Cellulose (2020) 27:6425–6443

https://doi.org/10.1007/s10570-020-03239-x (0123456789().,-volV)
( 01234567
89().,-volV)

ORIGINAL RESEARCH

Vanillin modified chitosan as a new bio-inspired corrosion

inhibitor for carbon steel in oil-well acidizing relevant
to petroleum industry
M. A. Quraishi . K. R. Ansari . Dheeraj Singh Chauhan . Saviour A. Umoren .
M. A. J. Mazumder

Received: 17 December 2019 / Accepted: 14 May 2020 / Published online: 23 May 2020
Ó Springer Nature B.V. 2020

Abstract Due to strict environmental regulations,
the use of toxic chemicals as corrosion inhibitors for
the oil-well acidizing is restricted. Environmentally
benign Vanillin-modified chitosan (Van-Cht) is syn-
thesized using a microwave-induced green synthetic
protocol and thoroughly characterized by FTIR and
NMR spectroscopy. The inhibitor has been evaluated
for the first time for carbon steel in 15% HCl. The
corrosion inhibition performance was assayed using
weight loss and electrochemical methods comple-
mented with the surface analysis of the corroded
carbon steel samples without and with the inhibitor
immersed in the corrosive medium. Results obtained
showed that the Van-Cht acted by adsorption on the
surface of carbon steel to inhibit corrosion and
exhibited a mixed-type behavior with cathodic pre-
dominance. The adsorption of Van-Cht on the carbon
steel surface obeyed the Langmuir isotherm. The
excellent corrosion inhibition efficiency of [ 98%
observed at a concentration of 500 mg L-1. Surface
analysis using SEM and FTIR-ATR measurements
supported the adsorption of Van-Cht inhibitor on the
carbon steel surface. The pKa analysis proved that the
inhibitor Van-Cht exists mainly in the protonated form
at the experimental pH. The density functional theory
(DFT) analysis proved that the protonated form of the
Van-Cht inhibitor behaves better compared to that of
the Van and neutral Van-Cht.

Electronic supplementary material The online version of

this article (https://doi.org/10.1007/s10570-020-03239-x) con-
tains supplementary material, which is available to authorized
users.

M. A. Quraishi (&)  K. R. Ansari 

D. S. Chauhan (&)  S. A. Umoren
Center of Research Excellence in Corrosion, Research
Institute, King Fahd University of Petroleum and
Minerals, Dhahran 31261, Saudi Arabia
e-mail: mumtaz.quraishi@kfupm.edu.sa
D. S. Chauhan
e-mail: dheeraj.chauhan.rs.apc@itbhu.ac.in

