen 2-yl propanehydrazide derivatives is registered
in Table 5 along with that of the synthesized Ad-Th and Fe-Th molecules [21–23,63,64]. It could
be obviously noted that the synthesized Ad-Th and Fe-Th molecules show promising performance
compared to the earlier reports with high protection capacity at a meaningfully low inhibitor dose.
This supports the practical applicability of the prepared thiocarbohydrazones (Ad-Th and Fe-Th) in
the acid pickling process.

Table 5. Comparison of the protection capacity of Ad-Th and Fe-Th molecules with the earlier reported
findings based on other hydrazone derivatives as inhibitors for steel corrosion in acidic medium.

Inhibitor Protection
Inhibitors Measurement Method References
Concentration Capacity/%
Naproxen-based hydrazones PDP and EIS 0.1–5.0 mmol/L 80.2–89.2 [21]
Dinitrophenyl hydrazone Weight loss
0.1–5.0 mmol/L 84.7–91.2 [22]
derivatives measurements
Propanehydrazide derivatives PDP 0.1–5.0 mmol/L 63.0–84.1 [23]
Four benzohydrazide derivatives EIS 5.0 mmol/L 84–95 [63]
Methoxynaphthalen 2-yl
PDP 0.1–5.0 mmol/L 74–91 [64]
propanehydrazide derivatives
Ad-Th PDP 20–200 mg/L 30.9–93.6 This work
Fe-Th PDP 20–200 mg/L 38.8–97.9 This work

4. Conclusions
The current work reports a thiocarbohydrazones based on adamantane (Ad-Th) and ferrocene
(Fe-Th) as novel inhibitors for C-steel corrosion in HCl using thorough experimental and surface
morphology analysis supported using computational investigations. The molecules were synthesized
by a facile chemical method. The following major conclusion can be drawn out of the present study:

• PDP and EIS measurements revealed an increase in the corrosion inhibition capacity with a rise in
the inhibitor dose which reached >97.9% at a dosage of 200 ppm of Fe-Th.
• The inhibitors adsorption on the C-steel followed the isotherm of Langmuir model and the value
of ∆G0ads indicated the presence of both physical and chemical adsorption modes.
• EIS study designates the occurrence of a one-time constant phenomenon for the inhibitor adsorption
in which the polarization resistance increasing with an increment in the inhibitor concentration.
Coatings 2020, 10, 1068 17 of 20

• PDP study exhibited that the adsorption of the inhibitors resulted in a mixed-type with
cathodic predominance.
• FESEM measurements showed the appearance of a smoother surface morphology compared to
the blank specimen. The FTIR studies supported the adsorption of compound additives on the
metallic interface.
• DFT calculations indicate that the protection of C-steel from corrosion is achieved more via the
adsorption of protonated Fe-ThH and Ad-ThH forms than that by neutral Fe-Th and Ad-Th forms.
• MC simulation findings displayed that both Fe-Th and Ad-Th molecules adsorb intensely on the
iron (110) interface and the inclination of expected binding energies agreed with the empirical
protection capacitates.

Author Contributions: H.M.A.E.-L. and A.R.S.: conceptualization, supervision, investigation, methodology,

resources, formal analysis, data curation, funding acquisition, writing—original draft, writing—review and
editing. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors extend their appreciation to the Deputyship for Research & Innovation, Ministry of
Education in Saudi Arabia for funding this research work through the project number IFT20050.
Conflicts of Interest: The authors declare no conflict of interest.

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