Corrosion Science 88 (2014) 246253

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Corrosion inhibition of mild steel in acidic medium by polyacrylamide

grafted Guar gum with various grafting percentage: Effect of intramolecular
synergism
Pialee Roy, Paramita Karfa, Utpal Adhikari, Dipankar Sukul
Department of Chemistry, National Institute of Technology, Durgapur 713 209, India

a r t i c l e

i n f o

Article history:
Received 26 March 2014
Accepted 16 July 2014
Available online 27 July 2014
Keywords:
A. Mild steel
B. EIS
B. IR spectroscopy
C. Acid corrosion

a b s t r a c t
Polyacrylamide grafted guar gum (GG-g-PAM) with various grafting levels has been tested as potential
green inhibitor against corrosion of mild steel in 1 M HCl. Upto 86% grafting, grafted copolymer maintains
inhibition efciency higher than 90% for about 50 h of exposure. Grafted polysaccharide behaves as
mixed type inhibitor and forms an inhibitive layer on the metal surface following Langmuir adsorption
isotherm. GG and PAM moieties are found to synergistically inuence each other on adsorption and
subsequent corrosion inhibition. FTIR spectroscopy reveals the possible binding sites of grafted polymer
during adsorption on metal surface.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Combating metal corrosion in acid medium is a long standing
endeavor of scientists and engineers. Application of suitable inorganic and organic inhibitors is one of the most effective remedial
measures in this regard. Use of many inorganic inhibitors, particularly those containing phosphate, chromate and other heavy metals are now being gradually restricted by various environmental
regulations. Many organic inhibitors are also been reported as toxic
and environmentally harmful. As a result, scientists are now examining the other possible avenues, and designing of environmental
friendly bio-compatible green corrosion inhibitors has got tremendous impetus. Among many green inhibitors, natural products
such as plant extract, amino acids, proteins and bio-polymers have
been reported to have the potentiality of efcient corrosion inhibitors [116]. Polysaccharides form a special class of bio-polymers.
A few polysaccharides have a gelling ability by themselves at low
concentration, whereas, a lot of non-gelling polysaccharides are
used as a thickener and stabilizer [17]. Apart from this, they are
also long been known for various biological activities like, antitumour properties, anti-oxidants, and many others [18]. In recent
years, some polysaccharides, including gums and chitosan have
found a new role as corrosion inhibitors for metals in acidic,
alkaline, as well as in saline environment [916]. Chemical modication of polysaccharides has resulted into much improvement in
Corresponding author. Fax: +91 343 254 7375.
E-mail address: dipankar.sukul@gmail.com (D. Sukul).
http://dx.doi.org/10.1016/j.corsci.2014.07.039
0010-938X/ 2014 Elsevier Ltd. All rights reserved.

their corrosion inhibition efciency [1316]. Srivastava et al. have

shown the inhibitive effect of polyacrylamide grafted Fenugreek
mucilage [13] and Okra mucilage [14] toward corrosion of mild
steel in acidic medium. Grafting of acrylonitrile, acrylamide or
methyl methylmethacrylate on various gums and other polysaccharides employing conventional chemical method, as well as by
microwave assisted synthesis has been reported [1925]. Grafting
of gum by these synthetic polymers normally brings about some
modication of the physical properties of gum, like enhancement
of hardness, tensile strength and thermal stability [1925]. Biodegradable characteristic of the parent gum is retained after grafting.
Chemically, guar gum (GG) is a high molecular weight natural
polysaccharide consisting of a (1 ? 4)-linked b-D-mannopyranose
backbone with branch points from their 6-positions linked to aD-galactose (i.e. 1 ? 6-linked-a-D-galactopyranose). There are
between 1.5 to 2 mannose residues for every galactose residue
[26]. In 1 M H2SO4, guar gum has been reported to provide good
corrosion inhibition toward C-steel [11]. In this communication,
we have focused on the effect of percentage grafting (%G) on the
inhibition property by polyacrylamide grafted guar gum (GG-gPAM) toward corrosion of mild steel in 1 M HCl.
2. Experimental
2.1. Inhibitor preparation and characterization
GG-g-PAM is prepared employing reported procedure (Scheme.
1) [22,23]. A brief description is given here. One g of GG is