M. A. J. Mazumder
Chemistry Department, King Fahd University of
Petroleum and Minerals, Dhahran 31261, Saudi Arabia

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Graphic abstract
Keywords Chitosan  Vanillin  Carbon steel  Acid
corrosion  Corrosion inhibition  Green corrosion
inhibitor
Introduction
The oil-well acidizing process is carried out in the oil
and gas industries for enhancing the oil recovery.
Generally, the process is carried out using a 15–28%
HCl solution, which is pumped into the wellbore to
dissolve the calcareous material, which facilitates the
flow of oil. In such a condition, severe corrosion of the
steel pipes takes place. Therefore, to protect the steel
surface against corrosion, inhibitors are mixed into the
acidic solution (Abdel Ghany et al. 2017; Cizek 1994;
Crowe et al. 1992; Frenier et al. 1988; Singh et al.
2020). In this context, the organic compounds having
heteroatoms are considered as the most effective
corrosion inhibitors (Chauhan et al. 2016, 2019a, b;
Fadil et al. 2018; Haque et al. 2017; Ituen et al.
2017, 2019a, b; Quraishi et al. 2020; Quraishi and
Jamal 2000; Quraishi et al. 2002; Singh et al. 2019a).
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Cellulose (2020) 27:6425–6443
Naturally occurring substances as inhibitors of corro-
sion during various industrial processes have received
considerable attention as an attractive and eco-friendly
replacement for synthetic organic inhibitors, which are
toxic and expensive. Besides, they are readily avail-
able and present a sustainable source of materials. A
review of the literature shows that several environ-
mentally benign molecules such as natural extracts
(Karthik et al. 2015; Krishnegowda et al. 2013; Li
et al. 2014; Verma et al. 2018), amino acids (Adam
et al. 2018; El-Lateef et al. 2015; Srivastava et al.
2017), and biopolymers utilized as inhibitors against
corrosion of active metals and their alloys. Biopoly-
mers such as starch (Bello et al. 2010), pectin (Fiori-
Bimbi et al. 2015; Umoren et al. 2015), Gum Arabic
(Azzaoui et al. 2017) have been reported to exhibit
appreciable corrosion inhibition behavior. However,
they suffer from poor solubility, which restricts their
practical applicability.
Chitosan obtained via the N-deacetylation of chitin,
which forms the exoskeleton of insects and marine
organisms (Dutta et al. 2004; Muzzarelli 1973;
Sashiwa and Aiba 2004). Chitosan-based corrosion
inhibitors have been particularly fascinating because
Cellulose (2020) 27:6425–6443
the higher molecular weight can afford significant
coverage of the metal surface (Chauhan et al.
2018a, b, 2019c, 2020; Cheng et al. 2007a; de Araújo
Macedo et al. 2019; El Mouaden et al. 2018; Mouaden
et al. 2020). The abundant availability of –OH and –
NH2 functional groups allow the immense potential
for the functionalization of chitosan with organic
molecules to yield superior corrosion inhibition
behavior (Cheng et al. 2007a; de Araújo Macedo
et al. 2019; El Mouaden et al. 2018). Schiff bases are
the nitrogen analogs of aldehydes or ketones, where
the azomethine (–C=N–) linkage replaces the –C=O
group. The low toxicity, ease of synthesis, and film-
forming ability encourage the use of Schiff bases as
inhibitors for corrosion of metals and alloys (Ansari
and Quraishi 2014; Ansari et al. 2014; Gupta et al.
2016; Haque et al. 2018; Singh and Quraishi 2016).
The Schiff bases of chitosan reported for antimicrobial
activity, metal complexation, and as catalysts in
organic synthesis.
Carbon steel is always favored as the primary
construction material for application in the oil and gas
industry due to its low cost and excellent mechanical
properties. However, its vulnerability against corro-
sion in severely acidic environments such as 5–15%
HCl solutions such as in oil-well acidizing process
poses a serious concern (Sastri 1998, 2012; Schmitt
1984). We have reported the chemical modification of
chitosan with several chemical modifiers and studied
the derivatives in corrosion inhibition of mild steel in
acid solutions (Chauhan et al. 2018a, b, 2019c). The
promising results prompted our quest to explore the
applicability of chemically modified chitosan on
carbon steel in 15% HCl. Therefore, herein, for the
first time, we have used vanillin functionalized
chitosan (Van-Cht) as an inhibitor for the corrosion
of carbon steel in 15% HCl.
The promising feature of the inhibitor is the facile
single-step synthesis of chitosan with vanillin, which
contains the –OH and the –OCH3 groups, both of
which have free lone pair electrons readily available
for adsorption on the steel surface. Further, the
chitosan and vanillin have LD50 values (oral, rat)
16,000 mg/kg and 3900 mg/kg, respectively, and
were used to synthesize the Van-Cht Schiff base in a
single-step reaction. This emphasizes the environ-
mentally benign nature and the cost-effectiveness of
the synthesized Schiff base. The prime novelty of the
work lies in the fact that this is the first report on the
6427
utilization of chemically modified chitosan as a
corrosion inhibitor in the oil-well acidizing environ-
ment. A comprehensive investigation involving
weight loss measurements and electrochemical anal-
ysis was carried out in the present work. Surface
analysis using SEM and FTIR techniques of the
corroded carbon steel specimens without and with the
inhibitor also reported in the present work.
Experimental
Synthesis of Van-Cht Schiff base
All the chemicals belonged to analytical grade and used
as received. Chitosan (Cht, the degree of deacetylation
85%, molecular weight 190,000 Da) and Vanillin (4-
hydroxy-3-methoxy benzaldehyde, Van) procured
from Sigma-Aldrich. The synthesis of the chitosan
Schiff base was carried out using a single step
microwave irradiation as described below. Briefly,
1 g glacial acetic acid mixed with 99 mL distilled water
followed by the addition of 3 g Cht and stirred. Vanillin
solubilized in 95% ethanol, and the solution was
introduced dropwise in 30 min to the Cht solution by
performing constant stirring at 303 K. The mixture was
irradiated at 60 °C for 15 min in a Sineo MASII
(Shanghai, China) microwave reactor (se-
lectable power: limit 1000 W, frequency:
2450 MHz). Acetone was used to precipitate the
resulting yellow gel of the Chitosan-Vanillin Schiff
base, followed by several steps of acetone washing. A
schematic of the synthesis of Van-Cht is given in Fig. 1
(Elshaarawy et al. 2016). The sample was subjected to
vacuum drying at 303 K and analyzed for purity using
thin-layer chromatography using 90% n-hexane/ethyl
acetate as mobile phase. The product was characterized
(for structure determination) using FTIR (Nicolet iS5),
and 1H NMR spectrum (Fig. S1) was measured using a
500 MHz NMR spectrometer (Bruker). IR (mmax/
cm-1): 3420 (–O–H), 1650 (–C=N–), 1520 (–C–C–),
1010 (–C–O–). 1H NMR (500 MHz): dH 1.63 (Ac–H),
3.48. (3H, –OMe), 6.63–7.10 (3H, Ph).
Weight loss studies
The weight loss studies were performed in a stagnant
aerated solution of 15% HCl without and with varying
concentrations of Van-Cht. The experiments
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Fig. 1 Schematic of the synthesis of Van-Cht Schiff base
were performed for an immersion time of 6 h. The
elemental composition of the carbon steel samples was
as follows (wt%): Fe 99.3; C 0.218; Si 0.0198; Mn
0.188; P 0.0091; S 0.0246; Ni 0.0256; Al 0.0456; Cu
0.0376; Cr 0.0189; Mo 0.0089. The carbon steel
samples were precisely weighed before and after
immersion to obtain the average weight loss values
utilized in calculating the corrosion rate (mm year-1)
as follows (Ansari et al. 2014; Chauhan et al. 2018a;
Srivastava et al. 2018):
87:6w
CR ¼
AtD
where w is the average weight loss (mg) recorded from
triplicate measurements, A is the surface area of the
steel sample (cm-2), t is the immersion time (h), D
denotes the carbon steel density (g cm-3), the value
87.6 is a factor used to obtain the CR in mm year-1.
The inhibition efficiency (g%) and the surface cover-
age (h) were obtained from the CR, using the following
expressions (Chauhan et al. 2018a; Haque et al. 2018;
Srivastava et al. 2018; Yadav et al. 2013):
CR  CRinh
g% ¼  100
CR
CR  CRinh
h¼
CR
where CR and CRinh represent the values of the
corrosion rate obtained without and in the presence
of Van-Cht, respectively.
Electrochemical corrosion tests
The electrochemical measurements were undertaken
using a Gamry Reference 3000 Potentiostat/Galvanos-
tat and Echem Analyst software suite for data analy-
sis. The working electrode was made up of a carbon
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Cellulose (2020) 27:6425–6443
steel sample having an exposed area of 1 cm2. A
saturated calomel electrode (SCE) and a cylindrical
graphite rod were employed as the reference and the
counter electrodes, respectively. The working elec-
trode was abraded using varying grades of emery
papers viz. 600–1200 to obtain a freshly abraded
surface before each experiment. Before each opera-
tion, the carbon steel electrode was immersed in the
test electrolyte of 15% HCl to attain a steady-state
open circuit potential (EOCP). Freshly prepared elec-
trolyte solution of 15% HCl was used for each
ð1Þ experiment. The electrochemical impedance spec-
troscopy (EIS) measurements were performed at EOCP
by applying a frequency range of 100 kHz–0.01 Hz at
10 mV amplitude. The experiments were carried out
in triplicate for validating the reproducibility. The
corrosion inhibition efficiency was evaluated using the
polarization resistance (RP) as shown below (Yadav
et al. 2010, 2013; Yadav and Quraishi 2012):
 inh 
RP  RP
gEIS ð%Þ ¼  100 ð4Þ
RP
where RP and Rinh P denote the polarization resistances
ð2Þ without and in the presence of Van-Cht, respectively.
The EFM measurement performed at 2.0 and 5.0 Hz at
a base frequency of 1.0 Hz and 10 mV amplitude. The
ð3Þ inhibition efficiency was calculated as follows:
 
