Author’s Accepted Manuscript

Ricinus communis – A green extract for the

improvement of anti-corrosion and mechanical
properties of reinforcing steel in concrete in
chloride media

S.P. Palanisamy, G. Maheswaran, A. Geetha

Selvarani, C. Kamal, G. Venkatesh
www.elsevier.com/locate/jobe

PII: S2352-7102(17)30426-6
DOI: https://doi.org/10.1016/j.jobe.2018.05.020
Reference: JOBE497
To appear in: Journal of Building Engineering
Received date: 28 July 2017
Revised date: 17 May 2018
Accepted date: 17 May 2018
Cite this article as: S.P. Palanisamy, G. Maheswaran, A. Geetha Selvarani, C.
Kamal and G. Venkatesh, Ricinus communis – A green extract for the
improvement of anti-corrosion and mechanical properties of reinforcing steel in
concrete in chloride media, Journal of Building Engineering,
https://doi.org/10.1016/j.jobe.2018.05.020
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 Ricinus communis – A green extract for the improvement of anti-corrosion
and mechanical properties of reinforcing steel in concrete in chloride media
S.P. Palanisamy*1, G. Maheswaran1, A. Geetha Selvarani2, C. Kamal1 and G. Venkatesh1

1
Department of Civil Engineering, VSA Group of Institutions,
Salem – 636 010, Tamil Nadu, India.
2
Department of Civil Engineering, Veltech Dr. RR & Dr. SR University,
Chennai – 600 062, Tamil Nadu, India.

*Corresponding author e-mail address: palaniswamyspcivil@gmail.com

: kvchempro@gmail.com
Abstract

Various Standard methods such as electrochemical impedance spectroscopy (EIS),

potentiodynamic polarization study (PDS) and atomic force microscopy (AFM) have been
utilized to study the corrosion characteristics of reinforcing steel in concrete in without and with
various concentrations of Ricinus communis (R. communis) in NaCl media in different time
intervals. The ability of the plant extract to produce protective layer on steel surface in concrete
and mixed mode (anodic as well as cathodic) inhibitive action have been established from the
findings of electrochemical measurements (EIS & PDS). Further, the formation of protective
layer on the steel surface by plant extract has been supported by surface morphology analysis
(AFM). The adsorption of R. communis extract on steel surface followed the Temkin adsorption
isotherm. The results of density functional theory (DFT) analysis brought out the active centers
of major ingredients responsible for adsorption of molecules present in R. communis over the
steel surface that influenced the anti-corrosion potential of plant extract. The increase in
compressive strength and splitting tensile strength of concrete has been observed. The inhibitive
mechanism of the R. communis extract against reinforcing steel corrosion in concrete in 3.5%
NaCl media has also been proposed.
Graphical Abstract

Keywords: Ricinus communis, reinforcing steel, compressive strength, EIS, AFM, DFT.

1.0. Introduction

A massive number of reinforcing concrete infrastructures include buildings and bridges

used reinforcing steel, often [1]. Several reinforcing concrete structures showed greater service
with minimal maintenance. The presence of aggressive chloride ions in a concrete gradually
destroys its structure and which is a huge threat of damaging occurred worldwide. This concrete
corrosion caused the enhancement of deflection, minimizing bearing capacity and ductility
followed by the decrease in bond strength of steel and concrete which led to the decrease in
lifetime of concrete [2-4]. The corrosion occurred in reinforcing steel associated with external
factors namely, alkalinity, concentration of aggressive chloride ion, cracks, protective concrete
layer thickness, etc., influenced the quality of concrete structures. So, it is very significant to
control the concrete corrosion using standard methods [5, 6]. Since large variety of corrosion
control measures are proposed and analyzed, there has not been any ideal method found till date.
The proposed methods includes increasing the amount of concrete cover on the reinforcing steel,
altering water–cement ratios, using tightly packed concrete, using polymers as blends, adding
hydrophobic layers with asphalt overlay, applying epoxy coating on steel or zinc, protecting the
steel cathodically and application of admixtures which are capable of inhibiting corrosion.
Corrosion inhibitors for steel embedded in concrete could be classified into admixed inhibitors
and surface applied inhibitors.

