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Research Article
Water-Soluble and Biodegradable Pectin-Grafted
Polyacrylamide and Pectin-Grafted Polyacrylic Acid:
Electrochemical Investigation of Corrosion-Inhibition
Behaviour on Mild Steel in 3.5% NaCl Media
Copyright © 2014 R. Geethanjali et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Pectin-g-polyacrylamide (denoted as Pec-g-PAAm) and pectin-g-polyacrylic acid (denoted as Pec-g-PAA) were synthesized using
pectin, acrylamide, and acrylic acid as starting materials. The grafted polymers were characterized using Fourier transform infrared
spectroscopy (FTIR), thermogravimetric analyser (TGA), and scanning electron microscopy (SEM). The corrosion inhibition
behaviour of the grafted polymers on mild steel in 3.5% NaCl was evaluated electrochemically through Tafel polarization and
impedance studies. The corrosion inhibition performance of both the polymers was found to be around 85%.
2. Experimental
Pec-g-PAAm
2.1. Instruments and Chemicals. Instruments used in the
present research include Remi-Magnetic stirrer, Shimadzu
Electronic weighing balance, Tensor-27 FTIR spectrometer,
Transmittance (%)
4000 3500 3000 2500 2000 1500 1000 500 2.2. Water-Soluble Pec-g-PAAm and Pec-g-PAA. The graft
Frequency (cm−1 ) polymerization of acrylamide on pectin was carried out by
slightly modifying the procedure given by Mishra et al. [10]
Figure 1: FTIR spectrum of Pec-g-PAAm and Pec-g-PAA. to achieve water soluble products as per our requirement.
Mishra et al. synthesized a pH sensitive hydrogel using the
pectin and acrylamide, but in this study, the solubility of the
polymer products was achieved by adding sodium hydroxide
to the reaction mixture and carrying out the polymerization
provided a highest corrosion inhibition percentage of 95% in acetone/water medium. When pectin was present in higher
in 10% HCl acid medium at 25∘ C and 80∘ C. The corrosion amount, insoluble hydrogels resulted, so the amount of
inhibition performance may be due to the comprehensive the pectin was taken in minimum quantities. The detailed
synergistic effect through the graft reaction among lignin, reaction procedure is as follows.
AM, and DMDAAC. 1.9 g of recrystallized acrylamide and 0.1 g of pectin were
Fares et al. [6] studied the corrosion inhibition perfor- as mixed in 5 g of water and 2.5 g of acetone. The reaction mix-
mance of pectin as promising green corrosion inhibitor of ture was neutralised with 0.2 mL of 30% sodium hydroxide.
aluminium in hydrochloric acid solution. Polyacrylamide Then 0.2 mL of 10% polyvinyl alcohol was added. The whole
was grafted on okra fruit mucilage and corrosion behaviour reaction mixture was purged with nitrogen for 30 minutes
was investigated in acid medium [7]. Akbarzadeh et al. [8] to ensure an inert atmosphere. As a redox initiator 0.1 mL
evaluated corrosion inhibition of mild steel in near neutral of potassium persulphate/0.05 mL of sodium bisulphite was
solution by kraft and soda lignins extracted from oil palm added, and the reaction was allowed to continue for 4 hours.
empty fruit bunch. The reaction temperature was maintained in the range of 45–
Several polymers have been grafted onto the backbone 50∘ C. The resulting viscous solution was precipitated using
of natural polymers like starch, chitosan, alginate, pectin, acetone. The fibrous polymer products were lyophilized and
carrageenan, and so forth and used as hydrogels in drug- used for further studies. The same procedure was followed for
delivery systems, sensor applications, flocculating agents and graft polymerization of acrylic acid on pectin.
adsorbents, and so forth.
In this paper, the natural polymer pectin was modified
2.3. Characterization of the Polymers
by grafting it with polyacrylic acid (Pec-g-PAA) and poly-
acrylamide (Pec-g-PAAm), and the compatibility as corro- 2.3.1. FTIR Spectroscopy. The structures of the prepared
sion inhibitors has been evaluated for mild steel in neutral polymers were confirmed using FTIR spectrometer having an
medium, and the optimum ratio has been found in the ATR assembly. The scan range was 400–4000 cm−1 .
study. Pectin is known to be rapidly degraded by colonic
microorganisms which makes it a potential carrier for colon
targeted drug delivery. Pec-g-PAA and Pec-g-PAAm were 2.3.2. Thermogravimetric Analysis. The thermal stability of
reported as pH sensitive hydrogels to be used in the colon the polymers was determined using thermogravimetric anal-
drug delivery [9–12]. Hence the polymers can be claimed to yser at a heating rate of 20∘ C/minute from 30 to 650∘ C under
be biodegradable and environmentally friendly. Nitrogen purge.