icorr  iinh
corr
gEFM ð%Þ ¼  100 ð5Þ
icorr
where icorr and iinh
corr represent the corrosion current
density respectively obtained without and in the
presence of the inhibitor. Potentiodynamic polariza-
tion (PDP) studies were performed by scanning the
potential in the range ± 250 mV versus EOCP at a
sweep rate of 0.1 mV s-1. The anodic and the
cathodic branches of the PDP curves
Cellulose (2020) 27:6425–6443 6429

were extrapolated till the point of intersection for respectively as I = - EHOMO and A = - ELUMO. The
computing the corrosion potential (Ecorr), the corro- absolute electronegativity (v) and global hardness (g)
sion current density (icorr) and the corrosion inhibition of an inhibitor can be expressed as (Chauhan et al.
efficiency utilizing Eq. (6) (Yadav et al. 2010, 2013; 2018a; Chauhan et al. 2019c; Obot et al. 2015):
Yadav and Quraishi 2012): 1
  v ¼  ðELUMO þ EHOMO Þ ð7Þ
icorr  iinh
corr
2
gPDP ð%Þ ¼  100 ð6Þ
icorr 1
g ¼  ðELUMO  EHOMO Þ ð8Þ
where the symbols have the same meaning as 2
described above. and,

Surface studies 1
r¼ ð9Þ
g
The influence of the corrosive attack of the blank and where r denotes the global softness. The electrophilic-
the inhibited acid solutions on the steel surface was ity index x and its inverse, the nucleophilicity e can be
studied using a scanning electron microscope (SEM), expressed as (Dohare et al. 2017a, b; Gece 2008; Obot
Jeol Japan, having Model No. JSM-6610LV. For this et al. 2015):
purpose, the carbon steel samples were prepared to a
surface finish as described above and immersed in v2 1
x¼ ¼ ð10Þ
15% HCl without and containing 500 mg L-1 of Van- 4g e
Cht. After an immersion time of 6 h, the samples were
retrieved, dried, and subjected to SEM surface anal-
ysis. The inhibitor adsorption on the carbon steel
Results and discussion
surface was examined using FTIR spectroscopy by
employing a Nicolet iS5 instrument having an iD5
Weight loss studies
ATR.
Influence of inhibitor dosage
Computational studies
The weight loss measurements provide a simple yet
For predicting the possibility of protonation in the acid
effective means to analyze the effect of varying
solution, a study on speciation analysis was carried out
concentrations on the corrosion inhibition behavior of
in the pH range 0–14 using the Chemicalize-Instant
an inhibitor. The variation of the corrosion inhibition
Cheminformatics Solutions Suite (Southan and Stracz
efficiency upon adding the different strengths of Van-
2013; Swain 2012). The computational estimation of
Cht is displayed in Fig. 2a. It is revealed from Fig. 2a
the inhibitor adsorption was undertaken by analyzing
that the inhibition efficiency increases with concen-
the reactivity indices of the inhibitor applying the
trations of Van-Cht and reached up to 98.3% at a
Density functional theory based calculations. The
concentration of 500 mg L-1. This observation can be
basis set used was the 6–31G (d,p), and the B3LYP
ascribed to the coverage of the active sites available
was the correlation functional. The Gaussian 09
for the corrosive attack of the 15% HCl by the
program suite was used for carrying out the compu-
molecules of Van-Cht (Chauhan et al. 2018a; El-
tations. The influence of the aqueous solution was
Hajjaji et al. 2018; Haque et al. 2018; Srivastava et al.
modeled by applying the IEFPCM module in the
2018). Further increase in concentration did not
Gaussian software. The frontier molecular orbital
produce any significant increase in inhibition, and
energies were computed, and using them, the different
hence this was taken as the optimum concentration. In
reactivity indices were calculated. Following Koop-
other words, at this concentration, the Van-Cht
man’s theorem (Obot et al. 2015), EHOMO and ELUMO
molecules exhibited the optimum coverage of the
of a corrosion inhibitor can be correlated with the
steel surface. This behavior could arise due to the fact
ionization potential (I) and the electron affinity (A),
that, at this concentration, the number of adsorbed

