Materials Chemistry and Physics 233 (2019) 120–132

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Materials Chemistry and Physics

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

Experimental, theoretical modeling and optimization of inhibition

efficiency of pigeon pea leaf extract as anti-corrosion agent of mild steel in
acid environment
V.C. Anadebe a, *, O.D. Onukwuli b, M. Omotioma c, N.A. Okafor d
a
Department of Chemical Engineering, Federal University Ndufu Alike Ikwo, Ebonyi State, Nigeria
b
Department of Chemical Engineering, Nnamdi Azikwe University Awka, Anambra State, Nigeria
c
Department of Chemical Engineering Enugu State University of Sci. & Tech, Enugu, Nigeria
d
Department of Chemical Engineering, Chukwuemeka Odumegwu Ojukwu University, Nigeria

H I G H L I G H T S G R A P H I C A L A B S T R A C T

� The inhibition phenomenon was

controlled by the nature of the corrosive
medium.
� Polarization measurements signify that
PPL acted as a mixed type inhibitor.
� Theoretical modeling predicted the
active constituents of PPL to the overall
inhibition process.
� Quadratic regression is the best RSM
model for the inhibition process.
� Smooth surface morphology was noted
in 0.9g/L 1 inhibitor concentration
medium.

A R T I C L E I N F O A B S T R A C T

Keywords: This study is on the application of pigeon pea leaf (PPL) extract as anti-corrosion agent for mild steel in acid
Anti-corrosion agent environment (HCl solution). The work involves investigation of the corrosion inhibition process using combi­
Acid corrosion nation of experimental, theoretical modeling and optimization studies. The chemical compositions and func­
Langmuir isotherm
tional groups of the extract were identified using gas chromatography mass spectrophotometer (GC-MS) and
Theoretical modeling
Optimization
Fourier transform infrared (FTIR) spectroscopy respectively. For the response surface methodology (RSM),
Design Expert software was used for the optimization of the inhibition efficiency. Scanning electron microscopy
(SEM) was used to inspect the surface morphology of the mild steel. The inhibition efficiencies of 87.13%, 91%,
92.1% and 90.7% were obtained from the experimental studies of thermometric, gravimetric, potentiodynamics
polarization and electrochemical impedance spectroscopic techniques respectively. A quadratic model showing
the relationship between inhibition efficiency and inhibition variables was generated. The model was scrutinized
with various criteria, which include coefficient of determination (R2 ¼ 0.9733), p value (<0.0001), adequate
precision (22.44), adjusted R2 (0.9485) and coefficient of variation (4.98). The RSM model adequately predicted
the optimum inhibition efficiency of 91% at inhibitor concentration of 0.9 g/L 1. The theoretical modeling re­
veals that 1-Tridecene and Luteolin were the most active constituents of pigeon pea leaf responsible for the in­
hibition process. Polarization study revealed that pigeon pea leaf extract acted as a mixed-type inhibitor.
Furthermore, the inhibition process was in accordance with Langmuir isotherm. Spectra of the corrosion particles
and SEM analysis confirmed the physical attachment of the extract species on the mild steel surface.

* Corresponding author.
E-mail address: anadebe.valentine@funai.edu.ng (V.C. Anadebe).

