Surfaces and Interfaces 23 (2021) 101037

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Surfaces and Interfaces

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Synthesis and theoretical studies of novel conjugated polyazomethines and

their application as efficient inhibitors for C1018 steel pickling
corrosion behavior
Hany M. Abd El-Lateef a, b, *, Abdelwahed R. Sayed a, c, K. Shalabi d
a
Department of Chemistry, College of Science, King Faisal university, P.O. Box 400 Al-Ahsa 31982, Saudi Arabia
b
Chemistry Department, Faculty of Science, Sohag University, Sohag 82524, Egypt
c
Chemistry Department, Faculty of Science, Beni-Suef University, Beni-Suef 62514, Egypt
d
Chemistry Department, Faculty of Science, Mansoura University, Mansoura, Egypt

A R T I C L E I N F O A B S T R A C T

Keywords: The idea of the existing work is to progress the preparation of four conjugated polyazomethines contained
Polyazomethines thiazole through the backbone of the polymer. The synthesized conjugated polyazomethines were categorized
Inhibition and assessed as novel inhibitors for the C1018 steel pickling corrosion behavior at 298–328 K using surface
Surface morphology
morphology of C1018 steel electrode, potentiodynamic polarization (PDP), and electrochemical impedance
Theoretical study
Acidic corrosion
spectroscopy (EIS). The assessed polymers performed as effective inhibitors for C1018 steel corrosion in pickling
solution. The protection capacity of the polyazomethines augmented with a rise in concentration to attain 98.2%
efficacy with 150 mg L − 1 at 298 K. PDP plots designated that the conjugated polyazomethines performs as
mixed-type inhibitors and adsorbed on the C1018 steel interface via chemisorption. Isotherm model of Langmuir
was found the preeminent mode for the adsorption of polymers. The surface morphology examinations estab­
lished the development of a protective layer getting a thick coverage at the optimal dose. Moreover, theoretical
study of Monte Carlo (MC) simulations and density functional theory (DFT) were used to govern the association
among protection capacity and molecular structure. This study could be provided novel polyazomethines in­
hibitors for C1018-steel corrosion protection in different industrial environments, especially in the pickling
solution.

1. Introduction With the aim of treat the aggressive attack of these acids, inhibitors
are introduced to the corrosive medium, which diminishes the aggres­
C-steel (carbon steel) has been chosen as unique of the greatest sig­ siveness of acids to the C-steel surface. The chemical materials with both
nificance and extensively utilized structural accessories in numerous inorganic and organic sources have been applied as inhibitors to pre­
industries, including automotive, chemical processing water, petroleum, serve minerals from harsh solutions [7]. Organic molecules containing
and power generation, and a diversity of other applications [1,2]. The hetero-atoms like nitrogen, oxygen and sulfur, and aromatic rings
wide and important use of C- steel is related to its outstanding me­ π-electrons are originated to be actually effective in quashing the
chanical features and low-cost [2,4]. Nevertheless, C-steel is inclined to corrosion of the metal in various mediums [8,9]. Among the
corrosion in refinery categorized mineral acids such as H2SO4 (sulfuric carbon-based materials, polymeric corrosion inhibitors are a very wide
acid), HCl (hydrochloric acid), H2SO3 (sulfurous acid), and thio­ choice owing to their huge efficient groups and their capability to
sulfurous [5]. Among the previous corrosion mediums, hydrochloric complex with metal ions at interfaces [10,11]. By covering great surface
acid is generally used in various industrial implementations like acid extents of alloys and metals in the corrosive solutions, these formed
pickling, industrial cleaning, scale and rust elimination, acidification of pincers effectively “complete” the surface from aggressive ions and
oil wells in petrochemical procedures, and oil retrieval at temperatures molecules attack thus contributing the required inhibition [12]. Addi­
up to 333 K [6]. tionally, small inhibitor molecules incline to destroy at higher

* Corresponding author. .
E-mail addresses: hmahmed@kfu.edu.sa, hany_shubra@science.sohag.edu.eg (H.M. Abd El-Lateef).

https://doi.org/10.1016/j.surfin.2021.101037
Received 27 December 2020; Received in revised form 28 January 2021; Accepted 17 February 2021
Available online 20 February 2021
2468-0230/© 2021 Elsevier B.V. All rights reserved.
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

