Journal of Bio- and Tribo-Corrosion (2020) 6:53

https://doi.org/10.1007/s40735-020-00351-0

A Creation of Poly(N‑2‑hydroxyethylaniline‑co‑2‑chloroaniline)
for Corrosion Control of Mild Steel in Acidic Medium
H. M. Abd El‑Salam1 · G. M. Abd El‑Hafez2 · H. G. Askalany1 · A. M. Fekry3

Received: 13 December 2019 / Revised: 24 February 2020 / Accepted: 12 March 2020 / Published online: 23 March 2020
© Springer Nature Switzerland AG 2020

Abstract
The current work discusses the synthesis and characterization of two homopolymers poly(N-2-hydroxyethylaniline)
(PNHEANI), poly(2-chloroaniline) (P2ClANI), and a copolymer of poly(N-2-hydroxyethylaniline-co-2-chloroaniline)
(PNHEANI-co-PClANI). PNHEANI-co-PClANI is chemically synthesized using ammonium persulfate as an oxidant in an
acidic medium at room temperature under N ­ 2 atmosphere. All created polymers are characterized by IR spectroscopy, XRD,
SEM, and TGA analysis. The efficiency, for all the created polymers as a coating on steel in acidic medium, is performed
and is well compared. Corrosion and impedance fitting parameters reveal that the prepared polymers under investigation are
good corrosion inhibitors and in the following order: PNHEANI ≈ PNHEANI-co-P2ClANI > P2ClANI.

Keywords Poly(N-2-hydroxyethylaniline-co-2-chloroaniline) · Corrosion inhibitors · Mild steel · Equivalent circuit

parameters

1 Introduction PANI tungstate [33] for corrosion protection of steel was

Conducting polymer is significant in various technological
applications including rechargeable batteries [1, 2], sensors
[3, 4], and others [5–12]. Also, it was utilized as coatings
for the corrosion protection of oxidizable metals [13–19].
Among all conducting polymers, polyaniline (PANI) has
rigorous research owing to its high electrical conductivity,
easy fabrication, low cost, high stability, and anticorrosivity
[20–26]. Thus, the research on polyaniline as anti-corrosion
becomes a significant issue [27, 28]. PANI sulfate coatings
are effective than PANI phosphate for stainless steel [29],
PANI nitrate was much better due to the formation of oxide
layers at the PANI/metal interface [30]. Also, PANI sulfa-
mate coatings have notable anodic protection to stainless
steel [31]. The usage of both PANI molybdate [32] and
* A. M. Fekry
amanym.fekry@gmail.com
1
Department of Chemistry, Faculty of Science,
Polymer Research Laboratory, Beni-Suef University,
Beni Suef 62514, Egypt
2
Chemistry Department, Faculty of Science, Fayoum
University, Faiyum, Egypt
3
Chemistry Department, Faculty of Science, Cairo University,
Giza, Egypt
also established. PANI-NFs showed better protection relative
to an aggregated PANI [34]. The potential–time curves got-
ten from the electrochemical galvanostatic polymerization
of aniline on low carbon steel have three distinctive steps.
First is its dissolution and then forming polycrystalline iron
oxalate interphase. Second is whole passivation. Finally, the
aniline is electropolymerized [35, 36]. Nickel-coated mild
steel corrosion protection utilizing PANI coatings was also
stated [37, 38]. Several research groups [16, 39–47] have
prepared and characterized polyaniline derivatives and poly-
aniline copolymers as anti-corrosion. The common features
of these investigations are based on the coating ability of
PANI, PANI derivatives, and their copolymers on the metals
to prevent metal dissolutions.
Mild steel [48–50] corrosion has a significant considera-
tion due to its industrial concern. The mechanical proper-
ties and reasonable friendly nature of mild steel make it an
efficient tool not only in the industrial application, but also
in construction subjects like building bridges and furniture.
However, mild steel utilization is controlled with its dissolu-
tion in contact with acids, like acid pickling, etching indus-
tries, and others. In this case, mild steel loses its physical and
mechanical properties by its corrosion. Thus, its protection
is a significant topic especially to lessen economic losses.

