Received: 22 August 2018

DOI: 10.1002/maco.201810501
| Accepted: 17 September 2018

ARTICLE

Chitosan as a green inhibitor for mild steel corrosion:

Thermodynamic and electrochemical evaluations

Taher Rabizadeh | Shahin Khameneh Asl

Faculty of Mechanical Engineering,

Department of Materials Engineering,
University of Tabriz, Tabriz 51666-16471,
Iran
Correspondence
Shahin Khameneh Asl, Faculty of
Mechanical Engineering, Department of
Materials Engineering, University of
Tabriz, Tabriz 51666-16471, Iran.
Email: khameneh@tabrizu.ac.ir
In this research, the effects of chitosan on the corrosion behavior of mild steel in 0.1 M
hydrochloric acid was investigated by different approaches. According to weight loss
measurements, increasing the concentration of chitosan from 0.3 to 1.8 mM,
significantly reduced the corrosion rate of mild steel, for example, from 95.5 ± 5 to
7.5 ± 5 mpy at 298 K. The thermodynamic calculations indicate an increase in the
corrosion activation energy and the enthalpy of activation when 1.8 mM chitosan was
added to the aggressive solution. The electrochemical polarization technique revealed
a decrease in corrosion current density which is compatible with the observed
increase in the charge transfer resistance measured by electrochemical impedance
spectroscopy. The EDS spectra confirmed the adsorption of chitosan on mild steel.
Analyzing the surface topography of the coupons by atomic force microscopy showed
a remarkable decrease in the corrosion rate of the specimens in the presence of
chitosan.

