Journal of Molecular Liquids 258 (2018) 89–97

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Journal of Molecular Liquids

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

Use of Saraca ashoka extract as green corrosion inhibitor for mild steel in
0.5 M H2SO4
Akhil Saxena a, Dwarika Prasad a,⁎, Rajesh Haldhar a, Gurmeet Singh b, Akshay Kumar b
a
Department of Chemistry, Lovely Professional University, Phagwara 144411, Punjab, India
b
Department of Chemistry, University of Delhi, India

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

Article history: The corrosion inhibition effect of Saraca ashoka seeds extract, a plant belonging to Legume family, has been exam-
Received 2 October 2017 ined on mild steel corrosion in 0.5 M H2SO4 by using weight loss measurements, potentiodynamic polarization
Received in revised form 19 February 2018 measurements and electrochemical impedance spectroscopy (EIS) techniques. The presence of this epicatechin
Accepted 23 February 2018
containing extract decreases the corrosion rate of mild steel in acidic solution. The best inhibition effect of Saraca
Available online 27 February 2018
ashoka extract for mild steel in 0.5 M H2SO4 was obtained at 100 mg/L using electrochemical and weight loss
Keywords:
measurements. The adsorption of Saraca ashoka seeds extract on the surface of mild steel has been investigated
Saraca ashoka by using AFM study, SEM study and absorption spectroscopic techniques. Due to the existence of hetero atoms in
Green corrosion inhibitor the main components, Saraca ashoka extract is considered to be a good inhibitor.
Mild steel © 2018 Elsevier B.V. All rights reserved.
Electrochemical impedance spectroscopy
Polarization measurements
SEM
AFM

1. Introduction Plant extract, a kind of natural products, constitute a considerable

class of corrosion inhibitors because they are easily available, renewable
Mild steel is utilized to make an extensive variety of hardware and and non-toxic. The abundant chemical constituents, such as flavonoids,
metallic structures because of its minimal effort and great mechanical polyphenols, and polysaccharide, endow plant extract with the poten-
quality. A great economic loss may be caused during the process of tial of inhibiting the corrosion process of mild steel [4]. The vast majority
acid pickling of mild steel (MS) in the industry because the compounds of the natural products containing functional groups of the sort NH2,
that we use to remove the impurities and unwanted surface deposits C_O and CHO is known to be viable inhibitors. These compounds get
from the metal surface, consist of strong acids [1]. Because of the overall adsorbed on the metal surface to stimulate the improvement of a defen-
aggression of acid solutions, inhibitors are normally accustomed to re- sive layer.
tard the acidic attack on metallic materials. Throughout past decades, Entering into the twenty first century, alongside people's growing
some industrial inhibitors are synthesized and used with success to in- consciousness of protecting the atmosphere, an oversized range of pre-
hibit corrosion of steel in acidic media [2]. However the most important cise manuscripts about plant extracts as effective corrosion inhibitors of
drawback associated with most of those inhibitors is that they are not iron or steel in acidic media have been published; the studied plants like
eco-friendly however venomous and pricy. Therefore the study of latest Salvia officinalis shows 96% inhibition efficiency at 2500 mg/L [5],
non-toxic or low toxic corrosion inhibitors is important to beat this Osmanthus fragran shows 94% inhibition efficiency at 340 mg/L [6],
drawback. The analysis within the field of eco-friendly corrosion inhib- Musa paradisica shows 90% inhibition efficiency at 300 mg/L [7], Man-
itors has been self-addressed towards the goal of victimization of low grove tannins shows 89% inhibition efficiency at 6000 mg/L [8],
cost, effective compounds at low or zero environmental impact. How- Jasminum nudiflorum shows 92% inhibition efficiency at 1000 mg/L [9],
ever the synthetic compounds may have some negative consequences Lawsonia inermis shows 92% inhibition efficiency at 1200 mg/L [10],
for the environment and they may also be harmful to human health. Dendrocalamus brandisii shows 90% inhibition efficiency at 1000 mg/L
In recent times, the exploration of cheap, ecofriendly and biodegradable [11], Aqueous coffee grounds shows 83% inhibition efficiency at
corrosion inhibitors is getting more attention [3]. 400 mg/L [12], Phyllanthus amarus shows 81% inhibition efficiency at
4000 mg/L [13], Black radish shows 92% inhibition efficiency at
1000 mg/L [14], Ginkgo shows 80% inhibition efficiency at 100 mg/L
⁎ Corresponding author. [15], Kola nitida shows 78% inhibition efficiency at 1200 mg/L [16], Rad-
E-mail address: [email protected] (D. Prasad). ish seeds show 79% inhibition efficiency at 10 mg/L [17], Murraya

