Journal of Molecular Liquids 232 (2017) 9–19

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Adsorption characteristics of Iota-carrageenan and Inulin biopolymers as

potential corrosion inhibitors at mild steel/sulphuric acid interface
Nirmala Devi Gowraraju a, Saranya Jagadeesan b, Kiruthika Ayyasamy a, Lukman O. Olasunkanmi c,d,
Eno E. Ebenso c,⁎, Chitra Subramanian a,⁎
a
Department of Chemistry, PSGR Krishnammal College for Women, Coimbatore, India
b
Department of H & S (Chemistry), CMR Institute of Technology, Hyderabad, India
c
Material Science Innovation and Modelling (MaSIM) Research Focus Area, Faculty of Agriculture, Science and Technology, North-West University, Mafikeng Campus, Private Bag X2046, Mma-
batho 2735, South Africa
d
Department of Chemistry, Faculty of Science, Obafemi Awolowo University, Ile-Ife 220005, Nigeria

a r t i c l e i n f o a b s t r a c t

Article history: The corrosion inhibition efficiency performance of biopolymers Iota-carrageenan (IC) and Inulin (INU) on mild
Received 29 November 2016 steel in 0.5 M H2SO4 solution was evaluated using weight loss, potentiodynamic polarization and electrochemical
Accepted 14 February 2017 impedance spectroscopy (EIS) techniques. The inhibition efficiency of the inhibitors increased with increase in
Available online 16 February 2017
concentration. Thermodynamic parameters (ΔGads) and activation parameters (Ea, ΔHo, ΔSo) were calculated
to investigate the mechanism of inhibition. Polarization studies revealed that the studied inhibitors are mixed
Keywords:
Biopolymers
type. Scanning electron microscope (SEM), energy dispersive X-ray spectroscopic (EDX) and atomic force mi-
Weight loss croscopy (AFM) studies were used to characterize the surface morphology of inhibited and uninhibited mild
Electrochemical technique steel.
Mixed-type inhibitors © 2017 Elsevier B.V. All rights reserved.
Mild steel
Corrosion inhibition

1. Introduction corrosive medium. The compounds generally contain heterocyclic

A number of physical, chemical and mechanical properties favour
the use of mild steel for construction and manufacturing purposes.
Such properties include high carbon content of about 0.2 to 2.1% and
ability to conduct electric current effectively without tarnishing the
metal surface among others. Since it is prominently used as structural
and instrumental material, the prevention of its corrosion is very essen-
tial [1–3]. Most organic compounds with presumed defending action
against corrosion of metals and alloys do contain heteroatoms or elec-
tronegative atoms, especially N, O, S and P [4]. But the perils of these in-
hibitors are universally known and the restrictive ecological guidelines
of many countries enforced researches to emphasis on developing eco-
nomical, non-toxic and naturally viable products [5].
Natural polymers have started to gain tremendous attention in cor-
rosion inhibition studies in recent years. This is because they are effort-
lessly obtainable, biocompatible, non-toxic, economical, and safe to use
without side effects [6]. Just like other organic corrosion inhibitors, nat-
urally occurring polymers are capable of forming metal-polymer com-
plexes that eventually protect metal surface from exposure to
⁎ Corresponding authors.
E-mail addresses: Eno.Ebenso@nwu.ac.za (E.E. Ebenso), rajshree1995@rediffmail.com
(C. Subramanian).
rings whose heteroatoms, mainly O and N serve as active centers of ad-
sorption to metal surface [7,8]. Numerous works Literature search re-
vealed that numerous works have been done on the use of synthetic
and natural polymers as potential corrosion inhibitors in the last one de-
cade [9–14]. Umoren and Ebenso have worked extensively with a num-
ber of other prolific authors on inhibitive effects of polymers on mild
steel and aluminium corrosion in acidic environments [15–27]. A con-
cise recap of the progress in application of carbohydrate polymers as
corrosion inhibitors for metals is contained in a recent review paper
by Umoren and Eduok [28].
Considerable efforts are still being channeled towards populating re-
search database on environmental friendly polymeric corrosion inhibi-
tors. Numerous naturally occurring polymers are yet to be duly
appraised for their potential abilities to inhibit metal corrosion.
Among them are water soluble polysaccharide based natural polymers,
Iota-carrageenan (IC) and Inulin (INU). Iota-Carrageenan is a sulphated
polysaccharide extract from the seaweed called carrageen. The structur-
al units of a carrageenan comprise 3,6-anhydro-galactose (3,6-AG) and
β-D-galactose joined together by α-1,3 and β-1,4-glycosidic bonds
(Fig. 1a). Carrageenan can have different structures depending on the
extent of sulphonation and the nature of substitution of the hydroxyl
groups on the polysaccharide chain. Some known forms of carrageenan
include iota (ι), kappa (κ), Lambda (λ), and Nu (ν) carrageenan. The use