13
Vol.:(0123456789)
53 
Page 2 of 14
So, to accomplish corrosion inhibition of mild steel, corro-
sion inhibitors can be used.
Polymers [51] containing two or more heteroatoms such
as O, N, S, benzene ring, or multiple bonds are of specific
attention owing to their better inhibition efficiency with lone
pair of e’s or resonance of benzene ring. The influence of the
molecular structure on chemical activity has been the subject
of interest in chemistry. The achievement of inhibitors in
acid solutions is usually adsorption at the metal–solution
interface.
Mineral acids such as HCl and H ­ 2SO4 are exceedingly
utilized significantly in industrial applications specifically
for cleaning and pickling [24]. Thus, the multi-uses of steel
make it imperative to be present in different acidic media
that lead to its decay with the loss of many billion dollars.
Thus, it is significant economically to protect it and this is
done by utilizing different coatings. Polymers in general are
easily synthesized and low cost for this purpose.
In the present work, the activities of both poly(N-2-hy-
droxyethylaniline), poly(2-chloroaniline), and their copoly-
mer as some corrosion inhibitors towards mild steel in acidic
medium were performed using both weight loss and electro-
chemical techniques.
2 Experimental
2.1 Materials and Solutions
N-2-hydroxyethylaniline, 2-chloroaniline, and N-methylpyr-
rolidone were Sigma-Aldrich. Ammonium persulfate was
Merck. Hydrochloric acid, methanol, and ammonia solution
(33%) were of chemically pure grade products gotten from
Prolabo-chemical Company (England). Double distilled
water was utilized during the present work. The working
electrodes were prepared from commercially mild steel the
chemical composition of which is presented in Table 1. The
electrode consists of a massive rod of area 0.5 cm2.
Acidic solution of pH 2 was prepared accord-
ing to the composition given by 44.2  mL 0.1  M
­COOKC6H4COOH + 54.3 mL 0.1 M HCl. In all solutions,
before each experiment, the pH of the solution was con-
trolled by a sensitive pH meter BT-500 model (Made in
Germany).
Table 1  Chemical composition Element C Si Mn
(weight %) of the mild steel
electrode Analysis 0.34 0.26 0.93
13
Journal of Bio- and Tribo-Corrosion (2020) 6:53
2.2 Preparation of PNHEANI, PClANI, and Their
Copolymer
The chemical oxidative polymerization of NHEANI
using APS as an oxidant in an aqueous hydrochloric acid
medium was performed as mentioned before [52]. Based
on the obtained polymer yield, the polymerization of
0.0040 mol L−1 2-chloroaniline was achieved using 0.0250
mol L−1 APS under nitrogen atmosphere at 30 °C for 3 h
in 1.000 mol L−1 hydrochloric acid medium. The prepara-
tion of NHEANI/2ClANI copolymer was performed using
0.0100 mol L−1 APS as an oxidant in 1.000 mol L−1 aque-
ous hydrochloric acid solution under nitrogen atmosphere at
25 °C for 3 h. The monomer feeds are 0.05 mol from each
monomer per liter.
2.3 Infrared, UV–Visible, and 1HNMR Spectroscopy
The infrared measurements were carried out using Shimadzu
FTIR Vertex 70 Bruker Optics technique. Ultraviolet spec-
troscopy was carried out using Shimadzu visible spectropho-
tometer Double-beam 2600. The 1HNMR measurements of
the prepared polymer were carried out using Varian EM360L
60 MHz NMR spectrometer. The signals were recorded in
dimethylsulfoxide (DMSO) by using tetramethylsilane as an
internal reference.
2.4 Electron Microscope and XRD
The electron microscopy analysis was carried out using
JSM-6510LA Scanning electron microscope, JEOL, Japan.
The XRD pattern of the prepared polymers was character-
ized with the help of panalytical Empyrean X-ray diffrac-
tometer 202964. The scan range was (5°–140°). The above
five sets were found at Beni-suef University, Egypt.
2.5 Thermogravimetric Analysis (TGA)
TGA analysis was done using a detector type Shimadzu
TGA-50H with its component platinum cell, nitrogen atmos-
phere, and 20 °C min−1 rates flowing at Cairo University,
Egypt.
S P Cu Cr Ni Mo Al Fe
0.02 0.04 0.01 0.01 0.02 – 0.01 Balance
Journal of Bio- and Tribo-Corrosion (2020) 6:53 Page 3 of 14  53
2.6 Electrolytic Cell
The cell was a three-electrode cell, with a platinum counter
electrode, a saturated calomel reference electrode, and the
working electrode.
2.7 Open‑Circuit Potential Measurements
The potential of the working electrode under open-circuit
conditions was measured separately against the saturated
calomel electrode (Hg/Hg2Cl2/Cl-sat) as a reference elec-
trode [E° = − 242 mV vs. the standard hydrogen (SHE)].
Open-circuit potentials were followed over 1 h using a high
impedance autoranging multimeter.
2.8 Electrochemical System
The electrochemical impedance investigations and polari-
zation measurements were performed using the Voltalab
10PGZ100 “All-in-one” potentiostat/Galvanostat. The
instrument is interfaced to an external IBM 1200 CPU com-
puter. The voltamaster4 software is designed to measure and
analyze corrosion quickly, easily, and reliably using a variety
of techniques, potentiodynamic polarization, and electro-
chemical impedance spectroscopy (EIS), and the experi-
mental setup allows the direct application of any required
techniques. In our experiments, both linear and Tafel polari-
zation techniques were used after each impedance experi-
ment which was always carried out at open-circuit potential.
2.9 Potentiodynamic Polarization Techniques
The corrosion rate can be obtained usually by using the
linear polarization and Tafel extrapolation methods. Poten-
tiodynamic measurements were conducted at a scan rate of
10 mV s−1. The resulting current is linearly plotted versus
the potential and the slope of this potential–current function
at corrosion potential Ecorr is referred to as the polarization
resistance Rp, and is used with the Tafel constants to deter-
mine the corrosion current density icorr. The linear polariza-
tion technique is extremely rapid. This makes the measure-
ments of the linear polarization very useful in the applied
potential which is never far from the corrosion potential,
so the surface of the specimen is not significantly affected
by the experiment and can often be used for other studies.
The potential range is about ± 700 mV from the open-circuit
steady-state potential.
2.10 Impedance Measurements
An AC 10 mV amplitude signal peak to peak is used. The
working frequency range is 0.1–105 Hz. The measurements,
processing, storage, retrieval, and analysis of data have been
automated. The experimental impedance data were fitted to a
suggested equivalent circuit model and the impedance plots
were then recorded and analyzed.
3 Results and Discussions
3.1 Characterization of the Prepared Polymers
3.1.1 Spectroscopic Analysis
Ultraviolet–visible spectroscopy reveals that the π–π* transi-
tions (both ­E2-band and ­A1g–B2u) characteristic for benzene
ring are present as absorption bands at 254 and 328, 245, and
344 nm in case of PNHEANI, P2ClANI, and PNHEANI-co-
P2ClANI (Scheme 1), respectively [24, 53]. The absorption
band due to the conjugation in polymer chain appears at
416, 558, and 580 for PNHEANI, P2ClANI, and PNHEANI-
co-P2ClANI, respectively. The shift in the bands between
both PNHEANI, P2ClANI monomer, and PNHEANI-co-
P2ClANI copolymer confirms the copolymerization process.
Infrared and proton nuclear magnetic resonance of the pre-
pared polymers are presented in Figs. 1 and 2.
Infrared absorption bands and their assignments of the
three prepared polymers are tabulated in Table 2. From
Fig.  1 and Table  2 it is clear that the absorption bands
appear at 515 and 580, and 445 and 567 cm−1 in case of
PNHEANI and P2ClANI, respectively, which are charac-
teristics for transitional oscillation, and aryl C–Cl appears
at 616 cm−1 with a shift towards high wave number. In addi-
tion, the absorption band appears in both homopolymers
at 1153 and 1106 cm−1 which could be attributed to N=C
quinoid unit structure which is absent in the case of copol-
ymer. The absence of absorption band characteristics for
intermolecular H-bond and OH stretching vibration (in case
of PNHEANI) in the case of the copolymer also confirm the
copolymerization process [24].
1
HNMR signals show that the protons of solvent appear as
singlet and strong band at 2.5 and 3.5 ppm in all polymeric
samples. The aliphatic ­CH2-protons appear at 1.24 ppm in
case of PNHEANI is shifted and enclosed with solvent pro-
tons to appear at 2.5 ppm. Benzene protons are present as
multiples in range of 6.5 to 8.27 ppm with small differences
in the three prepared polymers. NH appears at 6.762 ppm in
the case of PNHEANI as a weak singlet band but in the case
of both P2ClANI and their copolymer it appears at 9.2 ppm.
3.1.2 Scanning Electron Microscope and X‑ray Diffraction
Patterns
SEM and XRD of the prepared polymeric samples are
given in Figs. 3 and 4. From the figures, it can be concluded
that PNHEANI is crystalline (A sharp peaks obtained at
13
53 
Page 4 of 14 Journal of Bio- and Tribo-Corrosion (2020) 6:53