https://doi.org/10.1016/j.matchemphys.2019.05.033
Received 9 February 2019; Received in revised form 27 April 2019; Accepted 15 May 2019
Available online 22 May 2019
0254-0584/© 2019 Elsevier B.V. All rights reserved.
V.C. Anadebe et al.
1. Introduction
In engineering industry, iron and steel are the most dominant ma­
terial used for operations [1]. They are susceptible to corrosion in
different media including atmospheres. They are usually recommended
for industrial operations because they have satisfactory qualities such as
low cost, high strength and ease of fabrication. Iron and steel display
differences in corrosion resistance in atmospheric and acid corrosion.
Metal decomposition is insidious in its nature and because it is not
pronounced, it is neglected until the situations worsen. In view of this
industrial problem, protective skills have been employed to eliminate or
minimize corrosion attack of equipment thereby reducing replacement
cost or permit the use of cheaper methods [2,3]. Organic compounds of
plants origin are clean protective materials for such corrosion mitigation
due to the natural compositions in their molecules (N, O, S heteroatoms)
and absence of heavy metals [4–7]. A corrosion inhibitor exhibits its
character in an aggressive environment by obstructing the invading of
electrochemical reactions. The extract molecules shield the metal from
acid attack by forming a coating layer which acts as a barrier between
corroding and metal surface [8].
Currently, corrosion scientist/engineers are showing great research
interest in developing green corrosion inhibitors of plant origin [9–12].
It has been reported that plant extracts possess good inhibitive charac­
teristics [13], with little or no negative impact on the environment [14].
Several investigations are available justifying the fitness of plant-based
inhibitor. Among the various plant inhibitors studied, Ficus tikoua
leaves extract gave efficiency of 95.8% for carbon steel in 1 M HCl at
298 K [15]. Bitter kola leaf extract gave efficiency of 90% for mild steel in
1.2 M HCl at 0.9 g/L 1 [16]. Glycyrrhiza glabra leaves extract gave effi­
ciency of 88% for mild steel in 1 M HCl at 800 ppm [17]. Elaeis guineensis
extract (EG) and silver nanoparticles (AgNPs) gave efficiency of 94.1% for
mild steel in 1 M HCl at 10% (v/v) [18]. Xanthium strumarium extract
gave efficiency of 94.8% for carbon steel in 1 M HCl at 10 g/L 1 [19].
Plant extracts are known to contain some chemical constituents. As
such, it is complex to predict a definite constituent responsible for
corrosion inhibition. The process of predicting the assistance of various
constituents to the overall inhibiting effect of plant-based materials is
usually difficult. Thus, there is need for simple and novel approach for
investigation of the interaction of metal-inhibitor from the angle of
molecular adsorption using simulation and density functional theory
(DFT). In addition, modeling through (RSM) is vital for the optimization
of inhibition efficiency. It involves the use of mathematical and statis­
tical codes for modeling, optimization and factor evaluation in complex
interactions of processes.
Review of previous studies revealed that research gap exist in iden­
tifying the effect of individual constituents of plant extract in the anti-
corrosion process. Thus, the aim of this study is to investigate pigeon
pea leaf extract as anti-corrosion agent for mild steel in acid environ­
ment. It involves integration of experimental and theoretical method
(DFT) of modeling and optimization of anti-corrosion process. The
choice of pigeon pea leaf is justified by its anti-microbial and anti-
oxidant properties. Pigeon pea belongs to the fabacea family. It is used
for treatment of diabetes and the juice extract from the leaf is given
orally and applied externally for prevention of measles and rashes in
children. Having been used successfully for pharmaceutical purposes, it
is important to consider pigeon pea leaf extract for corrosion control as
anti-corrosion agent.
2. Experimental
2.1. Preparation of extract
Fresh pigeon pea leaves were obtained from pigeon pea orchard at Uli
in Anambra State of Nigeria. The leaves were scrutinized and identified
by Dr. Tony Ekesiobi of Biological Science Department Chukwuemeka
Odumegwu Ojukwu University. 1.0 kg of leaves was collected from
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Materials Chemistry and Physics 233 (2019) 120–132
matured plants. The sample leaves were conveyed in a plastic bag to the
laboratory. At the start of the experiment the samples were washed
under running water and sun-dried for 4 days in a control environment.
It was thereafter ground into powder and stored in sample bottle for
extraction process. Cold extraction process was adopted. 30 g of the
pigeon pea leaf powder were weighed and immersed in 1000 mL of
ethanol for 48 h. The product was then filtered to obtain the plant
extract [19]. The HCl (JHD) and ethanol (JHD) used for the practical
were of analytical grade.
2.2. Metals preparation
Corrosion studies were performed on mild steel of compositions P
(0.02%), Mn (0.11%), Si (0.02%), S (0.02%) Cu (0.01%),C (0.23%), Ni
(0.02%), Cr (0.01%) and Fe (99.56%). Prior to corrosion process, the
mild steel was mechanically cut. The surface of each coupon were then
polished using 220, 800 and 1200 emery papers to obtain a smooth area.
The coupons were further degreased with acetone, rinsed with distilled
water to remove debris and dried in warm air, this is in line with tech­
nique of previous report [20].
2.3. Characterization of Pigeon pea leaf extract
Titrimetric method was used to identify the phytochemicals of the
extract. Prior to the experiment, FTIR analysis was carried out on the
neat sample pigeon pea (PPL) to identify the active functional group.
Metal coupons were introduced into the inhibited medium. After the
corrosion investigation, corrosion products were scooped, mixed with
KBr (potassium bromide) and subjected to infrared spectroscopy using
(SHIMADZU Model IR affinity-1,S/NA213747013651) to identify the
functional group in the corrosion products. Furthermore, the PPL extract
was subjected to Gas chromatography mass spectrometric analysis using
(SHIMADZU QP2010 PLUS) to identify the chemical structures and
compositions of the PPL extract and test them as corrosion inhibitor.
2.4. Thermometry
Thermometric test was performed using a thermostatic bath set at
30 � C. 50 mL of beaker containing mild steel in the inhibited medium
was placed in the thermostatic bath. Rise in temperature was noted
regularly until a stabilize temperature value was reached. The reaction
number (RN) was calculated using equation (1) as previously expressed
[16].
Tm Ti
RN ¼ (1)
t
Where Tm and Ti denote the maximum and initial temperatures in oC, t is
the duration in mins taken to reach Tm .
The inhibition efficiency was calculated by applying Equation [2].
IE% ¼
ð1 RNadd Þ
x 100 (2)
RNfree
RNfree and RNadd are the considered reaction numbers for mild steel
degradation in free and protected HCl solution.
2.5. wt loss method
Weight loss method was performed at temperatures of 300 K, 312 K
and 324 K respectively. As previously expressed [16,21], the variation in
the initial and final weight was studied for unprotected and protected
test solution. At the end of corrosion study the coupons were removed,
dipped in acetone, cleaned and finally re-weighed. The experimental
data were recorded and evaluated using equations (3)–(6) respectively
as adopted from literature [22].
V.C. Anadebe et al. Materials Chemistry and Physics 233 (2019) 120–132

Δw ¼ wi wf (3) Table 1
IR spectral Analysis of Pure PPL extract and corrosion products in 1.2 M HCl.
wbl winh
CR ¼ (4) Pure Pigeon pea leaf Corrosion product in 1.2 M HCl with
Areaðm2 ÞxðtimeÞday 0.9 g/L 1 PPL

wbl winh 3666.76cm-1 - O-H Strecth of Alcohols 3693.78cm-1- O-H Strectch of Alcohols
IE% ¼ x100 (5) 3384.98 cm 1 - N-H Strecth of Amines 3462.18 cm 1- N-H Stretch of Amines
wbl
3145.66 cm 1 - C-H Stretch of Alkanes 3137.94 cm 1- C-H Stretch of Alkanes
wbl winh 2643.86 cm 1- C-H Stretch of 2871.60 cm 1- C-H Stretch of Aldehydes
θ¼ (6) Aldehydes
wbl 2257.86 cm 1- C�N of Unsaturated 2246.28 cm 1
- C�N of Unsaturated
nitrogen nitrogen
Where wi and wf are initial and last weight of the coupons. wbl and winh 1813.96 cm 1
- C¼O of Acid anhydrides 1597.80 cm 1-N¼H deformation
are the weight loss values obtained in the unprotected and protected carbonyl group
environments, A is the entire area of the coupon and t denotes period of 1566.92 cm 1- N-H deformation 1412.52 cm 1- C-H stretch of Aromatics,
immersion. carbonyl group Alkanes
1474.28 cm 1- C-H stretch of 1285.14 cm 1- N¼O stretch of Nitroso
Aromatics, Alkanes
2.6. Activation and heat of adsorption 1381.64 cm 1 - NO2 Stretching Nitro 1011.08 cm 1
– C-O Stretch of Ethers
1134.60 cm 1 – C-O Stretch of Ethers
Considering corrosion rates of the mild steel at T1 and T2 as CR1 and
CR2 , equation (7) was used to scrutinize and predict the activation en­
control of low and high concentration of PPL extract on the electro­
ergy. The heat of adsorption Qads (KJ mol 1) was calculated using
chemical behavior of mild steel in 1.2 M HCl and 0.3 M HCl were
equation (8) according to Ref. [16].
analyzed using inhibitor concentrations of 0.3 g/L 1 and 0.9 g/L 1
� � �� �
Ea 1 1 respectively. Each test was run in triplicate to scrutinize and justify the
ln CR2 = CR1 ¼ (7)
2:303R T1 T2 reproducibility of average values obtained. The inhibition efficiency was
� � � � �� evaluated using equation (14).
θ2 θ1 T2 T1
Qads ¼ 2:303R log log x (8) iCorrðblÞ iCorrðinhÞ
1 θ2 1 θ1 T2 T1 IE% ¼ (14)
iCorrðblÞ
Where Ea is the activation energy, R denotes gas constant, θ1 and θ2
Where ICorrðblÞ and ICorrðinhÞ are the current density values in the absence
represent degree of surface coverage at temperature T1 and T2 . θ1 and θ2
and presence of inhibitor.
were evaluated using Equation (6) of section 2.5.