Though weight-loss measurement is a reliable and univer-
sally accepted method, the huge time factor for studying the 2.3.3. Scanning Electron Microscopic and Elemental Analysis.
mild steel corrosion in sodium chloride medium has to be The grafted polymers were dissolved in water and coated as a
considered. Therefore, electrochemical measurements could thin layer on carbon tape and imaged in a SEM instrument.
be the best alternative for testing corrosion at a faster rate
with more information and can be used in field detection 2.4. Electrochemical Measurements. The specimen used for
combined with other methods. After all, electrochemical the study is mild steel coupon of 1 cm2 exposed surface
technique is a nondestructive, quantitative technique and a area attached to a steel rod by brass welding. Before each
powerful tool for researching corrosion process [13]. test the specimen was ground using different grades of
Indian Journal of Materials Science 3
500.0 331.9 ∘ C
249.5 ∘ C 510.8 𝜇g/min
14.61% 491.4 𝜇g/min 8.000
450.0 90.00
400.0
80.00 7.000
9.53%
350.0
4.93%
DTG (𝜇g/min)
70.00 6.000
300.0
TG (mg)
TG (%)
250.0 60.00
69.1 ∘ C 29.36% 5.000
194.9 𝜇g/min
200.0 143.6 ∘ C
50.00 167.7 𝜇g/min
150.0 177.6 ∘ C 4.000
128.8 𝜇g/min
40.00
100.0 9.49%
3.000
50.0 30.00
100.0 200.0 300.0 400.0 500.0 600.0
Temperature (∘ C)
Figure 2
18.00 10.00
341.3 ∘ C
206.7 C∘ 17.86 mg/min
8.00
16.00 7.01 mg
6.00
14.00
4.00
12.00 2.00
DTG (mg/min)
276.0 ∘ C
TG (mg)
0.00
10.00 −1.03 mg
DTA (𝜇V)
−2.00
8.00
337.6 ∘ C −4.00
−3.13 mg
6.00 −6.00
343.5 ∘ C
−7.11 mg −8.00
4.00
252.5 ∘ C
3.52 mg/min −10.00
2.00
−12.00
Figure 3
emery paper to achieve a mirror-finish polished surface. and cathodic Tafel slopes (𝑏𝑎 and 𝑏𝑐 ) were obtained. Corrosion
A platinum electrode as counter electrode and a calomel current density was measured from the intersection point
electrode containing saturated potassium chloride solution as obtained by the extrapolation of Tafel lines. The inhibition
reference electrode were used for the electrochemical studies efficiency can be calculated from corrosion current 𝐼corr using
in 3.5% sodium chloride as electrolyte solution. The electro- the following equation:
chemical investigation was conducted as two different phases,
namely potentiodynamic polarization and electrochemical
impedance measurements. 𝐼corr
IE (%) = 100 × [1 − ∘
], (1)
The potentiodynamic polarization was conducted with 𝐼corr
constant sweep rate of 1 mV/sec in the range of −0.1 to −1 mV
with respect to 𝐸corr .
∘
Various corrosion kinetic parameters such as corrosion where 𝐼corr and 𝐼corr are the corrosion current densities of
current density (𝐼corr ), corrosion potential (𝐸corr ), and anodic uninhibited and inhibited solutions, respectively.
4 Indian Journal of Materials Science
Table 1: Polarisation parameters obtained for MS in 3.5% NaCl in the presence of various concentrations of Pec-g-PAAm.
Table 2: Polarisation parameters obtained for MS in 3.5% NaCl in the presence of various concentrations of Pec-g-PAA.
Figure 4: Scanning electron microscopic image of pectin. Figure 5: Scanning electron microscopic image of Pec-g-PAAm
(magnified view).
Table 3: Impedance parameters and inhibition efficiency values for mild steel sample in 3.5% NaCl containing various concentrations of
Pec-g-PAAm.
Table 4: Impedance parameters and inhibition efficiency values for mild steel sample in 3.5% NaCl containing various concentrations of
Pec-g-PAA.