KEYWORDS
adsorption, AFM, chitosan, corrosion, EIS, inhibitor

1 | INTRODUCTION In addition, the post-reaction disposal of toxic industrial

Due to its availability and suitable physical properties, mild
steel is widely used in different industries such as oil and gas
where acid pickling, chemical cleaning, oil well acidification,
etc., is commonly performed.[1] However, this material
suffers from a major drawback which is insufficient corrosion
resistance in acidic solutions.[2] Therefore, the corrosion of
mild steel has been an academic and industrial concern and
has received a considerable amount of attention.
Among various methods to inhibit or reduce the corrosion
of metallic substrates, the addition of chemicals called
“corrosion inhibitors” is the most economical and efficient
way.[3] According to the literature, the effective corrosion
inhibitors such as pyrimidine, triazole, and pyrazole
derivatives are organic compounds with N, O, and S elements
in their complicated molecular structure.[4,5]
Materials and Corrosion. 2018;1–11. www.matcorr.com
corrosion inhibitors leads to pollution of the environment and
have jeopardizing consequences on ecosystem processes.[6]
For example, benzotriazole derivatives which are com-
monly used to inhibit the corrosion of heat exchangers, poison
the laboratory organisms and aquatic species even at very low
concentration of 3 ppm.[7]
Therefore, the concept of “Green Chemistry” was
proposed and the natural and biodegradable chemicals that
are not detrimental to our environment have become a recent
focus for preventing the corrosion of industrial facilities.[6] In
this regard, many types of green corrosion inhibitors (e.g.,
Equisetum arvense,[8] Alghel[9]) with high corrosion inhibi-
tion efficiency have been extracted from natural resources
such as plants.
Chitosan is an N-deacetylated natural cationic polymer
derived from chitin which is found in the crust and shells of
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim | 1
2
| RABIZADEH
crabs, lobster, or butterflies and in cell walls of fungi.[10]
Because of its biodegradability, biocompatibility, and
antibacterial activities, this polysaccharide polymer has
recently been a subject of many studies.[11] Some researchers
have demonstrated the potential application of chitosan in
different industries such as water treatment to remove heavy
metals from contaminated water[12]; pharmaceutical and
medical industries for orthopedic tissue-engineering[13];
surface industry to produce smart coatings for corrosion
protection,[14] etc.
For instance, self-healing chitosan-based coatings doped
with cerium nitrate were synthesized for corrosion protection
of aluminum alloy 2024.[15] High corrosion resistance for
mild steel was also reported when a nano-ZnO containing
chitosan layer was applied on substrates by sol–gel
method.[16] In addition, an electrochemically deposited
chitosan coating enhanced the corrosion resistance of mild
steel in 0.5 M H2SO4 solution.[17]
Although the anticorrosion performance of chitosan-
based coatings has been reported, a more in-depth analysis is
still required to elucidate the corrosion inhibition effects of
this biodegradable polymer when it is dissolved in hydro-
chloric acid. Besides, the exact mechanism by which chitosan
with high molecular weight decreases the corrosion rate of
mild steel is yet unclear.
To address these gaps in our knowledge, we reported here
the effects that chitosan has on the corrosion behavior of mild
steel in 0.1 M hydrochloric acid solution. A weight loss
method together with different analytical techniques such as
atomic force microscopy, potentiodynamic polarization, and
electrochemical impedance spectroscopy were utilized to
evaluate the role of chitosan with high molecular weight on
the corrosion resistance of mild steel. It was hypothesized that
considering its molecular structure, chitosan has potential to
be used as a green corrosion inhibitor.
2 | EXPERIMENTAL PROCEDURE
ST37 mild steel specimens with dimensions of
∼40 mm × ∼15 mm × ∼1.5 mm were cut from a steel sheet,
with the elemental composition of C: 0.15–0.2 wt.%; Si: 0.24 wt.
%; Mn: 0.2–0.5 wt.%; S: 0.06 wt.%; Fe: balance. Prior to all
experiments, each sample was carefully polished with SiC emery
papers (from grades #100 to #1200), degreased in acetone,
washed in distilled water, dried in air, and kept in a desiccator.
Chitosan with high molecular weight of ∼350 kDa and a
deacetylation degree of about 85% was purchased from
Sigma–Aldrich. The 0.1 M hydrochloric acid solution was
prepared by dilution of analytical grade hydrochloric acid
(37%; Sigma–Aldrich) with deionized water. To study the
corrosion inhibitory effects of chitosan, 0.3–1.8 mM of this
polymer was dissolved in 0.1 M hydrochloric acid solution.
AND KHAMENEH ASL
The weight loss measurements were conducted by
weighing the cleaned mild steel coupons before and after
immersion in 200 mL of 0.1 M hydrochloric acid
solutions in the presence and absence of chitosan for
24 h. Unless otherwise specified, the working temperature
was 298 K. After 24 h, the coupons were retrieved, washed
as outlined in ASTM G1-72, dried in acetone, and re-
weighed again.
The electrochemical corrosion tests were conducted in a
standard three electrode cell consisting of a platinum sheet, a
mild steel coupon, and a saturated calomel electrode (SCE) as
counter, working, and reference electrodes, respectively.
Potentiodynamic polarization measurements were
carried out using a potentiostat (model SP1, WonATech
Co., Ltd.) in the potential range of −0.5 to 0.5 V versus
open circuit potential (OCP) at the scan rate of 1 mV s−1.
Tafel extrapolation method was applied to each plot to
determine the electrochemical polarization parameters of the
specimens. The open circuit potential (OCP) was also
recorded for 3600 s prior to each electrochemical polarization
and impedance test.
The EIS measurements were performed at OCP in a
frequency range of 100 kHz–10 mHz with an applied AC
signal of 10 mV. Zview2 as an equivalent circuit simulation
program was used for data analysis, determining the
appropriate equivalent circuit and experimental data fitting.
The surface topography and the roughness average (Ra) of
the as-polished mild steel specimen and those retrieved from
the blank and chitosan-containing 0.1 M hydrochloric acid
solutions were examined using atomic force microscopy
(AFM; Nanosurf Flex). An AFM probe (BudgetSensors; Tap
190-Al-G) with a resonance frequency and time/line of
140 kHz and 780 ms were also utilized, respectively. The
scanning area in the images was 10 × 10 µm2.
In addition, the elemental composition of chitosan powder
and the tested steel specimens was determined using an
energy dispersive spectroscopy (EDS; Phenom proX,
Phenom-World BV, the Netherlands).
3 | RESULTS AND DISCUSSION
3.1 | Weight loss method
The effects of chitosan on the corrosion resistance of mild
steel in 0.1 M hydrochloric acid were evaluated by weight loss
method. The corrosion rate (CR) in mils per year (mpy), the
degree of surface coverage (θ) and the corrosion inhibition
efficiency (IE%) values in the absence and presence of
different concentrations of chitosan were calculated based on
the changes in the weight of the mild steel coupons immersed
in 0.1 M hydrochloric acid for 24 h at 298 K (Eqs. (1)–(3)).[18]
The results are depicted in Figure 1 and summarized in
Table 1.
RABIZADEH AND KHAMENEH ASL
| 3

