Anti Corrosion 1

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Page 1 of 31 New Journal of Chemistry
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Chemically modified biopolymer as an eco-friendly corrosion inhibitor for
DOI: 10.1039/C7NJ00553A
mild steel in neutral chloride environment
Vimal Kumar K., B. V. Appa Rao*
New Journal of Chemistry Accepted Manuscript

Department of Chemistry, National Institute of Technology Warangal,
Warangal-506004, Telangana, India.

Published on 30 May 2017. Downloaded by University of California - San Diego on 02/06/2017 13:46:02.
*Address for correspondence:
Dr. B. V. Appa Rao
Professor of chemistry (Retd.),

Research Fellow (Emeritus)
National Institute of Technology Warangal,
Telangana 506004,
INDIA.
Email: bva.nitw@gmail.com, vimalnitw@gmail.com.
*
Corresponding author. Tel.: (91)-9866575276,
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Chemically modified biopolymer as an eco-friendly corrosion inhibitor for
DOI: 10.1039/C7NJ00553A
mild steel in neutral chloride environment
Abstract

The present study is aimed at the development of novel, eco- friendly corrosion
inhibitor based on a naturally occurring biopolymer. Chitin or poly (N-acetyl-1,4--D-

glucopyranosamine) is one of the most abundant naturally occurring polysaccharides. It is a
biological polymer, which is known to be non-toxic, biocompatible and enzymatically
biodegradable. In the present study, chitin has been chemically modified to phosphorylated
chitin (P-chitin or PCT) in order to increase its solubility in aqueous medium and its ability of
complexation with the metal ions. The inhibition effect of PCT and PCT in combination with
low concentrations of Zn2+ on the corrosion of mild steel in an aqueous environment containing
200ppm NaCl has been studied using weight-loss, potentiodynamic polarization and
electrochemical impedance techniques. The synergistic effect of this functionalized
biopolymer and Zn2+ is established from the results. This synergistic formulation afforded an
inhibition efficiency of 94% for mild steel in low chloride environment. The protective film
formed on the mild steel surface has been investigated by scanning electron microscopy (SEM)
and X-ray photoelectron spectroscopy (XPS). The mechanistic aspects of corrosion inhibition
are discussed.
Keywords: mild steel, chitin, phosphorylated chitin, corrosion inhibition, electrochemical
studies, XPS studies.
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DOI: 10.1039/C7NJ00553A
Introduction
Mild steel is used in the fabrication of recirculating cooling water systems, heat

exchangers and various other materials in the industry. In cooling water systems corrosion of
mild steel is a major problem. This problem can be tackled and minimized by the addition of a
variety of organic and inorganic compounds as corrosion inhibitors to the environment.
However, most of the traditionally employed corrosion inhibitors are known to be toxic and
lethal to the environment. There is a need to minimize the use of these toxic chemicals and
make an effort to conserve our environment from the present vulnerable condition. Therefore,
attention was drawn to the development of novel corrosion inhibitors based on ecological
approaches. In recent years, considerable efforts have been made to study the corrosion
inhibition efficiency of some natural products1. Application of natural polymers as
environment-friendly corrosion inhibitors constitutes an attractive and significant approach to
the development of green corrosion inhibitors. Researchers have given a lot of importance in
exploring this area and a significant number of reports have been published in the literature on
natural gums (guar gum, gum acacia, etc.,), natural polymers (cellulose, starch, chitosan,
pectin, alginate, etc.,) as inhibitors for instance 25. However, very few studies are reported in
the literature on the application of chitin as corrosion inhibitor6. In this background, chitin, a
natural polymer has been selected in the present study for the following reasons. Chitin is the
second most abundant polysaccharide next to cellulose on the earth. Chitin is non-toxic and is
inert in the gastrointestinal tract of mammals. It is also biodegradable. Chitin is the main
component in the shells of crustaceans such as shrimps, crab, and lobster and is also found in
the exoskeleton of mollusks, insects and the cell walls of some fungi7. Every year, around 6 to
8 million tonnes of waste from crab, shrimp and lobster shells are produced globally8. These
waste shells are often just dumped and cause a lot of environmental problems. There is a large
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scope of research in using this abundant and cheap renewable resource by developing new
DOI: 10.1039/C7NJ00553A
application methods. In the present study, chitin has been chemically modified to
phosphorylated chitin (P-chitin or PCT) in order to increase its solubility in aqueous medium

and increase its complexing ability with the metal ions. The inhibition efficiency of P- chitin
on corrosion of mild steel in neutral chloride environment has been investigated in the present
study. The synergistic inhibition effect of P- chitin in combination with Zn2+ ions has also been
investigated and the mechanistic aspects of inhibition are discussed.
Experimental
Materials:
Preparation of the mild steel specimens:
Mild steel specimens of the composition, 0.02- 0.03 % sulphur, 0.03- 0.08 % phosphorous, 0.4-
0.5 % manganese, 0.1- 0.2% carbon and the rest iron were chosen from the same sheet of mild
steel. Mild steel specimens of the dimensions, 3.5 cm x 1.5 cm x 0.2 cm, were used in the
weight-loss studies. The specimens of the dimensions, 1 cm x 1 cm x1 mm, were used in the
surface examination studies by scanning electron microscopy (SEM) and X-ray photoelectron
spectroscopy (XPS). In all the investigations, mild steel specimens were abraded initially with
a series of emery papers (grade 1/0, 2/0, 3/0, and 4/0 respectively) and a mirror like finish was
obtained by polishing finally on alumina slurry. The specimens were then washed with double
distilled water, degreased with acetone and dried.
Preparation of phosphorylated chitin (PCT):
Chitin has been chemically modified to phosphorylated chitin using phosphorous pentoxide
(P2O5) methane sulphonic acid method, reported in the literature 912. The reaction product is
found to have a high degree of substitution of phosphonate group and is soluble in water. The
structure of PCT is shown in figure 1.
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DOI: 10.1039/C7NJ00553A