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6430
Fig. 2 a Variation of corrosion inhibition efficiency with the concentration of Van-Cht as obtained from weight loss technique at
25 °C; b Plot of Langmuir isotherm for adsorption of Van-Cht on carbon steel in 15% HCl
corrosion inhibitor molecules reaches a critical value
followed by rearrangements on the metallic substrate
leading to no further increase in the inhibition
efficiency (Huang et al. 2017).
Adsorption parameters
The inhibition behavior of an organic corrosion
inhibitor molecule on a metal surface, especially in
the acid solution, can be understood by adsorption of
an inhibitor molecule on the target metallic surface.
The adsorption of a corrosion inhibitor on a metal
surface in a given corrosive environment is governed
by the nature of the metal and its surface charge, the
structure of the organic molecule, the charge distribu-
tion, and the quality of the surrounding aggressive
medium (El-Hajjaji et al. 2018). An adsorption
isotherm elucidates an understanding and interpreta-
tion of the interaction that takes place between the
molecules of the corrosion inhibitor and a corroding
metal surface (El-Hajjaji et al. 2018; Singh et al.
2016, b). To obtain more information on the adsorp-
tion of the Van-Cht on the carbon steel surface in the
15% HCl, the degree of surface coverage (h) data
incurred from the weight loss measurements were
fitted to several isotherms among which the best fit
observed in the case of Langmuir adsorption isotherm.
The Langmuir isotherm correlates the surface cover-
age of the inhibitor on a given metal surface (h) with
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Cellulose (2020) 27:6425–6443
the equilibrium constant of adsorption (Kads ) as
follows:
h=ð1  hÞ ¼ Kads Cinh ð11Þ
where Cinh denotes the inhibitor concentration in mg
L-1. Figure 2b shows the Langmuir adsorption
isotherm plot of C versus C/h for Van-Cht adsorption
on carbon steel in 15% HCl. The obtained plots are in
the form of straight lines with slope values close to
unity, which satisfies the criteria for the Langmuir
isotherm. The standard free energy of adsorption
DGoads can be correlated with Kads as follows:
DGoads ¼  RTln(1000Kads Þ ð12Þ
The value 1000 represents the concentration of
water (g L-1) (Chauhan et al. 2018b; Srivastava et al.
2018). The DGoads value for the adsorption of Van-Cht
is - 28.52 kJ mol-1. This indicates the existence of
physical as well as the chemical adsorption of Van-Cht
on the steel surface. The negative sign is indicative of
the spontaneity of the adsorption process.
Impedance measurements
Impedance spectroscopy (EIS) presents a non-destruc-
tive analytical means to obtain an understanding of the
corrosion inhibitor adsorption at the solid electrode
surfaces in the electrolytes. The EIS data can be
represented graphically as the Nyquist plots, which
Cellulose (2020) 27:6425–6443
show the variation of complex resistance (- Zim,
arising due to the presence of capacitors/inductors,
etc.) as a function of real resistance (Zreal, due to pure
resistors) in the circuits. The inhibitor Van-Cht
was added in increasing concentrations to the corro-
sive electrolyte of 15% HCl, and the obtained Nyquist
plots are shown in Fig. 3a in the absence and presence
of Van-Cht in varying concentrations. It revealed that
the Nyquist plots are characterized by the presence of
single depressed semicircles representing a single time
constant process for the blank and the inhibited
samples and a two-time constant process for the
inhibited samples at higher concentrations. The
appearance of the capacitive semicircles in the
absence and the presence of inhibitor Van-Cht having
their center lying below the real axis is a typical
behavior exhibited by solid metallic electrodes show-
ing frequency dispersion (Umoren et al. 2010). To
accurately model the frequency dispersion behavior in
such cases, a constant phase element (CPE) is
conventionally used instead of an ideal double-layer
capacitor (Chauhan et al. 2018a; Haque et al. 2018;
Singh et al. 2017; Srivastava et al. 2018; Yadav et al.
2013). The resistance corresponding to the CPE is the
polarization resistance (RP), which collectively repre-
sents the charge transfer resistance (Rct), and the
additional resistance contributions viz. the diffuse
layer resistance (Rd), and the resistance of other
accumulations (Ra) (Chauhan et al. 2018a; Singh et al.
2017; Srivastava et al. 2018). The impedance of the
CPE (ZCPE ) represented as:
ZCPE ¼ Y01 ðjxÞn ð13Þ
where Y0 is a proportionality coefficient, x denotes the
angular frequency (x ¼ 2pf which has units in rad
sec-1), and n symbolizes the phase shift.
The fitted Nyquist, Bode, and phase angle plots for
the steel surface without and in the presence of Van-
Cht shown in Fig. 3c, d. The electrical equivalent
circuit diagrams used for fitting the EIS data are
depicted in Fig. 3e, f. It can be observed from Fig. 3
that for the blank steel sample and the low concen-
trations of the inhibited samples, a modified Randle’s
circuit was used. However, the higher dosages of the
inhibitor (i.e. the 400 mg L-1 and 500 mg L-1)
resulted in the appearance of inductive loops at the
low-frequency ends of the Nyquist plots. The appear-
ance of the inductive behavior can be ascribed to the
6431
adsorption relaxation process of intermediates such as