https://doi.org/10.1016/j.molliq.2018.02.104
0167-7322/© 2018 Elsevier B.V. All rights reserved.
90 A. Saxena et al. / Journal of Molecular Liquids 258 (2018) 89–97

2.2. Weight loss measurements

For weight loss estimations the mild steel specimens were set up as
ASTM G 31-72 [22]. The cleaned and dried steel specimens were
weighted and exposed in the test solution at 25 °C in the absence and
presence of inhibitor for 24-h immersion period. According to ASTM G
31-72, the volume of the test solution was kept at around 20 mL per
cm2 surface area of single panel used. The temperatures of the experi-
ments were kept up by keeping the beakers in a water circulated ther-
mostat (±0.5 K exactness). After indicated time, the steel specimens
were taken out from the corrosive solution, rinsed with acetone, dried
under nitrogen flow and weighted. Three values were obtained by re-
peating experiments three times, and an average value was recorded.

Fig. 1. Chemical structure of Epicatechin.

2.3. Electrochemical measurements

koenigii shows 96% inhibition efficiency at 600 mg/L [18], Bamboo leaf
shows 89% inhibition efficiency at 200 mg/L [19] and Butea monosperma CH Instrument Electrochemical Workstation was used to carry out
shows 98% inhibition efficiency at 500 mg/L [20].Through these studies electrochemical measurements. The cell system, an easy three-elec-
it is in agreement that the inhibition performance of plant extract is trode, contains the mild steel electrode, a platinum electrode, and a sat-
often ascribed to the presence in their composition of complicated or- urated calomel electrode (SCE) as the working electrode, the counter
ganic species like tannins, alkaloids, carbohydrates, amino acids, and electrode and the reference electrode, respectively. For electrochemical
proteins. These organic compounds contain polar functions with N, O measurements, the specimens were embedded in epoxy resin leaving a
atoms further as conjugated double bonds or aromatic rings in their mo- working area of 1 cm2. At the beginning of the tests, the working elec-
lecular structures which are the major adsorption centers. trode was immersed in the test solution for 1 h to get a stabilized
The objective of the present work is to explore the corrosion inhibi- open circuit potential (OCP). Electrochemical impedance spectroscopy
tion analysis and adsorption behaviour of Saraca ashoka extract. It is an (EIS) was scanned from the frequency of 100 kHz to 0.01 Hz with a sig-
Indian plant commonly known as ashoka. The Saraca ashoka extract nal amplitude perturbation of 5 mV at OCP. Respecting to OCP at the
consists of tannin, saponins and flavonoids like epicatechin [21]. The an- scan rate of 1 mV/s, potentiodynamic polarization curves were recorded
tioxidant constituents in the extract of Saraca ashoka seeds, epicatechin, with a scan of ±250 mV vs. SCE. Reliable values were achieved by re-
(Fig. 1), have a strong electron-donating and chelating capacity with peating all electrochemical measurements three times.
iron, giving the extract the ability to inhibit the corrosion of metal.
Herein, the Saraca ashoka seeds were extracted and their inhibition effi-
ciencies for MS were optimized in 0.5 M H2SO4. The inhibition perfor- 2.4. UV–visible spectroscopy
mance and mechanism were also discussed. Fourier transform
infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) By using UV 1800 absorption spectrophotometer, the UV spectra of
were employed to characterize the extract and the surface morphology Saraca ashoka extract in 0.5 M H2SO4 were recorded. The spectra were
of MS, respectively. taken out in two distinct circumstances i.e. solution of inhibitor in
which the mild steel specimens were not immersed and the solution
2. Experimental in which the steel specimens were immersed for 24 h. Both these spec-
tra were compared to explain the mechanism of inhibition [23,24].
2.1. Materials preparation