Figure 1: Structure of phosphorylated chitin (PCT)
Characterization of phosphorylated chitin:
The synthesized phosphorylated derivative of chitin was characterized by Fourier Transform

1315
Infrared spectroscopy (FTIR). Results are in good agreement with the literature values .
Figure S1 presents the FTIR spectra of pure chitin and phosphorylated chitin (PCT). In the
spectrum of PCT, a broad peak at 3428 cm-1 is because of P-OH groups. Due to
phosphorylation, a shoulder peak appeared around 1220 cm-1 and this peak is assigned to
phosphate group (P=O asymmetric stretching)6. The Peak at 1050 cm-1 is because of C-O-P
stretching in phosphate ester and the peak at 975 cm-1 is due to P-OH stretching. A broad band
between 900 cm-1 to 1100 cm-1 is also an indication of phosphorylation8.
The 13C NMR spectrum (Figure S2) of phosphorylated chitin exhibits characteristic chemical
shift values for non-equivalent carbons at appropriate positions with respect to
tetramethylsilane (TMS). The carbon atoms attached to the functionalised amine and hydroxyl
groups appeared in the spectrum. The 13C NMR signal at 53.87 ppm corresponds to the C2
carbon of pyranose ring (CH-NH-). The signal at 66.68 ppm corresponds to C3 carbon of
pyranose ring (-CH-O-P). The signals at 38.35 ppm, 68.23 ppm and 69.04 ppm correspond
to the C4, C5 and C6 carbons of pyranose ring respectively.
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Other chemicals: DOI: 10.1039/C7NJ00553A
All the other chemicals were of analytical reagent grade and used without further purification.
Methods:

Weight-loss measurements:
The mild steel specimens were weighed accurately and then immersed in 100 mL of 200 ppm
sodium chloride environment in the absence and presence of different concentrations of the
PCT at a pH value of 7.0. After seven days of immersion, the samples were cleaned, dried as
stated by the standard technique16 and weighed again. By taking the weight-loss into
consideration the corrosion rates and inhibition efficiencies have been calculated. All the
experiments were carried out in duplicate and the mean value is taken as the final weight-loss
value. The standard deviation of the weight-loss values is found to be 0.1 mg. Accuracy in
weighing up to 0.01 mg has been done using Shimadzu AY 120 balance. Accuracy in surface
area measurement is 0.1 cm2. These are in accordance with the recommendations of 17 ASTM
G31 and are followed in the present study (ASTM Standard G 31-72, 2004)18. The relative
standard deviation in corrosion rate determination is of the order of 2% 19.
The inhibition efficiency has been calculated using the given equation,
Inhibition efficiency (%) =[( )/ ].. (1)
Here, = corrosion rate in aq. NaCl environment without inhibitor,
= corrosion rate in aq. NaCl environment with inhibitor (PCT).
Electrochemical studies:
Electrochemical studies were performed using a three-electrode cell assembly with mild steel
coupon having the dimensions of 1.5 cm x 3.5 cm x 0.2 cm as the working electrode. One cm2
surface area of this coupon has been exposed to the corrosive environment and the rest is coated
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with epoxy resin. An Ag| AgCl| 3M KCl electrode was used as reference electrode and a
DOI: 10.1039/C7NJ00553A
platinum electrode was used as counter electrode. The studies were carried out using ZAHNER
IM6e Electrochemical Workstation (Germany). All the investigations were performed at a

temperature of 300.1 C by taking 500 mL of 200 ppm NaCl solution. The pH of all the
solutions was adjusted to 7.0 using 0.1 N NaOH solution. While performing the experiments
the solutions were maintained in a stagnant condition (naturally aerated). The electrochemical
impedance studies were carried out at the open circuit potential (OCP) in the frequency range
of 10 mHz to 60 kHz with an ac signal of 10 mV, peak to peak. In all the experiments the OCP
was achieved after 1 h of sample immersion in the corrosive environment.
From the charge transfer resistance values, the inhibition efficiency was calculated for
each inhibitor concentration using the equation (2).
( ) ( )
. . % = ()
( )
( ) = charge transfer resistance in presence of PCT as inhibitor
( ) = charge transfer resistance without inhibitor.
Potentiodynamic polarization experiments were performed on mild steel surface immersed
in the corrosive environment without and with different concentrations of inhibitor
formulation. The potential range was between -750 mV to +250 mV, and the scan rate was 0.1
mV sec-1.
From the corrosion current density values, the inhibition efficiency was calculated for each
inhibitor concentration using the equation (3).
( ) ( )
. . % = ()
( )
7
Where (Jcorr)control, (Jcorr)PCT represent corrosion current density values without, and View Article Online
with
DOI: 10.1039/C7NJ00553A
inhibitor, respectively.
In order to calculate different kinetic parameters like entropy of activation( ),