Hþ ads and Clads on the electrode surface, exhibiting a
negative change in the surface coverage with potential
(Umoren et al. 2010). For fitting these data, a different
circuit was used comprising of an inductive element
(L) and the corresponding resistance (RL) as shown in
Fig. 3f (Singh et al. 2019b). The corrosion inhibition
efficiency was evaluated from the RP values using the
Eq. (4). The calculated electrochemical parameters
and the corrosion inhibition efficiency are shown in
Table 1. The fitness accuracy of the used equivalent
circuit diagrams is given by the low values of the
goodness of fit parameter (v2 ).
It can be observed from Fig. 3 that an increase in
the inhibitor concentration brings about a successive
increase in the Nyquist semicircle diameter, which
shows that the inhibitor adsorption at the metal/solu-
tion interface impedes the mass and charge transfer
processes taking place due to the corrosive electrodis-
solution (Umoren et al. 2010). The increase in the RP
values is joined by a concomitant decrease in the
values of the CPE constant and an increment in the
values of the n parameter. The double-layer between
the charged steel surface and the surrounding solution
of the electrolyte can be considered an electrical
capacitor. The Van-Cht inhibitor molecules adsorb on
the surface of the carbon steel and form a protective
film via replacement of the water molecules and other
ions that are already adsorbed on the metallic surface.
This can be attributed to the observed lowering in the
CPE values with an increase in the inhibitor concen-
tration (Sudheer and Quraishi 2013; Yadav et al.
2013). A closer look at Table 1 shows that in the
presence of the 500 mg L-1 concentration of Van-
Cht, the Rp values increased from 14.22 X cm2 in the
blank to 195.2 X cm2, which corresponds to a high
inhibition efficiency of 92.72%. This suggests that the
adsorption of the Van-Cht molecules created a kind of
barrier against the corrosion and dissolution of the
carbon steel, which supports the protective behavior of
the Van-Cht inhibitor. The Bode and the phase angle
curves for the carbon steel surface without and in the
presence of the different concentrations of Van-Cht
are displayed in Fig. 3b. The EIS spectra in the high-
frequency region can be associated with the uncom-
pensated electrolytic resistance (Gerengi et al. 2016;
Popova et al. 1996, 2003). After this, in the interme-
diate frequency region, linearity between the log |Z|
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6432 Cellulose (2020) 27:6425–6443

Fig. 3 a Nyquist and b Bode, phase plots obtained from EIS for plots obtained for carbon steel in the absence and the presence of
the adsorption of different concentrations of Van-Cht on carbon Van-Cht in 15% HCl e and f equivalent circuit models used to fit
steel surface in 15% HCl. Fitted c Nyquist and d Bode, phase the EIS data

123
Cellulose (2020) 27:6425–6443 6433

Table 1 Electrochemical EIS parameters for carbon steel in 15% HCl obtained at different concentrations of Van-Cht
Inhibitor concentration (mg L-1) Rs (X cm2) Y09 10-6 (S sn) RL (X cm2) RP (X cm2) n v29 10-3 g%

Blank 0.63 582.3 – 14.22 ± 0.80 0.76 3.35 –

100 1.81 126.6 – 41.72 ± 0.21 0.81 2.35 59.40
200 1.52 146.9 – 54.21 ± 0.27 0.85 1.92 71.86
300 0.94 80.52 – 106.4 ± 0.58 0.84 3.61 85.30
400 1.31 221.9 17.72 174.5 ± 1.18 0.88 0.83 91.85
500 1.63 142.9 44.38 195.2 ± 1.12 0.81 1.26 92.72

versus log f values are seen and a slope close to 0.9 and
a phase angle close to - 80° supporting the capacitive
behavior of the surface (Singh et al. 2017, 2019b). The
n values showed a successive increase with an increase
in the inhibitor concentration, supporting the improve-
ment in the capacitive behavior. The slope of the Bode
plots and the phase angle gradually approach towards
- 1° and - 90°, respectively, which can be attributed
to a retardation in the rate of steel dissolution and the
inhibited system and reflects the inhibitive behavior of
Van-Cht.
Electrochemical frequency modulation
where i symbolizes the instantaneous current density
obtained for the carbon steel electrode at a frequency
x and U0 is the amplitude. The electrochemical
intermodulation spectra observed for carbon steel
surface in 15% HCl without and in the presence of the
Van-Cht inhibitor are displayed in Fig. 4, and the
obtained kinetic parameters are shown in Table 2. The
corrosion current densities show a decreasing trend in
the presence of Van-Cht, and the inhibition efficien-
cies show a corresponding increase with an increase in
the inhibitor concentration. The values of the causality
factors are quite close to the theoretical values which
supports the validity of the obtained EFM data.

The EFM technique presents a non-destructive and Potentiodynamic measurements

highly sensitive electrochemical analysis tool that can
allow the electrochemical parameters to be obtained The polarization curves obtained for carbon steel in
directly, i.e., the corrosion current density (icorr), the 15% HCl without and containing the varying concen-
causality factors 2 and 3 and the calculated inhibition trations of Van-Cht at 25 °C are displayed in Fig. 5.
efficiency (Khaled 2008; Kuş and Mansfeld 2006). The obtained electrochemical parameters and the
The kinetic parameters can be obtained, as shown inhibition efficiency of the Van-Cht computed using
below (Khaled 2008; Onyeachu et al. 2019): Eq. (5) are given in Table 3. It is clear from the data
i2x that the adsorption of the increasing concentrations of
icorr ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð14Þ the Van-Cht molecules at the steel surface resulted in a
48ð2ix i3x  i2x Þ
decrease in the corrosion current density (icorr ) and an
ix U0 increase in the inhibition efficiency (gPDP ). This
ba ¼ pffiffiffiqffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi ð15Þ supports the adsorption of the Van-Cht molecules at
2i2x þ2 3 2ix i3x  i22x the steel/15% HCl interface.
The introduction of Van-Cht to the corrosive
ix U0 electrolyte of 15% HCl causes a considerable decrease
bc ¼ pffiffiffiqffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð16Þ
2 3 2ix i3x  i22x  2i2x in the corrosion current densities of both the anodic
and the cathodic electrochemical processes. It can be
ix2 x1 observed from Table 3 that the icorr value is decreased
Causality factor ð2Þ ¼ ¼ 2:0 ð17Þ to 77.3 lA cm-2 in the presence of 500 mg L-1 of
i2x1
Van-Cht compared to 1127.3 lA cm-2 in the blank
ix2 x1 solution. This resulted in a corrosion inhibition
Causality factor ð3Þ ¼ ¼ 3:0 ð18Þ
i3x1 efficiency of 93.14%. The adsorption of the inhibitor
Van-Cht produces a decrease in the values of the icorr