0
−0.1
Ewe (V versus SCE)
−0.2
−0.3
−0.4
−0.5
−0.6
−0.7
−0.8
−0.9
−1
−4 −3 −2 −1 0 1 2
log(|⟨I⟩ (mA)|)
Ewe versus log(|⟨I⟩|)
3.5% NaCl · mpr 600 ppm Pec-g-PAAm · mpr
100 ppm Pec-g-PAAm · mpr 700 ppm Pec-g-PAAm · mpr
300 ppm Pec-g-PAAm · mpr 800 ppm Pec-g-PAAm · mpr
500 ppm Pec-g-PAAm · mpr 900 ppm Pec-g-PAAm · mpr
Figure 6: Scanning electron microscopic image of Pec-g-PAA.
Figure 7
1.5 80
0.5
log(|⟨I ⟩ (mA)|)
70
−Im(Z) (Ohm)
−0.5 60
50
−1.5 40
−2.5 30
−3.5 20
10
−4.5 0
−1 −0.8 −0.6 −0.4 −0.2 0 50 100 150 200
Ewe (V) Re(Z) (Ohm)
log(|⟨I⟩|) versus Ewe −Im(Z) versus Re(Z)
3.5% NaCl · mpr 300 ppm Pec-g-PAA · mpp 3.5% NaCl · mpr 400 ppm Pec-g-PAA · mpp
50 ppm Pec-g-PAA · mpp 400 ppm Pec-g-PAA · mpp 50 ppm Pec-g-PAA · mpp 500 ppm Pec-g-PAA · mpp
100 ppm Pec-g-PAA · mpp 500 ppm Pec-g-PAA · mpp 100 ppm Pec-g-PAA · mpp
200 ppm Pec-g-PAA · mpp 200 ppm Pec-g-PAA · mpp
300 ppm Pec-g-PAA · mpp
Figure 8
Figure 10
80
70 Cads
−Im(Z) (Ohm)
60
50
40
30
20 Rel
10 Cdl
0
50 100
Re(Z) (Ohm) Rads
−Im(Z) versus Re(Z)
900 ppm Pec-g-PAAm · mpr 400 ppm Pec-g-PAAm · mpr Rp
800 ppm Pec-g-PAAm · mpr 300 ppm Pec-g-PAAm · mpr
700 ppm Pec-g-PAAm · mpr 100 ppm Pec-g-PAAm · mpr
600 ppm Pec-g-PAAm · mpr 3.5% NaCl · mpr Figure 11: Equivalent circuit model used to fit the impedance data.
500 ppm Pec-g-PAAm · mpr
Figure 9
observed. Pectin is specifically called pectinic acid which is
a polyacid. The interaction of pectinic acid and acrylamide
grafted links between the pectin and polyacrylamide. The depends on ionization of the polyacid and structural com-
second step of degradation occurs at 200–300∘ C, where a patibility between the polymers [17]. When pectin gets dis-
weight loss of 9.53% and 4.93% is observed indicating the loss solved in water, it exists as complex network-like structures
of lateral chains of the polymer. The final step of degradation containing branched and linear structures in the form of rods,
occurs in the range of 300–600∘ C with a major weight loss segmented rods, and kinked rods [18, 19]. In this case, pectin
indicating the breakdown of the polymer backbone matrix appears like a feather-like structure (Figure 4). In Figures 5
[16]. and 6, a floral structure composed of agglomerated feather-
A similar trend was observed for Pec-g-PAA till 200∘ C. like portion containing crystalline particles can be found
But the second step of degradation occurs steadily compared which accounts for the grafted structure of the polymer. Such
to that in Pec-g-PAAm which is attributed to the easy break- an organization potentially reveals the grafted structure of the
ing up of the lateral chains of the polymer. At 350∘ C there is polymers on the pectin scaffold.
a steep fall, indicating major mass loss at this temperature. In
the temperature range of 350–600∘ C, further breakdown of
the polymer backbone matrix might have taken place. 3.2. Electrochemical Studies
This thermal degradation profile provides an additional 3.2.1. Tafel Extrapolation. The polarization parameters calcu-
evidence for the grafting of the polymers and also ensures lated for the pectin grafted polymers are listed in Tables 1 and
the use of the polymers even at high temperature saline 2. The polarisation curves for the pectin grafted polymers are
environments. shown in Figures 7 and 8.