temperatures, which consequence of the contagion of the hydrocarbon 2.2. Overall procedure for the synthesis of conjugated polyazomethines
stream owing to the unstable yields that occur [13]. (4a-d) (PAM-1-PAM-4)
Conjugated polyazomethines materials have stayed extensively
familiar for electronic devices [14-17]. Sun et al. stated the preparation An equimolar amount of [4,4′ -bithiazole]− 2,2′ -diamine 1 and
of polyazomethines having the thiazole moiety from polycondensation carbonyl compounds 2 in DMSO. The reaction mixture solution was
of diamine with dicarbonyl compounds [18]. Hyperbranched conju­ stirred at 393 K for 12 h, cool the reaction mixture to room temperature,
gated materials having bithiazole moiety were prepared from poly­ the solution was then poured over water, the final substance was filtered
condensation of [4,4′ -bithiazole]− 2,2′ -diamine and benzene-1,3, and then washes away numerous times with water and solid products
5-tricarbaldehyde are reported in [19,20]. The chemical investigations were dried at 65 ◦ C for 48 h (yield 82–88%) (Scheme 1).
of some prepared polyazomethines as corrosion additives were reported Polyazomethine (4a-PAM-1): Black solid; Yield (95%); mp > 573
in [21-24]. K, FT-IR showed signals at 3083 (aromatic rings), 1618 (C = N) and
Recently, theoretical approaches like density functional theory 1600 (C = C) cm− 1. FT-IR confirmed end capped aldehyde changed to
(DFT) have demonstrated to be beneficial computational methods in carboxylic (2400–3400 COOH) cm− 1. The 1H NMR spectrum revealed
inspecting the molecular construction and explaining the electronic signals at (1H NMR (500 MHz, DMSO‑d6): δ 6.69 (s, H-thiazol ring), and
structure and reactivity of corrosion inhibitors [25]. Review on DFT as a 8.14 (s, CH– – N) ppm (Fig. S1; ESI).
potent method in the designing of corrosion additive molecules have Polyazomethine (4b-PAM-2): Pale green; Yield (82%); mp > 573 K.
been reported by Obot, et al. 2015 [26]. Moreover, Monte Carlo (MC) FT-IR (cm− 1) (KBr): νmax 3302, 3174 (NH), 1652 (C = N), 1603 (C = C)
simulation, as an efficient approach, could deliver visions into the cm− 1. The appearance at 3302, 3174 (NH), is attributed to polymer
designing of structures comprising a comparatively great number of chain end (end capped group). 1H NMR spectrum (DMSO d6): 6.62 (s, H-
molecules, permitting investigators to investigate the adsorption routes thiazole ring), 7.10–8.15 (m, ArH’s), 8.61 (CH– – N) ppm (Fig. S2; ESI).
at the molecular level [27]. Polyazomethine (4c- PAM-3): Red Brown; Yield (89%); mp > 573
The current research designates the preparation of polyazomethines K. FT-IR (cm− 1) (KBr): νmax 3372, 3299 NH), 1663(C = N), 1628 (C = C)
(PAM) by condensing dicarbonyl, with a diamine. The prepared conju­ cm− 1. The appearance at 3372, 3299 (NH), is attributed to polymer
gated polymers were completely investigated through FT-IR and NMR. chain end (end capped group). 1H NMR spectrum (DMSO d6): 2.66 (s,
The protection performance of the four prepared conjugated poly­ CH3), 6.62 (s, H-thiazole ring), 7.01–8.19 (m, ArH’s), 8.44 (CH–– N) ppm
azomethines and their monomer diaminebisthiazole on C1018 steel (Fig. S3; ESI).
pickling corrosion behavior are evaluated. The corrosion inhibition Polyazomethine (4d- PAM-4): Black solid; Yield (91%); mp. 530 K.
features of these polymers were analyzed respectively using WL mea­ FT-IR (cm− 1) (KBr): νmax 3325 (NH), 1660 (C = N), 1580 (C = C) cm− 1.
surements, PDP plots, EIS, adsorption considerations, and surface The appearance at 3325 (NH), is attributed to polymer chain end (end
morphology (FESEM/EDX analysis). MC simulations and DFT calcula­ capped group). 1H NMR spectrum (DMSO d6): 2.72 (s, CH3), 6.84 (s, H-
tions have been as well achieved to decide the relationship among the thiazole ring), 7.41–8.17 (m, ArH’s), 8.99 (CH– – N) ppm (Fig. S4; ESI).
corrosion mitigation characteristics of the prepared conjugated poly­
azomethines and their molecular constructions. This work also pointed
to describe the impact of molecular construction on the ability of the 2.3. Corrosion tests (PDP and EIS measurements)
prepared conjugated polyazomethines to be adsorbed on the steel
interface. All the electrochemical tests were achieved at atmospheric pressure
in a one-L glass cell. The glass cell contains a characteristic 3-electrode
2. Experimental procedure profile where C1018 steel was served as a working electrode (WE), sil­
ver/silver chloride was applied as a reference electrode, and a Pt-wire
2.1. Apparatus, materials and solutions utilized as a counter electrode. Corrosion inspections were completed
by means of a Gamry Galvanostat/Potentiostat/ZRA at temperatures
Glyoxal, terephthaldehyde, isophthaldhyde and 1,1′ -(1,4-phenylene) ranging from 298 to 328 K. Before each experiment, the C-steel sample
bis(ethan-1-one), and dimethyl-sulfoxide (DMSO) were gotten from the was immersed in the solution to be tested (for 30 min) in advance until
company of Sigma-Aldrich. The substances were utilized as customary the open-circuit voltage (EOCP) was stable. In the EIS experiments, a
deprived of additional cleansing. The spectra of Fourier transform perturbation wave of sole sine and 10 mV amplitude was used, and the
infrared (FT-IR) were done by an FT-IR spectrometer Bruker Equinox-55 frequency was scanned in the range 10 mHz to 100 kHz at EOCP. Addi­
using 32 scans at 4 cm1 resolves. The compounds were compacted into tionally, PDP assessment was measured by substituting the potential of a
pellets of potassium bromide at 2.0% loading heights. The NMR spectra WE from − 250 to +250 mV based on EOCP at a 0.2 mV/s scan rate of
were got on Varian Mercury and 300-MHz spectrometer by 5-mm o.d. [28].
tubes with sample amounts of 5–15% (w/v) in DMSO‑d6 having an in­
ternal reference (tetramethylsilane). IA-9000 Electro-thermal sequence
digital was used for measuring melting points. 2.4. Surface morphology
The C1018 steel substrate had a one cm2 exposure area with chem­
ical constitution (wt.%): C, 0.21; Cr, 0.72; Ni, 0.016; S, 0.05; Si, 0.16; The surface inspection by FE-SEM of the working electrode was
Mn, 0.07, and the remainder Fe. characterized after exposing these specimens for 48 h in molar HCl so­
The corrosive medium (1.0 M HCl) was prepared by diluting 37% lutions lacking and with 150 mg/L of diaminebisthiazole (monomer)
HCl (Analytical grade) with triple distilled water. To ensure the solu­ and 150 mg/L of PAM-4 polymer at 303 K, correspondingly the
bility of all the prepared polyazomethines were dissolved as 0.01 g of elemental configuration of the adsorbed film registered with 5410-JSM
polymer in 3 mL of solvent. It was found that these compounds are (JEOL Model) equipped with EDX investigation.
partially soluble in dimethlsulfoxide (DMSO), and dimethylformamide FT-IR spectrum of the adsorbed PAM-4 polymer on C-steel surface
(DMF) and completely soluble in molar HCl solution. Moreover, the was detected after soaking of 2-polished metal specimens in an acidic
polyazomethines are insoluble in acetone, ethanol, methanol, Tetrahy­ solution of PAM-4 for 48 h. The adsorbed polymer layer of PAM-4
drofuran, methylene chloride, toluene, chloroform, and petroleum ether molecules was scratched from the metal surface and characterized by
(Table S1; ESI). The tests were performed in a half-liter of 1.0 M HCl in FT-IR spectroscopy. UV–visible spectra of an acidic solution of PAM-4
the lack and occurrence of 10–150 mg/L polymers. polymer prior and after C-steel dipping were carried out with SHI­
MADZU UV/vis spectrophotometer (model UV-1800 – Japan).

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H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

2.5. DFT calculations PAM-4). The polyazomethines incorporated in backbone thiazoles

moiety were planned as showed in Scheme 1. The cheap, respectable
DFT calculations were conducted employing Spartan™14 software yielding, simple reaction conditions, and commercial accessibility of the
from Wave function Inc. USA. The monomer structure of poly­ chemicals make these methods worthwhile. The tools will be used to
azomethines has been fully optimized by applying the B3LYP /6 − 31G∗ elucidate new chemical structures by FT-IR (Fig 1) and 1H NMR spectra
basis set in the gas phase [28]. Various quantum parameters such as that characterized the structures of conjugated polyazomethines. The
ionization potential (I), electronegativity (χ), global hardness (η), elec­ poor solubility of isolated materials cannot measure 13C NMR and mo­
tron affinity (A), and global softness (σ) values were reckoned in lecular weight for the polythiazoles.
accordance with the equations below [29]:
3.2. Tafel polarization studies
I = − EHOMO (1)

A = − ELUMO (2) Tafel polarization profiles for corrosion of C1018-steel in molar HCl
solution lacking and with various doses of PAM-4 and in the presence of
1 150 ppm of different polymeric inhibitors at 298 K are reported in Fig. 2.
χ=− (EHOMO + ELUMO ) (3) At a first view, it is remarkable that Tafel polarization performance is
2
presented by both cathodic and anodic divisions. Furthermore, all pro­
η=−
1
(EHOMO − ELUMO ) (4) files display comparable figures which show that neither anodic (i.e.,
2 C1018-steel corrosion) nor cathodic (i.e. reaction of hydrogen evolution
HER) mechanisms were changed as a result of the addition of the
1
σ= (5) polymers into the aggressive medium. The extracted Tafel indices i.e.,
η
corrosion current density (jcor), corrosion potential (Ecor), anodic (βa),
The fraction of electrons transferred (ΔN) from the polymer mole­ and cathodic (βc) Tafel slopes related to the polarization extents of
cules to the metallic interface during the adsorption could be computed thiazole amine polymers are registered in Table 1. The protection ca­
utilizing the below Eqn: pacity (ηP/%) and the portion of surface coverage (θ) of polymeric ad­
χ Fe − χ inh ditives on the C-steel corrosion were intended as following Eqn. [34]:
ΔN = (6) (0 )
2(ηFe + ηinh ) / j − Ji
ηp % = cor 0 cor × 100 = θ × 100 (7)
jcor
where, ηFe,ηinhχFeandχinh, are the hardness and electronegativity values
of Fe and additive molecules, correspondingly. The value of χFe is 7.00
where j0cor and jicor are respectively, the jcor in the lack and occurrence of
eV and ηFe is 0 [30].
PAM polymers. Examination of Fig. 2 exhibits equivalent cathodic Tafel
shapes, which designate that the HER is charge-transfer control (under
2.6. MC simulations activation) [35]. Moreover, there is no noteworthy modification in the
both βaandβc values of upon addition of different PAM polymers con­
For MC simulation, the adsorption locator module in software V.7.0 centrations indicating that the protection mechanism of the last profits
Materials Studio from Accelrys Inc., USA was applied. The adsorption via hindering the active cathodic and anodic branches on the interface of
locator discovers the proper adsorption configurations of the monomer C1018-steel [36]. The inhibitory influence of PAM polymers is corre­
structures of polyazomethines with Monte-Carlo examinations on the Fe spondingly shown as shows a shift in both cathodic and anodic branches
(1 1 0) interface for assessment of the inhibiting performance of PAM to lesser jcor values as the concentration of studied polymeric additives
molecules [31]. In a simulation, the box has dimensions of 32.27 Å × rises; this reproduces a lessening in the C1018-steel corrosion rate in the
32.27 Å × 50.18 Å with periodic boundary circumstances, the in­ corrosive solution. Not to mention, the addition of the synthesized PAM
teractions of PAM species and the Fe (1 1 0) surface were achieved. The polymers has no palpable influence on the Ecor value where the Ecor
energy optimization of PAM molecules (PAM-1, PAM-2, PAM-3, and changes over the inhibitor concentration range was within ±85 mV
PAM-4) was executed using the Forcite classical simulation engine [32]. around uninhibited medium, and this specifies that the mixed-inhibitors
The layer builder was employed to establish the corrosion system in type classification of the as-prepared PAM polymers [35].
aqueous media, which involves the optimized PAM molecules, Fe (1 1 0) The close inspection of Table 1 affirms that the addendum of poly­
surface, and water. To simulate the adsorption capability of PAM in­ mers has a high influence on the jcor even in low doses. jcor is intensely
hibitors on Fe (1 1 0) surface, the COMPASS simulation study with force
field was performed [33].