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6434 Cellulose (2020) 27:6425–6443

Fig. 4 Intermodulation spectra recorded for carbon steel immersed in 15% HCl solution in the absence and the presence of different
concentrations of Van-Cht at 25 °C

with an increase in the inhibition efficiencies, which as a barrier to restrict the processes of the mass and the
suggests the formation of a protective film which acts charge transfer taking place due to corrosion.

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Cellulose (2020) 27:6425–6443 6435

Table 2 Electrochemical Inhibitor concentration (mg L-1) icorr (lA cm-2) CF 2 CF 3 g%

EFM parameters obtained
for carbon steel in 15% HCl Blank 1586.3 2.073 3.157 –
without and with different
100 584.3 2.085 3.179 63.16
concentrations of Van-Cht
200 396.4 2.061 3.111 75.01
300 182.3 2.023 3.186 88.51
400 114.6 1.992 3.084 92.78
500 97.5 1.831 2.995 93.85

observation of Tables 1, 2 and 3 shows that the

inhibition efficiencies observed from the weight loss
method and the different electrochemical measure-
ments are in perfect agreement. Slight differences in
the quantitative values is observed, which is quite
common and within the acceptable range.

Surface studies

The surface characterization of the carbon steel

Fig. 5 Polarization curves obtained for carbon steel immersed
in 15% HCl in the absence and presence of different
concentrations of Van-Cht at 25 °C
It can be observed that the Ecorr value in the absence
of Van-Cht was - 393 mV, which shifted signifi-
cantly towards the negative direction and reached
- 441 mV at 500 mg L-1 concentration. The sup-
pression of the anodic, as well as the cathodic
corrosion current densities and a small cathodic shift
in the Ecorr value in the presence of Van-Cht, indicates
that the inhibitor exhibited a mixed type of behavior
with a cathodic predominance (Chauhan et al. 2018a;
Singh et al. 2017; Srivastava et al. 2018). A close
samples without and with the optimum concentration
of Van-Cht was undertaken using scanning electron
microscopy (SEM). Figure 6a shows the images
recorded using the scanning electron microscopy in
the absence and the presence of 500 mg L-1 Van-Cht.
The carbon steel surface in the absence of Van-Cht
shows several striations, cracks, and pits due to
significant corrosion damage due to the aggressive
acid attack of the 15% HCl. On the contrary, the
surface of the carbon steel in the presence of Van-Cht
shows a considerably smooth morphology indicating
the adsorption and the formation of a protective film of
the Van-Cht on the surface of carbon steel. The
significant improvement in the smoothness of the steel
surface without and containing the inhibitor indicates
an increase in the corrosion resistance.
The chemical composition of the surface of carbon
steel without and in the presence of Van-Cht was

Table 3 Polarization parameters for carbon steel in 15% HCl obtained at different concentrations of Van-Cht
Inhibitor concentration (mg L-1) icorr (lA cm-2) - Ecorr (mV/SCE) ba (mV/dec) - bc (mV/dec) g%

Blank 1127.3 393 67.1 141.1 –

100 499.7 407 72.1 164.2 55.65
200 385.4 403 66.4 182.4 65.82
300 176.8 417 68.3 172.4 84.31
400 110.1 427 79.1 169.4 90.24
500 77.3 441 77.3 173.4 93.14