Scheme 1  PNHEANI, Poly (2-chloroaniline) PClANI

P2ClANI, and PNHEANI-co- Cl Cl Cl Cl
P2ClANI

N N N N
n
H H H H

H
+e -e

Cl Cl Cl Cl

Cl Cl
N N N N
n*
H H H H

Poly (N-2-hydroxyethyl aniline) PNHEANI

N N N N NH

C2H4OH C2H4OH C2H4OH C2H4OH C2H4OH

n

Copolymer (PNHEANI-co-P2ClANI)
Cl Cl

N N N

C2H4OH H C2H4OH 1-n

n

2θ = 17–30°) [24] and ordered spherical particles ranged in
size from nanosphere to microsphere (SEM image). A broad
peak at 2θ = 17–30° was obtained for both P2ClANI and
PNHEANI-co-P2ClANI indicating an amorphous structure
with different particle sizes and shapes. The variation in both
size and shape of the particles for the three polymers con-
firms that they are different or copolymer is formed.
3.1.3 Thermogravimetric Analysis (TGA)
The thermal stability of the polymers under investigation
is checked using TGA (Fig. 5). The study of weight loss
with raising temperature reveals that the water present
in PNHEANI is lost in two stages one at ~ 100 °C and
the second in the range 100–263 °C which confirms the
bonded water in the polymer chain. But in the case of
both P2ClANI and their copolymer, water is lost in one
stage started at 80 and 60 and ended at 220 and 150 °C,
respectively. The alkyl groups attached to N-atom in case
of PNHEANI are thermally degradable on two stages; the
first is in the temperature range 263–430 °C and the sec-
ond at 430–525 °C. These fragments and dopant molecules
are lost in case of the copolymer in one stage started at 150
and ended at 550 °C. In the case of P2ClANI, the dopants
and side Cl atoms are lost at 220–300 and 300–570 °C,
respectively. Above 600 °C, the remaining weight % in
case of PNHEANI is ~ 35 but the remaining weight percent
in the case of both P2ClANI and PNHEANI-co-P2ClANI
above 1000 °C are about 6%.
3.2 Application of PNHEANI, P2ClANI,
and PNHEANI‑co‑P2ClANI as Corrosion
Inhibitors on Mild Steel in Acid Medium (pH 2)
3.2.1 Effect of Prepared Polymeric Samples on the Weight
Loss of Mild Steel in Acidic Medium
A standard sample of steel was immersed in 50 mL of aque-
ous HCl (1.0 mol L−1) for different time ranges 5, 10, 20,
30, 45, 60, and 3 h at room temperature. Steel was washed
by distilled water and then in acetone and dried in an oven
for constant weight (w1). The weight loss (w) was calculated
after washing and drying the steel sample till constant weight
(w2) was obtained according to the relation w = w1 − w2. The
obtained data reveal the weight loss of steel in the absent of
polymers increases with time. The weight loss at 180 min is
0.00829 g per unit area ­(cm2).

13
Journal of Bio- and Tribo-Corrosion (2020) 6:53 Page 5 of 14  53
Fig. 1  IR spectra of the pre-
pared polymers
3.2.1.1  Determination of Steel Weight Loss in the Presence
of Polymers  The effect of PNHEANI, P2ClANI, and their
copolymer on weight loss of steel was studied in 1.0 molar
HCl for 180  min at room temperature. Polymer quantity
was changed from 10 to 1000 ppm. The polymers are dis-
solved in N-methylpyrrolidone. Weight losses per unit area
are given in Table 3 and presented in Fig. 6. From Table 3
and Fig.  6, it is clear that the weight loss increases up to
100 ppm but still less than the weight of steel in the absence
of PNHEANI (0.00829 g cm−2). After this, the weight loss
decreases up to 1000 ppm. These results may be contributed
to the formation of the passive layer on the most steel sur-
13
53 
Page 6 of 14 Journal of Bio- and Tribo-Corrosion (2020) 6:53

Fig. 2  1HNMR signals of the prepared polymeric samples

face at higher concentration of PNHEANI inhibitor [55, 56]. presence of PNHEANI. In the case of P2ClANI, the weight
The inhibition efficiency % of PNHEANI (IE%) is 87.94 loss decreases with increasing the polymer content up to
calculated from the relation IE% = [1  −  (W/W0)] × 100, 1000 ppm and the IE % = 87.09. IE% for the copolymer is
where W0 and W are the weight loss in the absence and 76.12. The inhibition of these prepared polymers is ordered