http://dx.doi.org/10.1016/j.molliq.2017.02.054
0167-7322/© 2017 Elsevier B.V. All rights reserved.
10 N.D. Gowraraju et al. / Journal of Molecular Liquids 232 (2017) 9–19
Fig. 1. Repeating unit (monomer) of (a) IC and (b) INU.
of carrageenan in food industries has been documented [29,30]. Its cor-
rosion inhibition potential for aluminium in HCl medium has also been
reported by Fares et al. [31]. The inhibitive effects of three classes of car-
rageenan (μ, ι and κ-carrageenan) on iron in 1 M HCl have also been re-
ported [32].
Inulin (INU) is also a polysaccharide, formed from a mixture of olig-
omers and polymers that belong to the group of gluco-fructans. It is
found in plants such as garlic, onion, artichoke and chicory. INU contains
repeating units of fructose joined by β(2,1) linkages and terminated by
glucose unit [33,34]. The chemical structure of INU repeating unit is
given in (Fig. 1b).
In the present work, corrosion inhibition performances of IC and INU
were investigated for mild steel in 0.5 M H2SO4. Corrosion rates and in-
hibition efficiencies were determined using both weight loss and elec-
trochemical techniques. Protective performances of the polymers
were further examined using surface morphology analyses, namely
scanning electron microscopy (SEM) and atomic force microscopy
(AFM) techniques.
2. Experimental procedure
2.1. Materials and solutions
Cold rolled mild steel specimens of dimension 3 × 1 × 1 cm having
composition of P (0.025% P), S (0.027%), Mn (0.369%), Si (0.129%), C
(0.084%) Cr (0.022%), Mo (0.011%), Ni (0.013%) and Fe (99.08%) were
utilized for corrosion rate estimate by weight loss method. The metal
coupon preparation, cleaning and weight loss measurements were
made as per the standard methods described in ASTM G1-03 and corro-
sion rate determined as described in ASTM D2688-15 [35,36]. The spec-
imens used for electrochemical corrosion studies were of exposed
surface area of 0.785 cm2.
Corrosive test solution was 0.5 M H2SO4 prepared by dilution of the
AR grade commercial concentrated acid with double distilled water and
standardized with standard sodium hydroxide. IC having molecular
weight 946.76 g/mol (200,000 to 800,000 Da) and INU with molecular
weight 522.45 g/mol (~ 5000 Da) used as inhibitors were purchased
from Sigma-Aldrich.
2.2. Weight loss measurements
The weights of mild steel coupons were taken and recorded before
immersion in test solutions containing 100 ml of 0.5 M H2SO4 without
the inhibitors (blank) and with different concentrations of IC and INU
(the inhibitors). Steel samples were recovered from the solutions after
3 h and their final weights were taken and recorded. The measurements
were carried out in triplicate measurements at different concentrations
(blank, 1 ppm, 10 ppm, 100 ppm, 1000 ppm) of the inhibitors and dif-
ferent temperatures (313−333 K).
Corrosion rate (CR, mpy) was calculated from the weight loss data
according to the equation:
534  W ðgÞ
CR ðmpyÞ ¼ ð1Þ
Density  Area ðcmÞ  Time ðhÞ
where W is the average weight loss in gram. Corrosion inhibition effi-
ciency (%IE) was also calculated from the weight loss data using the
equation:
100 ðWblank −Winhibitor Þ
%IE ¼ ð2Þ
Wblank
where, Wblank is the weight loss in uninhibited blank solution, and
Winhibitor is the weight loss in the presence of inhibitor. Percentage inhi-
bition efficiency (%IE) is related to the degree of surface of coverage (θ)
as:
%IE
θ¼ ð3Þ
100
2.3. Electrochemical measurements
Electrochemical corrosion of mild steel 0.5 M H2SO4 in the absence
and presence of different concentrations of IC and INU was monitored
using both Tafel polarization and electrochemical impedance spectrosco-
py (EIS) techniques. The measurements were recorded using a conven-
tional three-electrode system with IVIUM Compactstat Potentiostat/
Galvanostat. The three-electrode set-up comprises a saturated calomel
electrode (SCE) as the reference, mild steel as the working, and platinum
as the counter electrodes, respectively.
Impedance spectral were recorded in the frequency range of
10 kHz–0.01 Hz using 10 mV amplitude ac signal. Percentage inhibition
efficiency (IE%) was evaluated from charge transfer resistance (Rct)
values according to the equation:
100 ðRct  −Rct Þ
IE% ¼ ð4Þ
Rct 
where Rct and Rct⁎ are the charge transfer resistances in the absence and
presence of inhibitors respectively.
Tafel polarization curves were recorded in the potential range of
− 100 mV to + 100 mV with respect to OCP at the scan rate of
0.001 V/s. Tafel parameters such as corrosion potential (Ecorr), corrosion
current (Icorr), anodic and cathodic Tafel slopes (βa and βc respectively)
 N.D. Gowraraju et al. / Journal of Molecular Liquids 232 (2017) 9–19 11