enthalpy of activation( ) and activation energy (Ea) using transition state theory and
Arrhenius equation the potentiodynamic polarization studies were also performed at different
temperatures mainly 303 K, 313 K, 323 K, 333 K.
Surface morphological studies by SEM:
Scanning electron microscopic studies were carried out after immersing the specimens for
seven days in corrosion environment in the absence and presence of various concentrations of
the inhibitor using the scanning electron microscope, model VEGA 3 TESCAN, USA.
X-ray photoelectron spectral (XPS) studies
XPS studies of the mild steel specimens immersed in control as well as in the inhibitor
formulation were carried out using the X-ray photoelectron spectrometer, ESCA Kratos model
AXIS-165, with Mg K radiation (1253.6 eV) and sensitivity of 0.1 eV. Computer
deconvolution was applied to identify the elemental peaks of iron, carbon, oxygen,
phosphorous, nitrogen, and zinc present in the film formed on the surface.
Results and discussion:
Weight-loss Studies:
The corrosion inhibition efficiency of the chemically modified chitin (PCT) and the synergism
of this polymer and Zn2+ have been investigated using weight-loss studies at 30C after 7 days
immersion period. The experimental data of the corrosion rates and the inhibition efficiencies
are given in table 1.
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Table 1. Corrosion parameters for mild Steel in 200ppm NaCl (aq) in absence DOI: and10.1039/C7NJ00553A
presence of different concentrations of inhibitor obtained from the gravimetric method.
Concentration(pp Corrosio
m) Weight - Corrosion
S.No. n Rate I.E.%
loss(mg) Rate(mdd)
Zn2+ (mmpy)

PCT
1 0 0 12.14 17.47 0.08111 -
2 50 0 8.94 11.92 0.05534 26.30
3 100 0 5.83 7.78 0.03612 51.00

4 150 0 3.22 4.29 0.01991 73.00
5 200 0 4.75 6.34 0.02943 60.80
6 0 100 14.15 20.36 0.09455 -16.15
7 50 100 5.43 7.24 0.03361 55.27
8 100 100 3.96 5.28 0.02451 67.38
9 150 100 3.14 4.18 0.01940 74.13
10 200 100 0.83 1.10 0.00513 93.16
11 300 100 1.50 2.00 0.00928 87.60
12 400 100 1.55 2.07 0.00961 87.23
The results showed that the corrosion rate decreased and the inhibition efficiency increased
appreciably by the addition of PCT. It is very clear that the PCT inhibits corrosion of carbon
steel in aqueous chloride environment at all concentrations. The inhibition efficiency increased
with increasing concentration of the modified polymer and the highest inhibition efficiency of
73% is obtained at 150 ppm concentration of the polymer. This result could be the consequence
of an increase in the number of molecules of P- chitin adsorbed on mild steel surface. From the
literature, it is noticeable that Zn2+ alone accelerates the corrosion rate of mild steel in neutral
chloride environment20,21. The inhibition efficiency reached up to 93.16 % when Zn2+ (100
ppm) is added as a synergist along with 200 ppm PCT.. The synergistic parameter (S) values
for various PCT concentrations are listed in table 2. The S value is greater than one for all PCT
concentrations suggests that there is a synergistic effect between PCT and Zn2+. This result
shows the synergistic effect of PCT and Zn2+ in inhibiting corrosion of mild steel. Similar
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results on synergistic effects of synthetic phosphonates and Zn2+ in controlling corrosion View Article Online
of
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carbon steel have been reported in the literature22,23. The inhibition mechanism has been
discussed in the section on mechanistic aspects.

The synergistic parameter (S) has been calculated using the equation given below24,
+
= . ()
Here 1+2 = 1 + 2- (1.2)
1= surface coverage by Zn2+, 2= surface coverage by PCT
1+2 = surface coverage by PCT in combination with Zn2+.
Table 2: Synergistic parameters for different concentrations of PCT.
Concentration(ppm) Synergistic
S.No. I.E.%
PCT Zn 2+ parameter
1 50 100 55.27 1.55
2 100 100 67.38 1.73
3 150 100 74.13 1.22
4 200 100 93.16 7.25
Electrochemical Studies:
Impedance analysis:
The electrochemical impedance studies were conducted at the open circuit potential (OCP is at
-325 mV vs Ag| AgCl (3M KCl)) in the absence and presence of various concentrations of PCT
and PCT in combination with Zn2+ions in the neutral chloride environment. The studies were
performed at various immersion times namely 1 h, 6 h, 12 h and 24 h. Figures 2A & 2B
represent the Nyquist plots of mild steel in 200 ppm sodium chloride solution in the absence
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View 2+
and presence of different concentrations of PCT and PCT in combinationDOI:
with ZnArticle Online
10.1039/C7NJ00553A
respectively.