2.8. Theoretical modeling

2.6.1. Adsorption models
The experimental data and surface coverage were fitted into Lang­
The quantum chemistry analysis was carried using the Density
muir, Frumkin, Temkin and Flory-Huggins isotherm of Equations (9)–
Functional Theory (DFT) electronic diagram programs Forcite and
(12) respectively:
DMol3 as embedded in the materials studio 4.0 software.
C 1
¼ þC (9)
θ Kads 2.9. Gravimetric study using response surface methodology
h � θ �i
log ðCÞx ¼ 2:303 log K þ 2αθ (10) Using response surface methodology (RSM), the inhibition efficiency
1 θ of PPL extract was optimized by central composite design (CCD) tool of
2:303 log K 2:303 log C Design Expert Software (version 10).
θ¼ (11)
2a 2a
2.10. Scanning electron microscopy
h� θ �i
log ¼ log K þ x logð1 θÞ (12)
C Surface morphology of the corroded coupons was carried out at
C represent concentration of PPL, Kads denotes adsorption equilib­ Chemical Engineering Department Ahmadu Bello University, Zaria
rium, α is the mutual interaction term explaining the nature of adsorbed using the scanning electron microscope of model no MVE016477830,
layer, a is the attractive parameter, x is size parameter (This evaluates Netherlands.
the dosage of the adsorbed H2O molecules sub-planted by PPL mole­
cules). Then the free energy of adsorption (ΔGads ) was evaluated using 3. Results and discussion
Equation ð13Þ.
3.1. Phytochemical screening
ΔGads ¼ 2:303RT logð55:5KÞ (13)
Qualitative analysis of the pigeon pea leaf extract revealed the pres­
2.7. Electrochemical technique ence of flavonoids (þþþ), phenolics (þþ), alkaloids (þþþ), saponins
(þþ) and tannins (þþ). The presence of these phytochemicals is an
Thorough electrochemical analysis was performed with the aid of a indication that PPL extract is a potential corrosion inhibitor.
potentiostat/galvanostat 263 electrochemical system workstation.
Within the context of this study a graphite bar and a saturated calomel 3.2. Results of the FTIR analysis of the extract and corrosion products
electrode (SCE) were employed as a supplementary material. Mild steel
specimen of 1 cm2 dimension was used as working electrode. The The infra-red spectroscopy revealed scientific information on the
experiment was performed in aerated and unstirred solution at the end nature of interactions between the accumulated PPL and mild steel
of 1800 s of immersion at 300 K, this makes the solution to stabilize. surface in 1.2 M HCl solution (inhibited with 0.9 g/L 1 PPL extract) at
Experiment was performed considering �250 mV vS ECorr and further temperature 300 K. The peak numbers signifies the functional groups.
examine sequentially at speed of 0.333 mV/s 1. Tests to investigate the Table 1 shows the spectral analysis of neat sample PPL extract and that

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Table 2 Table 4
Influence of concentration of PPL on the IE (%) of mild steel in 1.2 M HCl. Activation and heat of adsorption studies.
1
Inhibitor concentration (g/L ) RN (0C/min) IE (%) Inhibitor concentration Activation Energy (Ea ) Heat of adsorption (Qads )

0.0 0.02758 0.1 20.525 39.604

0.1 0.01616 41.39 0.2 29.427 11.270
0.2 0.01161 57.89 0.3 22.489 44.879
0.3 0.00703 74.50 0.6 45.508 17.759
0.6 0.00408 85.22 0.9 66.326 26.697
0.9 0.00355 87.13