13
Journal of Bio- and Tribo-Corrosion (2020) 6:53 Page 7 of 14  53

Table 2  IR bands and their assignments of the investigated polymer samples

Wave number ­(cm−1) Assignments [54]
PNHEANI P2ClANI PNHEANI-
co-
P2ClANI

515s 445s 616w Torsional oscillation of protonated ­NH3

580w 567m group and C–Cl
713w 755m 752s out of plane C–H deformation showing substitution in benzene ring
817s 821m 830m
881m 871m
1043m 1043s 1064s C–N stretching vibration plane deformation of CH aromatic or OH deformation (coupled) or NH deforma-
1153m 1106s – tion
1242m 1207s – CH2 stretching vibration
1312m 1294s 1293sh
1495s 1338s 1336s C–H aliphatic and/or C–N stretching vibration or combination bands of asymmetric bending and torsional
1473s 1449sh oscillation of the protonated amine group
1570s 1580s 1506s stretching vibration of C=C and/or C=N in the suggested polymer structure
– 1665s –
– 2376w 2339w C–N overtone stretching vibration, deformation of aliphatic C–H or NH
2374w
2977w 2925m 2930w
3020w 3067w 3069w Stretching vibration of C-H aromatic
3251s 3373b 3276b N–H stretching vibration
3674w – – Stretching vibration of intermolecular H-bond

as PNHEANI ≈ PNHEANI-co-P2ClANI > P2ClANI. The
presence of hydroxyl group in PNHEANI enhancen the abil-
ity of adsorption on the surface of steel by the co-ordination
bonding with vacant d-orbitals in the steel and lone pair of
electrons from the hydroxyl group [57, 58].
It is clear that as the concentration of the polymer
increases for the three tested polymers, the weight loss
decreases. This is attributed to the increase in the adsorp-
tion strength for the polymer through lone pair of electrons
and/or resonance with the steel surface by increasing its con-
centration [48–51].
3.2.2 Open‑Circuit Potential Measurements
Open-circuit potential of mild steel in the presence of
PNHEANI, P2ClANI, and PNHEANI-co-P2ClANI was
followed over 1 h in a stagnant naturally aerated in aqueous
acidic solution (1 M HCl) at 25 °C. The values of the steady-
state potentials were reached within 60 min for mild steel
electrode immersion in the blank solution and in different
concentrations of used polymer (10 ppm, 20 ppm, 50 ppm)
at pH 2. These data are presented in Fig. 7. The results show
that the presence of polymers shifts the steady-state poten-
tial to more positive values which indicate the presence of
a healing and passivation process [59]. This is attributed to
the lone pair of electrons on the heteroatoms such as O, N,
benzene ring, and/or multiple bonds. This increases well
coating adsorption to the steel surface with time giving pas-
sivation. Evidently, the most positive potential is obtained
also for this homopolymer PNHEANI indicating its high
passivity.
3.2.3 Electrochemical Polarization or the Corrosion Rates
Measurements on Mild Steel
The electrochemical behavior of mild steel in different con-
centrations (blank, 10 ppm, 20 ppm, 50 ppm) of the three
polymer samples at pH 2 was investigated under polarization
conditions, the linear polarization and Tafel extrapolation
techniques were used at a scan rate of 10 mV s−1. The poten-
tiodynamic polarization curves of different concentrations
for the prepared polymers (blank, 10 ppm, 20 ppm, 50 ppm)
after holding the mild steel electrode at the open-circuit
potential for 60 min in naturally aerated aqueous solution
of pH 2 are presented in Fig. 8. The corrosion parameter
potential Ecorr, corrosion current density icorr and corrosion
rate were calculated [60–63] and tabulated in Table 4.
From both Table 4 and Fig. 8 it is clear that corrosion
potential E corr shifted in negative direction in the pres-
ence of polymer samples. Both corrosion current density
i corr and corrosion rate measured after 60  min of mild
steel electrode immersion in the acidic solution of pH

13
53 
Page 8 of 14
Fig. 3  SEM pictures of the prepared polymeric samples
2 decrease with increasing polymer concentration up to
50 ppm; this indicates that the polymeric samples are good
corrosion inhibitors [42]. Also, the data reveal the order of
inhibition of these prepared polymers which is as follows:
PNHEANI ≈ PNHEANI-co-P2ClANI > P2ClANI.
This may be attributed to the resonance and/or the elec-
tron pairs on nitrogen and oxygen atoms that adsorbed well
on the alloy surface in PNHEANI [24]. However, chloride
atom in this homopolymer P2ClANI helps in alloy corro-
sion and the resonance and/or the electron pair on nitro-
gen help to protect the surface. However, it is not to the
same percentage of PNHEANI. However, the copolymer is
13
Journal of Bio- and Tribo-Corrosion (2020) 6:53
Fig. 4  XRD patterns of the prepared polymeric samples
better than this polymer P2ClANI but not like this polymer
PNHEANI due to the same reason for chloride atom.
Also, on comparing our results with others on corrosion
inhibition of mild steel, PNHEANI gives the best results of
lower corrosion current density (corrosion rate) than others
as shown in Table 5.
3.2.4 The Electrochemical Impedance Measurement:
The impedance spectra are recorded at the open-circuit
potential for mild steel in different concentrations of the
investigated polymers in naturally aerated acidic solutions of
pH 2. The obtained results of the impedance measurements
are illustrated in Figs. 9 and 10 in the form of Nyquist plot
(Fig. 9) and Bode plot (Fig. 10). The response of the system
in the Nyquist complex plane consists of one semicircle. The
time constant or diameter of the semicircle increased with
the increase of polymer concentration [24, 55, 65].
Figure 10 shows that a clear phase maximum is present
for mild steel electrode at the intermediate frequency. This
one time constant appears as a well-defined capacitive loop
in the intermediate frequency region of Nyquist presenta-
tion. The intermediate time constant is attributed to the
presence of a protective surface film. The impedance data
were evaluated using software provided with the impedance
Journal of Bio- and Tribo-Corrosion (2020) 6:53 Page 9 of 14  53

Fig. 6  Effect of polymer concentration on weight loss of steel in 1

molar HCl medium

polymer samples. This behavior was attributed to the pres-

ence of a passive film on the electrode surface.
Generally, PNHEANI is of the highest impedance value
owing to the lone pair of electrons on nitrogen or oxygen
plus the resonance [71–75]. However, the copolymer or the
polymer P2ClANI containing chloride atom aids in alloy
corrosion. So they are lower of impedance, however, the
copolymer is better than P2ClANI polymer owing to the
number of electron pairs on it is higher.
Fig. 5  TGA curves of the prepared polymeric samples