TABLE 1 Calculated weight loss parameters for the corrosion of

mild steel in 0.1 M hydrochloric acid at 294 K in presence and
absence of chitosan
Concentration (mM) CR (mpy) IE % θ
0 95.5 ± 5 – –
0.3 33.8 ± 5 64.5 ± 3 0.645 ± 0.03
0.6 20.2 ± 5 78.8 ± 3 0.788 ± 0.03
1.2 13.6 ± 5 85.6 ± 3 0.856 ± 0.03
1.8 7.5 ± 5 92.1 ± 3 0.921 ± 0.03

were also investigated in the absence and presence of 1.8 mM

chitosan. The calculated data are summarized in Table 2.
As can be seen from Table 2 that in contrast to the positive
FIGURE 1 The effect of chitosan on the corrosion rate and the effects of concentration, increasing the temperature from 298
corrosion inhibition efficiency of mild steel in 0.1 M hydrochloric to 328 K had adverse influences on the corrosion inhibition
acid at 294 K performance of chitosan. In other words, increasing the
temperature dramatically increased the corrosion rate of mild
steel from 7.5 ± 5 to 51.4 ± 5 mpy which is probably due to
rapid etching, desorption and/or decomposition of inhibitor
Corrosion rate in mpy ¼ ðK  ΔW Þ=ðA  t  DÞ ð1Þ molecules at high temperatures.[5]
This is in accordance with many published reports in
CR0  CR
θ¼ ð2Þ which a decrease in the efficiency of organic inhibitors with
CR0 temperature was observed.[18]
Modifying the corrosion activation energy is another
IE% ¼ θ  100 ð3Þ
mechanism by which a corrosion inhibitor reduces the corrosion
rate of a metallic substrate.[20] In this regard, the Arrhenius
where K is a constant (3.35 × 106 for mpy), ΔW is the changes
equation (Eq. (4)) and the transition state equation (Eq. (5)) were
in the weight of the coupons in grams, A is the total surface
employed to calculate the thermodynamic parameters including
area in cm2, ρ is density of the specimens (7.8 g cm−3), t is the
corrosion activation energy (Eact), entropy of activation (ΔSact),
exposure time of the mild steel specimens (in this research:
and enthalpy of activation (ΔHact)[21]:
24 h), CR0 and CR are the corrosion rates in the absence and
presence of chitosan in mpy, respectively.  
Eact
It can be seen from Table 1 that the surface coverage, and CR ¼ Aexp  ð4Þ
RT
the corrosion inhibition efficiency of chitosan are directly
dependent on the concentration of the biopolymer dissolved  
RT ΔSact ΔH act
in the aggressive solution. That means, at constant tempera- CR ¼ expð Þexp  ð5Þ
Nh R RT
ture of 298 K, further dissolution of chitosan (from 0.3 to
1.8 mM) increased both the surface coverage and the
where A is frequency factor, R is the universal gas constant, T
corrosion inhibition efficiency from 0.645 to 0.921 and
is the experimental temperature in Kelvin, N is the Avogadro's
from 64.5 to 92.1%, respectively. Whereas, the corrosion rate
constant, and h is the Plank's constant.
of the tested coupons decreased from 95.5 mpy in the absence
of inhibitor to 7.5 mpy in the presence of 1.8 mM of chitosan
which is attributed to the adsorption of chitosan on the surface TABLE 2 Results of the weight loss measurements related to
of the mild steel samples. This is in agreement with de Souza the corrosion of mild steel in 0.1 M hydrochloric acid at different
et al., who observed a decrease in the active corroding areas of temperatures in presence of 1.8 mM chitosan
the mild steel coupons due to the surface adsorption of an Temperature CRblank CRchit
organic molecule (geometric blocking effect).[19] (K) (mpy) (mpy) θchit IEchit%
298 95.5 7.5 0.921 92.1
3.2 | Thermodynamic analysis 308 110.5 16.2 0.85 85.3
318 137 31.5 0.77 77
The effects of temperature on the corrosion rate, surface
328 156 51.4 0.67 67
coverage, and the corrosion inhibition efficiency of chitosan
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| RABIZADEH AND KHAMENEH ASL

FIGURE 2 (a) [ln CR vs. (1/T)] and (b) [ln (CR/T) vs. 1/T] plots related to the corrosion of mild steel in 0.1 M hydrochloric acid in the
absence and presence of 1.8 mM chitosan.