work [25].
Table 3
Gravimetric results of mild steel specimen in 1.2 M HCl with PPL extract. 3.3. Thermometry
Time Temp. I (g/ Wt. loss CR (mm/ IE (%) SC (θ)
(hr) (K) L 1) (g) y) In thermometry, the temperature of the system where the mild steel
21 300 0.0 0.21 0.5
was immersed was noted regularly until a stabilize temperature value
0.3 0.09 0.214 57.14 0.5714 was reached. It is vital to note that the level of decrease in temperature
0.6 0.05 0.119 76.19 0.7619 value and the corresponding time rely on the nature of the solution. As
0.9 0.02 0.049 91 0.91 listed in Table 2 addition in thickness of PPLE reduces the reaction
312 0.0 0.24 0.571
number, but increased concentration enhances the inhibition efficiency,
0.3 0.11 0.262 54.17 0.5417
0.6 0.07 0.167 70.83 0.7083 this collaborates with result of previous work [26]. Maximum inhibition
0.9 0.05 0.119 79.17 0.7917 efficiency of 87.13% was attained at 0.9 g/L 1 of inhibitor. Further
324 0.0 0.26 0.619 observation reveals that the temperature of all the systems reduced
0.3 0.12 0.286 53.85 0.5385 again after attaining their optimum range. This behavior could further
0.6 0.09 0.214 65.38 0.6538
0.9 0.07 0.167 73.08 0.7308
be explained in respect of decreasing the acid concentration with
enhancing the reaction number.
14 300 0.0 0.16 0.571
0.3 0.07 0.25 56.25 0.5625
0.6 0.04 0.143 75 0.75 3.4. Result of mass loss method
0.9 0.03 0.107 81.25 0.8125
312 0.0 0.18 0.643 The rate of metal dissolution is simply explained as the loss in weight
0.3 0.09 0.321 50 0.5
0.6 0.06 0.214 66.67 0.6667
of the sample within its area multiply by the period (time) in which the
0.9 0.04 0.143 77.78 0.7778 experiment was performed. The major advantage of this technique is
324 0.0 0.19 0.679 that tested inhibitors dissolve in water, it is simple and convenient to
0.3 0.1 0.357 47.37 0.4737 ascertain corrosion conditions and few dose of inhibitor is desired for
0.6 0.08 0.286 57.89 0.5789
further experiments. The variations of dissolution rate and protection
0.9 0.06 0.214 68.42 0.6842
efficiency in the unprotected and protected solutions are shown in
7 300 0.0 0.12 0.857 Table 3. Results presented therein signifies that PPL is a potential
0.3 0.06 0.429 50 0.5
0.6 0.04 0.286 66.67 0.6667
candidate for corrosion control of mild steel in acidic environments
0.9 0.03 0.071 85.71 0.8571 implying that the reaction rate was impeded in the protected solution
312 0.0 0.13 0.929 compared to the unprotected solution. Thorough examination of Table 3
0.3 0.07 0.5 46.15 0.4615 proves that dissolution rates increased with increase in temperature
0.6 0.05 0.357 61.54 0.6154
with the maximum values seen at 324 K for all the systems studied. The
0.9 0.06 0.143 71.43 0.7143
324 0.0 0.15 1.071 protection efficiency increases by enhancing the concentration of PPL
0.3 0.09 0.643 40 0.4 and is more obvious due to the bulky attachment of active constituents
0.6 0.06 0.429 60 0.6 of PPL on the corroding metal surface. On the contrary, protection ef­
0.9 0.05 0.357 66.67 0.6667 ficiency reduces drastically with enhancing the temperature level,
I ¼ Inhibitor concentration, CR ¼ corrosion rate, IE ¼ inhibitor efficiency, reason being that increase in temperature disperses the extract mole­
SC ¼ surface coverage. cules from the surface of the mild steel (separate the heterocyclic bonds
existing in the PPL thereby minimizing the surface coverage). Maximum
of mild steel immersed in inhibited 1.2 M HCl solution respectively. protection efficiency of 91% was recorded at temperature of 300 K and
From Table 1 it was observed that stretch O-H at 3666.76 cm 1 peak of 0.9 g/L 1 at 21 h immersion time which suggests that mild steel disso­
the pure extract shifted to 3693.78 cm 1 in the corrosion products. Also lution and protection efficiency rely on the period of exposure with
stretched C-H, N-H and stretched C-O recorded changes in peaks and enhancing the concentration of the active species of PPL. Furthermore, it
intensities. Furthermore, the anticorrosion performance of PPL can be reveals that anticorrosion ability of PPL can be attributed to the nature
attributed to the nature and characteristics of the heterocyclic com­ and structure of the heteroatoms.
pounds existing in PPL. Corrosion protection of mild steel in 1.2 M HCl
solution with PPL extract can be investigated from the angle of molec­ 3.5. Activation and heat of adsorption
ular adsorption. The phenomenon takes place with the heteroatoms of
phytochemical constituents in PPL extract; they establish a co-ordinate Ea and Qads for protection of mild steel in 1.2 M HCl with PPL extract
bond with vacant d-orbital of Fe and attached on the steel surface by are shown in Table 4. From the table below, calculated Ea value for the
forming a stable thin film layer which obstructs the invading of elec­ inhibited solution with PPL extract ranges from 45.508 to
trochemical reactions [23,24]. This proves that PPL extract contains 66.326 kJ mol 1 in the presence of inhibitor concentration of 0.6 and
mixtures of compounds. On the contrary, after immersion in 1.2 M HCl 0.9 g/L 1, while in 0.1 and 0.2 g/L 1 inhibitor concentration, the
solution some peaks deviated, the deviation and shifting mechanism in activation energies ranges from 20.525 to 29.427 kJ mol 1. This inves­
the wavelength of absorption signifies the interactions between the PPL tigation proved that the partial reactions of mild steel in the inhibited
extract and the surface of the steel this is in agreement with previous medium was impeded due to the adsorption of the film layer on the

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V.C. Anadebe et al. Materials Chemistry and Physics 233 (2019) 120–132

Fig. 1. Plot of Langmuir for mild steel in HCl with PPL extract.

Fig. 2. Plot of Frumkin for mild steel in HCl with PPL extract.

Fig. 3. Plot of Temkin for mild steel in HCl with PPL extract.

Fig. 4. Plot of Flory-Huggins for mild steel in HCl with PPL extract.

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V.C. Anadebe et al. Materials Chemistry and Physics 233 (2019) 120–132