3. Results and discussions

3.1. Chemistry

Our benefits in the preparation of polyazomethines having thiazole

moiety not only as its worthy coordination affinity with metal ions, but
also this thoughtful of conjugated polymer for application as corrosion
inhibitors [14]. We synthesized polyazomethines incorporated in
backbone thiazole [18,19] by treatment of [4,4′ -bithiazole]− 2,
2′ -diamine with glyoxal, terephthaldehyde, isophthaldhyde and 1,1′ -(1,
4-phenylene)bis(ethan-1-one) afforded polyazomethines 4a-d (PAM-1,
PAM-2, PAM-3, and PAM-4). The final products can be clarified via
step-growth polymerization by the formation of the final poly­
azomethines compounds can be clarified through nucleophile attack of
the primary amine group with carbonyl, followed by elimination of
water to give the final products 4a-d (PAM-1, PAM-2, PAM-3, and Fig 1. FTIR analysis of the prepared polyazomethine 4a-d (PAM-1-PAM-4).

3
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

metal dissolution rate.

It is observed (Table 1) that the protection capacity increased with
increasing the polymer dose. At 150 mg/L, PAM-1, PAM-2, PAM-3 and
PAM-4 reached a maximum value of (ηP/%) 91.3%, 93.8%, 96.4%, and
98.2%, respectively. For these polymeric materials, the protection ca­
pacity orders are: PAM-4 > PAM-3 > PAM-3 > PAM-1.

3.3. EIS studies

In order to attain more evidence on the mechanism of corrosion re­

action and progress the previous findings acquired from PDP in­
vestigations, Nyquist and Bode graphs of C1018-steel in blank and
inhibited systems at 298 K are displayed in Fig. 3. The Nyquist plots in
the lack and attendance of various concentrations of PAM-4 polymer,
(Fig. 3A) and in the absence and occurrence of optimal dose 150 ppm of
four polymeric materials (Fig. 3B) are represented in Fig. 3A, B. It is
appreciated from Fig. 3A, B that all Nyquist graphs have only a solitary
capacitive loop in the inhibited and uninhibited mediums, with nearly
comparable features. These outcomes indicate that the addendum of
polymeric additives causes no modification in the corrosion reaction
mechanism, and the protection is mostly controlled by the process of
charge transfer [37]. The diameter size of the semi-circular loop as well
rises with the increment in the polymer dose as compared to the unin­
hibited system, which is owing to the creating of a dense anti-corrosive
layer of polymer molecules onto the C-steel interface; thus, effectively
suppressing the metal corrosion [38]. Moreover, these Nyquist profiles
are not idealistic semi-circles. The semicircles variation from the perfect
feature is frequently due to the frequency scattering of interfacial
impedance [39]. This attitude is frequently related to the heterogeneity
of the C-steel interface producing from interfacial phenomena or surface
Fig 2. Tafel polarization profiles for C-steel in 1.0 M HCl solution without and roughness [40]. The significant idea here is that in the existence of
with different concentrations of PAM-4 (A) and in the presence of 150 ppm of PAM-3 and PAM-4 polymers having N = C–CH3 in addition to the
different polymeric inhibitors (B) at 298 K. benzene ring, the semicircular size is great as compared to PAM-1 and
PAM-2 (Fig. 3B) which have fewer electron-donating groups. This im­
declined compared to the uninhibited system. This refers to the plies that more electron-donating groups have more influence on pro­
adsorption ability of the prepared polymers due to the occurrence of tection capacity.
high electron density centers heteroatoms of N, S, and π-electrons. The Bode plots of PAM-4 in the existence of different doses are exem­
adsorption of the polymer molecule over the interface of C1018-steel plified in Fig. 3C and 3D. From the Bode plot analysis, in all cases the
increases the part of surface coverage (θ) and in turn, decreases the phase angle profiles have only a one-time constant i.e., one maximum

Table 1
PDP parameters for C-steel in 1.0 M HCl without and with various concentrations of the as-prepared polymer additives at 298 K.
− 1 2 − 1 − 1
Inhibitor code Ci/ mg L jcor ±SD/ µAcm− -Ecor/ V (SCE) βa/ mV dec -βc/ mV dec θ ηP/%
Blank 0.0 347.5 ± 25.2 0.402 84.2 167.4 – –
Diaminebisthiazole (M) 150 57.6 ± 5.1 0.395 90.7 172.3 0.834 83.4
PAM-1 10 182.7 ± 13.6 0.397 91.5 183.1 0.474 47.4
25 127.5 ± 9.8 0.391 96.7 183.9 0.633 63.3
50 107.3 ± 8.3 0.403 98.8 179.9 0.691 69.1
75 73.6 ± 6.2 0.409 87.3 180.9 0.788 78.8
100 42.7 ± 3.5 0.401 90.5 185.1 0.877 87.7
150 30.2 ± 2.2 0.411 94.6 187.2 0.913 91.3
PAM-2 10 173.1 ± 13.4 0.413 98.8 186.1 0.502 50.2
25 115.3 ± 10.1 0.407 95.7 189.2 0.668 66.8
50 79.5 ± 6.5 0.405 92.5 183.2 0.771 77.1
75 64.6 ± 5.3 0.417 97.7 191.3 0.814 81.4
100 39.9 ± 3.1 0.419 90.5 192.4 0.885 88.5
150 21.5 ± 1.5 0.421 94.6 188.2 0.938 93.8
PAM-3 10 165.7 ± 13.9 0.406 98.8 180.9 0.523 52.3
25 103.5 ± 8.8 0.401 90.5 185.1 0.702 70.2
50 44.4 ± 4.2 0.415 95.7 183.4 0.872 87.2
75 55.2 ± 3.6 0.406 95.9 180.9 0.841 84.1
100 32.6 ± 2.8 0.414 92.5 180.3 0.906 90.6
150 12.5 ± 1.1 0.409 96.7 190.3 0.964 96.4
PAM-4 10 157.1 ± 11.3 0.393 96.9 180.9 0.548 54.8
25 92.1 ± 7.8 0.396 97.8 183.2 0.735 73.5
50 68.8 ± 5.6 0.392 98.8 185.2 0.802 80.2
75 44.8 ± 4.0 0.398 91.5 183.2 0.871 87.1
100 23.2 ± 1.8 0.402 94.6 183.8 0.933 93.3
150 6.2 ± 0.7 0.391 96.7 188.4 0.982 98.2

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H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

Fig 3. EIS plots for C- steel in 1.0 M HCl solution (A) Nyquist in the absence and presence of different concentration of PAM-4, (B) Nyquist in the absence and
presence of 150 ppm of different polymer inhibitors, (C) Bode and (D) phase angle representations in the absence and presence of different concentration of PAM-4 at
298 K.