Figure 2: Nyquist plots of mild steel immersed in 200 ppm NaCl in presence of (A) Different
concentrations of PCT and (B) Different concentrations of PCT +Zn2+ combination.
Figure 3: Bode plots of mild steel immersed in 200 ppm NaCl in presence of (A) Different
concentrations of PCT and (B) Different concentrations of PCT +Zn2+ combination.
Figures 3A and 3B represent the corresponding Bode plots of the working electrode.
The experimental data fitted well with the simple Randles equivalent circuit shown in
figure 4. The equivalent circuit consists of solution resistance (Rs), charge transfer resistance
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(Rct), and a constant phase element (CPE). Similar equivalent circuit was also reported by other
DOI: 10.1039/C7NJ00553A
researchers25,26. The calculated parameters from EIS data are presented in table 3.

Figure 4: Equivalent circuit used (Simple Randles Circuit)
Rs- Solution Resistance, Rct - Charge transfer resistance, Q - Constant phase element (CPE).
Capacitors formed in EIS experiments often do not behave ideally. Instead, they act
like a constant phase element (CPE). This is because of the non-uniform current distribution
on the surface. The non-homogeneous nature (surface roughness) of the inhibitor film on the
metal surface mainly causes this effect. The impedance function of the CPE component is
calculated using the equation 5.

= = () ()

Here, Qo has the numerical value of the admittance (1/|Z| at =1rad s-1)
= angular frequency
n= CPE exponent (for a constant phase element the n value is generally less than unity)
j = imaginary number (j2= -1)
For an ideal capacitor the n value is equal to 1, the Qo value is equal to C

= = () = () ()

For the case of a depressed semicircle (CPE in parallel with a resistance as such in the present
case) the true capacitance of the double layer can be calculated from the equation 7
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= ( ) . . () View Article Online

DOI: 10.1039/C7NJ00553A
max represents the frequency at which the imaginary component reaches a maximum.

Table 3. Impedance parameters for mild steel in 200ppm NaCl (aq) in absence and
presence of different concentrations of inhibitor.
Concentration(ppm) Rct(k
S.No. Cdl(F cm-2) n I.E.%
PCT Zn2+ cm2)
1 0 0 1.854 14.35 0.58 -

2 50 0 2.928 13.85 0.568 36.6
3 100 0 3.28 12.74 0.593 43.75
4 150 0 9.104 12.11 0.713 79.6
5 200 0 10.66 12.02 0.758 82.66
6 50 100 7.693 14.3 0.733 75.9
7 100 100 15.08 13.88 0.699 87.7
8 150 100 24.48 11.14 0.735 92.42
9 200 100 32.92 10.19 0.782 94.36
In the case of control, a small depressed semicircle is observed in Nyquist plots
with an Rct value of 1.85 k cm2. When PCT alone is used as an inhibitor, the diameter of the
semicircle increased with an increase in concentration of the inhibitor. An Rct value of 10.66
k cm2 is obtained for 200 ppm of PCT, which afforded an inhibition efficiency of 82.66 %.
When a small concentration of Zn2+ (100 ppm) is used as synergist in combination with 200
ppm PCT, the Rct is increased to 32.92 k cm2 and the inhibition efficiency is increased to
94.36 %. These results indicate the significance of the synergism between zinc ions and P-
chitin in enhancing inhibition efficiency.
In Bode plots it can be clearly seen that the phase angle maximum is only 15 in the presence
of control and is increased to a value of around 60 in the presence of binary inhibitor
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formulation, 200 ppm PCT + 100 ppm Zn2+. The total impedance of the system is also View Article Online
increased
DOI: 10.1039/C7NJ00553A
from 2.50 k cm2 to 35.02 k cm2 in the presence of binary inhibitor system. This result is
indicative of the protective film formation on the metal surface. It is interesting to note that the

charge transfer region is in the low frequency range namely 10 Hz to 10 mHz in the presence
of the binary inhibitor formulation, which affords the highest inhibition efficiency. The total
impedance vs. frequency plot showed a clear tendency for an increase in impedance even at
the lowest frequency namely 10 mHz.
From the impedance parameters, we can also observe a change in the n value. The n value
is shifted towards higher values in the presence of the inhibitor formulation. In the case of
control, the n value is 0.58, which is increased to 0.74 when the binary inhibitor formulation
of PCT (200 ppm) + Zn2+ (100 ppm) is used. The value of n is close to 0.5 in the case of control
and in the presence of inhibitor formulations, which afforded low inhibition efficiency. Such a
low value of n indicates mass transport also. Even in the presence of inhibitor, which afforded
the highest efficiency, the value of n is far less than 1. This result is indicative of a non-
homogeneous nature of the protective film.
Thus, all the results of the impedance studies indicate that there is the formation of a protective
film on the metal surface in presence of the binary inhibitor formulation.
Potentiodynamic polarization studies:
Figure 5(A&B) represents the anodic and cathodic polarization curves of mild steel
immersed in 200 ppm NaCl solution in the absence and presence of different inhibitor
formulations.
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Figure 5: Potentiodynamic polarization curves (A) Only PCT (B) PCT +Zn2+ (100ppm).
The corrosion parameters were calculated from the polarization curves by extrapolating
the cathodic and anodic Tafel regions. The potential range, which has been used to extrapolate
the Tafel regions is between 30 mV from the corrosion potential value. The corrosion
potential (Ecorr), corrosion current density (icorr), anodic and cathodic Tafel slopes (a and c)
are presented in table 4. In control system, a corrosion potential (Ecorr) of -323.0 mV is observed
and the corresponding corrosion current density (Jcorr) is 11.77 Acm-2. When PCT alone was
used as the inhibitor, the corrosion potential is shifted towards more negative side with respect
to control, and the corresponding corrosion current density is decreased with increasing
concentration of PCT. The lowest corrosion current density of 3.20 Acm-2 is obtained at 200
ppm PCT. When Zn2+ ions alone are added to the control, they increase the corrosion rate of
mild steel. Such an increase in corrosion rate in the presence of zinc ions alone was reported in
the literature 27. When Zn2+ (100 ppm) was used along with 200 ppm PCT, it acts as a synergist
and improves upon the inhibition efficiency of PCT.
Table 4. Corrosion parameters obtained for mild steel in 200 ppm NaCl (aq) in absence and
presence of different concentrations of the inhibitor by potentiodynamic polarization studies.
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Concentration(ppm)
E corr Jcorr c a
S.No. I.E.%
(mV) (Acm-2) (mV dec-1) (mV dec-1)
PCT Zn2+
1 0 0 -323.0 11.77 -441 189 -