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6436
Fig. 6 a Surface morphology (SEM) of carbon steel samples
after immersion in 15% HCl in the absence (blank) and the
presence of optimum concentration of Van-Cht (inhibited) for
recorded using the FTIR studies of the steel surface,
and the results for the pure and the inhibited sample in
the range of 4000–400 cm-1 are shown in Fig. 6b,
respectively. For comparison, the FTIR spectrum of
pure chitosan samples also shown in Fig. 6 (Chauhan
et al. 2018a; Fernandes Queiroz et al. 2015). For a
comparison with the FTIR spectrum of pure vanillin,
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Cellulose (2020) 27:6425–6443
6 h at 25 °C. b FTIR spectra of pure chitosan, Van-Cht, and film
of Van-Cht adsorbed steel surface after immersion in 15% HCl
for 6 h at 25 °C
readers can refer to the earlier report (Shekarforoush
et al. 2017). It can be observed that the spectrum of the
adsorbed sample displays similar characteristic fea-
tures as the pure Van-Cht molecule discussed above
(Experimental section). The characteristic absorbance
maxima of Van-Cht can be seen in the range of
3300–3400 cm-1, which corresponds to N–H stretch
Cellulose (2020) 27:6425–6443
(Fig. 6). Small peaks related to the (–HC=N–)
stretching in the field of 1598–1575 cm-1 can be
observed in the adsorbed sample. The slight shift in the
position of the above band in the adsorbed sample
in comparison to the pure Van-Cht sample with a
decrease in the intensity could indicate the involve-
ment of this group in the adsorption of the inhibitor on
the steel surface (Singh et al. 2019b). The disappear-
ance in the vibrations of the fingerprint region in the
FTIR and the shift in the other bands could be
attributed to the formation of the inhibitor-Fe complex
adsorbing on the carbon steel surface, as described
earlier (Li et al. 2012).
Computational studies
pKa calculations
An organic corrosion inhibitor, in an acidic environ-
ment, exhibits a high tendency of protonation. To
identify the most probable sites in a corrosion
inhibitor that are likely to get protonated, the pKa
calculations under a suitable pH range become critical.
In the present study, we performed the pKa analysis in
the pH range of 0–14 to find out the possible sites for
protonation. The results are shown in Fig. 7 and it can
be seen that the azomethine nitrogen –C=N– (pKa
3.37) shows a high tendency of undergoing protona-
tion in the experimental pH range. This indicates that
Fig. 7 Microspecies distribution of Van-Cht at different pH values
6437
at the pH values close to the experimental pH, the Van-
Cht molecule primarily exists in the protonated state.
DFT based estimation of the reactivity indices
As described earlier, this is the first report on the
synthesis and application of the Vanillin-Chitosan
Schiff base as a corrosion inhibitor for oil-well
acidizing. Earlier, a number of authors have used pure
chitosan as a corrosion inhibitor either alone or its
composites. Therefore, the effect of the chemical
functionalization of the chitosan on the tendency to
adsorb on the metal surface and exhibit the corrosion
inhibition behavior was analyzed. A comparative
study of the reactivity parameters of the vanillin,
Van-Cht, and Van-Cht (protonated) was performed,
and the results of the various theoretical parameters
obtained are given in Table 4. Figure 8 shows the
electron density distributions of the HOMO and the
LUMO of the vanillin, Van-Cht, and Van-Cht (proto-
nated). The corresponding structures of the protonated
form of the Van-Cht molecule based on the pKa
calculations is also shown in Fig. 8. The energy of the
highest occupied molecular orbital (EHOMO) and the
energy of the lowest unoccupied molecular orbital
(ELUMO) are the key parameters for estimation of the
adsorption tendency of an inhibitor molecule (El-
Hajjaji et al. 2018; Gece 2008; Geerlings et al. 2003;
Obot et al. 2015; Saady et al. 2018). From the results
shown in the Table, it can be seen that the EHOMO
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6438 Cellulose (2020) 27:6425–6443

Table 4 Computational analysis of the reactivity indices of the Vanillin, Van-Cht and Van-Cht protonated (all the energy values in
eV; r is in eV-1)
Component EHOMO ELUMO DE v g r x e

Vanillin - 6.0948 - 1.4618 4.63 3.78 2.32 0.43 1.54 0.65

Van-Cht - 4.9625 - 0.9143 4.04 2.94 2.02 0.49 1.07 0.94
Van-Cht (protonated) - 6.1329 - 2.8406 3.29 4.49 1.65 0.61 3.06 0.33

Fig. 8 Optimized geometrical structures and the frontier molecular orbital electron density distributions of a Van, b Van-Cht and
c Van-Cht (protonated)

value of the Van-Cht is higher compared to chitosan as
well as that of the Vanillin. This suggests that the
newly synthesized Schiff base exhibits the highest
tendency to donate the electrons to the metal surface.
In addition, the Van-Cht possesses the lowest value of
the molecular orbital energy gap (DE), which is
indicative of its highest reactivity.
Earlier it has been shown that the difference in the
electronegativity provides the driving force for the
electron transfer process to take place between two
molecules (Dohare et al. 2017a, b; Gece 2008; Obot
et al. 2015). The electron transfer process has to
overcome the barrier of the global hardness (g), which
acts as the resistance in the electron flow. The inverse
of the hardness, global softness (r), on the other hand,
indicates the likelihood of the electron transfer process
to take place. From the results displayed in the Table,
it can be observed that the electronegativity (v) value
was the highest in the case of Van-Cht compared to the
parent molecule vanillin. Also, the hardness value was

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Cellulose (2020) 27:6425–6443 6439