corresponds to a corrosion reaction by adsorbing on C1018-steel/HCl experiential exponent which measures the inhomogeneity of the C-steel
interface [41]. Additionally, the values of phase angle in the inhibited interface [43]. Eqs. (9) and (10) express the Cdl and the protection ca­
system containing PAM-4 seemed to be higher i.e. − 84.5◦ than the un­ pacity (ηI/%) [45]:
inhibited medium (~ − 51.1◦ ). These findings approving that the
as-prepared polymeric additives adsorbed more onto the C-steel inter­ Y0 (ω)n− 1
Cdl = (9)
face also the enhance of resistance performance of the protecting film sin(nπ /2)
owing to the development of double-layer as well as polymer doses [42]. (( i ))
In the Bode graph (log |Z| vs. log f; Fig. 3C) the impedance value rises Rp − R0p
with the polymer addendum as compared to the uninhibited medium, ηI / % = × 100 (10)
Rip
which indicates that the rate of corrosion is declined with the inhibitor
injection. where R0p is [Rct +Rf ] in the lack of polymer, and Rip is [Rct +Rf ] in the
To fit the empirical findings, the comparison of precise EIS findings
occurrence of polymer. The impedance parameters including Rp, Cdl, the
(points) measured for C1018-steel in the nonexistence and occurrence of
part of surface coverage (θ) [θ= ηI/100], and ηI/% values are demon­
the polymer additive is presented in Fig. 4A and 4B. The proposed
strated in Table 2. It was found that, the Rp was augmented from 39.8 Ω
equivalent circuit model (EQCM) that has been used is revealed in
cm2 to 552.7, 621.8, 686.2, and 780.4 Ω cm2 in the presence of 150 ppm
Fig. 4A and 4B (inset). The fitness accuracy (χ2) of the equivalent circuit
of the PAM-1, PAM-2, PAM-3, and PAM-4, respectively. These findings
is recorded in Table 2. This EQCM that fit the impedance indices in the
indicate that the PAM polymer inhibitors function by adsorption on the
blank and inhibited solutions comprises of Rs as the electrolyte resis­
C1018-steel/HCl surface and also affirm that the synthesized PAM
tance, the constant phase element (CPE), in parallel to Rp [Rp (the po­
polymers show worthy inhibitive action for the corrosion of C1018-steel
larization resistance) = Rf (film resistance) + Rct (charge transfer
in molar HCl. Furthermore, the maximum Cdl values declined from
resistance)], which is in series to the parallel of Cads as capacitance
679.7 µF cm− 2 to 46.7, 33.7, 24.8, and 19.9 µF cm− 2 in the occurrence of
attributed to the inhibitor adsorption layer and the resistance owing to
150 ppm of the PAM-1, PAM-2, PAM-3, and PAM-4 inhibitors, respec­
adsorption of the additive layer (Rads) in the circumstance of inhibited
tively. This decline in Cdl values might be owing to the diminution in
system. The C1018-steel/HCl interface is not performing as a real
dielectric constant and/or upsurge in the double layer thickness than the
capacitor, thus the Cdl as the capacitance of double-layer is frequently
blank, signifying that the PAM polymers work by adsorption at the
substituted by the CPE for the obtainment of an ideal behavior [43]. The
C1018-steel/medium interface. On rise, the defensive layer thickness
CPE impedance could be expressed as follows [44]:
formed with growing inhibitor doses, since more PAM molecules adsorb
ZCPE = [Y0 (jω)n ]− 1
(8) on the C1018-steel interface, resulting in lower Cdl values [46]. The
change in Rct and Cdl values was persuaded by the successive substitu­
where j represents the imaginary number, Y0 signifies the CPE magni­ tion of the adsorbed H2O molecules by the polymer inhibitors on the
tude, ω symbolizes the frequency angular, and n characterizes an C1018-steel interface. This in turn declines the steel anodic reaction

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H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

an adequately high concentration of inhibitor. Since more polymer

molecules are necessary to adsorb at high additive doses, the protected
effect improves. Moreover, it should be noted that the intended ηI/%
value improved with the polymer addition, and, at 150 ppm inhibitors,
the maximum ηI/% reached 92.8%% for PAM-1, 93.6% for PAM-2,
94.2% for PAM-3, and 94.9% for PAM-4, respectively. The effective
protection action of the PAM-4 polymer can be also observed from the
values of phase-angle at high frequency and the highest impedance at a
low frequency of the specimens, in accordance with the findings of the
PDP studies.

3.4. Adsorption isotherm approaches

The adsorption routine of inhibitors on the interface of C-steel/HCl is

one of the major stages for the corrosion mechanism investigations.
Adsorption isotherms provide knowledge about the interactions among
the C1018-steel interface and inhibitor additives as well as corrosion
protection behavior. The adsorption of polymeric additives on the
C1018-steel interface comprises two main kinds of adsorption i.e.,
chemisorption and physisorption. Nevertheless, chemical adsorption is
the most possibly critical kind of reaction between an inhibitor species
and the electrode surface. Competitive adsorption route takes placed at
the interface of metal/solution between H2O or/and Cl− ions and in­
hibitor molecules are stripped by the quasi–substitution route based on
the following Eqn. [48]:

PAM(sol)
+ nH2 O/Cl(ads) →PAM(ads) + nH2 O/Cl(sol) and/orPAM/Cl(ads) + nH2(sol)
(11)
The protecting layer designed on the C1018-steel interface coverage
is owing to the adsorption phenomenon. For PAM polymeric inhibitors,
Fig 4. Experimental and fitted Nyquist results of C-steel in uninhibited system the part of surface coverage values (θ) at various concentrations were
(A) and inhibited system (B). Inset equivalent circuits model for fitted to different adsorption isotherm models such as Temkin, Flor­
the phenomena. y–Huggins, Frumkin, Freundlich, and Langmuir. By extreme the verified
models the greatest fit was achieved via the isotherm model of Langmuir
[47]. In the current investigation, the polymer concentrations are (as presented in Fig. 5.) that describes inhibitor adsorption route
appropriately high, the part of surface coverage (θ) of adsorbed mole­ correctly according to the following Eqn. [49]:
cules is enhanced and a high θ is extended. The highest θ was obtained at

Table 2
EIS parameters for C-steel in 1.0 M HCl without and with various concentrations of the as-prepared polymer inhibitors at 298 K.
Inhibitor codes inh/ppm Rs/Ω cm RP/Ω cm2±SD F cm-2 × 10- QCPE χ2× 10–4 θ ηI/%
1 n
0/μΩ
−
s cm-2 n

1.0 M HCl 0.0 0.31 39.8 679.7 62.67 0.667 5.46 – –

Diaminebisthiazole (M) 1.56 228.7 55.6 4.404 0.751 4.81 0.826 82.6
PAM-1 10 0.39 73.4 256.8 22.49 0.746 4.50 0.458 45.8
25 0.46 107.2 207.9 18.38 0.755 4.56 0.629 62.9
50 0.55 135.8 116.3 10.23 0.830 4.61 0.707 70.7
75 0.91 194.1 76.4 6.62 0.773 4.67 0.795 79.5
100 1.10 294.8 67.4 5.32 0.820 4.85 0.865 86.5
150 1.46 552.7 46.7 4.11 0.782 4.71 0.928 92.8
PAM-2 10 0.43 75.3 203.1 17.77 0.755 4.56 0.472 47.2
25 0.51 114. 1 168.6 14.76 0.746 4.58 0.651 65.1
50 0.61 156.6 106.0 9.33 0.764 4.61 0.746 74.6
75 0.99 209.4 56.4 4.91 0.773 4.76 0.81 81.0
100 1.22 406.1 44.7 3.10 0.846 4.80 0.902 90.2
150 1.61 621.8 33.7 2.91 0.789 4.67 0.936 93.6
PAM-3 10 0.48 80.1 153.1 13.35 0.773 5.06 0.503 50.3
25 0.55 126.7 104.6 9.14 0.785 5.02 0.686 68.6
50 0.54 188.6 85.3 7.42 0.773 4.80 0.789 78.9
75 1.09 299.2 46.1 5.42 0.782 4.29 0.867 86.7
100 1.35 523.6 35.1 4.11 0.806 4.46 0.924 92.4
150 1.73 686.2 24.8 2.21 0.812 4.88 0.942 94.2
PAM-4 10 0.58 81.2 126.2 9.23 0.811 5.15 0.51 51.0
25 0.67 137.7 86.3 6.32 0.824 5.10 0.711 71.1
50 0.65 200.1 70.4 5.11 0.819 4.88 0.801 80.1
75 1.31 290.5 37.8 3.71 0.821 4.36 0.863 86.3
100 1.63 414.5 29.7 2.81 0.846 4.54 0.904 90.4
150 2.01 780.4 19.9 1.52 0.850 4.98 0.949 94.9