were extracted from the Tafel curves via Tafel extrapolation with the aid experiences stronger polymer-solvent interactions compared to poly-
of IVIUM Stat software. Percentage inhibition efficiency is related to the mer-polymer interactions may proceed to slow gel dissolution.
Icorr as: On the contrary, dissolution in any solvent at ordinary temperature

is quite unlikely for polymers with strong hydrogen bonding or cross-
100 Icorr −IcorrðinhÞ linking crystallinity that results in polymer-polymer intermolecular
IE ð%Þ ¼ ð5Þ
Icorr forces. Such materials will only display slight degree of “puff” gel.
The current results revealed that, the high efficiency of 92–96% ex-
where Icorr and Icorr(inh) are corrosion current densities for the blank and hibited by the polymer IC is due to overpowering of polymer-polymer
inhibitor-containing systems respectively. attraction forces by polymer-solvent attraction forces, making diffusion
of the polymer easier and resulting in rapid and efficient adsorption.
2.4. Surface morphology studies Whereas with INU, the maximum inhibition efficiency of 78.16% indi-
cates that the polymer-polymer attraction forces was able to overcome
The polished samples of mild steel specimen of dimension polymer-solvent attraction forces only to a certain extent which may be
3 × 1 × 1 cm were fully immersed in 0.5 M H2SO4 blank solution, and due to strong intermolecular forces.
in 0.5 M H2SO4 solution containing 1000 ppm of the polymers for 3 h.
The specimens were removed and dried after 3 h immersion period. 3.2. Temperature effect on inhibitive performances of IC and INU
Scanning electron microscope (SEM) and energy dispersive X-ray
(EDX) analyses were then performed on the samples. SEM images and Weight loss measurements at different temperature provide more
EDX spectral were taken with the aid of Biomedical Research Micro- detailed insights into the kinetics and thermodynamics of metal corro-
scope (Mumbai, India), and the results provided information about sion in aqueous solutions. Such measurements on corrosion inhibitors
the surface characteristics and chemical composition of the layer. Atom- provide a clear route of adjudging whether an inhibitor adsorbs physi-
ic force microscopy (AFM) analysis was also carried on the same sam- cally or chemically onto metal surface. Chemical adsorption is strength-
ples. Multimode Scanning Probe microscope (NTMDT, NTEGRA prima, ened by increase in temperature, while physisorption is stronger at
Russia) operated on NOVA software was used for the AFM study. The lower temperature and vice versa.
analysis was performed with cantilever length, 135 lm, width, 30 lm, Corrosion rate (CR), and inhibition efficiency (%IE) obtained from
thickness, 2 lm, and force constant, 0.35–6.06 N/m. weight loss measurements at different temperatures (303 − 333 K)
are presented in Table 2. It was observed that in the presence of INU
3. Results and discussion as inhibitor, CR of mild steel in 0.5 M H2SO4 increases with increasing
solution temperature. The increase in CR with rise in temperature is
3.1. Weight loss method due to desorption of initially adsorbed inhibitor molecules, resulting in
exposure of greater surface area of metal to corrosive medium [38–
Corrosion rate (CR) and percentage inhibition efficiency (IE%) values 41]. Moreover rapid etching, desorption, decomposition and/or rear-
derived from weight loss experiments are listed in Table 1. CR was ob- rangement of inhibitor molecules leads to decrease in efficiency of the
served to decrease with successive increase in inhibitor concentration. inhibitors at high temperatures. Such behavior confirmed physisorption
Both IC and INU exhibited substantial protection efficiency for mild of INU on the metal surface. However, in the presence of IC as corrosion
steel in 0.5 M H2SO4. Maximum inhibition efficiencies of 96.67% and inhibitor, CR decreases (i.e. inhibition efficiency increases) with in-
78.16% were observed for IC and INU respectively at 1000 ppm. crease in temperature. This implies that the molecules of IC inhibit
Arukalam et al. [37] reported that the dissolution of polymer was steel corrosion in 0.5 M H2SO4 via chemisorption mechanism [42–44].
considered to be a slow and two stage processes. In the initial stage, dif-
fusion of solvent molecules into the polymer takes place thus producing 3.3. Activation parameters
a swollen gel, while the second stage features slow dissolution of the
swollen gel leading to the formation of a true solution. This dissolution Corrosion rate (CR) is related to apparent activation energy (Ea) ac-
results in fast and efficient adsorption of the polymers onto the metal cording to the Arrhenius equation:
surface. However, only the first step occurs more frequently, thereby
limiting the polymer adsorption process. Whether polymer dissolution −Ea
logCR ¼ þ logA ð6Þ
stops at the first stage or goes through the second stage also depends 2:303RT
on the nature of the polymer. The dissolution of a polymer that
where, T is absolute temperature, R is molar gas constant
(8.314 J K−1 mol− 1), and A is the Arrhenius pre-exponential factor.
Table 1
Corrosion rate, surface coverage and inhibition efficiencies for mild steel in 0.5 M H2SO4 in
the absence and presence of different concentrations of IC and INU at 303 K.
Table 2
Name of the inhibitor Conc. (ppm) IE (%) Surface coverage (θ) CR (mpy) Corrosion rate and inhibition efficiencies for mild steel in 0.5 M H2SO4 in the absence and
Blank – – – 10,128.23 presence 1000 ppm at different temperatures.
IC 1 78.99 0.7899 2121.22
Name of the inhibitor Temperature (K) IE (%) CR (mpy)
10 79.42 0.7942 2077.33
25 80.63 0.8063 1955.42 Blank 303 – 3374.45
50 84.25 0.8425 1589.69 313 – 14,136.63
100 92.32 0.9232 775.344 323 – 15,033.87
500 96.04 0.9604 399.86 333 – 23,416.37
1000 96.62 0.9662 341.34 IC 303 96.68 112.16
INU 1 56.23 0.5623 4417.99 313 97.27 385.23
10 64.20 0.6420 3613.39 323 97.37 394.99
25 66.62 0.6662 3369.57 333 97.40 609.55
50 66.81 0.6681 3350.07 INU 303 76.73 785.10
100 71.64 0.7164 2862.43 313 70.54 4164.43
500 73.43 0.7343 2682.00 323 67.24 4925.14
1000 78.16 0.7816 2204.12 333 59.31 9528.44
12 N.D. Gowraraju et al. / Journal of Molecular Liquids 232 (2017) 9–19