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P. Roy et al. / Corrosion Science 88 (2014) 246253

OH

OH
O

HO
OH
O
HO
H

O
OH

HO
OH
n

O
OH

Ce4+

O
MW

OH
NH2
OH
O

Guar Gum-OH
O

n
C

GG-g-PAM

NH2

Scheme 1. Mechanistic pathway for synthesis of GG-g-PAM.

dissolved in 40 mL distilled water in a 1000 mL borosil beaker, and

is made homogeneous by stirring. 1.5 g of acrylamide (AM), dissolved in 10 mL distilled water is added into the GG solution with
constant stirring for 15 min, followed by addition of required
amount of ceric ammonium sulfate (CAS). Prior to addition of the
initiator (CAS), a few drops of concentrated HCl are added. The
solution so obtained is irradiated by a domestic microwave oven
(800 W of power) for 3 min. Different concentration of CAS is used
to prepare various percentage of grafted GG keeping the other factors same. The gel like mass is then cooled by placing the reaction
vessel in cold water, and then poured into excess of acetone with
constant stirring. The precipitated grafted copolymer is ltered
and washed with acetone and alcohol water mixture. The residue
after drying in oven for 2 h at temperature 7080 C, is kept in a
vacuum desiccator to obtain a constant weight. It is proposed that
some of the free AOH groups of mannopyranose backbone convert
_ radicals by the action of the free radical initiator and the
into AO
microwave irradiation, which in turn, reacts with the AM monomer resulting into GG-g-PAM (Scheme 1). The percentage grafting
(%G, Eq. (1)) as obtained for different concentrations of CAS, are
summarized in Table 1 [22,23].
%G

mass of the grafted product  mass of guar gum taken

 100
mass of guar gum taken

It is observed that in absence of AM, 0.8 g of GG is recovered

from 1 g of GG after performing the whole process. %G for each
reaction between GG and AM (entry 25 in Table 1) is calculated
taking into consideration of the amount of recovered GG (entry 1
in Table 1). It is noteworthy that without any GG, AM does not
produce any precipitate of PAM. This is because the maximum

concentration of CAS used in this study is low enough to rule out

the possibility of formation of any polyacrylamide homopolymer.
Grafted polymer is characterized by FTIR (Thermo-Nicolet iS10 IR
spectrometer in the range 4000400 cm1). The FTIR spectra of
GG, PAM and GG-g-PAM are shown in Fig. 1(AD) and the characteristic frequencies are tabulated in Table 2. All the characteristic
absorption bands for GG and PAM are present in the FTIR spectrum
of GG-g-PAM, suggesting proper grafting of PAM on the GG backbone [2225].
As the molecular weight of GG-g-PAM cannot be ascertained
accurately due to its inherent molecular complexity and the possibility of partial hydrolysis in acid solution on prolonged exposure,
concentration of the inhibitor is expressed in terms of ppm by
weight.
2.2. Metal coupons preparation
Test specimens are cut from a commercially available mild steel
rod (wt% composition: 0.22 C, 0.31 Si, 0.60 Mn, 0.04 P, 0.06 S and
the remainder iron). The cross-sectional surface is ground with different grade emery papers (400, 600, 800, 1200 and 1600), washed
with water, rinsed with acetone, again washed thoroughly with
doubly distilled water for many times and used as the working
electrode in electrochemical measurements.
2.3. Electrochemical measurements
Potentiodynamic polarization and electrochemical impedance
measurement are done by conventional three-electrode system
(model: Gill AC, ACM Instruments, UK) consisting of mild steel

Table 1
Synthetic details of microwave-assisted grafting.
System

wt. of Guar gum (g)

wt. of Acrylamide (g)

Wt. of CAS (g)

Final wt. of grafted polymer (g)

Times of irradiation (min)