Table 3  Effect of polymer concentration on weight loss of mild steel 4 Conclusions

in 1.0 molar HCl medium
Conc. of polymer Wight loss per area (g cm−2) In the present work, a discussion of the method for synthe-
(ppm) sizing and characterization of two homopolymers poly(N-
PNHEA P2ClANI PNHEA-
co- 2-hydroxyethylaniline) (PNHEANI), poly(2-chloroaniline)
P2ClANI (P2ClANI), and a copolymer of Poly(N-2-hydroxyethyl-
aniline-co-2-chloroaniline) (PNHEANI-co-PClANI) has
0.0 0.00829 0.00829 0.00829
been done. A simple chemical oxidative polymerization
10 0.00153 0.00394 0.0056
method is used for the creation of all studied polymers.
50 0.00426 0.00285 0.00286
All created polymers are characterized by IR spec-
100 0.0047 0.0028 0.00369
troscopy, XRD, SEM, and TGA analysis. The obtained
200 0.0033 0.00226 0.00263
copolymer is more thermal stable than both PNHEANI
500 0.00131 0.00269 0.00647
and P2ClANI.
1000 0.001 0.00107 0.00197
The obtained polymeric samples are utilized as corro-
sion inhibitors for mild steel in acidic medium pH 2. The
efficiency for all of the created polymers is calculated from
system (Table 6), and fitted [66–70] according to the simple both impedance and polarization results. I.E % of these
equivalent circuit model and presented in Fig. 11. The value polymers is in the order of PNHEANIs ≈ PNHEANI-co-
of the charge transfers resistance increases in the presence of P2ClANI > P2ClANI. So, the polymers can be used indus-
trially in aggressive media owing to their stability.

13
53 
Page 10 of 14 Journal of Bio- and Tribo-Corrosion (2020) 6:53

0
P2ClANI

-1

-2
-2

logi/mA.cm
blanck
10ppm
-3 20ppm
50ppm
-4

-5

-800 -600 -400 -200 0

E/mV

-440 0
PNHEANI
-450 -1
PNHEANI
-460

2
-2

logi/mA.cm
blanck
-470
-3 10ppm
20ppm
-480 50ppm
E/mV

-4
blanck
-490
10ppm
-5
20ppm
-500
50ppm -800 -600 -400 -200 0 200 400

-510 E/mV

-520
0
0 10 20 30 40 50 60
PNHEANI-CO-P2CLANI
time/min
-1

-460 PNHEANI-co-P2ClANI
-2

-2
logi/mA.cm

-470 blanck
-3 10ppm
20ppm
-480
50ppm
-4
E/mV

-490
blanck -5
10ppm
-500
20ppm -800 -600 -400 -200 0 200 400
50ppm
E/mV
-510

-520 Fig. 8  Potentiodynamic polarization curves of mild steel in different

0 10 20 30 40 50 60 concentrations of polymer samples in stagnant naturally aerated aque-
time/min ous acidic solutions (pH 2) at 25 °C

Fig. 7  Variation of the potential of mild steel with time in different

concentrations of the prepared polymers in stagnant naturally aerated
aqueous acidic solutions (pH 2) at 25 °C

13
Journal of Bio- and Tribo-Corrosion (2020) 6:53 Page 11 of 14  53

Table 4  Corrosion parameters of mild steel after 60 min of the elec-

2.5
trode immersion in different concentrations of polymer samples in P2CIANI
stagnant naturally aerated aqueous acidic solutions (pH 2) at 25 °C
2.0
Polymer samples Corrosion parameters
Name Concen- Ecorr (mV) icorr Corro- η (%) 1.5
tration (mA cm−2) sion rate

2
Zi/ Ω.cm
ppm (mm y−1) 1.0

Blank 0 − 521.5 2.75 33.32 – blank

0.5
PNHEANI 10 − 520.3 1.07 12.97 61.09 10 ppm
20 ppm
20 − 541.6 0.80 9.69 70.91 50 ppm
0.0
50 − 533.6 0.83 9.98 69.82
P2ClANI 10 − 522.8 1.67 20.17 39.27 -0.5
20 − 519.3 1.56 18.87 43.27 0 1 2 3 4 5 6 7
2
50 − 523.5 1.21 14.62 56.00 Zr/Ω.cm
PNHEANI- 10 − 520.8 1.61 19.44 41.45
blank PNHEANI
co- 20 − 526.2 0.93 11.23 66.18 8
10 ppm
P2ClANI
50 − 532.5 0.86 10.42 68.73 20 ppm
50 ppm
6

2
Zi/ Ω.cm
Table 5  Comparison of our results with others on mild steel alloy 4

Inhibitor Concentration icorr (mA cm−2) References

Phenylephrine 1000 ppm 1.42 [48] 2

Polyaniline 3 (µM) 3.4 [64]

PNHEANI 50 ppm 0.83 This work 0
P2ClANI 50 ppm 1.21 This work
PNHEANI-co- 50 ppm 0.86 This work 0 2 4 6 8 10 12 14 16 18 20
P2ClANI Zr/Ω.cm
2

5
PNHEANI-CO-P2CLANI

3
2
Zi/ Ω.cm

1 blank
10 ppm
20 ppm
0
50 ppm

-1
0 2 4 6 8 10 12
2
Zr/Ω.cm

Fig. 9  Nyquist plots of mild steel in different concentrations the poly-

mers samples, in stagnant naturally aerated aqueous acidic solutions
(pH = 2) at 25 °C

13
53 
Page 12 of 14 Journal of Bio- and Tribo-Corrosion (2020) 6:53

Table 6  The equivalent circuit parameters of mild steel in different

800 P2CIANI -40
concentrations of the polymer samples recorded after 1 h of electrode
-30
immersion in stagnant naturally aerated acidic solutions (pH 2) at
600 steady-state potential at 25 °C
-20
400
Polymer samples Equivalent circuit parameters

phase/deg
2
logZ/Ω.cm

-10 Name Concentra- Rs (Ω cm2) Rp (Ω cm2) C (µF cm−2)