Fig. 3. Langmuir adsorption isotherm plots for mild steel in 0.5 M H2SO4 in the presence of
IC and INU.

Both Arrhenius and Transition state plots for mild steel dissolution in
0.5 M H2SO4 in the absence and presence of IC and INU are shown in
Fig. 2.
The values of Ea were evaluated from the slopes of straight lines in
Fig. 2a. The values of ΔHo and ΔSo were also determined from the
straight lines (Fig. 2b) corresponding to form of Eq. (7) through the
slope [−ΔHo / (2.303R)] and intercept [log (R/Nh) + ΔSo / (2.303R)] re-
spectively. The values of Ea, ΔHo and ΔSo are listed in Table 3.
Generally, a lower value of Ea for inhibited system compared to the
uninhibited one is an indication of chemisorption mechanism, while a
higher value of Ea for the inhibitor-containing solution compared to
the blank suggests physisorption mechanism [45,46]. Moreover, the
shift of net corrosion process from exposed surface to adsorbed sites ac-
counts for decrease in Ea at higher levels of inhibition. Also, increase in
Ea at higher temperatures can be associated with decrease in adsorption
of inhibitor molecules onto metal surface [47]. The results in Table 3
showed that the values of Ea in the presence of INU are higher than
that of the blank. This supports physisorption mechanism in which
the inhibitor molecules form protective barrier to charge and mass
transfer, which consequently reduces the corrosion rate [46]. However,
a lower value of Ea in the presence of IC compared to blank suggests
chemisorption of inhibitor molecules. These observations support the
Fig. 2. Arrhenius (a) and transition state (b) plots for mild steel corrosion in 0.5 M H2SO4 in
the absence and presence of IC and INU.
variation of CR with temperature earlier reported in Table 2.
The values of Ea and ΔHo in Table 3 are relatively close and follow the
same pattern. This is in line with the concept of transition-state theory
Furthermore, other thermodynamic activation parameters were calcu-
[47]. A positive value of ΔHo indicates that the metal dissolution is an
lated using the equation:
endothermic process. This has also been reported to be indicative of re-
 o   tarded dissolution of metal in inhibitor-containing solution [48]. There-
RT ΔS −ΔHo fore, the values of ΔHo obtained in the present study (Table 3) indicate
CR ¼ exp exp ð7Þ
Nh R RT that mild steel dissolution is an endothermic process and was retarded
by the inhibitors.
where, h is Planck's constant, N is Avogadro's number, T is absolute tem- The values of ΔSo for both inhibitors are negative, indicating that the
perature, R is the universal gas constant, ΔHo is the enthalpy of activa- rate determining step witnessed association rather than dissociating
tion and ΔSo is the entropy of activation. phenomenon in the formation of activated complex. In other words,

Table 3
Activation parameters for mild steel corrosion in 0.5 M H2SO4 in the absence and presence of 1000 ppm of IC and INU at different temperatures.