%G

GG
GG-g-PAM
GG-g-PAM
GG-g-PAM
GG-g-PAM
GG-g-PAM

1
1
1
1
1
1

1.5
1.5
1.5
1.5
1.5

0.005
0.005
0.01
0.05
0.075
0.10

0.80
0.86
1.00
1.49
1.55
1.64

3
3
3
3
3
3

0
7.5
25
86
93
105

1
2
3
4
5

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P. Roy et al. / Corrosion Science 88 (2014) 246253

where, Q is a proportionality coefcient, x is the angular frequency,

n is a measure of surface irregularity. For whole numbers of
n = 1, 0, 1, CPE is reduced to the classical lumped elements capacitor (C), resistance (R), and inductance (L), respectively. To obtain
a direct correlation between charge-transfer resistance (Rct) and
double layer capacitance (Cdl), the later has been recalculated using
the following equation [30,31]:

868

1154 1078

3420
B

3180

C dl Q  R1n
ct

4000

3180
3370

2000

1500

gZ %
1000

500

Wavenumber (cm -1 )
Fig. 1. FT-IR spectra of (A) GG, (B) PAM, (C) GG-g-PAM 1, and (D) GG-g-PAM 3.

Table 2
Characteristic FTIR bands of the inhibitors.
Functional group

OAH Stretch
Amide A
Amide B
CAH Stretch
Amide I C@O Stretch
Amide II NAH bending
CH2 scissoring
CAN Stretch
OAH in plane bending
CAOAC Stretch

GG

PAM

GG-g-PAM

3420

29222880

1434

1380
1154, 1078, 868

3420
3180

1660
1595
1445
1407

3420
3180
29222880
1665
1610
1455
1420
1380 for low grafting
1154, 1078, 868

icorr  icorrinh
 100
icorr

where icorr and icorr(inh) are the values of corrosion current density of
uninhibited and inhibited specimens, respectively.
Electrochemical impedance (EIS) measurements are performed
in the frequency range 10 mHz to 100 kHz with a.c. amplitude of
10 mV (rms) at the rest potential. Nyquist plots obtained show
only one time constant corresponding to one capacitive loop
without any trace of inductive loop at low frequency range. These
capacitive loops are depressed with centre under the real axis,
which may correspond to the microscopic roughness of the
electrode surface and inhibitor adsorption on it. Accordingly,
these are tted with an equivalent circuit containing parallel
combination of charge transfer resistance-constant phase element
(Rct  CPE) which is connected in series with the electrolyte resistance (Rs) [2730]. The constant phase element (CPE) is related to
the double layer capacity (Cdl) and its impedance is given by:
n

Z CPE Q 1 ix

Rct  R0ct
 100
Rct

where Rct and R0ct are the values of charge transfer resistance
observed in the presence and absence of inhibitor.
All the experiments have been carried out at around the room
temperature of 30 C.
2.4. Weightloss measurements

Characteristic absorption (s) cm1

working electrode (WE) with an exposed area of 0.25 cm2, platinum as counter electrode and saturated calomel electrode (SCE)
as reference. Volume of HCl solution taken for each experiment
is 200 mL. Before electrochemical tests, the WE is kept in the test
solution for 30 min and the open circuit potential (OCP) is then
monitored for another 10 min for conrmation of steady state.
The potential sweep rate for potentiodynamic polarization
curves is 30 mV per min. Corrosion current density (icorr) is determined from the intercept of extrapolated cathodic and anodic Tafel
lines at the corrosion potential (Ecorr). The values of percentage
inhibition efciency, gP (%) are calculated from the following
equation:

gP %

The percentage inhibition efciencies gZ (%) in terms of Rct are

calculated through the following equation:

1420
1450
1610
1665

3420

1=n

For weight loss measurement, polished rectangular mild steel

coupons (2.5  2.5  0.1 cm3) (wt% composition: 0.19 C, 0.21 Si,
0.21 Mn, 0.01 P, 0.01 S and the remainder iron) are immersed in
75 mL of 1 M HCl without and with 500 ppm GG-g-PAM of two different %G (7.5% and 105%) for a duration of 196 h at room temperature around 30 C. Before immersion, accurate weights of the
polished, cleaned and dried specimens are taken. After different
intervals of time, the coupons are removed from the acid solution,
washed thoroughly with distilled water, dried in a vacuum desiccator and then weighed. Percentage inhibition efciency, gW (%)
is calculated at different time intervals following the relation:

gW %

W0  W
 100
W0

where W0 and W are the weight loss of the metal coupons in acid
medium without and with inhibitor for same immersion time.
2.5. Surface analysis
Scanning electron microscope (SEM, S-3000 N, Hitachi) is used
to study the surface morphology of metal surface. Before the measurement, test coupons are exposed to 1 M HCl solution without
and with 500 ppm GG-g-PAM (86%G) for 4 h, washed with distilled
water and then kept in vacuum desiccator. The surface of the dried
specimen is scratched with a knife and the resultant powder is
used for FTIR studies (KBr pellet method, Thermo Nicolet, model
iS10).
3. Results and discussion
3.1. Polarization measurements
Potentiodynamic polarizarion curves for mild steel in 1 M HCl,
in presence of 500 ppm GG, 500 ppm PAM and 500 ppm GG-gPAM with 86% grafting are shown in Fig. 2(ad). Comparing the
curves for GG and PAM with that of uninhibited sample, it is
observed that when GG and PAM are used as inhibitors, the Ecorr
values for mild steel in 1 M HCl shift slightly toward more negative
direction from that for the uninhibited sample (Fig. 2, Table 3).
Moreover, both the cathodic and anodic current are seen to
decrease using GG and PAM as inhibitors (Fig. 2). These suggest
that both GG and PAM act as mixed type inhibitor by getting
adsorbed on anodic as well as cathodic sites on the metal surface.

P. Roy et al. / Corrosion Science 88 (2014) 246253

GG-g-PAM is also seen to act as mixed type inhibitor, as cathodic and anodic currents are found to decrease simultaneously with
increase in GG-g-PAM concentration without any considerable
change in Ecorr values (Fig. 3, Table 3). It is hereby proposed that
H+ ions present on the cathodic sites of the metal surface get
attached with lone pair of electrons present on the hetero atoms
of GG-g-PAM and therefore, the cathodic sites ate blocked diminishing the rate of cathodic hydrogen evolution reaction. On the
other hand, GG-g-PAM forms complexes with Fe2+ ions present
on the anodic sites covering the anodic metal dissolution sites.
Details of possible modes of adsorption of GG-g-PAM on metal surface have been assigned following FTIR studies.
It is interesting to observe that inhibition efciency of GG and
PAM are low (about 7175% at a concentration level of 500 ppm).
It increases drastically with grafting of PAM on GG and attains a
value higher than 90% for 7.5%G at a concentration of 500 ppm.
High inhibition efciency maintained up to around 86% of grafting,
thereafter it begins to fall (Table 3).
3.2. Electrochemical impedance measurements
Results obtained from electrochemical impedance spectroscopy
(EIS) also support the observations obtained from potentiodynamic
polarization techniques regarding variation of IE with concentration of GG-g-PAM with various %G. Nyquist plots obtained from
EIS for mild steel in 1 M HCl, in presence of 500 ppm GG,
500 ppm PAM and 500 ppm GG-g-PAM with 86% grafting are
shown in Fig. 4(ad). Diameter of the capacitive loop is observed
to increase signicantly on grafting of GG with PAM from those
observed only for GG or PAM (Fig. 4). For a particular %G, gradual
increase in the diameter of capacitive loop is seen with increase
in the concentration of GG-g-PAM (Fig. 5). This is manifested in
the increase in Rct values and with simultaneous decrease in the
values of Cdl (Table 4). It suggests increased resistance in the charge
transfer process at the electrodeelectrolyte interface due to the
formation of protective layer on the metal surface by the action
of adsorption of inhibitor molecules [2732]. Under similar concentration levels, Rct value for GG-g-PAM is much more than the
combined Rct values of GG and PAM (Fig. 4, Table 4). This reects
the existence of some kind of intramolecular synergism toward
cooperative adsorption of the GG and PAM units present in GGg-PAM. Such a positive interaction sustains up to around 86% of
grafting and beyond that level this is seen to diminish gradually.
Following both the polarization and EIS studies, it is observed
that the inhibition efciency becomes almost same at a concentration