The activation energy (Eact) related to the corrosion of 3.3 | Adsorption isotherms
mild steel in 0.1 M hydrochloric acid in the absence and
In order to broaden our knowledge of the chitosan/mild steel
presence of 1.8 mM chitosan was calculated from the slope
interactions and to determine the mechanisms by which
(−Eact/R) of the linear [ln CR vs. 1/T] plots (Figure 2a).
chitosan inhibited the corrosion of mild steel, the results from
Besides, considering Eq. (5) the ΔHact and ΔSact values were
the weight loss experiments were analyzed by Langmuir
determined from the slopes (−ΔHact/R) and the intercepts ([ln
adsorption isotherm with the following equation[28]:
(R/Nh) + (ΔSact/R)] of the linear [ln (CR/T) vs. 1/T] plots,
respectively (Figure 2b). The obtained parameters are given
C 1
in Table 3. ¼ þC ð6Þ
θ kads
The computed Eact in the presence of 1.8 mM chitosan
was higher than that of in the additive-free solution
where C shows the concentration of the inhibitor in the
(13.7 kJ mol−1 vs. 52.3 kJ mol−1) which is due to an increase
solution, θ is the surface coverage, Kads is the adsorption–
in the double layer thickness because of the surface adsorption
desorption equilibrium constant.
of chitosan.[22]
It can be seen from Figure 3 that the experimental data
Furthermore, the addition of corrosion inhibitor increased
were best fitted to the Langmuir isotherm (R2 = 0.999)
the enthalpy of activation from 11.1 kJ mol−1 in the blank
confirming that the adsorption of chitosan on mild steel in
solution to 49.7 kJ mol−1 in the 1.8 mM chitosan-containing
0.1 M hydrochloric acid followed the Langmuir adsorption
solution demonstrating an increase in the amount of energy
isotherm according to which the adsorbed chitosan molecules
required to achieve the activated state.[23] Moreover, the
positive sign of ΔHact in both cases reflects an endothermic
nature of the corrosion of mild steel in 0.1 M hydrochloric
acid solution.[24]
The ΔSact in the blank solution was negative and tended to
become more positive when 1.8 mM chitosan was dissolved
in the aggressive solution indicating a decrease in disorder
during the inhibition process (Table 3).[25] The observed
increase in entropy was also due to the replacement of water
molecules present on the surface of the specimen with the
adsorbed chitosan molecules.[26] This observation is in
accordance with the findings of other researchers.[27]

TABLE 3 Thermodynamic parameters calculated for the corrosion

of mild steel in 0.1 M hydrochloric acid in the presence and absence of
1.8 mM chitosan
Ea ΔHact ΔSact
Concentration (kJ mol−1) (kJ mol−1) (J mol−1)
Blank 13.7 11.1 −170.1 FIGURE 3 Graph of the Langmuir isotherm study calculated for
the adsorption of chitosan on the mild steel specimens in 0.1 M
1.8 mM 52.3 49.7 −61.1
hydrochloric acid at 298 K
RABIZADEH AND KHAMENEH ASL
were supposed not to interact with each other. Moreover,
Langmuir adsorption isotherm suggests the formation of a
monolayer of inhibitor molecules on an adsorbent surface.[29]
By
using Eq. (7), the Gibbs free energy of adsorption
ΔG°ads which gives a clear indication of the adsorption
process was calculated to be −31.4 KJ mol−1.[28]
ΔG°ads ¼  RTlnðkads  Csolvent Þ ð7Þ
where Kads is the equilibrium constant of the adsorption
process, Csolvent represents the molar concentration of the
solvent (55.5 in mol L−1 for water), R is the gas constant, and
T is the experimental temperature in Kelvin.
The negative sign of the obtained ΔG°ads implies the
spontaneous adsorption of the chitosan molecules and the
stability of them on the surface of the tested coupons.[30]
In general, the ΔG°ads values less than −20 kJ mol−1 or
higher than −40 kJ mol−1 represent the physisorption or
chemisorption of an inhibitor, respectively. However, if the
corresponding values are between −20 and −40 kJ mol−1,
both physisorption and chemisorption are contributed in the
adsorption process.[31]
In this study, the ΔG°ads value was −31.4 KJ mol−1
pointing out the occurrence of both types of adsorption (i.e.,
physisorption and chemisorption) during the corrosion
inhibition of mild steel.
3.4 | Electrochemical measurements
The open circuit potential of the working electrodes immersed
in 0.1 M hydrochloric acid solution without and with different
concentrations of chitosan was recorded for 3600 s (Figure 4).
During the first 100 s, the OCP in the blank solution increased
FIGURE 4 Time variation of open circuit potential related to the
corrosion of mild steel in 0.1 M hydrochloric acid without and with
different concentrations of chitosan at 298 K
| 5
abruptly from −572 to −563 mV. Thereafter, the correspond-
ing plot continued to increase gradually until it reached the
OCP of −556 mV after 60 min. According to Umeron et al.,
the increase in the OCP of mild steel in 0.1 M hydrochloric
acid is because of the corrosion of the specimen.[32]
However, in the presence of 0.3, 0.6, 1.2, and 1.8 mM
chitosan, the OCP of mild steel shifted toward the positive
direction so that the end-OCP values of −540, −532, −522,
−506 mV were recorded, respectively. This indicates the
adsorption of chitosan on the mild steel specimens which
resulted in the surface coverage of the substrates by this
biopolymer.[33]
It is worth mentioning that when chitosan was dissolved in
0.1 M hydrochloric acid solution, the OCP graphs had
different development trends than that of recorded for the
blank solution. For example, with 0.3 mM chitosan and during
the first 1000 s, the OCP increased from the initial value of
−562 to −542 mV. From this point, the OCP plot started to
level off and stayed almost constant for the next 2600 s.
However, by increasing the concentration of chitosan less time
was required for the OCP graphs to reach plateau (e.g., 300 s
for 1.8 mM chitosan) which can be attributed to the quicker
surface adsorption of chitosan at higher additive concen-
trations. An increase in the OCP of mild steel in the presence of
other organic inhibitors was also noticed previously.[34]
In order to obtain more details on the corrosion inhibition
performance of chitosan, the potentiodynamic polarization
technique was employed (Figure 5). The electrochemical
corrosion parameters including corrosion potential, corrosion
current density, and Tafel slopes were calculated and
summarized in Table 4. These parameters were obtained
from the extrapolation of the anodic and the cathodic Tafel
lines located next to the linearized current regions.
FIGURE 5 Electrochemical polarization curves for the corrosion
of mild steel in 0.1 M hydrochloric acid with and without various
concentrations of chitosan
6
| RABIZADEH AND KHAMENEH ASL