Inhibitor Activation parameters +ΔGo

−1 o −1 o
Ea (kJ mol ) ΔH (kJ mol ) ΔS 303 K 313 K 323 K 333 K
(J mol−1 K−1)

Blank 49.77 47.13 −61.80 18.77 19.39 20.01 20.62

IC 43.22 40.58 −112.16 34.02 35.14 36.26 37.38
INU 64.74 62.10 −24.44 7.47 7.71 7.95 8.20
 N.D. Gowraraju et al. / Journal of Molecular Liquids 232 (2017) 9–19 13

Table 4
Langmuir adsorption parameters for adsorption of IC and INU on mild steel surface in
0.5 M H2SO4 at 303 K.

Inhibitor R2 Slope K mol lt−1 −ΔGoads kJ mol−1

IC 0.999 1.03 4132.28 31.09

INU 0.998 1.28 8908.19 33.03

transition from reactants to activated complex was accompanied by de-

crease in disorderliness [49]. The values of ΔSo obtained in the present
study are negative, indicating that the transition state of mild steel dis-
solution in 0.5 M H2SO4 is features more ordered species than the
starting materials. In the presence of inhibitors, the discharge of hydro-
gen ions to form adsorbed hydrogen atoms at the metal surface will be
prevented by the adsorption of inhibitor molecules. This causes the sys-
tem to pass from a more orderly to a less orderly arrangement [45]. It
was also observed that the ΔSo in the presence of IC is more negative
than that of INU. This may be attributed to the larger molecular weight
of IC, resulting in a more pronounced decrease in disorderliness upon
activated complex formation.
The change in free energy (ΔGo) activation for mild steel in 0.5 M
H2SO4 in the absence and presence of IC and INU was calculated using
the equation:

ΔGo ¼ ΔHo −TΔSo ð8Þ

The values of ΔGo are listed in Table 3. Positive values of ΔGo obtain-
ed in the present study suggest that the activated complex is unstable.
ΔGo increases very slightly with increasing temperature, suggesting
that relative thermodynamic favourability of activated complex forma-
tion decreases with increasing temperature.

3.4. Adsorption isotherms

More relevant information about the interaction between inhibitors Fig. 4. Van't Hoff (lnK vs 1 / T) (a) and Gibbs-Helmholtz (ΔG / T and 1 / T) (b) plots for mild
steel in 0.5 M H2SO4 in the presence of IC and INU as corrosion inhibitors.
and metal surface can be obtained from various adsorption isotherms.
The possible modes of adsorption of inhibitor molecules on metal sur-
face are physisorption and chemisorption mechanisms [50].
Kads were evaluated from the intercepts of the plots. Change in free en-
The values of surface coverage (θ) (Table 1) obtained from weight
ergy of adsorption (ΔGoads) was calculated from Kads according to the
loss experiments were put into various adsorption isotherm models in-
equation:
cluding Temkin, Flory-Huggins, Langmuir and El-Awady. The best fitting
was obtained from Langmuir adsorption. Langmuir adsorption isotherm
can be expressed as: ΔGo ads ¼ −2:303RT log ð55:5 KÞ ð10Þ

C 1 where T is the absolute temperature, R is the gas constant, and 55.5 is

¼ þC
θ Kads
where C is inhibitor concentration and Kads is the equilibrium constant
for adsorption. Langmuir adsorption isotherm plots for the corrosion
of mild steel in 0.5 M H2SO4 in the presence of various concentrations
of IC and INU are shown in Fig. 3.
The straight line graphs with R2 values close to unity are indicative of
conformity of the experimental results to the isotherm. The values of
ð9Þ
the concentration (mol L−1) of water in solution.
The R2 values for the isotherm plots, Kads and ΔGoads are listed in
Table 4. The results showed that Kads values are very large for the two
inhibitors, which imply strong adsorption of the inhibitor molecules
and mild steel surface, and hence efficient corrosion inhibition potential.
A value of ΔGoads up to − 20 kJ mol−1 is ascribed to electrostatic or
Vander Waals interaction between charged molecules and charged
metal surface, that is physisorption, while those more negative than

Table 5
Thermodynamic parameters derived from Van't Hoff equation for the adsorption of IC and INU on mild steel surface in 0.5 M H2SO4 at different temperatures.

Name of the inhibitor Van't Hoff equation Gibbs-Helmholtz equation −ΔGoads kJ mol−1
o −1 −1
ΔH ads kJ mol ΔSoads ΔHoads kJ mol 303 K 313 K 323 K 333 K
kJ mol−1 K−1

IC 6.75 −0.1050 6.75 36.01 37.73 39.04 40.27

INU −21.82 −0.02869 −21.82 30.53 30.70 31.27 31.29
14 N.D. Gowraraju et al. / Journal of Molecular Liquids 232 (2017) 9–19

Fig. 5. Nyquist plots for mild steel in 0.5 M H2SO4 in the absence and presence of different Fig. 6. Tafel curves for mild steel in 0.5 M H2SO4 in the absence and presence of different
concentrations of IC (a) and INU (b); and equivalent circuit used for EIS spectra analysis (c). concentrations of IC and INU.