Table 5 3.6. Polarization measurements

Adsorption parameter/Isotherm property.
Adsorption Temp K R2 Log K ΔGads KJ/ Isotherm Polarization test was performed to scrutinize the adsorptive strength
mol Property of PPL on the anodic and cathodic reactions of the dissolution process.
Langmuir 300 0.999 0.033 9.85 Fig. 5 shows the polarization curves for mild steel coupons in 1.2 M and
324 0.996 0.099 10.21 0.3 M HCl in protected and unprotected solutions. The steel sample in
Frumkin 300 0.998 1.109 3.64 α 1.971 HCl environment is observed to demonstrate high dissolution without
324 0.991 1.092 4.04 1.896 evidence of passivation within the investigated range [32]. The exper­
Temkim 300 0.995 1.629 1.05 a 2.048
324 0.975 1.560 0.71 2.492
imental data are shown in Table 6, the data presented revealed that ICorr
Flory- 300 0.965 0.602 13.48 x 1.282 reduced in the protected solution compared to the unprotected, this
Huggins 324 0.939 0.640 14.79 0.770 process expedite with enhancing the concentration of the active species
in PPL. Immersion of PPL into 1.2 M HCl solution gently push ECorr
values towards the anodic side, the effect was significant with increase
metal surface. The film layer is stronger than the degradation of the in the concentration of PPL, where as in 0.3 M HCl solution, ECorr shift
metal surface due to the nature of the heterocyclic compounds in the PPL was insignificant. The trend of inhibition in Table 6 is due to tough
extract which shield the metal from further dissolution [27]. Generally, intermolecular relationship between the protonated PPL molecules and
the negative values of Qads imply that the surface attachment of PPL valence electrons on the Fe surface. Also the irregularities in the trend of
molecules was exothermic and spontaneous in nature. βc and βa data shows the synergistic contribution of more than one class
of molecules attached on the metal solution interface which led to a near
3.5.1. Adsorption mechanism perfect surface coverage. Accordingly, it can be inferred that PPL
As a general observation, adsorption process takes place when semi- obstructed the anodic and cathodic metal dissolution. In same vain, a
liquid mixtures adsorbed on the solid interfaces resulting in formation of compound/molecule is normally categorized as anodic or cathodic in­
atomic film. The trend of adsorption phenomenon of PPL on mild steel hibitor when the deviation in ECorr value on addition of inhibitor is more
was scrutinized through the isotherms models. The isotherms interpret than 85 mV and if the deviation is less than 85 mV then PPL may be
the mechanism guiding the attachment of a substance from aqueous termed as mixed-type inhibitor [33–35]. Accordingly, the generated
phase to solid phase at stable temperatures and pH. Adsorption is an end data signifies that the phenomenon of inhibition is under mixed control
product of electrostatic magnetization on steel surfaces and heterocyclic
compounds of PPL, which includes the dehydration of water molecules
Table 6
and formation of a coating film. This phenomenon is usually complex
Parameter from tafel polarization measurements.
and relies on the functional groups of the PPL molecules, corrosiveness
and composition of the acid media. Experimental data were fitted into System ECorr (mV ICorr (μA bC (mV ba (mV sc ðθÞ IEð%Þ
vs. SCE) cm 2) dec 1) dec 1)
Langmuir, Frumkin, Temkin and Flory-Huggins adsorption isotherms as
shown in Figs. 1–4 respectively. 1.2 M HCl 503.4 183 92.4 47.3 – –
Trend line functions of Microsoft excel was used to generate the 1.2 M HCl þ 504.9 56.2 96.3 54.1 0.693 69.3
0.3 g/L 1
mathematical equations. As revealed by the plot of log Cθ as a function of
PPL
log C indicates a straight line graph and the coefficient of correlation 1.2 M HCl þ 456.9 14.8 90.3 42.8 0.921 92.1
(R2) close to unity ranging from 0.939 to 0.999. It shows that the 0.9 g/L 1
attachment of PPL molecules on the steel surface obey the mechanism of PPL
0.3 M HCl 461.7 89.6 88.4 55.8
physical adsorption [28–30]. But in all, the data were best fitted in
– –
0.3 M HCl þ 478.1 55.8 96.6 53.5 0.377 37.7
Langmuir isotherm which has the highest R2 of 0.999 and 0.996 at 0.3 g/L 1
temperature of 300 K and 324 K respectively. Comparing the equations PPL
in Figs. 1–4 with the isotherm equations the adsorption properties K, α, a 0.3 M HCl þ 467.2 15.8 98.2 50.2 0.823 82.3
0.9 g/L 1
and x were obtained [31]. The isotherms and the values of these pa­
PPL
rameters are presented in Table 5.

Fig. 5. Polarization curves of mild steel with 0.3 g/L 1and 0.9 g/L 1
PPL in (a) 1.2 M HCl and (b) 0.3 M HCl.

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Fig. 6. Impedance spectra of mild steel with 0.3 g/L 1and 0.9 g/L 1
PPL in (a) 1.2 M HCl and (b) 0.3 M HCl (c) Equivalent circuit design.

3.7. Electrochemical impedance spectroscopy (EIS)

Table 7
Impedance parameters of mild steel in HCl.
Impedance spectroscopy was employed to study the nature and re­
System RS ðΩcm2 Þ Rct ðΩcm2 Þ N Cdl ðFcm2 Þ IEð%Þ action mechanism occurring at the metal/solution interface and how
1.2 M HCl 1.659 102.7 0.89 6.908E-5 – they were modified by PPL extract. Fig. 6 depicts a typical Nyquist
1.2 M HCl þ 0.3 g/L PPL 2.007 270 0.84 7.094E-5 61.9 spectrum in 1.2 M and 0.3 M HCl over a period of 7 h with 0.3 g/L 1 and
1.2 M HCl þ 0.9 g/L PPL 2.923 1100 0.83 7.075E-5 90.7 0.9 g/L 1 of PPL extract respectively. The circumference of the Nyquist
0.3 M HCl 2.329 380 0.89 7.985E-5 – semicircle is connected to charge transfer process. The middle of this
0.3 M HCl þ 0.3 g/L PPL 2.987 540 0.89 7.231E-5 30.2
depressed semicircle was gently shifted below the real axis. It is also
0.3 M HCl þ 0.9 g/L PPL 3.353 1450 0.88 6.784E-5 81.8
imperative to note that virtually all impedance spectrums have a
depressed semicircle which may be ascribed to the influence of fre­
[36–38]. This high inhibition efficiency conforms with the one obtained quency dispersion because of the densely dark flakes and coarseness of
by EIS, proving that PPL can effectively protect mild steel dissolution at the steel surface.
a wide temperature range and unique action of PPL may be ascribed to Addition of PPL extract to 1.2 M and 0.3 M HCl solution improved
the attachment and structural characteristics of a film layer on the the magnitude of the impedance spectrum. It signifies the inhibiting
electrode surface [12]. strength of organic compounds in PPL which impeded the invading of

Fig. 7. Gas chromatography mass spectrometry for Pigeon pea Leaf extract.