The chemical composition of mild steel in this work is Fe 97.60%, C

0.083%, P 0.12%, Cr 0.45%, Ni 0.27% and Cu 0.43%. The specimens were
cut into 1 cm2 dimensions for weight loss, potentiodynamic polarization
measurements and electrochemical impedance studies. These speci-
mens were polished with 100, 200, 500, 1000, and 1500 grades of
emery papers, degreased with acetone and rinsed with distilled water
before inserting them into the test solution. The sulphuric acid was di-
luted to 0.5 M H2SO4 as the corrosive medium.
The seeds of Saraca ashoka were purchased from the market and it
was validated by Dr. Arbeen Ahmad Bhatt in the Department of Biotech-
nology Lovely Professional University Punjab, India. Fresh Saraca ashoka
seeds were obtained from market and after that cleaned with tap water
to take out fiery remains of mud, dried the seeds for two days in an oven
at 60 °C and ground to powder. 100 g powdered sample was refluxed
persistently with 450 cm3 of ethanol at 75 °C for 3 h. The refluxed solu-
tion was filtered and the pH of the aqueous solution was found to be 9.
The filter liquor was evaporated to 100 mL of dark brown residue, dried
in a vacuum drying oven at 60 °C for 2 days. At that point the dark
brown colored solid deposit (around 4.5 g) was acquired for finish dry-
ness and saved in a desiccator. The test solutions with specific concen-
trations (25, 50, 75, 100 mg/L) were obtained by diluting extract with
0.5 M H2SO4. The greatest solvency of Saraca ashoka extract in 0.5 M
H2SO4 was observed up to 100 mg/L. Fig. 2. FTIR spectrum of Saraca ashoka extract.
 A. Saxena et al. / Journal of Molecular Liquids 258 (2018) 89–97 91

Fig. 4. Langmuir adsorption isotherm for Saraca ashoka extract on mild steel in 0.5 M
Fig. 3. UV Spectra of Saraca ashoka extract before and after immersion of mild steel strips. H2SO4 at 298.15 K.

2.5. FTIR spectroscopy molecule on steel surface to reduce the corrosion of mild steel. In the
present work, the FTIR spectroscopy was employed to verify whether
For a better understanding of inhibition mechanism, the FTIR spectra the Saraca ashoka extract contains some of these groups. In the FTIR
of Saraca ashoka extract, was taken out. The Saraca ashoka extract spectra (Fig. 2), the stretching vibration of O\\H causes the peak cen-
blended with KBr powder was transferred into a pallet for FTIR charac- tered at 3379.40 cm−1 and the peak at 1013.52 cm−1 indicates C\\O
terization in a FTIR 8400S spectrophotometer with the wave number of stretching. The further peak at 1602.50 cm−1 is due to the presence of
500–4000 cm−1. aromatic ring. The results from FTIR characterization show that the
anti-corrosion property of Saraca ashoka extract is due to the presence
2.6. Surface analysis of O atoms and aromatic rings in the compounds which exist in extract.