200 tion (ppm)
0

0 blank Blank 0.995 5.64 355.8

10
10 ppm PNHEANI 10 1.07 9.73 408.8
20 ppm
-200 50 ppm 20 20 1.05 18.27 348.2
50 1.42 10.42 241.2
-1 0 1 2 3 4 5

log f/Hz
P2ClANI 10 1.04 4.97 403.2
20 1.003 5.58 570.5
1400 -60
PNHEANI 50 1.197 5.50 456.8
1200 -50
PNHEANI- 10 0.963 5.09 393.9
1000 -40 co- 20 1.18 8.04 249.6
P2ClANI
800 -30 50 1.28 9.58 332.3
phase/deg
2
logZ/Ω.cm

600 -20

400 -10

200 0
blank
0 10 ppm 10
20 ppm
-200 50 ppm 20

-1 0 1 2 3 4 5

logf/Hz

1200 Fig. 11  Equivalent circuit model

PNHEANI-co-P2ClANI -50
1000
-40
800
-30 Compliance with Ethical Standards 
600
-20
2

phase/deg

Conflict of interest  The authors declare that they have no conflict of

logZ/Ω.cm

400
-10 interest.
200
0
blank
0 10 ppm
20 ppm
10 References
-200 50 ppm 20
1. Cai Z, Geng M, Tang Z (2004) Novel battery using conduct-
-1 0 1 2 3 4 5 ing polymers: polyindole and polyaniline as active materials. J
logf/Hz Mater Sci 39:4001–4003
2. Karami H, Mousavi M, Shamsipur M (2003) A new design
Fig. 10  Bode plots of mild steel in different concentrations of the pol- for dry polyaniline rechargeable batteries. J Power Sources
ymers samples, in stagnant naturally aerated aqueous acidic solutions 117:255–259
(pH = 2) at 25 °C 3. Grennan K, Killard A, Hanson C, Cafolla A, Smyth M (2006)
Optimisation and characterisation of biosensors based on poly-
aniline. Talanta 68:1591–1600
Acknowledgements  This work has been acknowledged by Cairo Uni- 4. Sengupta P, Barik S, Adhikari B (2006) Polyaniline as a gas-
versity and Chemical testing laboratories, Egyptian Organization for sensor material. Mater Manufact Process 21:263–270
Standardization & Quality (EOS), Cairo, Egypt. 5. Wang Y, Jing X (2005) Intrinsically conducting polymers for
electromagnetic interference shielding. Polym Adv Technol
16:344–351
Funding  This work was supported by the Beni-Suef University Pro-
6. Jing X, Wang Y, Zhang B (2005) Electrical conductivity and
jects Funding, Egypt.
electromagnetic interference shielding of polyaniline/poly-
acrylate composite coatings. J Appl Polym Sci 98:2149–2156
Data availability  The raw/processed data required to reproduce these 7. Morita M (1993) Multicolor electrochromic behavior of
findings cannot be shared at this time as the data also form part of an polyaniline composite films combined with polythiophene
ongoing study.