the lowest, and consequently, the softness was the

highest in the case of the Van-Cht, suggesting that this
molecule possesses a better tendency to undergo
adsorption on the metal surface.
As described earlier, the Van-Cht molecule is likely
to undergo protonation at the Nitrogen atom involved
in the azomethine linkage. Therefore, the computa-
tions were also carried out for the protonated form of
the inhibitor molecule. It is clear that, following
protonation, there is a clear cut lowering in the values
of the EHOMO as well as that of the ELUMO. The lower
values of ELUMO indicate an increase in the inclination
of the molecule towards gaining the electrons from the
metal surface. The molecular orbital energy gap shows
a noticeable decrease in the protonated inhibitor
compared to that in the neutral form of the inhibitor
molecule, showing an increase in the reactivity. The
lower value of chemical hardness in the protonated
inhibitor molecule and consequently, a greater soft- Fig. 9 Mechanism of adsorption and inhibition behavior of
ness value together suggest an improvement in the Van-Cht on carbon steel surface
adsorption behavior of the inhibitor molecule in the
3d-orbitals of Fe. The filled orbitals of the Fe surface
protonated form. The electrophilicity has increased
significantly and the nucleophilicity, on the other atoms could also back-donate the electrons to the
hand, shows a considerable decrease after protonation, inhibitor molecule via retrodonation. The FTIR stud-
ies support the existence of the Van-Cht molecule on
suggesting an increase in the tendency to gain
electrons from the metal surface. the steel surface, which indicates the adsorption and
inhibition behavior of Van-Cht on the steel surface.
The analysis of pKa and the DFT based reactivity
Mechanism of adsorption and inhibition
parameters together suggest that the inhibitor mainly
The inhibition of carbon steel corrosion in the reacts in the protonated form. This observation
supports the cathodic predominance observed in the
presence of Van-Cht takes place via adsorption as
elucidated by the experimental methods. An increase inhibitor molecule as observed in the PDP analyses.
in the polarization resistance noticeable in the EIS
Comparison with earlier reports
results upon the addition of the increasing inhibitor
dose indicates the adsorption of Van-Cht molecules on
the carbon steel surface (Umoren et al. 2010). A As stated above, the present investigation is the first
application of chemically modified chitosan against
decrease in the corrosion current densities of the
anodic and the cathodic currents observed by the the corrosion of the carbon steel surface in 15% HCl,
polarization studies suggest the inhibition of steel which presents a complex and aggressive medium. A
comparative analysis of the performance of the
corrosion (Umoren et al. 2010). The adsorption of
Van-Cht molecules on the steel surface and the chitosan-based corrosion inhibitors is displayed in
inhibition behavior is schematically shown in Fig. 9. Table 5 (Cheng et al. 2007b; El-Haddad 2013; El
The negatively charged chloride ions of the acid Mouaden et al. 2018; Gupta et al. 2018; Solomon et al.
solution are firstly adsorbed on the steel surface via 2017a, b; Srivastava et al. 2018). A cursory look of the
electrostatic attraction (physical adsorption) and Table reveals only three studies are available on
attract the protonated form of the inhibitor. The chitosan as a corrosion inhibitor in acidizing condi-
inhibitor molecules could also undergo direct chem- tions (Solomon et al. 2016, 2017a, b). Further, these
ical adsorption by donation of the free lone pair studies involve the different composites of chitosan
electrons present on the O and N-atoms to the vacant with AgNp where the primary role of the chitosan

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6440 Cellulose (2020) 27:6425–6443

Table 5 Comparative chart listing the performance of chitosan-based corrosion inhibitors

Inhibitor Metal/alloy; corrosive medium Techniques used g (%) References

Chitosan Copper; sulfide polluted synthetic EIS, PDP; SEM–EDX 85.49 El Mouaden et al.
seawater (2018)
Chitosan- Mild steel; 1 M HCl WL, EIS, PDP; AFM; DFT 89.40 Srivastava et al.
Polyethyleneglycol (2018)
Chitosan Copper; 0.5 M HCl WL, EIS, EFM, PDP; SEM; 93.00 El-Haddad (2013)
DFT
Chitosan ? KI St37 steel; 15% H2SO4 WL, EIS, DEIS, PDP; SEM– 97.68 Solomon et al.
EDX (2017a)
Chitosan-AgNPs St37 steel; 15% HCl EIS, DEIS, PDP; SEM–EDX, 84.68 Solomon et al. (2016)
AFM
Chitosan-AgNPs St37 steel; 15% H2SO4 EIS, DEIS, PDP; SEM–EDX, 94.98 Solomon et al.
AFM (2017b)
Carboxymethyl Mild steel; 1 M HCl WL, EIS, PDP; Mulliken 91.97 Cheng et al. (2007b)
chitosan ? Cu2? charges
Chitosan ? KI Mild steel; 1 M sulphamic acid WL, EIS, PDP; SEM, AFM 90.30 Gupta et al. (2018)
Vanillin-Chitosan Carbon steel; 15% HCl WL, EIS, PDP; AFM, FTIR 98.30 Present work

inhibitor becomes unclear, and the stability of the
nanomaterial, which is the principal active constituent
of the inhibitor formulation becomes ambiguous
(Solomon et al. 2016; Solomon et al. 2017b). There-
fore, from the obtained experimental results and the
comparative chart, it can be observed that the Van-Cht
shows considerable corrosion inhibition behavior
which supports its applicability as a novel environ-
ment-friendly corrosion inhibitor in the acidizing
environment on the carbon steel surface.
Conclusions
In the present work, a Schiff base of chitosan using
vanillin was synthesized using a facile single-step
reaction using microwave irradiation. The application
of the chemically modified biopolymer vanillin-
chitosan (Van-Cht) is reported for the first time for
carbon steel corrosion in 15% HCl. Based on the
results obtained, the following conclusions can be
drawn:
1. The Van-Cht acts by the adsorbing on the steel
surface and obeys the Langmuir isotherm showing
high Kads and DG0ads which shows a mixed-mode
of physical and chemical adsorption.
2. The Van-Cht showed an increase in the inhibition
efficiency with concentration and reached 98% at
500 mg L-1.
3. EIS studies show that inhibitor adsorbs on the steel
surface while exhibiting a charge transfer con-
trolled mechanism by the increase in polarization
resistance and decreasing the double-layer
capacitance.
4. Polarization studies showed a mixed mechanism
of adsorption with cathodic predominance.
5. SEM studies show that the adsorption of the
inhibitor on the steel surface causes a decrease in
the surface roughness of carbon steel. FTIR
studies supported the adsorption of the corrosion
inhibitor on the metal surface.
6. The pKa analysis showed that the inhibitor Van-
Cht exists primarily in the protonated form in the
corrosive solution of 15% HCl. The DFT based
quantum chemical parameters provided evidence
that the protonated form of the Van-Cht corrosion
inhibitor shows better adsorption performance
compared to that of the Van and Van-Cht.
Acknowledgments The authors express their gratitude for the
financial assistance received from the King Fahd University of
Petroleum and Minerals (KFUPM), Kingdom of Saudi Arabia
under the Deanship of Scientific Research (DSR) Project
DF181007. DSC and KRA are thankful to the KFUPM for the
Post-Doctoral research fellowships.

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Cellulose (2020) 27:6425–6443
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