TABLE 4 Calculated corrosion parameters for the corrosion of mild steel coupons in 0.1 M hydrochloric acid without and with different
concentrations of chitosan
Concentration Ecorr (mV vs. SCE) Icorr (μA cm−2) βa (mV dec−1) −βC (mV dec−1) Rpol (Ω cm2)
Blank −545.5 156.54 55.5 59.28 79.5
0.3 mM −530.2 73.9 33 52 118.6
0.6 mM −523.6 62.2 35.6 49.8 144.9
1.2 mM −508.1 23.5 33 53 375.7
1.8 mM −491.4 11.2 35.3 44.8 765.4

The electrochemical polarization resistance for each plot The effects of chitosan on the corrosion resistance of mild
was also calculated using Eq. (8) where βa and βc are the steel at 298 K were further assessed by electrochemical
anodic and cathodic slopes, respectively.[35] impedance spectroscopy which gives accurate mechanistic
information on the metal–electrolyte interface. The EIS data
βa  βc are presented as Nyquist (Figure 6) and Bode phase angle
RPol ¼ ð8Þ
2:303  icorr  ðβa þ βc Þ plots (Figures 7a and 7b).
As can be seen from Figure 6, in the absence and presence
According to the results, the corrosion current density in the of chitosan, the Nyquist plots were composed of a single
inhibitor-free 0.1 M hydrochloric acid solution was semicircle at high frequencies and a “pseudo-inductive” loop
156.54 μA cm−2. Whereas a dramatically decrease in icorr at low frequencies. In addition, it is obvious that the
was measured when different concentrations of chitosan were dissolution of chitosan increased the diameter of the
added to the aggressive solution. For example, by increasing the capacitive loop indicating an increase in the impedance of
concentration of chitosan from 0.3 to 1.8 mM, the icorr decreased the inhibited substrates in the presence of the corrosion
from 73.9 to 11.2 μA cm−2 indicating the positive effects of inhibitor.[41] Moreover, by further increasing the concentra-
chitosan on the corrosion resistance of the working electrodes. tion of chitosan from 0.3 to 1.8 mM, the diameter of the
This was further confirmed by the shift in the corrosion plotted semicircles increased denoting the concentration
potential where the Ecorr in the presence of 1.8 mM chitosan dependence of the corrosion inhibition process. This also
was −491.4 mV, about 13% higher than the corresponding correlates with the calculated potentiodynamic polarization
value in the additive-free system (Ecorr = −545.5 mV). parameters (Figure 5).
It has been suggested that a corrosion inhibitor affects the Although, it is well-documented that the occurrence of a
anodic and/or cathodic reactions involved in the corrosion capacitive loop is related to the charge transfer resistance, the
process.[36] Furthermore, according to the previously pub- reasons for the observed pseudo-inductive loop at low
lished documents if the displacements in corrosion potential
in the absence and presence of a corrosion inhibitor is less
than 85 mV, the inhibitors can be considered as a mixed type
inhibitor. Otherwise, it will be classified as an anodic or a
cathodic type.[37] In this research, the maximum displacement
of Ecorr was 54 mV toward the anodic region indicating the
mixed type behavior of chitosan with an anodic tendency.
Similarly, the shift in Ecorr toward an anodic region has
previously been recorded for other organic inhibitors.[38]
However, in some cases a shift toward the cathodic direction
was reported. For instance, when chitosan was used to
decrease the corrosion of copper and mild steel specimens in
0.5 M hydrochloric acid solution[39] and 1 M sulfamic
acid,[40] respectively.
In addition, according to the calculated Tafel slopes, a six
times increase in the inhibitor concentration (from 0.3 to
1.8 mM) enhanced the polarization resistance (Rpol) from
79.5 Ω cm2 in the blank solution to 765.4 Ω cm2 in the FIGURE 6 Nyquist plots for mild steel samples measured in
presence of 1.8 mM chitosan further confirming the anticor- 0.1 M hydrochloric acid solution without and with various
rosion behavior of chitosan. concentrations of chitosan at 298 K
RABIZADEH AND KHAMENEH ASL
FIGURE 7 Variations in (a) Bode curves and (b) phase angles related to the corrosion of mild steel specimens in 0.1 M hydrochloric acid
without and with different concentrations of chitosan at 298 K
frequencies is still under debate. It has been attributed to the
accumulation of corrosion products on the surface of the
corroding electrode,[42] nonlinearity in the frequency re-
sponse,[43] relaxation of the adsorbed charged species such as