3.1.3. Scanning Electron Microscopic Analysis. The micro- Pec-g-PAAm. The potentiodynamic anodic and cathodic
structure morphology of the pectin, Pec-g-PAAm and Pec- polarisation curves of mild steel in NaCl medium containing
g-PAA is shown in the Figures 4–6, respectively. In Figures 5 different concentrations of the grafted polyacrylamide are
and 6, the distribution of grafted polymeric particles can be presented in Figure 7 and the corresponding electrochemical
Indian Journal of Materials Science 7
1100.0 that the cathodic and anodic reactions are not much altered
throughout the corrosion process.
900.0 Non-Tafel behaviour is observed for NaCl medium and
several authors have reported that accurate Tafel extrapola-
C/𝜃 (mg/L)
[26].
300 The results listed in the table reveal that there is a decrease
200
in corrosion current density with increase in polarisation
resistance and inhibition efficiency, which is in well accor-
100 dance with the dependency on inhibitor concentration. A
0 definite negative shift in the 𝐸corr values suggests that the
0 100 200 300 400 500 600 inhibitor is a strong cathodic inhibitor as it dominantly
Concentration (mg/L) controls the cathodic reduction reaction [27].
Figure 13: Langmuir isotherm for adsorption of Pec-g-PAA on mild
steel in NaCl.
3.2.2. Impedance Circles. The Nyquist plots in the presence
and absence of various concentrations of Pec-g-PAAm and
Pec-g-PAA are given in Figures 9 and 10, respectively. The
parameters are listed in Table 1. The data clearly shows that Nyquist plots are single capacitive semicircles which show
the 𝐸corr values shift to more positive values, and corrosion that the corrosion process is governed by charge-transfer
current density is reduced. Ferreira et al. [20] have reported process [28]. The diameters of the semicircles increase with
that (i) if the displacement in (𝐸corr ) values is >85 mV in the increasing inhibitor concentration. The impedance spec-
inhibited system with respect to uninhibited, the inhibitor could trum for mild steel in neutral media is interpreted with two
be recognized as cathodic or anodic type and (ii) if displacement time constants by using a simple equivalent circuit which
in 𝐸corr is <85 mV, it could be recognized as mixed-type. In this represents an imperfectly covered electrode [29–31].
case, the shift in 𝐸corr values is more than 85 mV, and analysis The equivalent circuit proposed to fit the impedance
of the polarisation curves shows that the anodic current data of both the grafted polymers is shown in Figure 11.
density is reduced significantly compared to the cathodic The 𝑅ads /𝐶ads is the high frequency time constant attributed
current density. Hence the polymer under investigation must to the adsorption of the inhibitor and 𝑅𝑝 /𝐶dl is the low
be predominantly an anodic inhibitor inhibiting the anodic frequency time constant attributed to the defect sites where
dissolution reaction [21, 22]. charge transfer processes take place. Different parameters
obtained from the fit are listed in Tables 3 and 4 and analysed.
Pec-g-PAA. Inspection of the polarisation curves (Figure 8) The total resistance of the system is calculated by adding all
of Pec-g-PAA reveals that the cathodic current density is the resistances 𝑅el , 𝑅ads , and 𝑅𝑝 [32] and the corresponding
controlled to a greater extent compared to the anodic inhibition efficiency obtained is given in the table. From the
current density. Though oxygen is present in the solution, table, it is evident that the resistance values increased and
the decrease in the cathodic current density cannot be the capacitance values decreased. The decrease in capacitance
attributed to the oxygen reduction, because oxygen reduction values is due to the adsorption of the inhibitor molecules
might have reached a diffusion-controlled limit which is not on the surface thereby causing a change in the double layer.
observed in the polarisation plot [23]. Thus we can conclude The double layer in between the charged metal surface and
that the grafted polyacrylic acid controls the corrosion solution is considered as electrical capacitor. Therefore, the
process mainly by blocking the cathodic sites rather than adsorption of the inhibitor on the metal surface decreases the
the anodic sites, and the polymer is a moderate cathodic electrical capacitance of the metal and also displaces the water
inhibitor and not of much anodic inhibitor [24]. The shape molecules and other ions adsorbed on the surface and forms
of the polarisation curves remains the same which indicates a protective layer [33, 34].
8 Indian Journal of Materials Science
COOCH3
COOCH3
H O
H O
H ∗ OH H O ∗
∗ OH H O ∗ + CH C K2 S2 O8 /NaHSO3 n
n H
H COOR N2
H OH
∗ C C ∗
H OH H
COOR
R = NH2 or H
Grafted polymer
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