−40 kJ mol−1 involves charge distribution or transmission from the in-
hibitor molecules to the metal surface to form a chemical adsorption
(co-ordinate type bond) [51]. The values of ΔGoads obtained in this
study (Table 4) are between −30 to −40 kJ mol−1 proving that in ad-
dition to electrostatic interaction there must be some other interactions.
Hence the adsorption of the polymers may be a combination of both
physisorption and chemisorption in which physisorption predominates
for INU (ΔGoads is − 31.2 kJ mol− 1 at 333 K) and chemisorption
predominates for IC (ΔGoads is − 40.2 kJ mol− 1 at 333 K) (Table.5).
The negative values indicate spontaneity of the adsorption process
and stability of the adsorbed layer on the mild steel surface.
3.5. Adsorption thermodynamic parameters
Additional information about thermodynamics of adsorption of IC
and INU on mild steel in 0.5 M H2SO4 could be obtained from enthalpy

Table 6
AC-impedance parameters for mild steel in 0.5 M H2SO4 in the absence and presence of different concentrations of IC and INU as inhibitors.

Name of the inhibitor Conc. (ppm) Rct (Ω cm2) Cdl (μF/cm2) IE (%)

Blank – 17.4 30.5 –

IC 1 86.0 21.2 79.76
10 97.6 21.0 82.17
100 107.5 19.1 83.81
1000 132.1 19.0 86.82
INU 1 56.02 28.4 68.93
10 65.40 26.4 73.39
100 70.06 24.9 75.16
1000 79.85 16.0 78.20
 N.D. Gowraraju et al. / Journal of Molecular Liquids 232 (2017) 9–19 15

Table 7
Corrosion parameters obtained from Tafel polarization curves for mild steel in 0.5 M H2SO4 in the absence and presence of different concentrations of IC and INU.

Name of the inhibitor Conc. (ppm) Tafel slopes (mV/dec) −Ecorr (mV) Icorr (μA/cm2) IE (%)

ba bc

Blank – 81 132 470 79.71 –

IC 1 73 172 485 50.85 36.20
10 56 162 477 27.06 66.05
100 48 156 471 21.21 73.39
1000 45 149 467 14.03 82.39
INU 1 62 148 479 34.9 56.21
10 53 159 475 26.64 66.57
100 46 156 467 19.47 75.57
1000 47 162 471 18.38 76.94

and entropy of adsorption (ΔHoads and ΔSoads respectively) using the
Van't Hoff equation:
ΔHo ads ΔSo ads 1 o
ln Kads ¼ − þ þ ln
RT R 55:5
The plot of lnKads vs. 1 / T (Fig. 4a) afforded straight line whose inter-
cept equals (ΔSoads / R) + ln (1 / 55.5) and slope equals ΔHoads / R. The
enthalpy of adsorption can also be calculated from the Gibbs-Helmholtz
equation, as follows
ΔGo ads ΔHo ads
¼ þ constant
T T
The plot of ΔGoads / T against 1 / T is shown in Fig. 4b. The Gibbs-
Helmholtz plots gave straight lines for both IC and INU and ΔHoads
was derived from the slope. Fig. 4b reflects a linear but inverse relation-
ship between ΔGoads / T and 1 / T. The values of thermodynamic param-
eters for the adsorption process derived from both Eqs. (11) and (12)
are listed in Table 5. A negative ΔHoads implies that the adsorption pro-
cess is exothermic, while a positive value is indicative of endothermic
adsorption process. An exothermic adsorption can be physisorption or
chemisorption, even though, an endothermic adsorption has been clas-
sified as chemical adsorption. However, in an exothermic process, ΔH-
ads values are generally used to distinguish physisorption and
ð11Þ
chemisorption process. For physisorption process, the magnitude of
ΔHoads is around −40 kJ mol−1 or less negative while the value around
− 100 kJ mol− 1 or more negative is associated with chemisorption.
Therefore, the values of ΔHoads obtained in this study (6.75 kJ mol−1
for IC, and −21.82 kJ mol−1 for INU) suggest chemisorption mode for
IC and physisorption mechanism for INU. The values of ΔHoads obtained
from the two thermodynamic equations (Eqs. (11) and (12)) are in
good agreement [52].
ð12Þ
3.6. Electrochemical impedance spectroscopy (EIS) studies
EIS technique is popularly used in corrosion inhibition study partly
because it provides essential information about the electrical nature of
the metal/solution interface. The electrochemical characteristics of
mild steel in 0.5 M H2SO4 in the absence and presence of IC and INU
(corrosion inhibitors) are represented as EIS Nyquist plots in Fig. 5. A
single depressed capacitive loop of a Nyquist plot is often related a