After immersing the pretreated mild steel samples from 0.5 M H2SO4 3.2. UV–visible spectroscopy
solution without and with 100 mg/L extract for 24 h, the surfaces of mild
steel samples were rinsed with ultrapure water and acetone, and dried. The UV spectra of Saraca ashoka extract with 0.5 M H2SO4 prior and
The SEM images of these samples were then taken out by using then afterward immersing the mild steel samples from the solution
LEO435BP and AFM images were taken by using NT-MDT-INTEGRA, to were thought about and they have been shown in Fig. 3. From the ab-
explain the surface morphologies. sorption spectra, the absorbance of solution in which steel specimen
was not immersed, is higher contrasted with the solution in which
2.7. Quantum chemical studies steel specimen was immersed for a time period of 24 h. Fig. 3 shows
peak at 255 nm and 310 nm which indicate π-π* and n-π* transition re-
Optimization of molecular structure was performed using the spectively. It clearly demonstrates that, when the mild steel specimen
Hyperchem 8.0 software. Theoretical calculations were carried out was immersed into the acidic solution of Saraca ashoka extract, at that
using DFT. Key parameters such as energies of LUMO (ELUMO) and point a few molecules from the solution have been adsorbed on the
HOMO (EHOMO), energy gap (ΔE) between LUMO and HOMO and metal surface [23,24].
the number of transferred electron (ΔN) were also determined.
3.3. Weight loss measurements
3. Results and discussion
Table 1 shows the weight loss values, inhibition efficiency (η %) and
surface coverage (θ) for mild steel at different concentrations of Saraca
3.1. FTIR characterization
ashoka extract, which were calculated from weight loss by the following
equations-
The existence of the heteroatoms (N, O), aromatic ring and double
bond in organic molecules may assist the adsorption of the inhibitor
w0 −wi
θ¼ ð1Þ
Table 1 w0
The data of weight loss for mild steel in 0.5 M H2SO4 without and with different concen-
trations of Saraca ashoka extract.
w0 −wi
Acid Inhibitor Weight loss Efficiency Surface coverage η ð%Þ ¼  100 ð2Þ
solution concentration (mg cm−2 h−1) (η %) (θ)
w0
(mg/L)

0.5 M 0 0.0563 00 00 Table 2

H2SO4 25 0.0158 71.93 0.7193 ∆G°ads for Saraca ashoka extract at 298 K.
50 0.0125 77.79 0.7779
S·No. Inhibitor Kads (103 M−1) ∆G°adsKJ Mol−1
75 0.00984 82.52 0.8252
100 0.00564 89.98 0.8998 1. Saraca ashoka 89.80 −21.09
92 A. Saxena et al. / Journal of Molecular Liquids 258 (2018) 89–97

value of ∆G°ads lies in the range of −20 KJ Mol−1 to −40 KJ Mol−1

that most likely indicates that each physisorption and chemisorptions
are taking place within the system.