2 50 0 -395.6 9.75 -102 59.5 17.16
3 150 0 -412.4 3.71 -106 53.2 68.40
4 200 0 -365.5 3.20 -102 51.7 72.00
5 50 100 -476.0 2.30 -190 88.8 80.40
6 150 100 -294.0 1.74 -184 95 85.20
7 200 100 -413.5 0.80 -245+ 155 93.20
Form figure 5B it is quite evident that the combination of PCT and Zn2+ (100 ppm)
significantly decreases the corrosion of mild steel by decreasing both the anodic and cathodic
current densities. Highest inhibition efficiency was obtained for the combination of PCT (200
ppm) + Zn2+ (100 ppm) with a corrosion current density of 0.80 Acm-2, which is ten times
lower than that of control. It is observed that both the anodic and cathodic curves showed lower
current densities in the presence of all binary inhibitor formulations. By adding inhibitor
formulation to the control solution, the a and c values decreased significantly. From the
results, it is evident that, although both the anodic and cathodic corrosion processes are retarded
by the inhibitor, the cathodic process is more affected. Taking into account the decrease in
Tafel slopes, it can be said that the present inhibitor formulation affects the kinetics of both
iron dissolution and oxygen reduction. From these results, we can infer that the inhibitor
formulation acts as a mixed type inhibitor. Zinc ions form zinc hydroxide on the cathodic sites
and inhibit the cathodic reaction. Consequently, the cathodic current densities are affected
more28. An Inhibition efficiency of 93.20 % was obtained with the combination of 200 ppm
PCT and 100 ppm Zn2+.

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Surface morphology studies by scanning electron microscopy: DOI: 10.1039/C7NJ00553A
Scanning electron microscopic images of the surface of the samples were taken to study the
morphology after immersion in the corrosive environment for seven days in the absence and

presence of inhibitor formulation. Figure 6A represents the SEM micrograph of the polished
mild steel specimen. Figure 6B is the SEM micrograph of the surface of mild steel immersed
in the control without inhibitor, which clearly shows the corrosion products and deep cracks
on the surface. Figures 6C & 6D are the SEM images of mild steel after immersion in 200
ppm PCT, and in the synergistic mixture of 200 ppm PCT and 100 ppm Zn2+ respectively.
These figures show the surface smoothness and the absence of any corrosion product on mild
steel surface. This is because of the formation of a protective film on the mild steel surface15.
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Figure 6: SEM images (10,000x magnification) of (A) polished specimen (B) Control
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(C) PCT (200 ppm) (D) PCT (200 ppm) +Zn2+ (100 ppm) in 200 ppm NaCl environment after
seven days immersion.

Surface analysis by X-ray photoelectron spectroscopic studies:
The XPS survey spectra of the surface films formed on mild steel in the absence and presence
of the binary inhibitor formulation containing PCT (200 ppm) and Zn2+ (100 ppm) are shown
in the figures 7A and 7B respectively.
Figure 7: XPS Survey spectrum of mild steel coupon (A) in control and (B) in presence of
PCT (200 ppm) +Zn2+ (100 ppm).
The XPS survey spectrum of the surface film formed on the mild steel surface in the
absence of the binary inhibitor system shown in figure 7A exhibits peaks for Fe 2p, O 1s, C 1s
and the Cl 2p. Whereas, the XPS survey spectrum of the surface film in presence of the inhibitor
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formulation shows peaks for P 2p, N 1s, Zn 2p, along with Fe 2p, O 1s and C 1s,DOI:
which give
10.1039/C7NJ00553A
the evidence for the adsorption of the inhibitor on the mild steel surface.
The computer deconvolution spectra for iron and oxygen of the film formed on the mild

steel surface in the corrosive environment without and with inhibitor formulation (200 ppm
PCT + 100 ppm Zn2+) are shown in Figures 8 and 9 respectively. Figure 10 presents the
spectra for carbon, phosphorus, nitrogen and zinc present in the film formed in the presence of
inhibitor.
Figure 8: XPS deconvolution spectra of Fe 2p for (A) control (B) PCT (200 ppm) + Zn2+ (100
ppm).
The deconvolution spectrum of the Fe2p of control consists of two peaks, one at
710.8 eV corresponding to Fe 2p3/2 and the other one at 724.2 eV corresponding to the Fe 2p1/2
electron (Figure 8A). There is a large shift in the binding energy value of Fe 2p 3/2 from the
characteristic elemental binding energy value of 707.0 eV. This shift of 3.8 eV suggests that
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iron is present as Fe3+ in the form of ferric oxide and hydroxide. Indeed, the peak DOI: View Article Online
at a10.1039/C7NJ00553A
binding
energy of 710.8 eV was attributed to ferric compounds such as Fe2O3, Fe3O4 and FeOOH in
the literature29,30. The peak located at 724.2 eV was attributed to the presence of a small