6
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

CInh. 1 Table 3
= CInh. + (12)
θ Kads. Langmuir Adsorption parameters for C-steel in molar HCl for PAM polymeric
additives at 298 K using PDP results.
Herein, Kads symbolizes the adsorption-equilibrium constant and Cinh
Inhibitor R2 S=slope Kads (L g − 1
) ΔG0ads /kJg− 1
is the polymer dose expressed in g/L. The correlation coefficient values
(R2) is calculated from the best fitted was found to be in the range of PAM-1 0.9985 0.995 63.45 − 44.51
0.9985, 0.9967, 0.9988, and 0.9983 (Table 3) for the Langmuir isotherm PAM-2 0.9967 1.004 76.04 − 44.95
of PAM-1, PAM-2, PAM-3, and PAM-4, respectively, which also deliv­ PAM-3 0.9988 0.988 87.95 − 45.32
PAM-4 0.9983 0.957 97.08 45.56
ered the most largest fitting for the empirical findings of PAM com­
−

pounds. This isotherm supposes that the adsorbed inhibitors are

occupied only one position and there are no attractions with other PAM-4 polymer at all studied temperatures (Fig. 6C); inferring that these
adsorbed molecules [50]. The Kads is connected with ΔG0ads (the standard polymeric materials significantly impede the C-steel corrosion.
free energy of adsorption), through Eqn. [51]: The protection capacity reduced for PAM-1, PAM-2, PAM-3, and
PAM-4 from 91.3, 93.7, 96.4, and 98.2% at 298 K to 90.6, 91.9, 95.7,
ΔG0ads = − RTln(CH2 O Kads ) (13)
and 97.7% at 328 K, respectively (Fig. 6D). Therefore, PAM polymer
where CH2O = 1 × 10− 6 stated in g L − 1, T = Kelvin temperature, and R= additives still display outstanding protection performance to inhibit C-
steel from corrosion by creating an adsorption layer on the metallic
universal gas constant. The values of Kads and ΔG0ads are registered in
interface even at higher temperature [53]. Arrhenius and Transition
Table 3. The higher Kads values designate the adsorption strength of the
Arrhenius diagrams of log(jcor)vs.1/Tandlog(jcor/T)vs.1/T of
as-prepared polymers and the negative sign of ΔG0ads refers to the
C1018-steel in molar HCl solution containing PAM-1, PAM-2, PAM-3
spontaneously of the process of adsorption. The higher ΔG0ads values less and PAM-4 polymers are exemplified in Fig. 7. The kinetic parameters
than − 40.0 kJ g − 1 (Table 3) designate that the chemical adsorption of corrosion process including activation energy (Ea), the activation
behavior of the prepared polymers which happens through the transfer enthalpy (ΔHa), and the activation entropy (ΔSa) for the C-steel corro­
of electrons from the free electron pairs from high electron sites to the sion in blank acidic solution and containing optimum dose of polymeric
empty 3d-orbital of the iron surface creating a covalent bond. The ΔG0ads additives (150 ppm) at the range of temperatures from 298 K to 328 K
values are matched with PDP and EIS findings [52]. are assessed from Arrhenius and transition state Eqns. as follows [54].
( )( )
Ea 1
3.5. Temperature effect and thermodynamic parameters of activation log jcor = logA − (14)
R T

The temperature impact on the corrosion reaction of C1018-steel is (

jcor
) [ ( ) (
R ΔSa
)]
ΔHa
( )
1
very convoluted due to the various modifications that take place at the log = log + − (15)
T Nh 2.303R 2.303R T
interface on the metal/solution like the adsorbed layer dissolution [53].
PDP diagrams for C1018-steel in blank molar HCl solution (A) and where, h, A, R, and N are Planck’s constant, the Arrhenius factor, the
containing 150 ppm PAM-4 at different temperatures (B) are repre­ universal gas constant, and Avogadro’s number, respectively. The Ea
sented in Fig. 6A and 6B. Compared with that in uninhibited medium, values were intended from the straight-line slopes (-Ea/2.303R). The
the value of jcor declines strangely with the addition of 150 ppm of

Fig 5. Langmuir isotherm adsorption mode of (A) PAM-1, (B) PAM-2, (C) PAM-3, and (D) PAM-4 on the C-steel surface in molar HCl at 298 K from PDP
measurements.

7
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

Fig 6. PDP diagrams for C-steel in blank 1.0 M HCl solution (A) and containing of 150 ppm PAM-4 at various temperatures (B). Variations of corrosion current
density (C) and inhibition efficiency (D) with temperature.

ΔHaandΔSa values could be intended from the slope and intercept of the corresponding diaminebisthiazole (monomer) [2,3].
relation between log (jcor/T)vs.1/T, respectively. The parameters of Particularly, a comparison of our findings with related polymeric
activation (Ea,ΔHa,andΔSa) for C1018-steel in molar HCl in the nonex­ inhibitors previously published elsewhere has been completed and
istence and existence of 150 ppm of PAM inhibitors are recorded in documented in Table 5. Azzam et al. [58] investigated the protection
Table 4. action of synthesized polymers based on polyacrylamide (PACM) on
The occurrence of the investigated polymeric additives improved the C1018-steel in HCl by using PDP, EIS, and weight loss approaches. They
energy barrier (Ea) of the impeding system above that of the uninhibited revealed that the protection efficiency in the presence of 800 ppm PACM
medium and subsequently the protection route (Table 4). This rise could was 75.2%. Bereket et al. [59] also inspected impeding the action of
be clarified by the continuing inhibitor molecules adsorption to produce polyvinylbenzyltrimethyl ammonium chloride on C-steel in 0.1 M hy­
a barrier layer on C-steel interface. These outcomes indicate a phys­ drochloric acid by EIS and PDP studies. They reported that the protec­
isorption route of PTA additives on the metallic interface [55]. The tion power was an increase by increasing the inhibitor concentrations up
positive ΔHa (enthalpy) sign proves the endothermic mode of the C-steel to a maximum of 94.8% at 1 × 10− 4 M. As another study, Dagdag et al.
corrosion process [56]. The negative ΔSa values (entropy) designate a [60] prepared diamine aromatic epoxy pre-polymers (DAEPs) and
decline in the randomness degree, which happened when the reactants studying its protection behavior on the erosion of C-steel in molar HCl.
are renovated to motivate complexes i.e., the association is preferable Their findings exhibited that, the protection capacity reached a
instead of the dissociation method [55-57]. maximum value of 93.5% in the occurrence of 1 × 10− 3 M of DAEPs.
Furthermore, the inhibitive action of chitosan and maltodextrin poly­
mers on the C-steel erosion in acidic chloride medium has been assessed
3.6. Comparison between the protection capacity of the
by Abdallah et al. [61]. The inhibition power value was found to 88.62%
diaminebisthiazole monomer and its polymers and with previous studies
in the existence of 500 ppm. Our findings support the prepared PAM
polymeric materials show promising performance compared to the
The inhibition action of the monomer i.e., diaminebisthiazole (M) on
previous studies with high protection efficiency at a significantly low
the C1018-steel corrosion in molar HCl was performed, in comparison
polymer concentration (91.3% to 98.2% in the presence of 150 ppm of
with the protection accomplishment of the prepared PAM polymers
polymer).
(PAM-1, PAM-2, PAM-3, and PAM-4) by Tafel polarization and imped­
ance investigations at 298±1 K. It was seen that in the inhibited HCl
solutions comprising 150 ppm of diaminebisthiazole (M) and PAM 3.7. Surface morphology studies
polymers, the ηP% value of the diaminebisthiazole (monomer) is 83.4%,
while the ηP% values for PAM-1, PAM-2, PAM-3, and PAM-4 polymeric 3.7.1. FE-SEM/EDX analysis
additives are 91.3%, 93.8%, 96.4%, and 98.2%, respectively, as recor­ FE-SEM analysis method provides 2D optical knowledge about the
ded in Table 5. The higher protection capacity of the PAM polymeric inhibitor performance toward the electrode corrosion. Fig 8A-C char­
additives with respect to the diaminebisthiazole (monomer) might be acterizes the C-steel electrodes in molar hydrochloric acid in the absence
due to the large size of the PAM polymers which shields broad area of and existence of 150 ppm of diaminebisthiazole (monomer) and PAM-4
the C-steel surface i.e. high surface coverage and also to the existence of polymer (as a best polymer additive). The morphology of the C-steel
more highly electron density centers in the polymer molecule than their surface (Fig. 8A, uninhibited medium), shows cracks and pits suggesting