3.4. Polarization measurements

Concentration effect of the Saraca ashoka extract on the polarization

behaviour of mild steel in 0.5 M H2SO4 was analyzed and the Tafel plots
were recorded for different inhibitor concentrations which are shown in
Fig. 5. The corrosion current densities were calculated by extrapolation
of linear parts of anodic and cathodic curves to the point of intersection
of the corresponding corrosion potential. The Tafel curves indicate re-
ductions in the current densities of the anodic and cathodic branches
in the presence of Saraca ashoka extract. The ascertained development
is also the results of covering of adsorbed inhibitor molecules on the
mild steel surface and decreasing dissolution of steel surface area. The
higher concentration results in a lower current density at 25 to
100 mg/L. For further analysis, the parameters, including corrosion po-
tential (Ecorr), corrosion current density (icorr), anodic and cathodic
Tafel slope (βa and βc) and inhibition efficiency (η %) calculated by Eq.
Fig. 5. Tafel polarization curves for mild steel in 0.5 M H2SO4 without and with different (6) [28], are shown in Table 3.
concentrations of Saraca ashoka extract.
I0corr −Iicorr
η ð%Þ ¼  100 ð6Þ
where wi and w0 are the weight loss values in presence and absence of I0corr
inhibitor, respectively. The corrosion rate of the steel is reduced, after in-
creasing the concentration of Saraca ashoka extract. This phenomenon is where I0corr and Iicorr represent the corrosion current density values
caused by the adsorption of active ingredients of Saraca ashoka extract without and with inhibitor respectively.
on the steel surface. The highest value of inhibition efficiency is obtained From Fig. 5 it is clear that each anodic metal dissolution and cathodic
at 100 mg/L. hydrogen evolution reactions were inhibited once the addition of inhib-
For further analysis of adsorption behaviour of Saraca ashoka extract itors to the aggressive medium. The inhibitons of these reactions are ad-
on mild steel surface, Langmuir adsorption isotherm was employed to ditional pronounced with the increasing inhibitor concentration. These
fit the experimental data obtained by weight loss. The Langmuir adsorp- results indicate that the studied inhibitor acts as a mixed type corrosion
tion isotherm is a plot of log C/ɵ vs. log C (Fig. 4). Adsorption of inhibitor inhibitor. The almost unaffected anodic and cathodic Tafel slopes before
molecules on mild steel surface by Langmuir adsorption isotherm is and after adding Saraca ashoka extract indicate that the anodic and ca-
given by the following equations [25]. thodic reaction mechanisms are still controlled by charge transfer.
Thus the main constituents of Saraca ashoka extract were just adsorbed
C 1 onto the steel surface and retarded the corrosion process of mild steel
¼ þC ð3Þ
θ K ads without any change of the reaction mechanisms. Saraca ashoka extract
contains many organic compounds, which not only can be adsorbed
η ð%Þ on steel surface through electrostatic interaction but also can form a
θ¼ ð4Þ
100 strong coordination bond with iron for the existence of heteroatoms
and aromatic rings. The combination of physisorption and chemisorp-
where θ is the surface coverage in Table 1, C is the concentration of
tion makes the active components of Saraca ashoka extract be strongly
Saraca ashoka extract and Kads is the adsorption equilibrium constant.
The value of Kads calculated from Eq. 3 is 89.80 g/L. Fig. 4 shows the
Table 3
plot of C/θ as a function of C, which is a straight line with R2 = 0.9899
Polarization parameters for mild steel in 0.5 M H2SO4 without and with different concen-
and slope almost equal to 1. It confirms the adsorption activity of Saraca trations of Saraca ashoka extract.
ashoka extract on the steel surface, which indicates that the typical ad-
Inhibitor Ecorr Icorr βa βc Efficiency
sorption sites at the steel-electrolyte interface is occupied by active
concentration (mg/L) (V vs. SCE) (A cm−2) (V/dec) (V/dec) (η %)
compounds of Saraca ashoka extract as some works reported [26].
0 0.008909 141.66 164.25 0
Now the Kads can be correlated with the standard free energy of ad- −0.465
25 −0.489 0.001851 91.44 122.91 79.22
sorption by the following equation: 50 −0.482 0.001254 79.15 106.23 86.01
75 −0.471 0.0008574 51.43 104.25 90.37
∆G °ads ¼ −R  T ln ð55:5  K ads Þ ð5Þ 100 −0.452 0.0004025 57.44 117.86 95.48