249

of 500 ppm for all the GG-g-PAM samples having %G of 7.586

(Table 3 and 4), suggesting almost equal extent of blocking of the
active sites on the mild steel surface under such condition.
3.3. Adsorption isotherm
To elucidate the nature of adsorption of GG-g-PAM having various %G on mild steel surface in acid medium and to determine the
free energy involved in such adsorption process, possible correlation between degree of surface coverage h (h = gZ(%)/100) and the
concentration of the inhibitor (C) has been assessed employing
several types of adsorption isotherms. Satisfactory tting of the
experimental values is obtained following the simplest Langmuir
monolayer adsorption model where equivalency of all the adsorption sites are considered (correlation coefcient, R2 = 0.999).
According to this model, h is related to C by the equation:

C
1

C
h K ads

where Kads is constant of adsorption. Plots of C/h with C at 30 C

(Fig. 6) for all the GG-g-PAM inhibitors yield straight line with slope
values very close to 1. From the values of the adsorption constant,
Kads, the standard free energy of adsorption (DG0ads ) for all the inhibitor systems are determined using the following equation:

DG0ads RT ln1  106 K ads

where 1  106 is the concentration of water molecules expressed in

mg L1, R is the universal gas constant and T be the temperature
(here, 303 K) (Table 5). It is seen that Kads is highest for 86%G. As
Kads and DG0ads are the thermodynamic parameters for a process
under equilibrium condition, no direct inference can be drawn from
these values regarding the nature of adsorption of GG-g-PAM on
mild steel surface. However, it may be noted that, in most of the
cases, biomolecules including polysaccharides are reported to get
adsorb on metals or alloys in acidic condition by weak electrostatic
bonding (i.e., physical adsorption) [914,32].
3.4. Weight loss measurement
The weight loss measurement shows that gW (%) increases
quickly after immersion, attains a maximum value of nearly 93%
after 5 h of immersion (Fig. 7). High inhibition efciency (>90%)
is maintained for about 50 h, after that it begins to decrease slowly.
It is also seen that for the whole time range, gW (%) is lower for the
GG-g-PAM sample with 105%G than that with 7.5%G (Fig. 7).
Increase in gW (%) with immersion time is due to increase in the
extent of surface coverage by inhibitor molecules forming corrosion resistive adsorbed layer over time. Gradual decline in gW (%)
after prolonged exposure may, most possibly, be related with the
breaking of the glycosidic linkages via hydrolysis in strongly acidic
environment, producing smaller fragments [33].
3.5. Surface analysis

Fig. 2. Potentiodynamic polarization curves for mild steel in 1 M HCl in presence of

(a) no inhibitor, (b) 500 ppm GG, (c) 500 ppm PAM, and (d) 500 ppm GG-g-PAM 3.

Scanning electron micrographs (SEM) of the surface of mild

steel immersed in 1 M HCl without and with the inhibitors are
shown in Fig. 8(A and B). Mild steel surface immersed in 1 M HCl
shows a very rough surface owing to severe uniform corrosion.
Presence of GG-g-PAM as inhibitor provides a cleaner and
smoother metal surface. This demonstrates the potentiality of
GG-g-PAM to act as an efcient corrosion inhibitor for mild steel
in acid media.
A detailed study on the FT-IR spectra of native GG, GG-g-PAM,
and those adsorbed on the mild steel surface has revealed some
key information regarding the mode of adsorption of the inhibitors

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P. Roy et al. / Corrosion Science 88 (2014) 246253

Table 3
Data from potentiodynamic polarization studies for mild steel in 1 M HCl in various inhibitor systems.
System

Conc (ppm)

Ecorr (mV/SCE)

icorr (mA cm2)

ba (mV dec1)

bc (mV dec1)

gP (%)