13
Journal of Bio- and Tribo-Corrosion (2020) 6:53 Page 13 of 14  53
and poly (3-methylthiophene) films. Die Makromol Chem
194:2361–2374
8. Srinivasan S, Pramanik P (1994) Ultraviolet-visible-near infra-
red spectral analysis of a chemically prepared W­ O3-polyaniline
composite. J Mater Chem Lett 13:365–368
9. Inzelt G, Pineri M, Schultze JW, Vorotyntsev MA (2000) Elec-
tron and proton conducting polymers: recent developments and
prospects. Electrochim Acta 45:2403–2421
10. Sexena V, Malhotra B (2003) Prospects of conducting polymers
in molecular electronics. Curr Appl Phys 3:293–305
11. Arulepp M, Permann L (2004) Influence of the solvent proper-
ties on the characteristics of a double layer capacitor. J Power
Sources 133:320–328
12. Mansouri J, Burford R (1994) Novel membranes from conduct-
ing polymers. J Membr Sci 87:23–34
13. Bereket G, Hur E, Sahin Y (2005) Electrochemical synthesis
and anti-corrosive properties of polyaniline, poly(2-anisidine),
and poly(aniline-co-2-anisidine) films on stainless steel. Prog
Org Coat 54:63–72
14. Herrasti P, Ocon P, Ibanez A, Fatas E (2003) Electroactive
polymer films for stainless steel corrosion protection. J Appl
Electrochem 33:533–540
15. Huerta-Vilca D, Siefert B, Moraes S, Pantoja M, Motheo A
(2004) Pani as prospective replacement of chromium conversion
coating in the protection of steels and aluminum alloys. J Mol
Cryst Liq Cryst 415:229–238
16. Shinde V, Sainkar S, Patil P (2005) Corrosion protective poly(o-
toluidine) coatings on copper. Corros Sci 47:1352–1369
17. Shinde V, Sainkar S, Patil P (2005) Electrochemical synthesis
and corrosion protection properties of poly(o-toluidine) coat-
ings on low carbon steel. J Appl Polym Sci 96:685–695
18. Zhang T, Zeng C (2005) Corrosion protection of 1Cr18Ni9Ti
stainless steel by polypyrrole coatings in HCl aqueous solution.
Electrochim Acta 50:4721–4727
19. Sathiyanarayanan S, Devi S, Venkatachari G (2006) Corrosion
protection of stainless steel by electropolymerised pani coating.
Prog Org Coat 56:114–119
20. Li Z, Hu J, Li Y, Zheng F, Liu J (2018) Self-healing active
anticorrosion coatings with polyaniline/cerium nitrate hollow
microspheres. Surf Coat Technol 341:64–70
21. Wang Y (2018) Preparation and application of polyaniline
nanofibers: an overview. Polym Int 67:650–669
22. El-Sherif AA, Shoukry MM, Hosny WM, Abd-Elmoghny MG
(2012) Complex formation equlibria of unusual seven coordi-
nate Fe(EDTA) complex with DNA constituents and related
bio-relevant ligands. J Solut Chem 41:813–827
23. Soliman AA, Amin MA, El-Sherif AA, Ozdemir S, Varlikli C,
Zafer C (2013) Synthesis and characterization of novel series of
Fe(II)-mixed ligand complexes involving 2,2′-bipyridyl ligand.
Dyes Pigm 99:1056–1064
24. Abd El-Lateef HM, Khalaf MM (2019) Novel dispersed ­Tl2O3–
SiO2/polyaniline nanocomposites: in-situ polymerization, char-
acterization and enforcement as a corrosion protective layer
for carbon-steel in acidic chloride medium. Colloids Surf A
573:95–111
25. Tammam RH, Fekry AM, Saleh MM (2016) Understanding dif-
ferent inhibition actions of surfactants for mild steel corrosion
in acid solution. Int J Electrochem Sci 11:1310–1326
26. Ameer MA, Fekry AM (2015) Corrosion inhibition by naturally
occurring Hibiscus sabdariffa plant extract on mild steel alloy
in HCl solution. Turk J Chem 39:1078–1088
27. Rohwerder M (2009) Conducting polymers for corrosion protec-
tion: a review. Int J Mater Res 100:1331–1342
28. Ren Y, Chen J, Zeng C (2010) Corrosion protection of type
304 stainless steel bipolar plates of proton-exchange membrane
fuel cells by doped polyaniline coating. J Power Sources
195:1914–1919
29. Ganash AA, Al-Nowaiser FM, Al-Thabaiti SA, Hermas AA
(2011) Comparison study for passivation of stainless steel by
coating with polyaniline from two different acids. Prog Org Coat
72:480–485
30. Lu H, Zhou Y, Vongehr S, Hu K, Meng X (2011) Electropolym-
erization of PANI coating in nitric acid for corrosion protection
of 430 SS. Synth Met 161:1368–1376
31. Ozyilmaz AT, Ozyilmaz G, Yigitoglu O (2010) Synthesis and
characterization of poly(aniline) and poly(o-anisidine) films in
sulphamic acid solution and their anticorrosion properties. Prog
Org Coat 67:28–37
32. Karpakam V, Kamaraj K, Sathiyanarayanan S, Venkatachari
G, Ramu S (2011) Electrosynthesis of polyaniline–molybdate
coating on steel and its corrosion protection performance. Elec-
trochim Acta 56:2165–2173
33. Kamaraj K, Karpakam V, Sathiyanarayanan S, Syed Azim S,
Venkatachari G (2011) Synthesis of tungstate doped polyaniline
and its usefulness in corrosion protective coatings. Electrochim
Acta 56:9262–9268
34. Yang X, Li B, Wang H, Hou B (2010) Anticorrosion perfor-
mance of polyaniline nanostructures on mild steel. Prog Org
Coat 69:267–271
35. Shinde VP, Patil PP (2012) Investigation on role of monomer(s)
during electrochemical polymerization of aniline and its deriva-
tives on low carbon steel by XPS. Electrochim Acta 78:483–494
36. Li Y, Zhang H, Wang X, Li J, Wang F (2011) Growth kinetics
of oxide films at the polyaniline/mild steel interface. Corros Sci
53:4044–4049
37. Chaudhari S, Patil PP (2011) Inhibition of nickel coated mild
steel corrosion by electrosynthesized polyaniline coatings. Elec-
trochim Acta 56:3049–3059
38. Rohwerder M, Isik-Uppenkamp S, Amarnath CA (2011) Appli-
cation of the Kelvin Probe method for screening the interfacial
reactivity of conducting polymer based coatings for corrosion
protection. Electrochim Acta 56:1889–1893
39. Abd-El-Nabey BA, Abdullatef OA, Salman RM (2018) Corro-
sion protection of steel by electropolymerization of o-chloro-
aniline and o-aminobenzoic acid in the presence of Tween 80
surfactant. Int J Corros Scale Inhib 7:62–77
40. Zhang C, Niu H, Zhang L, Bai X (2013) Preparation and elec-
trochemical properties of poly(p-chloroaniline). Adv Mater Res
634–638:1981–1984
41. Chaudhari S, Sainkar S, Patil P (2007) Anticorrosive proper-
ties of electrosynthesized poly (o-anisidine) coatings on copper
from aqueous salicylate medium. J Phys D 40(2):520–533
42. Pawar P, Sainkar S, Patil P (2007) Synthesis of poly(aniline-
co-o-toluidine) coatings and their corrosion-protection perfor-
mance on low-carbon steel. J Appl Polym Sci 103:1868–1878
43. Patil S, Sainkar S, Patil P (2004) Poly(o-anisidine) coatings on