126
V.C. Anadebe et al.
electrochemical reactions. On the contrary, as the temperature was
enhanced the magnitude of the capacitive loop diminishes. This can be
ascribed to the fact that at higher conditions the rate of metal corrosion
is rapid because of the corrosiveness and pH of the studied environment.
The impedance parameters are listed in Table 7. Within the context of
this study CPE is used to substitute a capacitor in order to investigate the
deviation from ideal dielectric behavior due to the coarseness and
texture of the electrode surface. The impedance of the CPE is denoted by
Ref. [25].
127
Materials Chemistry and Physics 233 (2019) 120–132
Fig. 8. Electronic properties of 1-Tridecene: (a)
Electrophilic F- (b) Nucleophilic Fþ, (c) Electron
density, (d) HOMO, (e) LUMO, (f) Attachment of
1-Tridecene on Fe (110) surface. Luteolin (g)
Electrophilic F-, (h) Nucleophilic Fþ, (i) Electron
density (j) HOMO, (k) LUMO, (l) Attachment of
Luteolin on Fe (110) surface, (m) Neutral opti­
mized structure (TC), (n) Neutral optimized
structure (LN). Atom legend: white ¼ H; gray ¼
C; red ¼ O; blue ¼ N. The blue and yellow iso-
surfaces depict the electron density difference:
the blue regions show electron accumulation
while the yellow regions show electron loss. (For
interpretation of the references to colour in this
figure legend, the reader is referred to the Web
version of this article.)
ZCPE ¼ Q 1 ðjwÞ n
(15)
Where Q and n signify CPE and exponent respectively, j ¼ 1 de­2
notes the imaginary axis and ωis regarded as the angular frequency in
rads 1 , (ω ¼ 2πf represents frequency in HZ ), W is regarded as Warburg
impedance, n is the shifting parameter, which describes the coarseness
of steel surface and RS denotes solution resistance. The values of the
impedance parameter were scrutinized and input to the circuit model
RS ðQdl =Rct Þ which was employed to model the metal interface (Fe/acid).
The EIS result evidently signifies that PPL enhanced the Rct values from
V.C. Anadebe et al. Materials Chemistry and Physics 233 (2019) 120–132

Table 8 Table 9
Computed values of quantum chemical parameter assessed at density functional Experimental range and levels of CCD using RSM.
theory range in compliance with Dmol3 for 1-Tridecene and Luteolin. Std Run AC I C (g/ T Time Wt. CR IE
Inhibitor EHOMO ELUMO Energy Molecular Binding (M) L 1) (K) (hr) loss (g) mm/y (%)
(molecule) gap (eV) mass (gM 1) energy
5 1 0.3 0.3 324 7 0.08 0.571 33.3
(Ebind)
6 2 1.2 0.3 324 7 0.09 0.643 40
TC 5.405 - 0.299 5.106 182 129.8 27 3 0.75 0.6 312 14 0.04 0.143 75
LN 4.587 3.281 1.306 286 109.4 17 4 0.3 0.6 312 14 0.07 0.25 50
28 5 0.75 0.6 312 14 0.04 1.143 75
30 6 0.75 0.6 312 14 0.04 1.143 75
102.7 to 1100 Ωcm2 in 1.2 M HCl and 380 to 1450 Ωcm2 in 0.3 M HCl at 2 7 1.2 0.3 300 7 0.06 0.429 50
13 8 0.3 0.3 324 21 0.12 0.286 45.45
the optimum concentration of 0.9 g/L 1. Conversely, the double layer
15 9 0.3 0.9 324 21 0.08 0.19 63.64
capacitance (Cdl ) value reduces slightly when the PPL concentration 14 10 1.2 0.3 324 21 0.12 0.286 53.85
increases [39]. Such decrease (reduction in the local dielectric constant 1 11 0.3 0.3 300 7 0.06 0.429 40
and/or an increase in the double layer thickness) may be ascribed to the 16 12 1.2 0.9 324 21 0.07 0.167 73.08
3 13 0.3 0.9 300 7 0.04 0.286 60
attachment of PPL active species on the metal/solution interface. This is
22 14 0.75 0.6 324 14 0.06 0.214 64.71
in accordance with the Helmholtz theorem given by the expression: 8 15 1.2 0.9 324 7 0.05 0.357 66.67
εεο A 10 16 1.2 0.3 300 21 0.09 0.214 57.14
Cdl ¼ (16) 12 17 1.2 0.9 300 21 0.02 0.049 91
δ 18 18 1.2 0.6 312 14 0.06 0.214 66.67
Where εο is the vacuum permittivity, A is the electrode area, ε is the 19 19 0.75 0.3 312 14 0.07 0.25 56.25
25 20 0.75 0.6 312 14 0.04 0.143 75
relative permittivity of the film, δ is the thickness of the interfacial layer.
21 21 0.75 0.6 300 14 0.03 0.107 76.92
Furthermore, the trend of (Cdl ) implies that the observed increase in 7 22 0.3 0.9 324 7 0.06 0.429 50
charge transfer resistance (Rct ) resulted from the increase, existence and 9 23 0.3 0.3 300 21 0.08 0.19 52.94
structure of the attached thin layer of PPL extract on the metal/solution 24 24 0.75 0.6 312 21 0.06 0.143 73.91
interface [40], which protects the metal surface from corrosion. 11 25 0.3 0.9 300 21 0.03 0.071 82.35
4 26 1.2 0.9 300 7 0.03 0.214 75
26 27 0.75 0.6 312 14 0.04 0.143 75
3.8. GC-MS characterization of Pigeon pea leaf 20 28 0.75 0.9 312 14 0.03 0.107 81.25
29 29 0.75 0.6 312 14 0.04 0.143 75
23 30 0.75 0.6 312 7 0.04 0.286 66.67
Gas chromatography mass spectrometry was performed on the
ethanol extract of PPL as shown in Fig. 7. The Y axis indicate the in­ AC: acid conc., IC: inhibitor conc., T: temperature, T: time, Wt. weight loss, CR:
corrosion rate, IE: inhibition efficiency.
tensity section and X axis denote time in minutes. The peaks were
scrutinized and evaluated with database spectrum in GC-MS library. The
peaks represent different heterocyclic compounds existing in PPL. The molecule and Fe surface. As revealed in Fig. 8, when the attachment of
most active compounds were 1-Tridecene and Luteolin. These molecules the active species of PPL attain equilibrium, all the atoms were arranged
were identified and tested as corrosion inhibitors. Other compounds in same plane, this trend revealed that a flat lying phenomenon could be
revealed by the GC-MS in PPL include hexadecanoic, pentadecanoic, acquire to secure a considerable protective region for the mild steel
tetradecanoic, octadecanoic and nonadecanoic. These constituents have surface because the electron density is distributed all-round the mole­
anti-corrosion and anti-oxidant characteristics. cules, the HOMO area is apparently seen around the aromatic indole
vicinity while the LUMO area is adequately distributed in the carbonyl
group [25]. A reasonable number of electrons in the heteroatoms as well
3.9. Theoretical modeling as π-electron clouds assisted significantly to the adsorption phenome­
non. This type of adsorption enhances the contact points and obstructs
In spite of the cumbersome nature connected with predicting what the water molecules from invading into the Fe surface.
and what constituents of plant extracts responsible for corrosion inhi­ In summary, the inhibitive performance of PPL could be attributed to
bition, quantum chemistry analysis was adopted to throw more insight the anti-corrosion properties and attachment of the various organic
into the inhibition phenomenon of molecules by scrutinizing the struc­ molecules on the surface of the steel. The major constituents of PPL
tural characteristics of the compounds existing in the extracts [41,42]. contain conjugate structures such as O, N atoms in the heterocyclic
Fig. 8 shows the electrophilic, nucleophilic, electron density, HOMO, compounds and functional groups as revealed by GC–MS and FTIR
LUMO and snap shot of 1-Tridecene and luteolin molecules on the Fe spectrum which is in conformity with the characteristics of local organic
surface. The molecules of PPL are in conformity with the fact that unique corrosion inhibitors. To evaluate the mutual interaction between the
corrosion inhibitors do not only give electrons to unoccupied orbital of molecules of the extract and the Fe surface, the adsorption energy (Eads )
the metal, but can receive free electrons from the metal. Invariably one of each system was evaluated using equation (17).
can conclude that oxygen and nitrogen atoms are the feasible adsorption
areas [43]. According to the explanation of frontier orbital theory, EInteract ¼ Etotal ðEPPL þ EFe Þ (17)
EHOMO denotes the ability of a species to give electrons, implying that
the greater is EHOMO values the better chance of achieving excellent Etotal is regarded as the entire energy of the simulation area involving
protection efficiency [44]. Also, ELUMO corresponds to the ability of a PPL molecules and Fe surface, EPPL; EFe and ETotal denotes the strength of a
species to receive electrons, thus a good corrosion inhibitor should be single molecule on the Fe slab.
evaluated by low ELUMO values [45]. The variation between the EHOMO
and ELUMO describe the energy gap of a molecule. Also molecules with 3.10. Result of gravimetric method using response surface methodology
low ΔE values may give high protection efficiencies [46]. The data
presented in Table 8 prove that PPL has high values of EHOMO and low Effects of the corrosion inhibition factors on the responses of weight
ELUMO. In order to obtain detailed knowledge on the adsorption phe­ loss, corrosion rate and inhibition efficiency are presented in Table 9.
nomenon, simulation approach were carried to simulate the adsorption Results of 30- run experiments were obtained in order to have detail
structure of the most active molecules of PPL on mild steel surface and understanding of the stability of PPL extract within the studied potential
further scrutinized the complementary relationship between PPL range [23]. The graphical analysis of inhibition efficiency of pigeon pea