Hþads , Clads , inhibitor species on the working electrode.
[41]
It is common to use an electrical equivalent circuit to
analyze the EIS data. Therefore, in this research, a circuit with
a configuration similar to the previously proposed ones was
employed.[21] In this circuit (Figure 8), Rs and Rct are the
solution resistance between the SCE and the working
electrodes and the charge-transfer resistance at the metal/
electrolyte interface, respectively. Rct also represents the
capacitive semicircle diameter and has an inverse proportion-
ality with the corrosion rate of the working electrode.[44]
Ideally, Cdl is used to display the capacitance of a double
layer formed at the interface between a metallic substrate and
the electrolyte. However, because of the surface roughness,
surface inhomogeneity and the surface adsorption phenom-
ena, there is a deviation from an ideal capacitive condition.[45]
Therefore, in this research CPE (constant phase element) is
considered instead of Cdl. CPE-T and n are also the two
characteristic parameters of a CPE element (Eq. (9))[46]:
Z CPE ¼ T 1 ðjωÞn ð9Þ
in which ω shows the angular frequency (rad s−1), T indicates the
magnitude of CPE (Ω−1 Sn cm−2), j = (−1)1/2 is the imaginary
FIGURE 8 Equivalent circuit used to fit the EIS plots related to
the corrosion of mild steel samples in 0.1 hydrochloric acid solution
without and with chitosan
| 7
number, ω = 2πf, where f is the frequency (Hz), and n is an
empirical exponent (0 ≤ n ≤ 1) signifying the deviation from the
ideal capacitive behavior.[47] L and RL are the inductance
(H cm2) and the inductive resistance (Ω cm2), respectively.
Here, it is worth noting that in some publications despite
the occurrence of an inductive loop at low frequencies, the
inductance element was not considered in the proposed
electrical equivalent circuit and just the variations in the
diameter of the capacitive arc was discussed.[48]
According to Table 5, the Rct value in the blank testing
solution was 88.55 Ω cm2. However, raising the concentra-
tion of chitosan in the solution from 0.3 to 1.8 mM increased
the charge transfer resistance at the metal/solution interface
from 259.8 to 973.9 Ω cm2 representing the significant
corrosion inhibition in the presence of chitosan.
In addition, due to the adsorption of chitosan molecules on
mild steel which increased the thickness of the electrical
double layer by forming a protective layer,[49] the CPE-T
decreased dramatically from ∼22.41 × 10−5 Ω−1 Sn cm−2
calculated for the uninhibited mild steel to for example
∼4.04 × 10−5 Ω−1 Sn cm−2 when 1.8 mM chitosan was dis-
solved in 0.1 M hydrochloric acid solution.
The n values also increased from 0.86 in the absence of
inhibitor to 0.9 in the presence of 1.8 mM chitosan implying a
decrease in the surface heterogeneity of the specimens
probably because of the adsorption of the inhibitor molecules.
Furthermore, by increasing the concentration of chitosan
from 0.3 to 1.8 mM, the L and RL values increased from 9084
to 39 678 H cm2 and 2111 to 8500 Ω cm2, respectively,
illustrating the adsorption of chitosan on the working
electrodes. An increase in the L and RL values as a function
of an inhibitor concentration has also been reported by
others.[50] In contrast to the additive-containing systems, in
the chitosan-free solution, the calculated L = 1064 H cm2 and
RL = 937 Ω cm2 values were obtained which was attributed to
the accumulation of corrosion products on the surface of the
mild steel coupon.
8
| RABIZADEH AND KHAMENEH ASL