where R is the gas constant, T is absolute temperature, ∆G°ads is stan-

dard free energy of adsorption and 55.5 is the molar concentration of
water in the solution in mol/L. The corresponding results obtained are Table 4
listed in Table 2. It has been investigated that if the value of ∆G°ads EIS parameters for mild steel in 0.5 M H2SO4 without and with different concentrations of
is – 40 KJ Mol−1 or more negative, then a coordinate bond type metal- Saraca ashoka extract.
lic bond is formed between the organic species present in the inhibitor Acid Concentration of Rs Rct CPE n Efficiency (η %)
and therefore the metal surface. This bond is formed as a result of chem- solution inhibitor (mg/L) (Ω cm2) (μF cm−2)
isorption wherever charge sharing or charge transfer happens from or- 0.5 M 0 4.65 25.16 1.3 × 10−3 0.48 0
ganic species to metal surface. On the opposite hand if the value of H2SO4 25 3.47 102.66 1.5 × 10−4 0.57 75.48
∆G°ads is around −20 KJ Mol−1 or less negative, then physisorption hap- 50 2.84 138.02 1.0 × 10−4 0.61 81.76
pens as a result of electrostatic attraction between inhibitor and there- 75 2.59 220.14 6.0 × 10−5 0.74 88.56
100 3.17 364.19 4.9 × 10−5 0.85 93.09
fore the charged metal surface [27]. Here within the present study the
 A. Saxena et al. / Journal of Molecular Liquids 258 (2018) 89–97 93

adsorbed onto the steel surface, preventing the steel from corrosion,
which can be verified by the reduction of corrosion current density
values. It can be seen from Table 3 that with increasing concentration
of Saraca ashoka extract, the corrosion current density decreases. The
lowest corrosion current density of 4.0 × 10−4A/cm2 and the highest in-
hibition efficiency of 95.48% is achieved at the concentration of
100 mg/L.

3.5. Electrochemical impedance spectroscopy

For studying the impedance parameters of mild steel specimens in

0.5 M H2SO4 with different concentrations of Saraca ashoka extract,
EIS measurements were carried out. The results are shown in Table 4.
The EIS curves (Nyquist and Bode plots) for mild steel with various con-
centrations of Saraca ashoka extract are shown in Fig. 6(a) and (b). Fig. 7
shows variation of potential of mild steel (vs. SCE) as a function of time
in aerated 0.5 M H2SO4 solution in the presence of the investigated in-
hibitor at 298 K. A steady potential (vs. SCE) was readily attained, corre-
sponding to the free Ecorr (vs. SCE) of the mild steel.
In Nyquist graph, due to the charge transfer resistance, a semicircle
in each curve stands for a time constant. Increasing Saraca ashoka ex-
tract concentration enlarges the diameter of the capacitive loop from
25 to 100 mg/L, which implies a promotion of inhibition effect. The inhi-
bition efficiency on the basis of impedance study can be calculated by
using the following formula [29]-

Rct −R0ct
η% ¼  100 ð7Þ
Rct

where Rct and R0ct are the charge transfer resistance with inhibitor and
without inhibitor, respectively. The inhibition efficiency is improved by
increasing the concentration of Saraca ashoka extract, getting the
highest value of 93.09% at 100 mg/L. From Table 4 it is clear that the
value of Rct increases. This incrementation in Rct value is attributed to
the formation of a protective film at the metal interface. The vicissitudes
in Rct and CPE values were caused by the replacement of water mole-
cules by adsorption of inhibitor on mild steel surface, reducing the ex-
tent of metal dissolution. The values of n were found to be higher in
the inhibited solutions than the uninhibited ones. This is a designation
that the inhibitor contributes to decrement surface heterogeneity due
to its adsorption at electrode electrolyte interface. For the EIS curves of
blank solution, inductive loops exist in low frequency, which results
from the relaxation of adsorbed intermediate products from steel sur-
face [26]. For the rest of concentrations, the disappearance of the

Fig. 6. (a): Nyquist plots for mild steel in 0.5 M H2SO4 without and with various
concentrations of Saraca ashoka extract. (b): Bode plots for MS in 0.5 M H2SO4 without
and with various concentrations of Saraca ashoka extract at 298.15 K.
Fig. 7. OCP vs. time plot for mild steel in 0.5 M H2SO4 in the absence and presence of Saraca
ashoka extract.
94 A. Saxena et al. / Journal of Molecular Liquids 258 (2018) 89–97

block MS from corrosion medium by impeding the transfer of charge

and ions.