concentration of FeCl3 on the metal surface31. In the presence of binary inhibitor system, the
Fe 2p deconvolution spectrum consists of two peaks, one at 711 eV, which is due to Fe 2p3/2,
and one at 724.3 eV which is due to Fe 2p1/2 (Figure 8B). The Fe 2p3/2 peak may be interpreted
due to the presence of (Fe3+- PCT complex) along with small amount of oxides and hydroxides
(Fe2O3, Fe3O4 and FeOOH) present in the surface film. There is no peak due to elemental iron
in the case of control or in the presence of the inhibitor formulation. This result is an indication
for the formation of a film in both cases. The film is non- protective in the case of control and
is protective in the presence of inhibitor formulation 32.
Figure 9: XPS deconvolution spectra of O 1s for (A) control (B) PCT (200 ppm) +Zn2+ (100
ppm).
The deconvolution spectrum of O 1s in the case of control consists of two peaks (Figure
9A), one peak at a binding energy value of 530.1 eV and the other one at a binding energy
value of 533.0 eV. The peak located at lower binding energy value (530.1 eV) can be attributed
to O2- and can be related to the bond with Fe3+ in iron oxides and hydroxides (Fe2O3, Fe3O4).
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The peak located at higher binding energy value (533.0 eV) can be ascribed to oxygen atoms
DOI: 10.1039/C7NJ00553A
of adsorbed water molecules. Whereas, the deconvolution spectrum of O 1s in the presence of
binary inhibitor formulation (Figure 9B) consists of two peaks, one at 529.9 eV and the other

one at 531.1 eV. The former one can be interpreted due to oxygen present in the oxides and
hydroxides of Fe (III), in the form of O2-. The later one (peak at 531.7 eV) is ascribed to OH
and is attributable to oxygen in hydrous iron oxides, such as FeOOH and Fe(OH)3 33, Zn(OH)2
and some contribution from the oxygen present in the inhibitor molecule (PCT). The peak at
533.0 eV is absent in the case of binary inhibitor system, which means that there are no
adsorbed water molecules on the metal surface, as a consequence of the replacement of
adsorbed water molecules by the inhibitor molecules.
Figure S3 represents the computer deconvolution spectrum of C 1s in the case of
control, which shows a single peak at 284.6 eV. This peak can be interpreted as a contaminant
carbon peak, which arises due to the cracking of vacuum oil used in the
instrument34.In the case of binary inhibitor formulation the carbon deconvolution spectrum
consists of three peaks (Figure 10A), one peak at the binding energy value of 284.6 eV with
high intensity and two peaks of lower intensities at 286.1 eV and 288.3 eV. These peaks can
be interpreted as follows. The inhibitor, PCT has different types of carbon environments like
C N, C C and C H, which explain the presence of three different peaks in the
deconvolution spectrum. These carbon peaks show an evidence for the presence of the PCT
molecules in the surface film.
21
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DOI: 10.1039/C7NJ00553A

Figure 10: XPS deconvolution spectra of (A) C 1s, (B) P 2p, (C) N 1s (D) Zn 2p for mild steel
specimen immersed in corrosive environment in presence of PCT (200 ppm) +Zn2+ (100 ppm).
The XPS deconvolution spectrum for P 2p in the presence of the inhibitor formulation
is shown in the Figure 10B. The spectrum shows two peaks, one at 132.9 eV and the other one
at 134.6 eV. The former peak is mainly because of phosphate group present in the PCT
molecule. The second peak is mainly attributed to phosphates of iron(III) and zinc (II) which
are the main components of the complex in the protective film formed on the mild steel
surface3538. Based on the literature reports, the characteristic binding energy value of this
coordinate phosphate is around 134.2 eV3941. With all these evidences, the P 2p peak observed
22
in the present study suggests the presence of PCT in the surface film formed in presence ofViewthe
Article Online
DOI: 10.1039/C7NJ00553A
binary inhibitor system.
Figure 10C represents the deconvolution spectrum of N 1s in the presence of inhibitor

formulation. Three different peaks are observed at 398.7 eV, at 399.8 eV and at 400.8 eV
respectively. The characteristic elemental binding energy of N 1s is 398.0 eV 42. That means,
all the peaks observed in the spectrum are shifted from the characteristic elemental binding
energy value. These peaks are mainly because of three different nitrogen environments present
in the PCT molecule (C-NH2, -NHCOCH3 and Nitrogen participated in the complexation by
virtue of its lone pair of electrons). This result indicates that the PCT present in the surface film
is probably in the form of a complex with Fe (III) and Zn (II) ions.
Figure 10D presents the deconvolution spectrum of Zn 2p in presence of the inhibitor
formulation. This spectrum shows two peaks, one at 1021.7 eV, which represents Zn 2p3/2, and
another peak at 1044.1 eV, which represents Zn 2p1/2. The presence of intense Zn 2p3/2 peak is
assigned to Zn(OH)2 43 present in the surface film and also because of Zn2+ involvement in the
complex formation with PCT39,42,44.
Langmuir adsorption isotherm:
The inhibition mechanism can be understood from the interaction between the inhibitor
molecules and metal surface. Different adsorption isotherm models were taken into
consideration to understand the inhibition mechanism of PCT + Zn2+ formulation. Among them
Langmuir adsorption isotherm model is well fitted (based on the correlation coefficient value).
The Langmuir adsorption is given in equation 8.
1
= + (8)