copper: synthesis, characterization and evaluation of corrosion
protection performance. Appl Surf Sci 225:204–216
44. Wankhede M, Gangal S, Sainkar S, Patil P (2005) Electrochemi-
cal synthesis of poly(o-anisidine) coatings on low carbon steel
and evaluation of corrosion protection performance. Corros Eng
Sci Technol 40:121–128
45. Shinde V, Sainkar S, Patil P (2005) J. Electrochemical synthesis
and corrosion protection properties of poly(o-toluidine) coat-
ings on low carbon steel. Appl Polym Sci 96:685–695
46. Patil V, Sainkar S, Patil P (2003) Growth of poly(2,5-dimeth-
oxyaniline) coatings on low carbon steel. Synth Met 140:57–63
47. Shinde V, Chaudhari S, Sainkar S, Patil P (2003) Electrochemical
polymerization of 2,5-dimethylaniline on low carbon steel. Mater
Chem Phys 82:622–630
13
53 
Page 14 of 14
48. Bashir S, Thakur A, Lgaz H, Chung I-M, Kumar A (2019) Com-
putational and experimental studies on Phenylephrine as anti-
corrosion substance of mild steel in acidic medium. J Mol Liq
293:111539
49. Ebenso EE (2003) Synergistic effect of halide ions on the corro-
sion inhibition of aluminium in ­H2SO4 using 2-acetylphenothia-
zine. Mater Chem Phys 79:58–70
50. Ebenso EE (2003) Effect of halide ions on the corrosion inhibition
of mild steel in ­H2SO4 using methyl red—part 1. Bull Electrochem
19:209–213
51. El Ashry HE, El Nemr A, Esawy SA, Ragab S (2006) Corrosion
inhibitors: Part II: quantum chemical studies on the corrosion inhi-
bitions of steel in acidic medium by some triazole, oxadiazole and
thiadiazole derivatives. Electrochim Acta 51:3957–3962
52. Abd El-Salam HM, Askalany HG (2017) Synthesis and charac-
terization of crystalline poly(N-(2-hydroxyethyl)aniline) micro-
spheres. High Perform Polym 29:227–236
53. Sayyah SM, Abd El-Khalek AA, Bahgat AA, Abd El-Salam HM
(2001) Kinetic studies of the chemical polymerization of sub-
stituted aniline in aqueous solutions and characterization of the
polymer obtained Part 1. 3-Chloroaniline. Polym Int 50:197–206
54. Trchová M, Stejskal J (2011) Polyaniline: the infrared spectros-
copy of conducting polymer nanotubes (IUPAC technical report).
Pure Appl Chem 83:1803–1817
55. Gowraraju ND, Jagadeesan S, Ayyasamy K, Olasunkanmi LO,
Ebenso EE, Subramanian C (2017) Adsorption characteristics
of Iota-carrageenan and Inulin biopolymers as potential corro-
sion inhibitors at mild steel/sulphuric acid interface. J Mol Liq
232:9–19
56. Umorena SA, Eduok UM (2016) Application of carbohydrate
polymers as corrosion inhibitors for metal substrates in different
media. Carbohyd Polym 140:314–341
57. Shaban SM, Aiad I, El-Sukkary MM, Soliman EA, El-Awady MY
(2015) Evaluation of some cationic surfactants based on dimeth-
ylaminopropylamine as corrosion inhibitors. J Ind Eng Chem
21:1029–1038
58. Singh AK, Mohapatra S, Pani B (2016) Corrosion inhibition effect
of aloe vera gel: gravimetric and electrochemical study. J Indust
Eng Chem 33:288–297
59. Fekry AM, Gasser AA, Ameer MA (2010) corrosion protection
of mild steel by polyvinylsilsesquioxanes coatings in 3% NaCl
solution. J Appl Electrochem 40:739–747
60. Fekry AM, Ameer MA (2010) Corrosion inhibition of mild steel
in acidic media using newly synthesized heterocyclic organic mol-
ecules. Int J Hydrogen Energy 34:7641–7651
61. Ameer MA, Fekry AM (2011) Corrosion inhibition of mild steel
by natural product compound. Prog Org Coat 71:343–349
62. Ahmed RA, Fekry AM, Farghali RA (2013) A study of calcium
carbonate/multiwalled-carbon nanotubes/chitosan composite coat-
ings on Ti–6Al–4V alloy for orthopedic implants. Appl Surf Sci
285:309–316
63. Ameer MA, Fekry AM, Othman A (2014) Electrochemical inves-
tigation of green inhibitor adsorption on low-carbon steel in pro-
duced water. Int J Electrochem Sci 9(4):1964–1985
13
Journal of Bio- and Tribo-Corrosion (2020) 6:53
64. Raotole PP, Gaikawad AB, Patil PP (2006) Electrochemical
synthesis of corrosion protective polyaniline coatings on mild
steel from aqueous salicylate medium. Sci Technol Adv Mater
7:732–744
65. Shaban SM, Aiad I, El-Sukkary MM, Soliman EA, El-
Awady MY (2015) Surface and biological activity of
N-(((dimethoxybenzylidene)amino)propyl)-N, N-dimethylalkyl-
1-ammonium derivatives as cationic surfactants. J Mol Liq
207:256–265
66. Abo-Ezz ER, Essa KS (2016) A least-squares minimization
approach for model parameters estimate by using a new magnetic
anomaly formula. Pure Appl Geophys 173:1265–1278
67. Abdelrahman EM, Saber HS, Essa KS, Fouda MA (2004) A least-
squares approach to depth determination from numerical horizon-
tal self-potential gradients. Pure Appl Geophys 161:399–411
68. Abdelrahman EM, Abo-ezz ER, Essa KS, El-araby TM, Soliman
KS (2007) A new least-squares minimization approach to depth
and shape determination from magnetic data. Geophys Prospect
55:443–446
69. Abdelrahman EM, Essa KS (2005) Magnetic interpretation
using a least-squares, depth-shape curves method. Geophysics
70:L23–L30
70. Abdelrahman EM, Abo-Ezz ER, Essa KS, El-Araby TM, Soliman
KS (2006) A least-squares variance analysis method for shape and
depth estimation from gravity data. J Geophys Eng 3:143–153
71. El-Taib Heakal F, Fekry AM, Fatayerji M (2009) Electrochemical
behavior of AZ91D magnesium alloy in phosphate medium—part
II. Induced passivation. J Appl Electrochem 39:1633–1642
72. Ahmed RA, Farghali RA, Fekry AM (2012) Study for the sta-
bility and corrosion inhibition of electrophoretic deposited chi-
tosan on mild steel alloy in acidic medium. Int J Electrochem Sci
7(8):7270–7282
73. El-Taib Heakal F, Fekry AM, Fatayerji M (2009) Electrochemical
behavior of AZ91D magnesium alloy in phosphate medium—part
I. Effect of pH. J Appl Electrochem 39:583–591
74. Nasr A, Gawad SA, Fekry AM (2020) A sensor for monitoring
the corrosion behavior of orthopedic drug calcium hydrogen phos-
phate on a surgical 316L stainless steel alloy as implant. J Bio
Tribo Corros 6(2):36
75. Fekry AM, Azab SM (2020) The development of an innovative
nano-coating on the surgical 316 L SS implant and studying the
enhancement of corrosion resistance by electrochemical methods
using Ibandronate drug. Nano-Structures & Nano-Objects. https​
://doi.org/10.1016/j.nanos​o.2019.10041​1
Publisher’s Note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.