1 M HCl
GG
PAM

500
500

494
497
500

1.40
0.40
0.35

74
96
105

105
113
110

71.4
75.0

GG-g-PAM 1%G = 7.5

50
100
250
500

495
503
505
512

0.55
0.36
0.22
0.13

94
105
108
90

100
110
115
105

60.7
74.3
84.3
90.7

GG-g-PAM 2%G = 25

50
100
250
500

495
494
498
504

0.34
0.29
0.18
0.13

95
91
89
100

101
100
101
106

75.7
79.3
87.1
90.7

GG-g-PAM 3%G = 86

50
100
250
500

498
497
502
505

0.28
0.21
0.17
0.12

93
91
99
97

102
111
104
102

80.0
85.0
87.8
91.4

GG-g-PAM 4%G = 93

50
100
250
500

488
500
495
498

0.43
0.28
0.21
0.16

97
95
98
98

108
103
105
113

69.3
80.0
85.0
88.6

GG-g-PAM 5%G = 105

50
100
250
500

494
498
500
500

0.39
0.32
0.28
0.22

97
98
90
98

100
102
108
110

72.1
77.1
80.0
84.3

21Hz

40

36.3Hz

-Z''/ cm2

30

36.3Hz

b
20

4.08Hz
47.6Hz

10

7.04Hz
9.25Hz

a
9.25Hz

20

40

60

80

100

Z'/ cm2

Fig. 3. Potentiodynamic polarization curves for mild steel in 1 M HCl in presence of

GG-g-PAM 3 having concentrations of (a) 50 ppm, (b) 100 ppm, (c) 250 ppm, and (d)
500 ppm.

21Hz

40

-Z''/ cm2

30
20

4.08Hz
82.3Hz

10

47.6Hz

21Hz

a
0

20

40

60

80

100

Z'/ cm2
Fig. 4. Nyquist plots for mild steel in 1 M HCl in presence of (a) no inhibitor, (b)
500 ppm GG, (c) 500 ppm PAM, and (d) 500 ppm GG-g-PAM 3.

Fig. 5. Nyquist plots for mild steel in 1 M HCl in presence of GG-g-PAM 3 having
concentrations of (a) 50 ppm, (b) 100 ppm, (c) 250 ppm, and (d) 500 ppm.

on metal surface (Fig. 9) [2225]. GG shows a broad peak at around

3420 cm1, which may be ascribed due to the extensive intramolecular hydrogen bonded AOH groups present in the polysaccharide (Fig. 9A). In the surface adsorbed GG sample, this band
centered at 3420 cm1 is seen to become narrow (Fig. 9B). The
change in the shape of the band at 3420 cm1 clearly indicates that
the extent of hydrogen bonding in absorbed GG is less compared to
that in native GG. This, in turn, reveals that some of the hydroxyl
groups of GG are denitely involved in adsorption on metal surface. The peaks at 1154, 1078 and 863 cm1, which are assigned
to different vibrational modes of CAOAC, are seen to be distinctly
shifted to 1105, 1055 and 846 cm1, respectively, with relatively
lower intensities. Therefore, it is presumed that endocyclic O
atom of mannose unit of GG together with C6 AO of the same
monosaccharide unit form a favorable ve membered chelate with
the Fe2+. This leads to a horizontal orientation of GG with respect to
metal surface and subsequent adsorption of GG on metal leading to
a decrease in the rate of metal corrosion. Involvement of C6 oxygen
of mannose unit in chelate formation is further supported by the
red shift of 1434 cm1 band, characteristic of ACH2A scissoring

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P. Roy et al. / Corrosion Science 88 (2014) 246253

Table 4
Impedance parameters for the corrosion of mild steel in 1 M HCl in various inhibitor systems.
Q (lX1 sn cm2)

Cdl (lF cm2)

gZ (%)

6
31
37

749
254
161

0.83
0.84
0.83

247
101
56.5

80.6
83.8

2.8
2.4
2.3
2.6

20
40
54
101

492
346
289
107

0.83
0.84
0.83
0.83

191
153
123
42.3

70.0
85.0
88.9
94.0

50
100
250
500

2.7
2.6
2.2
2.6

33
39
79
103

372
219
129
104

0.83
0.83
0.84
0.84

151
82.8
53.8
43.8

81.8
84.6
92.4
94.2

GG-g-PAM 3%G = 86

50
100
250
500

2.6
2.4
2.3
2.4

42
63
75
107

276
189
138
128

0.84
0.84
0.86
0.85

118
81.3
65.5
60

85.7
90.5
92.0
94.4

GG-g-PAM 4%G = 93

50
100
250
500

2.2
2.1
2.2
2.3

24
47
62
88

224
161
135
119

0.82
0.845
0.85
0.846

71.5
65.8
58.1
51.9

75.0
87.2
90.3
93.2

GG-g-PAM 5%G = 105

50
100
250
500

2.1
2.3
2.2
2.3

30
41
47
62

216
198
177
133

0.84
0.84
0.843
0.85

82.8
79
72.5
57

80.0
85.4
87.2
90.3

System

Conc (ppm)