128
V.C. Anadebe et al. Materials Chemistry and Physics 233 (2019) 120–132

Figure 9. Response Surface Optimization Plots for Inhibition Efficiency using Design Expert version (10). (a) Predicted vs actual (b) Inhibitor conc. vs Acid conc. (c)
Temperature vs Acid conc. (d) Time versus Acid conc. (e) Temperature vs Inhibitor conc.

129
V.C. Anadebe et al. Materials Chemistry and Physics 233 (2019) 120–132

Table 10
ANOVA results for response parameters.
SSq Dfr M.Sq F-V P-values

Model 5544.77 14 396.06 39.13 <0.0001 Significant

A-Acid Conc. 454.41 1 454.41 44.89 <0.0001
B-Inhibitor 2421.38 1 2421.38 239.23 <0.0001
Conc.
C-Temperature 443.62 1 443.62 43.83 <0.0001
D-Time 629.30 1 629.30 62.17 <0.0001
AB 14.38 1 14.38 1.42 0.2518
AC 4.68 1 4.68 0.046 0.5070
AD 32.98 1 32.98 3.26 0.0912
BC 30.77 1 30.77 3.04 0.1017
BD 3.09 1 3.09 0.31 0.5888
CD 3.14 1 3.14 0.31 0.5857
A2 404.05 1 404.05 39.92 <0.0001
B2 11.13 1 11.13 1.10 0.3109 Fig. 10. Mild steel in 1.2 M HCl.
C2 1.65 1 1.65 1.65 0.9968
D2 0.74 1 0.74 0.073 0.7911
Residual 151.83 15 10.12
Lack of Fit 151.83 10 15.18
Pure Error 0.000 5 0.000
Cor Total 5696.60 29 3.18
Std. Dev. 0.9733
R2 0.9485
Adj R Squared 0.8655
Pred R- 24.448
Squared 63.85
Adeq 4.98
Precision
Mean
C.V %