Fig. 7. SEM images for mild steel in 0.5 M H2SO4 without inhibitors (a), with 1000 ppm of IC (b), and 1000 ppm of INU (c).
16 N.D. Gowraraju et al. / Journal of Molecular Liquids 232 (2017) 9–19

charge transfer controlled corrosion process. Such nature of Nyquist

plots obtained in the present study suggests that the corrosion of mild
steel in 0.5 M H2SO4 is controlled by a single charge transfer process.
The increasing diameter of the Nyquist capacitive loop with increasing
inhibitor concentration is indicative of inhibitive actions of IC and INU
on mild steel corrosion in the acid and the protective performance of
the compounds increase with increasing concentration.
EIS spectra were analyzed using the equivalent circuit in Fig. 5c,
which comprises the solution resistance (Rs), charge transfer resistance
(Rct), and constant phase element (CPE). The double layer capacitance
(Cdl) was calculated from Rct using the equation:

1
Cdl ¼ f Rct ð13Þ
2π max

where fmax is the frequency corresponding to the maximum impedance

in the EIS spectra.
The values of Rct and Cdl for mild steel in 0.5 M H2SO4 in the absence
and presence of IC and INU are listed in Table 6. The calculated inhibition
efficiencies at different concentrations of the inhibitors are also listed.
The results revealed lower Cdl for inhibited systems compared to the
blank. This can be attributed to decrease in local dielectric constant
and/or increase in the thickness of electrical double layer formed on
the steel surface by the adsorbed inhibitor molecules. More so, Rct
values are higher for the inhibitor-containing systems than the blank
acid solution, which also showed increasing inhibition efficiency with
increase in inhibitor concentration. The adsorbed inhibitor molecules
form protective film on the mild steel surface and serve as impeding
barrier to mass and charge transfer phenomena that usually aid metal
corrosion [53–55].

3.7. Tafel polarization measurements

Tafel polarization curves for mild steel in 0.5 M H2SO4 in the absence
and presence of IC and INU are shown in Fig. 6. Some relevant kinetic
parameters such as Tafel slopes (ba and bc), corrosion potential (Ecorr)
and corrosion current (Icorr) obtained through Tafel analysis or extrapo-
lation of the linear segments of the curves are listed in Table 7. The inhi-
bition efficiency values calculated from the Icorr are also listed in Table 7.
Detailed examination of the Fig. 6 revealed that in the absence of the
studied polymers, mild steel in 0.5 M H2SO4 showed the maximum ca-
thodic and anodic currents. It can be inferred that the studied polymers
reduce the anodic dissolution of metal and also impede the cathodic hy-
drogen evolution reaction. This might have been due to adsorption of IC
and INU molecules on mild steel surface thereby blocking the active
sites on steel surface. The decrease in Icorr values with increase in inhib-
itor concentration leads to increase in inhibition efficiency [56,57].
The shifts or displacements in Ecorr values when the results in the
blank acid solution are compared with the inhibited ones are generally
less than 85 mV. This suggests that the studied polysaccharide polymers
inhibit both anodic and cathodic reactions involved in the corrosion of
mild steel in 0.5 M H2SO4 and they are therefore mixed-type inhibitors
[58]. The change in anodic and cathode Tafel slopes upon addition of in-
hibitors also points at the mixed mode inhibitive actions of the
compounds.
3.8. Surface morphology studies
Fig. 8. EDS analysis (a) for mild steel in the absence of inhibitor, (b) presence of 1000 ppm
IC, and (c) presence of 1000 ppm INU.
the surface. This confirms the adsorption of inhibitor molecules onto
mild steel surface and the formation of passive film that protects the ac-
tive sties on the steel from immediate attack by the acid.
3.8.2. Energy dispersion spectroscopy (EDS) studies
Elemental compositions of mild steel surface immersed in the corro-
sive media without with 1000 ppm of the polymer inhibitors were ob-
tained from EDS spectra analyses (Fig. 8). The results of EDS analyses
for the steel surface removed from the acid blank and inhibited systems
are shown in Fig. 8. The EDS spectrum for the blank shows that Fe, O,
Mn, Ni, and S are present, which confirms the formation of corrosion
product. Whereas, the EDS spectra for the steel retrieved from acidic so-
lutions that contain the inhibitors did not show Ni and Mn, and also
showed lower intensity of Fe signal which suggests that the inhibitors
are adsorbed on mild steel surface. Percentage compositions the ele-
ments based on atomic weights are listed in Table 8.
3.8.3. Atomic force microscopic (AFM) technique
Three dimensional (3D) cross-sectional profiles of AFM images of
the surface of mild steel immersed in 0.5 M H2SO4 (blank) and in the