Rs (X)

1 M HCl
GG
PAM

500
500

2.4
2.3
1.7

GG-g-PAM 1%G = 7.5

50
100
250
500

GG-g-PAM 2%G = 25

Rct (X cm2)

600

2
R =0.999

90

80

400

W(%)

C/ (ppm)

500

300
200

60

GG-g-PAM 1
GG-g-PAM 3
GG-g-PAM 5

100

100

200

300

400

500

600

Fig. 6. Langmuir adsorption plot for mild steel in 1 M HCl in presence of GG-g-PAM
with different %G.

Table 5
The parameters of the linear regression from the Langmuir adsorption isotherm.

GG-g-PAM
GG-g-PAM
GG-g-PAM
GG-g-PAM
GG-g-PAM

1
2
3
4
5

20

40

60

80

100

time / h

C (ppm by wt)

System

GG-g-PAM 1 (7.5% G)
GG-g-PAM 5 (105% G)

50

0
0

70

Slope

R2

Kads (L mg1)

DG0ads (kJ mol1)

1.029
1.039
1.048
1.049
1.088

0.999
0.999
0.999
0.999
0.999

5.28  102
8.9  102
1.52  101
8.12  102
8.9  102

27.4
28.7
30.1
28.5
28.7

vibration. After shifting, this band overlaps with 1380 cm1 band,
assigned to O-H in-plane bending vibration, and ultimately, a relatively broad band is observed centered at 1386 cm1. Such type of
horizontal adsorption of GG on metal surface driven by chelate
type ring formation involving O atoms is been reported previously
[11].
GG-g-PAM shows a broad absorption band at around
3420 cm1, originating from AOH and ANHA stretching vibrations
(amide A band, Fig. 9C) [2225]. The bands at 3180 cm1,

Fig. 7. Variation of inhibition efciency of 500 ppm of GG-g-PAM having different

%G with immersion time towards corrosion of mild steel in 1 M HCl.

1665 cm1 and 1610 cm1 are due to amide B, amide carbonyl
stretching (amide I) and ANH bending (amide II) vibrations respectively. Band corresponds to ACH2A scissoring vibration of GG-gPAM appeared at 1455 cm1 while ACH2A wagging and twisting
vibrations give broad band from 1350 cm1 to 1320 cm1.
In the IR spectrum of surface adsorbed GG-g-PAM sample
(Fig. 9D), amide A band is prominently seen to be red shifted from
3415 cm1 to 3370 cm1. Amide-I band also shifts to lower wave
number, from 1665 to 1630 cm1, with lower relative intensity.
ACH2A scissoring vibration of surface adsorbed GG-g-PAM exhibits a red shift and overlaps with the CAN vibration band (at
1420 cm1 for unadsorbed GG-g-PAM), giving rise to a relatively
broad band at around 1405 cm1. Similar to the case of surface
adsorbed GG sample, the CAOAC vibrational absorption bands
move toward lower frequency region with lower relative intensity
in surface adsorbed GG-g-PAM sample.
From the above observations, some conclusions may be drawn
regarding to the mode of adsorption of GG-g-PAM on the mild steel
surface. Simultaneous adsorption of GG backbone and PAM units of
GG-g-PAM are responsible for high degree of corrosion inhibition

252

P. Roy et al. / Corrosion Science 88 (2014) 246253

Fig. 8. SEM images of mild steel after immersion in 1 M HCl having (A) no inhibitor, (b) 500 ppm GG-g-PAM 3.