3.6. Surface analysis

3.6.1. Scanning electron microscope

Fig. 8. Equivalent circuit used to fit EIS. The surface morphology of mild steel in 0.5 M H2SO4 solution with-
out and with Saraca ashoka inhibitor has been shown in Fig. 9. Fig. 9[a] is
the SEM of polished mild steel, Fig. 9[b] is the SEM of mild steel sample
after 24 h immersion in 0.5 M H2SO4 and Fig. 9[c] is the SEM image of
inductive loop is usually regarded as a phenomenon of “degradation” mild steel specimen immersed in 0.5 M H2SO4 in the presence of Saraca
for EIS. In Bode plot, the variation trend of impedance value with Saraca ashoka extract. The morphology of mild steel specimen when immersed
ashoka extract concentration in the Bode modulus curves is consistent in 0.5 M H2SO4 solution within the absence of inhibitor is incredibly
with that of semicircle diameter in Nyquist plot. All phase angle-fre- rough and therefore the surface is damaged because of the corrosion
quency curves show single wave, which confirms the one-time constant of mild steel but the surface of mild steel within the presence of Saraca
obtained by Nyquist plot. According to literature, if phase angle equals ashoka extract shows less surface damage as compared to Fig. 9[b], sug-
to 90o or 0o, the electrochemical behaviour at the steelsolution interface gesting the formation of a protective inhibitor film at mild steel surface.
is capacitive or resistive, respectively. Thus a constant phase element The morphology of mild steel specimen within the presence of Saraca
(CPE) should be introduced into the equivalent circuit shown in Fig. 8 ashoka extract is smoother than the surface within the absence of inhib-
to fit the EIS curves. EIS spectra were analyzed using the equivalent cir- itor [30,31].
cuit in Fig. 8 which comprises the solution resistance (Rs), charge trans-
fer resistance (Rct), and constant phase element (CPE). It is reported 3.6.2. Atomic force microscope
that the extract of Saraca ashoka contains high levels of Epicatechin The three dimensional AFM images of polished mild steel, uninhib-
which can be adsorbed onto the steel surface by donating π electrons ited mild steel and inhibited mild steel in 0.5 M H2SO4 with Saraca
of aromatic ring or lone-pair of electrons of the hetero atoms to the va- ashoka extract have been shown in Fig. 10[a], [b] and [c] respectively.
cant d-orbital of iron. These compounds can form a protective film to The average surface roughness for polished mild steel is 2.099 nm. In

Fig. 9. SEM images of polished mild steel [a], mild steel immersed in 0.5 M H2SO4 without inhibitor [b] and mild steel immersed in 0.5 M H2SO4 in the presence of Saraca ashoka extract [c].
 A. Saxena et al. / Journal of Molecular Liquids 258 (2018) 89–97 95

Fig. 10. AFM images of polished mild steel [a], mild steel immersed in 0.5 M H2SO4 without inhibitor [b] and mild steel immersed in 0.5 M H2SO4 in the presence of Saraca ashoka extract [c].

the absence of Saraca ashoka extract the surface of mild steel is strongly electrons transferred from the inhibitor molecule to the metal surface
damaged due to the dissolution of metal in the acid solution. The aver- (ΔN) were calculated and are listed in Table 5. For the calculation of
age surface roughness in this case is 138.807 nm while in the presence quantum chemical parameters following equations were used-.
of Saraca ashoka extract the value of average surface roughness is
48.60 nm. The decrease in average surface roughness of the mild steel ΔE ¼ ELUMO –EHOMO ð8Þ
specimen is due to the adsorption of Saraca ashoka inhibitor on the
metal surface. It can be said that a protective layer is formed on the sur- ELþEH
χ¼− ð9Þ
face of metal. 2