TABLE 5 Electrochemical parameters obtained from EIS data of mild steel specimens in 0.1 M hydrochloric acid solution in the absence and
presence of different concentrations of chitosan
Rs (Ω cm2) CPE-T (Ω−1 Sn cm−2) n Rct (Ω cm2) L (H cm2) RL (Ω cm2)
−5
Blank 10.64 22.41 × 10 0.86 88.55 1064 937
−5
3 mM 10.51 11.25 × 10 0.86 259.8 9084 2111
6 mM 10.55 8.38 × 10−5 0.87 400.2 11 941 2386
−5
12 mM 10.60 5.59 × 10 0.88 771.2 22 873 5752
−5
18 mM 10.68 4.04 × 10 0.90 973.9 39 678 8500

In Bode plots (Figure 7a), the impedance modulus at the
lowest measured frequency (most commonly log f =–2 Hz)
represents the corrosion inhibition efficiency of an inhibi-
tor.[21] In our experiments the presence of 1.8 mM of
chitosan yielded the highest impedance modulus compared
to the additive-free system. One phase peak at high
frequency (log f = −2) and a valley at low frequency (about
log f = −1.5) in phase angle plots (Figure 7b) also confirm
the presence of two time constants related to capacitive loop
and inductive loop in Nyquist plots. In addition, by
increasing the concentration of casein, the phase angle
curves moved upward to larger values indicating the
adhesion of more inhibitor molecules to the working
electrodes which made them more homogeneous.[51]
3.5 | Surface characterization
3.5.1 | AFM
The surface topography of the as-polished specimen and those
immersed in 0.1 M hydrochloric acid solutions without and
with 1.8 mM chitosan for 24 h at 298 K was assessed by
atomic force microscopy. The AFM images and the
corresponding height profiles are given in Figure 9.

FIGURE 9 AFM surface topography of the mild steel samples: (a) as-polished sample; (b) after 24 h immersion in 0.1 M hydrochloric acid
solution at 298 K in the absence and (c) in the presence of 1.8 mM chitosan; (d) Height profiles of these samples
RABIZADEH AND KHAMENEH ASL
| 9

FIGURE 10 EDS spectra of (a) chitosan powder; (b) mild steel immersed in 0.1 M hydrochloric acid solution; (c) mild steel immersed in the
corrosive solution containing 1.8 mM chitosan

According to the 3D images, the as-polished sample had a
smooth surface with minor scratches related to the sample
preparation procedure. The height profile of this sample showed
small fluctuations in the range of about 40 nm. However, in the
chitosan-free 0.1 M hydrochloric acid solution, the mild steel
sample were severely corroded. Thus, the high corrosion rate
and the surface accumulation of the corrosion products were
mirrored by sharp peaks in the corresponding height profile.
In contrast, after 24 h immersion in a 1.8 mM chitosan-
containing solution, the mild steel coupon had a relatively