8
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

Table 5
Comparative table screening the corrosion inhibition capacities of the prepared
PAM polymers and other related polymeric inhibitors.
Substrate Corrosive Dose/inhibitor protection References
Media capacity

C-steel 1.0 M HCl 800 ppm/ polyacrylamide 75.2 Ref. [58]

(PACM)
C-steel 0.1 M HCl 1 × 10− 4 M/ 2, 6 ionen, 2, 94.8 Ref. [59]
10 ionen,
polyvinylbenzyltrimethyl
ammonium chloride
C-steel 1.0 M HCl 1 × 10− 3 M / Diamine 92.9 Ref. [60]
aromatic epoxy pre-
polymers (DAEPs)
C-steel 1.0 M HCl 500 ppm /Maltodextrin 88.62 Ref. [61]
and Chitosan Polymers
C-steel 1.0 M HCl 150 ppm/ PAM-1 91.3 Present
work
C-steel 1.0 M HCl 150 ppm/ PAM-2 93.8 Present
work
C-steel 1.0 M HCl 150 ppm/ PAM-3 96.4 Present
work
C-steel 1.0 M HCl 150 ppm/ PAM-4 98.2 Present
work

3.7.2. FTIR and UV-visible spectroscopy analyses

In order to estimate the various groups and/or atoms in the conju­
gated polyazomethines structures, which are participated in the
adsorption with the C1018-steel thru the protection method, FT-IR
spectra of adsorbed PAM-4 polymer and compared them with those of
pure PAM-4 was used. Fig 9A shows the FT-IR spectra of pristine PAM-4
polymer and their adsorbed layer on the metal substrate. The FTIR
spectrum of pure PAM-4 indicates that the peak at 3325 cm− 1 (peak I) is
related to the -NH group, while the bands at 1660 (peak II) and 1580
cm− 1 (peak III) are assigned for the C = N and C = C, respectively The
spectrum of the absorbed PAM-4 on C1018-steel displays significant
Fig 7. Arrhenius (A) and Transition Arrhenius (B) plots of C-steel in 1.0 M HCl
modification in absorption peaks of functional groups of PAM-4 poly­
containing 150 ppm of different polymer inhibitors.
mer. We could clearly detect, that the band strength is considerably
reduced compared to spectrum of pristine PAM-4; for instance, the
Table 4 broadband (peak 1) at 3325 cm− 1 related to the -NH group vanished in
Activation thermodynamic parameters for C-steel in molar HCl in the lack and the case of the adsorbed layer that might be ascribed to the chemical
existence of 150 ppm of TAP inhibitors. bond formed at the interface of metal/solution-polymer. The C = N and
Inhibitor systems Ea/ kJ mol− 1
ΔHa/ kJ mol− 1
ΔSa/ kJ mol− 1 C = C stretching frequency decreases from the intensities of 1660 (peak
II) and 1580 cm− 1 (peak III) to 1644 (peak II) and 1565 cm− 1 (peak III),
Blank 1.0 M HCl 43.48 36.51 − 135.27
150 ppm PAM-1 60.02 52.67 − 79.76
respectively. This indicates that the electron cloud of C = N and –NH is
150 ppm PAM-2 65.08 58.34 − 72.81 shifted from C = N and –NH up to Fe(II) resulting in the development of
150 ppm PAM-3 71.35 66.71 − 69.32 [Fe(II)–PAM-4] complex on the steel interface [63].
150 ppm PAM-4 76.36 73.12 − 57.43 The UV-visible absorption spectrum was accomplished to gain more
evidence on the nature of attractions recognized among PAM-4 polymer
and metal interface. Fig 9B displays UV-visible spectroscopy analysis of
that the metal interface was harshly scratched and damaged fulfilled
the acidic solution of PAM-4 polymer before and after 48 h C-steel
with corrosion products. While, after adding the optimum dose of dia­
dipping. Before dipping of C1018-steel, the spectrum of PAM-4 polymer
minebisthiazole (monomer) and PAM-4 polymer the surface becomes
displays observed adsorption bands at 213 nm (peak I) and 303 nm
smoother and free slightly from corrosion product this concluded the
(peak II), which are related to n‒π* and π‒π*, respectively [64]. How­
protection action of inhibitors through hindering the active centers of
ever, after C1018-steel dipping in HCl containing 150 mg/L of PAM-4
the C-steel surface. Instead, when comparing with diaminebisthiazole
compound shows some modification in the bands of PAM-4 adsorption
(monomer) (Fig. 8B), PAM-4 polymer appears to be less corroded
relative to the reference spectrum prior to immersion of C1018-steel.
(scratched) and more smooth (Fig 8C).
The spectrum specifies one weak peak at 313 nm in addition to a new
Fig 8D-F signifies the EDX analysis and the atomic content percentage
band at 396 nm (peak III), whereas the band around 303 nm was con­
of uninhibited and inhibited samples, respectively. Fig 8D displays the
verted to a very weak absorption band after C-steel dipping. The new
characteristic bands of the elements instituting the C1018-steel in the
developing band could highly be owing to the iron→ polymer (iron →
lack of inhibitors. As revealed in Fig. 8E and 8F the EDX spectrums of
polymer charge transfer), as detected in Fig. 9B. The attained findings
diaminebisthiazole (monomer) and PAM-4 polymer displays additional
from UV-visible examination of PAM-4 polymer prior and after
signals owing to the occurrence of N and S. The occurrence of N and S
C1018-steel dipping display that the thiazole ring and aromatic sub­
elements in the EDX patterns of inhibited surface designates that the
stituents mostly participate in the adsorption of these polymers on steel
inhibitor molecule is adsorbed on the C1018-steel interface and inhib­
electrode, which indicates that polyazomethine compounds could form
iting from corrosion. These interpretations are matched with the pre­
a complex with Fe atoms based on mechanism of donor-acceptor,
viously published findings [62].
approving the chemical adsorption route of PAM-4 on the metal

9
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

Fig 8. FE-SEM surface analysis micrograph for C-steel immersed in (A) blank 1.0 M HCl, (B) in the presence of 150 mg/L of diaminebisthiazole (M), and (C) in the
presence of 150 mg/L of PAM-4 polymer at 298 K for 24 hrs and (D, E, and F) EDX analysis at the same conditions.

interface as revealed the thermodynamic outcomes. Moreover, the ELUMO values are − 2.80 and − 2.88 eV for PAM-3 and
PAM-4 (Table 6) lower than PAM-1 and PAM-2, indicating the high
3.8. DFT studies inhibition performance for PAM-3 and PAM-4.
In a similar way, the ΔE (energy gap) is another vital factor to sup­
The optimized structure, LUMO and HOMO distribution of monomer port the corrosion protecting proficiency of the PAM molecule which
structure of the polyazomethines in gas phase are represented in Fig. 10, increases as the ΔE value is diminished [67]. As illustrated in Table 6,
and the related quantum chemical indices are found in Table 6. As re­ PAM-3 and PAM-4 have lower ΔE values (2.06 and 1.97 eV) than PAM-1
ported by the Frontier orbital theory, the interplay between the PAM and PAM-2, which approves a higher affinity for PAM-3 and PAM-4 to be
molecule and metal surface is governed by HOMO and LUMO energies adsorbed on the C1018S surface. Moreover, the small values of elec­
[65]. Where, EHOMO is a gage of the molecule capability to provide tronegativity (χ) also offer a high potential reactivity of the PAM mol­
electrons, while ELUMO is a gage of the molecule capability to receive ecules to provide electrons to the steel interface [68]. Furthermore, the
electrons [66]. Therefore, the corrosion inhibition performance is global hardness (η) and softness (σ) are vital features that assess the
enhanced for an inhibitor molecule that has large EHOMO and small stability and reactivity of the molecule. Where, the soft molecules are
ELUMO values. In a similar way, great corrosion protection capacity was highly reactive than hard molecules due to the effortlessly providing of
recommended for an inhibitor molecule has low value of the energy gap electrons to the metal surface during the adsorption [69]. According to
between LUMO and HOMO energy (∆E) result a small energy is required Table 6, it was found that PAM-3 and PAM-4 have higher σ values and
to offer an electron from EHOMO to ELUMO. lower η values than PAM-1 and PAM-2, indicating easily offering elec­
According to Table 6, PAM-3 and PAM-4 have the largest EHOMO trons to metal surface and high inhibition performance.
value of − 4.86 and − 4.85 eV as compared to PAM-1 and PAM-2. As The ΔN values measure the capability of the PAM to provide elec­
revealed in Fig. 10, for the PAM molecules, it is noticeable that the trons, and the larger ΔN value, the larger electron donation capability of
HOMO level is localized over the thiazole and imine moieties, signifying the inhibitor molecule. In accordance with Lukovits’s study [70], when
that the N- atoms are the favored location for electrophilic attacks on the ΔN < 3.6, the inhibition performance enhances with higher electron
steel interface. This approach enhances the adsorption capacity of PAM donation capability. According to the assessed values of ΔN are repre­
molecules on the surface of C1018 steel and hence, boosts the protection sented in Table 6, the higher ΔN values for PAM-3 and PAM-4 (1.54 and
efficiency, which is in great concord with the empirical results. 1.59) than PAM-1 and PAM-2. This suggests that PAM-3 and PAM-4