ELUMO−EHOMO
3.7. Quantum chemical calculations Ƴ¼ ð10Þ
2
To study the effect of electronic properties and molecular structure 1
on inhibition efficiency of the extract and to rationalize the experimen- σ¼ ð11Þ
Ƴ
tal data obtained from electrochemical readings and weight loss mea-
surements, quantum chemical calculation has been applied. The χFe−χinh
ΔN ¼ ð12Þ
geometry of the major constituent present in Saraca ashoka extract 2
and the frontier molecular orbital density distributions (HOMO and
LUMO) are shown in Fig. 11. The quantum chemical parameters, The HOMO and LUMO energies and ΔE are correlated with inhibition
EHOMO, ELUMO, ΔE (energy gap between LUMO and HOMO), absolute efficiency. A higher value of EHOMO leads to a stronger chemisorption
electronegativity (χ), global hardness (γ), softness (σ) and fraction of and higher inhibition behaviour for metal. Moreover, the lower ΔE
96 A. Saxena et al. / Journal of Molecular Liquids 258 (2018) 89–97

Fig. 11. Optimization geometry of Epicatechin with HOMO and LUMO density.

(ELUMO - EHOMO) can cause stronger chemisorption of the inhibitor (a)- Donor-acceptor interactions between the π electrons of aro-
molecule on metal surface. According to Lukovits, if ΔN b 3.6, the chem- matic ring and vacant d-orbitals of surface iron atoms.
isorption and inhibition efficiency tendency increases with the increase (b)- Interaction between unshared electron pair of hetero atoms of
in the electron-donating ability at the metal surface. This shows that as the inhibitor and vacant d-orbital of surface iron atoms.
the strength of the iron inhibitor bond increases (as a result of increas- Generally two modes of adsorption could be considered. In one
ing ΔN), the degree of corrosion inhibition due to chemisorption is in- mode, the inhibitor may be adsorbed on the surface of steel through
creased. The calculated value of ΔN in the present study is 0.1430 chemisorption mechanism, involving the displacement of water mole-
which again shows that the inhibitor chemisorbs more strongly [26]. cules from steel surface and sharing electrons between hetero-atoms
of inhibitor and steel iron atom. The inhibitor molecule can also be
adsorbed on the steel surface on the basis of donor- acceptor interac-
3.8. Mechanism of action tions between π electrons of heterocyclic ring and vacant d-orbital of
surface iron. The mechanism of corrosion inhibition is shown in Fig. 12.
Corrosion inhibition of mild steel in 0.5 M H2SO4 solution by Saraca
ashoka seeds extract can be explained on the basis of molecular adsorp-
tion. The investigated inhibitor would have got adsorbed on the mild 4. Conclusion
steel surface by one or more of the following ways-
The Saraca ashoka seeds extract act pretty much as good corrosion
Table 5
inhibitor for mild steel in 0.5 M H2SO4 solution at a very low concentra-
Quantum chemical parameters of epicatechin calculated with DFT method. tion. The potentiodynamic polarization study shows that the inhibitor
may be a mixed form of inhibitor. EIS measurements show that the
S. No. Parameter Epicatechin
charge transfer resistance will increase and double layer capacitance de-
1. EHOMO(ev) −10.81 creases within the presence of inhibitors, recommended the adsorption
2. ELUMO(ev) −0.13
of inhibitor molecule on the surface of mild steel. The inhibition effi-
3. ΔE (ev) 10.67
4. ΔN(e) 0.14 ciency results of the inhibitor calculated by electrochemical measure-
5. ΔEBack Donation(eV) −1.33 ments shows 95.48% inhibition efficiency at 100 mg/L inhibitor
6. γ 5.33 concentration. The inhibition efficiency will increase on increasing the
7. σ (eV−1) 0.18 inhibitior concentration. The results obtained from SEM, AFM and Lang-
8. χ (eV) 5.47
muir adsorption isotherm recommended that the mechanism of
 A. Saxena et al. / Journal of Molecular Liquids 258 (2018) 89–97 97

[9] S. Deng, X. Li, Inhibition by Jasminum nudiflorum Lindl. leaves extract of the corro-
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