23
Here, is the surface coverage of the inhibitor molecules (which is obtained by DOI: View Article Online
the 10.1039/C7NJ00553A
relation,
I. E. % = 100). The I.E. % values are taken from the results of weight-loss studies. C is
the concentration of PCT (mg L-1). Zn2+ concentration is not taken into consideration since it

is constant and is the equilibrium constant.
Figure S4 presents the / plot. A linear curve is obtained with a good

correlation coefficient value (R2= 0.9998). This result infers that the adsorption process follows
Langmuir adsorption isotherm model. Form the plot it can be seen that the value increases
with the increase in the PCT concentration (Zn2+ concentration being constant). This result can
be attributed to the increase in the surface coverage of the metal with inhibitor molecules (PCT)
and as a consequence higher inhibition efficiencies are obtained.
We have calculated the adsorption equilibrium constant and standard free energy of
adsorption (G0ads) from the equation 9
0 = (55.5 ) . . (9)
The adsorption equilibrium constant (Kads) is found to be 23648 M-1 (viscosity-average
molecular weight for the phosphorylated chitin is taken as 4 X 105). The standard free energy
of adsorption ( 0 ) is found to be 35.488 kJmol-1. The negative value of 0 indicates
the spontaneity of the adsorption process of the inhibitor molecule on to the metal surface. It is
well known from the literature that when the value of G0ads is between -20 kJ mol-1 and -40
kJ mol-1 the process may involve charge transfer from the inhibitor molecule to the metal
surface to form a coordination bond6,45. This result infers that the adsorption process involves
chemisorption of PCT on the metal surface and then formation of a coordinate complex
between PCT and metal ions.
The effect of temperature on the corrosion process has been evaluated by the use of
transition state equation given in 10.
24
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DOI: 10.1039/C7NJ00553A
ln ( ) = ln ( ) + ( )( ) . . (10)

Where h is planks constant, N is Avogadros number,
is the entropy of activation

is the enthalpy of activation
R is the general gas constant, T is absolute temperature.

Form the plot ln ( ) vs 1000/T drawn which is shown in the figure 11. A straight

line has shown with the slope equal to /R and an intercept equal to ln () + ( ).

Figure 11: Transition state plots for mild steel specimen in 200 ppm NaCl medium in the
absence and presence of inhibitor formulation.
Whereas the change in the activation energy of the inhibitor has been calculated using
Arrhenius equation shown below.

= ( ) + ln() . (11)

Where icorr is the corrosion rate, Ea is the apparent activation energy of the corrosion
process. A plot of vs 1000/T has been presented in the figure 12 and from the slope the
Ea was calculated. , and Ea values for control and inhibitor are listed in table 5.
25
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DOI: 10.1039/C7NJ00553A

Figure 12: Arrhenius plots for mild steel specimen in 200 ppm NaCl medium in the absence
and presence of inhibitor formulation.
Table 5: kinetic parameters of mild steel in 200 ppm NaCl in the presence and absence of
inhibitor formulation
sample Ea (J mol-1) (J mol-1) (J mol-1 K-1)
control 22.11 20.97 -139.6
200 ppm PCT+ 100 ppm Zn2+ 24.52 23.36 -141.8
From the table it can be noted that the activation energy (Ea) of the corrosion process
in 200 ppm NaCl in the presence of inhibitor formulation is higher than that in the control
solution. This result suggests that the addition of the inhibitor formulation to the control
elevates the energy barrier of the corrosion process45 and reduces the dissolution of mild steel.
The enthalpy ( ) value is also increased in the presence of the inhibitor formulation which
infers that higher energy is needed to cause the corrosion reaction in presence of the inhibitor
formulation when compared to control.
Mechanistic aspects of corrosion and corrosion inhibition:
The mechanism of corrosion of mild steel in nearly neutral aqueous medium is well
established46,47.
26
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When only PCT is used as inhibitor the inhibition efficiency increases withDOI:
an 10.1039/C7NJ00553A
increase
in concentration up to 150 ppm, at which the highest inhibition efficiency (IE%) of 73 % is
obtained. When the concentration of PCT is further increased to 200 ppm the IE% value is