FIGURE 11 Schematic of the interactions between chitosan and mild steel in hydrochloric acid solution
10
| RABIZADEH
flat surface with very minor signs of degradations indicating
a considerable decrease in the corrosion rate of the tested
sample in the presence of chitosan. The height profile of this
sample was almost similar to the as-polished one. It is
noteworthy that the Ra value for the as-polished, severely
corroded and the inhibited specimens was about 14, 200,
and 22 nm, respectively. These results can be interpreted by
the surface adsorption of the inhibitor molecules which
provides a protective layer of the inhibitor molecules
between the mild steel and the corrosive solution. The role
of corrosion inhibitors in reducing the surface roughness of
the metallic coupons has also been reported in other
documents.[52]
3.5.2 | EDS
The EDS analysis was employed to identify the elemental
composition of chitosan powder and to characterize the
surface of the specimens immersed in 0.1 M hydrochloric
acid solutions without and with 1.8 mM chitosan for 24 h at
298 K (Figure 10). It should be noted that although EDS is
not an accurate technique to quantify the atomic or weight
percent of the light elements, it still can be used to
demonstrate the presence of elements with low atomic
numbers.
The C, N, and O peaks in the chitosan EDS spectrum
(Figure 10a) were assigned to an amino/acetamido group as
well as both primary and secondary hydroxyl groups at the
C-2, C-3, and C-6 positions of the glucose unit of a chitosan
molecule.[53] The EDS profile collected from the surface of
the corroded sample, revealed the presence of Fe, C, O, and Cl
peaks indicating the presence of corrosion products (i.e., iron
oxides and/or iron chlorides) on the surface of the analyzed
sample (Figure 10b).
In contrast, the EDS spectrum obtained from the inhibited
sample did not show any chlorine peak which beside the
significant drop in the oxygen peak intensity implies a
considerable decrease in the corrosion rate of the tested mild
steel sample (Figure 10c). An additional N peak was also
detected in the spectrum of this sample confirming the strong
adsorption of chitosan on the surface of the mild steel. This is
in accordance with the publications in which the presence of a
nitrogen peak in the EDS spectrum of an inhibited metallic
substrate was attributed to the surface adsorption of a
corrosion inhibitor with nitrogen in its molecular
structures.[54]
3.6 | Mechanism of inhibition
It has been suggested that an organic molecule inhibits the
corrosion of a metallic substrate via electrostatic (phys-
isorption) and/or charge sharing (chemisorption) interac-
tions. There are some factors such as the surface charge of
AND KHAMENEH ASL
the adsorbent in an acidic environment (mild steel in this
research) and the molecular structure of the inhibitor
affecting the adsorption of an inhibitor. As can be seen from
the schematic representation in Figure 11 both physisorp-
tion and chemisorption interactions are involved in the
adsorption of chitosan on mild steel interaction. Mild steel
has a positive surface charge in an acidic solution which
results in the adsorption of Cl− ions on it.[55] Therefore, a
negative charge will be distributed over the surface of the
working electrode accelerating the adsorption of the
protonated functional groups of the corrosion inhibitor
(e.g., NHþ 3 in chitosan) via an electrostatic attraction
(physisorption).[55] On the other hand, during the chemi-
sorption process, the heteroatoms of chitosan such as
oxygen donate their lone-pair electrons to the vacant 3d-
orbitals of Fe (mild steel).[56]
It is noteworthy that molecular modeling can be employed
to provide better insight into the interaction of chitosan with
mild steel. However, it is beyond the scope of this study to
derive detailed information about this approach.
4 | CONCLUSION
In this work, chitosan was introduced as an efficient
corrosion inhibitor for mild steel in 0.1 M hydrochloric acid
solution. According to the results, increasing the concen-
tration of chitosan from 0.3 to 1.8 mM effectively decreased
the weight loss and the corrosion rate of mild steel.
However, increasing temperature from 298 to 328 K
deteriorated the corrosion inhibition effects of this
biodegradable additive.
As indicated by thermodynamic calculations, the
adsorption of chitosan on substrates was through both
physical and chemical adsorption which caused an increase
in the activation energy for corrosion process and the
enthalpy of activation. The selective adsorption of the
studied green corrosion inhibitor obeys the Langmuir
adsorption isotherm.
The results from OCP, electrochemical polarization,
and EIS analyses further confirm the inhibitory action of
chitosan. For example, by increasing the concentration of
chitosan in 0.1 M hydrochloric acid solution the corrosion
current density decreased. Furthermore, the diameter of
the capacitive loop in Nyquist plots increased in presence
of chitosan as compared to that of in the blank acid
solution. As indicated by AFM measurements, in the
presence of chitosan the studied coupon had a surface
topography and surface roughness close to the as-polished
sample. The EDS analysis also illustrated the adsorption of
chitosan on the surface of the inhibited sample via the
amide functional groups presented in the chitosan
molecular structure.
RABIZADEH AND KHAMENEH ASL
ORCID
Taher Rabizadeh http://orcid.org/0000-0003-3483-2764
Shahin Khameneh Asl http://orcid.org/0000-0001-9069-
3776
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How to cite this article: Rabizadeh T, Khameneh
Asl S. Chitosan as a green inhibitor for mild steel
corrosion: Thermodynamic and electrochemical
evaluations. Materials and Corrosion. 2018;1–11.
https://doi.org/10.1002/maco.201810501