10
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

PAM-2, the atoms C(1), N(3), N(6), C(8), C(9), C(11), C(12), C(13), C
(14), N(17), N(18), C(20), C(21), C(22) of PAM-3 and the atoms C(1), N
(3), N(6), C(8), C(9), C(10), C(11), C(13), C(14), C(15), N(18), N(19), C
(21), C(22) of PAM-4 are active sites located on thiazole, imine and
phenyl moieties, possess the capability of offering electrons as they
interplay with the steel interface.
The MEP mapping is regarded as an important 3D view tool to
discriminate the net electrostatic impact formed over a molecule from
the total charge distribution [75]. As displayed in Fig. 11, the red colors
describe the greatest electron density, where MEP is the highest negative
(nucleophilic reaction). In contrast, the blue colors portray the
maximum positive region (electrophilic reaction) [76]. As evidenced in
Fig. 11, the highest negative (red color) regions are mainly over N atoms
in thiazole and imine moieties, while the lesser density (green color)
over the phenyl moieties in PAM molecules. On the contrary, MEP
revealed the maximum positive (blue color) region methyl moieties in
PAM molecules. The positions with great electron density in PAM mol­
ecules would be the most suitable for interplay with the C1018 steel
surface.

3.9. MC simulation

MC simulation is a method for apprehending the interplay nature

between the PAM molecules and the C1018-steel interface during the
adsorption process by employing an adsorption locator module.
Consequently, Fig. 12 reveals the maximum proper adsorption confor­
mations for the PAM molecules on the C1018-steel interface which is
found in an approximately parallel or flat arrangement, indicating a rise
in the extent of adsorption and maximum surface coverage [77]. Be­
sides, the attained results employing the MC simulation were arranged
in Table 7, like the adsorption energy for relaxed adsorbate molecules,
Fig 9. FTIR spectra of pure PAM-4 polymer and PAM-4 polymer their adsorbed rigid adsorption energy for unrelaxed adsorbate molecules, and defor­
layer on C-steel interface after exposure in 1.0 M HCl for 48 h (A) and UV-
mation enegry for relaxed adsorbate molecules [78]. Table 7 exposed
visible spectral of acidic solutions of PAM-4 and PAM-4 polymer before and
that PAM-3 and PAM-4 (− 4876.97 and − 48,882.23 kcal mol− 1) have
after C-steel immersion (B).
larger adsorption energy as compared with PAM-1, and PAM-2
(− 4722.48 and − 4811.81 kcal mol− 1) which implies a robust adsorp­
molecules have higher inclinations to provide electrons to the metal
tion of PAM-3 and PAM-4 on the C1018-steel interface generating a
surface as compared with PAM-1 and PAM-2.
stationary adsorbed layer and shields the C1018 steel against the
Furthermore, the dipole moment (DPM) is a crucial factor that en­
corrosion which is consonant with the experimental findings. Addi­
dorses in prediction the pathway of corrosion protection [71]. The
tionally, the values in Table 7 reveal that the adsorption energies of
increment in DPM offers a rise in the deformation energy and progresses
PAM-3 and PAM-4 beforehand and afterwards the geometry optimiza­
the adsorption of molecule on steel surface, leading to strengthen the
tion step (unrelaxed and relaxed) are more than PAM-1 and PAM-2
corrosion inhibition performance [72]. As described in Table 6, PAM-4
affirming the high inhibition efficiency for PAM-3 and PAM-4 than
has a larger DPM value (4.86 debye) than PAM-1, PAM-2 and PAM-3,
PAM-1 and PAM-2.
which demonstrates a high tendency for PAM-4 to be adsorbed on the
The dEads/dNi values describe the energy of metal-adsorbate
C1018 steel interface and enhance the protection performance.
conformation when one of the adsorbates has been withdrawn [79].
Moreover, there is an evident correlation between the molecular
The value of dEads/dNi for PAM-4 (− 200.47 kcal mol− 1) is higher than
surface area of the PAM inhibitors and their proclivity to protect the
PAM-1, PAM-2, and PAM-3 molecules (− 57.32, − 163.06 and − 174.92
C1018 steel interface in aggressive media. The larger molecular struc­
kcal mol− 1) which affirms an excellent adsorption of PAM-4 molecule
ture size, the higher protection capacity as the contact area between the
than PAM-1, PAM-2 and PAM-3 molecules. Furthermore, the dEads/dNi
steel surface and PAM molecules increases [73]. As mentioned in
values for H2O are approximately − 17.71 kcal mol− 1, which is lower
Table 6, PAM-3 and PAM-4 show the greatest molecular surface area
than the values of PAM-1, PAM-2, PAM-3, and PAM-4 values showing
(366.58 and 366.52 Å2) and for this reason, they have higher inhibition
that a sturdy adsorption of PAM inhibitors than H2O molecule which
efficiency than PAM-1 and PAM-2.
approves the replacing of H2O molecules by PAM inhibitor. Therefore,
Moreover, the active sites of PAM inhibitors were discovered by
the PAM-1, PAM-2, PAM-3, and PAM-4 inhibitors are resolutely adsor­
molecular electrostatic potential mapping (MEP), natural bond orbital
bed on the C1018 steel interface and create powerful adsorbed pro­
(NBO) charges, and Mulliken atomic charges. These indicators are
tecting films which results a corrosion inhibition for the surface of
calculated by the Spartan™14 software. The NBO charges and Mulliken
C-steel in harsh media which affirmed by both empirical and compu­
atomic charges are additional indicators to identify the local reactivity
tational approaches.
of a compound, but NBO charges are considered more accurate tools, as
shown in Table S2 (ESI), NBO and Mulliken atomic charges are in accord
3.10. The mechanism of the corrosion mitigation
with each other. According to the NBO, and Mulliken atomic charge,
atoms that have high negative charges; they are assumed as electron
To expect the corrosion mitigation mechanism of the C1018 steel
suppliers (nucleophilic centers) [74]. Thus, The atoms C(1), N(3), N(6),
surface by PAM polymers, firstly it is necessary to know the corrosion
C(7), C(8), N(11), N(12), C(13) of PAM-1, the atoms C(1), N(3), N(6), C
mechanism of C1018 steel in HCl solution. The subsequent mechanism
(8), C(9), C(10), C(12), C(13), C(14), N(17), N(18), C(19), C(21) of
propositioned for the corrosion of C1018 steel in HCl solution [80]:

11
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

Fig 10. The optimized molecular structures, HOMO and LUMO for the monomer structure of PAM polymers using DFT caculations in the gas phase .