decreased to 60 %. This result can be explained as follows, PCT gets chemisorbed on the metal
surface and the optimum concentration to form a thin and adherent film is 150 ppm. At this
concentration all the Fe3+ present on the metal surface is converted into [Fe(III)-PCT] complex,
which acts as a barrier to corrosive environment and no more PCT is needed. When the PCT
concentration is increased beyond 150ppm, the extra PCT which is present in the solution
diffuses to the metal surface and induces the formation of Fe3+ to form a complex. This induced
effect may cause some dissolution of iron into the solution. As a consequence, less corrosion
inhibition efficiency is observed beyond the concentration of 150 ppm PCT.
Plausible inhibition mechanism in presence of PCT and Zn2+
When P- chitin (PCT) and Zn2+ ions are added to the aqueous solution, Zn2+ coordinates
through N, O and P donors present in PCT to form a complex, [Zn2+ PCT]. This complex
diffuses to the metal surface and binds to Fe(III) ions present on the surface due to initial
corrosion of iron.
[Zn (II) PCT] + Fe (III) [Fe (III), Zn (II) PCT]. (6)
The resulting bimetallic complex, [Fe(III), Zn(II) P- chitin] covers the anodic sites and
controls the corresponding anodic reaction.
Free Zn2+ ions diffuse to the metal surface and react with OH ions produced at the cathodic
sites to form a precipitate of Zn(OH)2 43, which controls the cathodic partial reaction.
Now a question arises about the need for 200 ppm PCT along with 100 ppm Zn2+ to provide
higher inhibition efficiency of 93.16 % against 74.13 % IE for the mixture of 150 ppm PCT
27
and 100 ppm Zn2+. As mentioned in the mechanism, PCT and Zn2+ first form a soluble View Article Online
complex
DOI: 10.1039/C7NJ00553A
in the solution. So, the optimum concentration of PCT is 200 ppm for the formation of adequate
amount of soluble PCT- Zn2+ complex, which diffuses to the metal surface in order to form the

bimetallic complex (equation 6) with a higher surface coverage of the metal.
Conclusion:
Phosphorylated chitin (PCT) acts as a good inhibitor to protect mild steel from
corrosion in low chloride aqueous environment. PCT shows excellent synergism with Zn2+
ions. The synergistic formulation (200ppm PCT + 100ppm Zn2+) showed an inhibition
efficiency of 94.36%. Potentiodynamic polarization studies inferred that the inhibitor functions
as a mixed type. Surface analysis by SEM and XPS inferred that there is the formation of a
protective film on mild steel surface, which is the reason for the corrosion protection of the
alloy by the inhibitor. The protective film consists of a [Fe(III), Zn(II) P- chitin] complex,
along with oxides and hydroxides of iron(III) and zinc (II).
Acknowledgement
The authors are grateful to the Director, NIT Warangal, Telangana State, India, for the
provision of space to work and a research fellowship to one of the authors.
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31

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mild steel in neutral chloride environment

Vimal Kumar K., B. V. Appa Rao*

New Journal of Chemistry Accepted Manuscript

Warangal-506004, Telangana, India.

*Address for correspondence:

Dr. B. V. Appa Rao

Professor of chemistry (Retd.),

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mild steel in neutral chloride environment

New Journal of Chemistry Accepted Manuscript

inhibitor based on a naturally occurring biopolymer. Chitin or poly (N-acetyl-1,4--D-

glucopyranosamine) is one of the most abundant naturally occurring polysaccharides. It is a

biological polymer, which is known to be non-toxic, biocompatible and enzymatically

electrochemical impedance techniques. The synergistic effect of this functionalized

Keywords: mild steel, chitin, phosphorylated chitin, corrosion inhibition, electrochemical

studies, XPS studies.

View Article Online

New Journal of Chemistry Accepted Manuscript

variety of organic and inorganic compounds as corrosion inhibitors to the environment.

inhibition efficiency of some natural products1. Application of natural polymers as

environment-friendly corrosion inhibitors constitutes an attractive and significant approach to

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New Journal of Chemistry Accepted Manuscript

investigated and the mechanistic aspects of inhibition are discussed.

Preparation of the mild steel specimens:

distilled water, degreased with acetone and dried.

Preparation of phosphorylated chitin (PCT):

structure of PCT is shown in figure 1.

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New Journal of Chemistry Accepted Manuscript

Figure 1: Structure of phosphorylated chitin (PCT)

Characterization of phosphorylated chitin:

The synthesized phosphorylated derivative of chitin was characterized by Fourier Transform

between 900 cm-1 to 1100 cm-1 is also an indication of phosphorylation8.

shift values for non-equivalent carbons at appropriate positions with respect to

to the C4, C5 and C6 carbons of pyranose ring respectively.

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New Journal of Chemistry Accepted Manuscript

standard deviation in corrosion rate determination is of the order of 2% 19.

Inhibition efficiency (%) =[( )/ ].. (1)

Here, = corrosion rate in aq. NaCl environment without inhibitor,

= corrosion rate in aq. NaCl environment with inhibitor (PCT).

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IM6e Electrochemical Workstation (Germany). All the investigations were performed at a

New Journal of Chemistry Accepted Manuscript

was achieved after 1 h of sample immersion in the corrosive environment.

each inhibitor concentration using the equation (2).

( ) = charge transfer resistance in presence of PCT as inhibitor

( ) = charge transfer resistance without inhibitor.

Potentiodynamic polarization experiments were performed on mild steel surface immersed

in the corrosive environment without and with different concentrations of inhibitor

inhibitor concentration using the equation (3).

In order to calculate different kinetic parameters like entropy of activation( ),

New Journal of Chemistry Accepted Manuscript

temperatures mainly 303 K, 313 K, 323 K, 333 K.

Surface morphological studies by SEM:

X-ray photoelectron spectral (XPS) studies

Results and discussion:

are given in table 1.