3.8.1. Scanning electron microscopy (SEM) studies

Table 8
Fig. 7 shows the SEM micrographs of mild steel samples in the blank
EDS elemental composition of mild steel surface after 3 hour immersion in 0.5 M H2SO4
(0.5 M H2SO4) solution and in the presence of 1000 ppm of IC and INU without and with 1000 ppm of IC and INU.
after exposure for 3 h. The micrographs clearly show crystals of rust
Name of the inhibitor Element (atomic weight/%)
(FeSO4) [59] formed on the mild steel surface in the absence of inhibitor.
This is due to severe corrosion attack on the blank sample in the absence Blank O (53.94), Fe(41.93)
of inhibitors. But in the presence of 1000 ppm of IC and INU (Fig. 7b & c), IC C(9.69), O(30.53), Fe(33.74)
INU C(11.69), O(35.63), Fe(36.23)
the micrographs show a uniform passive protective layer produced on
 N.D. Gowraraju et al. / Journal of Molecular Liquids 232 (2017) 9–19
Fig. 9. AFM images of mild steel surface exposed to (a) 0.5 M H2SO4 solution without inhibitors, (b) with 1000 ppm IC, and (c) with 1000 ppm of INU.
presence of the studied inhibitors are presented in Fig. 9. AFM images in
Fig. 9 revealed cracked and eroded mild steel surface due to the acid at-
tack. The surface of mild steel in the presence of inhibitors was not as af-
fected as the one without the inhibitors. Estimated average roughnesses
of mild steel in blank solution was 176.808 nm, while the corresponding
values in the presence of 1000 ppm of IC and INU are 92.36 nm and
102.36 nm respectively. These values of surface roughness confirm
that the steel surface is protected by the inhibitor molecules, most prob-
ably by formation of protective film on the surface.
3.8.4. Mechanism of corrosion inhibition
All the results pointed out that IC show higher inhibition efficiency
than INU. The higher inhibition efficiency of IC is attributed to their gel
forming capacity. The presence of oxygen (hetero atom) and electro-
statically negative sulphate atoms, which serve as adsorption centers
in IC enhanced its inhibition efficiency [31].
On the other hand, in 0.5 M H2SO4, mild steel is corroded to Fe2+ and
the surface of mild steel gets positively charged. The SO24 − ions are
Fig. 10. Schematic representation of the formation of adsorption layer of IC on mild steel
surface.
17
attracted by the charges on the metal surface which tends to be charged
negatively [60]. The obtained results could be explained on the assump-
tion that the negatively charged SO2− 4 would attach to the positively
charged surface. Such positively surface can electrostatically attract neg-
atively charged sulphate ions and the partial negatively charged oxygen
heteroatoms of IC resulting in adsorbed film/layer on the metal surface
[61].
Analyses of experimental data based on thermodynamic theories
and equations proposed that IC adsorbs via chemisorption mechanism,
while INU adsorbs via physisorption mechanism. The strong chemical
adsorption of IC is dependent on the presence of OSO3− in the chemical
structure. The OSO3− group increases the electron density and retards
cathodic and anodic reactions. Moreover, some functional groups are li-
able to be protonated in acidic medium [62], such that the protonated
form IC (IC + xH+ ⇌ [ICx]x +) may be adsorbed on the cathodic sites
of mild steel thereby retarding the cathodic hydrogen evolution reac-
tion (2H+ + 2e– → H2).
Adsorption of neutral and the protonated forms of inhibitors on
metal surface results in formation of coordinate covalent bonds. This oc-
curs via partial sharing of the electrons from the unprotonated oxygen
atoms and \\OSO3− atoms with the anodic sites of the metal surface.
The vacant d orbitals of Fe2+ ions receive the shared electrons and an-
odic metal dissolution will be inhibited [63]. The inhibitory mechanism
on metal dissolution is also related to the chelating effect of Fe2+ ions
close to mild steel surface. Schematic representation of adsorption of
IC on mild steel surface is shown in Fig. 10.
4. Conclusions
Corrosion inhibition characteristics of two natural polymers of poly-
saccharide genre, IC and INU were studied on mild steel corrosion in
0.5 M H2SO4 medium. It can be concluded from the results that:
18 N.D. Gowraraju et al. / Journal of Molecular Liquids 232 (2017) 9–19
1. Both IC and INU are efficient corrosion inhibitors for mild steel in the
studied medium and their inhibition efficiencies increase with in-
crease in concentration.
2. IC showed higher protection performance than INU and this might be
due to the presence of the\\OSO3−, which enhances adsorption of IC
on charged metal surface.
3. The adsorption characteristics of both IC and INU followed the Lang-
muir adsorption isotherm model.
4. IC adsorbed on mild steel surface via chemisorption mechanism,
while the adsorption of INU occurred through physisorption mecha-
nism as inferred from thermodynamic data (ΔGads and ΔHads).
5. EIS data indicated the corrosion process is controlled by charge trans-
fer reactions, and the inhibitors increased the charge transfer resis-
tances in the electrochemical systems.
6. Polarization measurements showed that both IC and INU are mixed
type inhibitors.
7. Surface morphology studies confirmed the mitigation of mild steel
corrosion by formation of protective film on the steel surface.
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