Table 6
The calculated quantum chemical parameters for the monomer structure of PAM
polymers in the gas phase.
Parameters Compound PAM-1 PAM-2 PAM-3 PAM-4

EHOMO/ eV − 5.14 − 4.99 − 4.86 − 4.85

ELUMO/ eV − 2.60 − 2.73 − 2.80 − 2.88
ΔE/ eV 2.54 2.26 2.06 1.97
I/ eV 5.14 4.99 4.86 4.85
A/ eV 2.60 2.73 2.80 2.88
χ/ eV 3.87 3.86 3.83 3.87
η/ eV 1.27 1.13 1.03 1.02
σ/ eV 0.79 0.88 0.97 0.99
ΔN/ e 1.23 1.39 1.54 1.59
Dipole moment/ Debye 2.43 4.11 4.65 4.80
Molecular surface area/ Å2 226.04 329.84 366.58 366.52

(i) The mechanism of anodic dissolution reaction for C1018 steel is:
Fe + Cl− ⇌(FeCl− )ads (16)

(FeCl− )ads ⇌(FeCl)ads + e− (17)

(FeCl)ads →(FeCl+ )ads + e− (18)

(FeCl+ )ads →Fe2+ + Cl− (19)

(ii) The mechanism of hydrogen evolution cathodic reaction is:

Fe + H + ⇌(FeH + )ads (20)

(FeH + )ads + e− →(FeH)ads (21)

Fig 11. Graphical presentation of the MEP for the monomer structure of PAM
(FeH)ads + H + + e− →Fe + H2 (22) polymers using DFT caculations in the gas phase.

12
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

Fig 12. The most suitable adsorption configuration for the monomer structure of PAM polymers on Fe (1 1 0) substrate obtained by adsorption locator module.

Table 7
Data and descriptors calculated by the Mont Carlo simulation (MC) for the
adsorption of the monomer structure of PAM polymers on iron (1 1 0). In the presence of PAM polymers, which have several active sites for the
Systems Adsorption Rigid Deformation dEads/ dEads/
adsorption process, various approaches of adsorption may occur in the
energy/kcal adsorption energy/kcal dNi: PAM dNi: inhibition phenomena including PAM polymers on steel surface as
mol− 1 energy/kcal mol− 1 kcal Water subsequent:
mol− 1 mol− 1 kcal
mol− 1
(a) The PAM polymers in the acid solution can be protonated as
Fe − 4722.48 − 4964.62 242.14 − 57.32 − 17.82 follows:
(110)
PAM-1 PAM + xH + ⇌[PAMHx ]x+ (23)
Water
Fe − 4811.81 − 5056.98 245.17 − 163.06 − 17.74
(110)
PAM-2
Water Therefore, the PAM molecules in acidic solutions exist as
Fe − 4876.97 − 5124.24 247.27 − 174.92 − 17.58 [PAMHx]x+. According to previously published researches, the C1018
(110) steel interface in hydrochloric acid solution is positively charged [81].
PAM-3
So, Cl− ions firstly adsorb onto the positively charged C1018 steel sur­
Water
Fe − 4888.23 − 5137.81 249.58 − 200.47 − 17.69 face based on reaction (16). Subsequently, the PAM molecules adsorb
(110) via electrostatic attraction between the negatively charged C1018 steel
PAM-4 surface (FeCl− )ads and positively charged PAM molecules [PAMHx]x+
Water
and create a protective adsorbed layer (i.e., physisorption). Thereby, the
oxidation reaction of (FeCl− )ads as demonstrated by reaction steps from

13
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

(17) to (19) can be prohibited [82]. (b) In addition to the physisorption,

PAM molecules might be adsorbed on the C1018 steel interface through
the chemisorption mechanism, including the coordinate bonds that may
be created between the lone pairs electrons of the N, S atoms of thiazole,
imine moieties, in addition, π electrons of thiazole, imine, phenyl moi­
eties and the empty d-orbital of Fe atoms which reinforced the inter­
action between the PAM molecules and C1018 steel surface [83], this
approach is approved with the higher negative values of ΔG0ads than
− 40.0 kJ g − 1. (c) Owing to the chelating ability of bithiazole, some
metal complexes of Fe2+—PAM polymers may be widely prepared [84].
Thus, [PAMHx]x+ may interact with Fe2+ ions produced on steel surface
forming Fe2+—PAM polymers complexes, which confirmed by FTIR and
UV-visible spectroscopy analyses:

[PAMHx ]x+ + Fe2+ ⇌[PAMHx − Fe](x+2)+ (24)

The formed complexes might get adsorbed onto the C1018-steel
interface by the Van der Waals force to construct a blocking barrier to
protect the C1018 steel surface from corrosion. (d) the occurrence of all
earlier approaches.
According to experimental and theoretical studies, the high inhibi­
Scheme 1. Synthesis of polyazomethine 4a-d (PAM-1-PAM-4).
tion of PAM molecules is assigned to the existence of thiazole, imine, and
phenyl moieties, which act as active sites that provided electrons to the
4. Conclusions
C-steel surface and forming a protective adsorbed layer. For these rea­
sons, PAM polymers may be also effective inhibitors for other steel with
In summary, we report the synthesis and characterize of conjugated
different compositions.
polyazomethines in good yields. The corrosion protection capacity of
Fig 13 designates the comparison of the inhibition efficiencies
prepared polyazomethines inhibitors from PDP, EIS, and FESEM/EDX
attained for PAM polymers at a concentration of 150 ppm using PDP and
approaches is in worthy agreement. PDP investigations exposed that
EIS studies. As demonstrated in Fig. 13, the calculated inhibition effi­
polyazomethines compounds behave as inhibitors of mixed-type. EIS
ciency with the PDP technique was higher (i.e., the difference less than
studies were evaluated to model the corrosion mitigation route by
5%), but they were still at the same order of magnitude as those obtained
analysis the suitable equivalent-circuit. The trend values of Rp and Cdl
with the EIS technique. So, the computed inhibition efficiency attained
were promising to approve a defensive layer construction via the poly­
from PDP and EIS measurements is in good accord. This small difference
azomethines adsorption, substituting primarily adsorbed H2O mole­
may be attributed to the technique principle, wherein EIS is an alter­
cules. The polyazomethines inhibitors were chemisorbed on the steel
nating current technique providing a nonlinear electric response to
interface and their adsorptions match to adsorption model of Lang­
frequency reliant potential disturbance near to the Ecorr of the corroded
muir’s. Surface morphology inspection through FESEM/EDX displays a
metal, thus, they can also explain the nonlinear kind of electrochemical
significant modification of C-steel corrosion by the development of a
corrosion of metals without damage to the corroded metal surface (i.e.,
preventative film on the metal surface getting a thickly packed
nondestructive technique) [85]. While PDP is a direct current electro­
morphology at the optimum dose (150 ppm). Spectroscopic methods
chemical technique that includes the applying of more positive and more
(FT-IR and UV-visible) suggest that PAM compounds are adsorbed at C-
negative potentials distant from the Ecorr to propel the electrochemical
steel interface via the thiazole ring and aromatic substituents based on
reaction so that either dominant anodic or cathodic reaction can take
the donor-acceptor mechanism. Both DFT and MD simulations rein­
place at the metal–electrolyte interface causing severe damage to the
forced the empirical findings that exhibited the prepared conjugated
corroded metal surface [86].
polyazomethines as effective inhibitors for the C1018-steel pickling
corrosion, and the order of protection capacity, for the prepared poly­
azomethines, is as follows: PAM-4 (98.2%) > PAM-3 (96.4%) > PAM-2
(93.8%) > PAM-1 (91.3%) > diaminebisthiazole (monomer) (83.4%).

CRediT authorship contribution statement

Hany M. Abd El-Lateef: Supervision, Investigation, Methodology,

Resources, Formal analysis, Data curation, Funding acquisition, Writing
- original draft, Writing - review & editing. Abdelwahed R. Sayed:
Supervision, Investigation, Methodology, Resources, Formal analysis,
Data curation, Funding acquisition, Writing - original draft, Writing -
review & editing. K. Shalabi: Supervision, Investigation, Methodology,
Resources, Formal analysis, Data curtion, Funding acquisition, Writing -
original draft, Writing - review & editing.

Declaration of Competing Interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence
the work reported in this paper.
Fig 13. Comparison of protection capacities obtained with PDP and EIS mea­
surements for 150 ppm concentration of PAM polymers.

14
H.M. Abd El-Lateef et al. Surfaces and Interfaces 23 (2021) 101037

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