leaf extract on mild steel in HCl is presented in Fig. 9. Fig. 9A was used to
evaluate the significance of the model’s order. The plots generated linear
graph with data points distributed randomly on the 45� line, indicating
that the model provides an acceptable fit for the experimental data. The
plot also indicates adequate agreement between real data and the output
of the model. The characteristics of the 3-D surface plot suggest that
there is a complementary interaction among the considered factors of
the corrosion control process. Fig. 9B shows that the effect of inhibitor
concentration and acid concentration on the inhibition efficiency is
positive, from Table 9; it was observed that inhibition efficiency stabi­
lizes by enhancing the inhibitor concentration of PPL molecules thereby
giving good protection efficiency. Fig. 9C shows that interactive effect of
temperature and acid concentration is negative, increasing both vari­
ables enhances the rate of metal dissolution this can be attributed to the
fact that at higher conditions the rate of reaction is rapid because of the
corrosion agents. Fig. 9D effects of time and acid concentration is a
factor in corrosion study as the rate of corrosion and inhibition rely on
the period of exposure and attachment of the PPLE on the metal surface,
thus effects of time and acid concentration is significant. Fig. 9E presents
the interaction between temperature and inhibitor concentration. In­
crease in temperature dispersed the rate of surface attachment of PPL
molecules thereby causing a decrease on the surface coverage [47] on
the contrary increase in inhibitor concentration enhances the manifes­
tation of adsorption film in the physical state thereby leading to
considerable surface coverage of the metal. From the overall analysis,
optimum inhibition efficiency of 91% was obtained at 0.9 g/L 1. This is
in conformity with the values obtained from order corrosion techniques.
Fig. 11. Mild steel in 1.2 M HCl/0.9 g/L 1PPL.
evaluated using Analysis of Variance (ANOVA) as shown in Table 10.
The model F-value of 39.13 was generated. It signifies that the model is
significant. The F-value generated could occur due to noise. The noise
can be attributed to flow rates of the chemical constituents of the in­
hibitor. “Prob > F” less than 0.0500 signifies that model terms are sig­
nificant. Thus A, B, C, D, AD, A٨2 are significant model terms. Values
above 0.1000 justify the model terms are not significant. From the
analysis of variance inhibitor concentration has the highest F-value,
followed by time, acid concentration and temperature. This implies that
inhibitor concentration has the highest impact on the inhibition effi­
ciency followed by time, acid concentration and temperature respec­
tively [49]. The “pred R-squared” of 0.8655 obtained is in conformity
with the “Adj R-Squared” of 0.9485; the variation is lower than 0.2.
“Adeq precision” estimates the signal to noise ratio. A ratio above 4 is
acceptable. The ratio of 24.448 demonstrates a good signal.
Equation in Terms of Coded Factors
IE % ¼ þ72.91 þ 5.02*Aþ11.60*B–4.96*Cþ5.91*Dþ0.95*AB
þ0.54*AC–1.44*AD–1.39* BC
þ0.44*BD–0.44*CD–12.49*A2–2.07*B2–7.982E–003*C2– 0.53*D2
———————————————— (18)
Equation in Terms of Actual Factors

IE% ¼ þ36.48149 þ 74.59956*Acid Conc.þ178.30018*Inhibition Conc.-

3.11. Interpretation of the protection efficiency, IE (%) using 3-D plot
0.14920* Temperature þ3.01142*Time þ 7.02315* Acid Conc.*Inhibitor
Conc.þ0.10012*Acid Conc. þTemperature – 0.45575*Acid Conc.*Time –
3.11.1. Mathematical model of the corrosion inhibition efficiency
0.38524* Inhibitor Conc.* Temperature þ0.20923* Inhibitor Conc.
Mathematical equations in terms of coded factors can be adopted for
*Time–5.27530E-003*Temperature*Time–61.66905*Acid Con­
proper evaluation. The coded equation is vital for identifying the rela­
c.2–23.03314*Inhibitor Conc.2–5.54337E–005*Temperature2 – 0.010877*
tive effects of the factors by comparing the factor coefficients. The R2 of
Time2 —————————————————————— (19)
the model was 0.9733 which shows mutual statistical relationship be­
tween the predicted values and laboratory data points. This is in
agreement with previous findings [48]. The quadratic model was

130
V.C. Anadebe et al.
Fig. 12. Fiber metric image and pore measurement of MS in blank and in presence of PPL.
3.12. Scanning electron microscopy
Surface chemistry of mild steel in unprotected and protected envi­
ronments is shown in Fig. 10 and Fig. 11 respectively. The surface
chemistry of the degraded steel in HCl shows a severe damage with
visible corrosion pits. The level of damage tends to be pronounced on the
steel in HCl due to electrochemical activities of Cl ions. Cl ions pro­
moted the conditions for creation of corrosion pits [50]. Presence of PPL
extract in HCl solution with mild steel modified and obstructed the
electrochemical process. Thus, the surface chemistry of mild steel is
relatively smooth compared to the one in the unprotected medium
proving the existence of thin film layer this is due to the (adsorption of
PPL cation onto the steel) which impeded the electrolytic transfer of Cl
ions [51,52]. The advantage of using SEM lies in the possibility of
pointing out cracks, through porometric analysis. The fiber analysis
gives the fiber length in the sample and the effect on the sample by pore
area measurement. The fiber metric image revealed the pores which
range from micro-pore to meso-pore (Fig. 12).
4. Conclusions
The following conclusions were drawn from the analysis of the
results:
� Inhibition efficiencies of 87.13%, 91%, 92.1% and 90.7% were ob­
tained from the experimental studies of thermometric, gravimetric,
potentiodynamics polarization and electrochemical impedance
spectroscopic techniques respectively.
� Adequate quadratic model showing the relationship between inhi­
bition efficiency and inhibition variables was generated.
� 1-Tridecene and Luteolin were the most active constituents of pigeon
pea leaf responsible for the inhibition process.
� The PPL molecules adopted a flat adsorption orientation with respect
to the mild steel surface.
� The pigeon pea leaf extract acted as a mixed-type inhibitor and the EIS
results apparently revealed that charge transfer resistance (Rct ) in­
creases and double layer capacitance (Cdl ) diminishes consistently in
the presence of PPL.
� The inhibition process was in accordance with Langmuir isotherm.
� FTIR spectra of the corrosion particles and SEM analysis confirmed
the physical attachment of the extract species on the mild steel
surface.
� The pigeon pea leaf extract can be used as anti-corrosion agent for the
mitigation of mild steel degradation in acidic solution.
Conflicts of interest
The authors declare that they have no conflict of interest.
131
Materials Chemistry and Physics 233 (2019) 120–132
Funding
The authors appreciate Tertiary Education Trust Fund (TETFUND)
for providing some of the analytical equipment used for the experiment
through Federal University Ndufu Alike Ikwo, Ebonyi state Nigeria.
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