PAM units of GG-g-PAM, on the other hand, use the amide group
for adsorption on both the cathodic and anodic sites of metal surface (Scheme 2). Lone pairs of electrons on N atom of ANHA, as
well as O atom of AC@O are presumably be involved for this (supported from the observation of red shift of the amide A and amide I
bands). Involvement of the amide group of PAM toward metal
complex formation is already been reported [34].
One of the most striking features of the work is the variation of
IE with %G. This may be explained considering the existence of
some kind of intramolecular synergism toward simultaneous
adsorption of GG backbone and the PAM units present in GG-gPAM. Effect of such kind of synergism [35], which cooperatively
strengthens adsorption phenomena of both the polysaccharide
and polymer units, exists from low to around 86% grafting. Intramolecular synergism develops as grafting increases effective
molecular volume of the inhibitor system, produces excess adsorption centres, and hence, gives higher surface coverage [35]. At still
higher %G, number of free AOH groups of GG accessible for adsorption on metal becomes very less, as well as chain length of PAM
units also increases. With increased chain length, polymer units
may be oriented along the GG backbone in such a fashion, that chelate formation with Fe2+ involving O atoms of the sugar units present in GG may become sterically hindered. Overall, at higher %G,
only the PAM units of GG-g-PAM become more and more responsible for the adsorption on mild steel and subsequent inhibition of
corrosion of the metal. As the inherent potentiality of PAM toward
corrosion inhibition of mild steel in acid medium is low, thus inhibition efciency decreases at high %G. After a long exposure in acid
solution, GG-g-PAM exhibits gradual decline in inhibition efciency. It may be due to breaking of the glycosidic linkages (due
to hydrolysis) reducing the effective molecular volume.

A
1386
1105
1055

846

C
1405
1630

D
3370
4000

3500

3000

2500

2000

1500

1000

500

Wavenumber (cm -1 )
Fig. 9. FT-IR spectra of (A) GG, (B) surface adsorbed GG, (C) GG-g-PAM 3, and (D)
surface adsorbed GG-g-PAM 3.

of mild steel in acid medium. GG backbone of GG-g-PAM gets

adsorbed on the anodic sites on metal surface mostly by chelate
formation with Fe2+ present on those sites involving endocyclic
O atom of mannose unit together with C6AO of the same monosaccharide unit (Scheme 2). Some of the free AOH groups (not
involved in copolymerization) are most possibly responsible for
adsorption of GG backbone on the cathodic sites of the metal surface involving H+ ions present there (Scheme 2). This is supported
from the observation that when GG gets adsorbed on the metal
surface, the 3420 cm1 band narrows down only, without any
change in peak position (i.e., in both native and surface adsorbed
GG, AOH bonds are involved in H-bonding up to different extent).

PAM

O O]
O

H2 N
H

PAM

OH

OH
H+

HO

O
Fe2+

NH
Gal 2

Fe2+
Fe

Scheme 2. Schematic representation of possible adsorption behavior of GG-g-PAM on mild steel surface in acid medium.

P. Roy et al. / Corrosion Science 88 (2014) 246253

4. Conclusions
Grafting of PAM on GG imparts profound inuence on the inhibition of corrosion of mild steel in HCl medium. GG-g-PAM, acting
as a mixed type inhibitor, provides high inhibition efciency at
around 86% grafting, and thereafter it falls gradually. EIS studies
also reveal the similar trend. It further conrms the formation of
stable adsorbed layer of GG-g-PAM on metal surface, which provides a barrier toward charge transfer process at the metal-electrolyte interface. Weight loss measurement has provided information
related to the duration of maintaining corrosion inhibition potentiality of such type of polymer grafted polysaccharides in strongly
acidic medium. Comparing the FTIR spectra of the inhibitors in
their native state and surface adsorbed state, it is concluded that
during adsorption, GG backbone of GG-g-PAM uses the endocyclic
and exocyclic O atoms of sugar units to form a chelate with Fe2+.
Free AOH groups of GG may also get involved in adsorption.
PAM units of grafted GG, on the other hand, interact with the metal
surface through the amide groups. Upto 86% grafting, adsorption of
GG backbone and that of PAM units are supposed to cooperatively
favor each other resulting in some intramolecular synergism,
responsible for the high degree of inhibition efciency.
Acknowledgements
PI thanks Department of Science and Technology, Govt. of India
for supporting a research project under Fast Track Scheme for
Young Scientists (no. SR/FT/CS-110/2010, dt. 20.09.2011).
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