The use of inhibitors to control the corrosion is one of the most reliable and less
economic methods. Several types of corrosion inhibitors from synthetic origin are available in
the literature which includes a drawback that they are most expensive and toxic in nature even
they were served well as excellent corrosion inhibitors [7-11]. To overcome this menace, a
concern about the development of green corrosion inhibitors which are bio-degradable and less
expense has been turned researchers to discover large number of corrosion inhibitors from
natural origin [11-17]. Several researchers reported the use of corrosion inhibitors derived from
natural sources for steel embedded in concrete [18-20]. This type of inhibitors retard the
corrosion of reinforcing steel caused by the aggressive chloride ions attack and increases the life
span of the reinforcing steel. Previously, we had also been reported the anti-corrosion potential
of P. juliflora extract on reinforcing steel in concrete which was acted well as excellent corrosion
inhibitor [2]. With a view to continue our efforts to develop corrosion inhibitors from natural
sources for reinforcing steel in concrete, we report here the anti-corrosion effect of R. communis
extract in NaCl media using standard methods viz., potentiodynamic polarization,
electrochemical impedance spectroscopy and AFM analyses.
 R. communis is belonging to Euphorbiaceae family. The plant includes terpenoids,
alkaloids, fatty acids, etc., and posses good anti-bacterial, anti-inflammatory, anti-pyretic and
cytotoxic activities [21, 22]. In addition, the R. communis has already proven to be excellent
corrosion inhibitor against the acid corrosion as well as chloride ion corrosion of steels [23, 24].
The corrosion inhibition effect of the extract on reinforcing steel in concrete has been evaluated
by electrochemical methods (EIS and PDS), surface morphology analysis (AFM) and theoretical
calculations (DFT) for active principles of R. communis extract.

Quantum chemical calculations provide the useful information about the corrosion
inhibition mechanism. The application of quantum chemical calculations to predict the inhibitive
mechanism has been previously documented well [25, 26]. The mechanism is proposed by
considering the structure activity relationship of inhibitors along with details about the electronic
interaction of metal atoms with inhibitors. DFT calculations are being used widely for the
prediction of corrosion inhibition mechanisms, recent past [27-30]. Theoretical parameters viz.,
highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO),
energy gap (∆E), dipole moment (µ), hardness (η), softness (σ), electronegativity (χ), ioniziation
potential (IE), electron affinity (EA), the electrophilicity index (ω), Nucleophilicity (e), chemical
potential (µ), total energy and the fraction of electrons transferred (∆N) were calculated using
DFT calculations for active principles of extract of R. communis in the present study.

2.0. Experimental

2.1. Preparation of test samples

The fruits of R. communis have been carefully collected and further, it was finely divided
using a mortar after proper drying and washing processes. The appropriate amount (600 g) of the
residue obtained was subjected to refluxing for 6 hours using methanol. The solution has been
left out for overnight after the completion of refluxing to enable the comprehensive extraction.
Then, the extract was evaporated after the filtration. The filtrate remained on evaporation was
finely divides as powder using mortar again. Concrete specimens prepared using water without
inhibitor has been served as blank or control specimen. The powdered inhibitor (R. communis
extract) has been dissolved in water in desired concentrations (25, 50 and 100 ppm), which will
be used to prepare concrete specimens.
2.2. Electrochemical methods

The cell set-up comprises three electrodes viz., a saturated calomel electrode (SCE), a Pt
wire and the steel used for making the concrete having following composition (%) C=0.37,
S=0.017, Mn=1.21, P=0.021, Si=0.23, Cu=0.016, Ni=0.02, Cr=0.02, V=0.003 and remaining Fe,
as the reference, a counter electrode (CE) and working electrode, respectively was utilized to
record EIS and PDS measurements. The lollipop shaped working specimens were formulated by
embedding steel rods in cement concrete without and with inhibitor. It has the dimension of
about 15cm height and 0.95 cm dia. The outer diameter of cement concrete which is adhered
around the steel is 7.5 cm. The concrete of the following composition, ordinary Portland cement
(291g), water (150g) and FA (500g) with CA size of 0.375 inch (1000g) has been used in the
present study.

Before each and every measurement, the steady state open circuit potential (OCP) was
reached in order to minimize solution effects. All the EIS and PDS measurements were recorded
using CHI electrochemical analyzer model 760D with an operating software package CHI 760D.

The EIS spectra were recorded at attained OCP in 0.01 Hz to 100000 frequency range
with 2 mV sine wave a.c. voltage excitation. Further, the EIS data were interpreted with the help
of EC-Lab SP300 software. From Nyquist plots as, the double layer capacitance (Cdl) and charge
transfer resistance (Rct) values were calculated as described elsewhere [31]. Using these
parameters, the inhibition efficiency was computed by following relation,

Rct (i ) - Rct (b )
IE(%) = ´ 100 - - - - - - - (1)
Rct (i )

where, Rct(i) and Rct(b) are the charge transfer resistances in presence and absence of inhibitor
respectively.

The PDS curves were determined with the considerable sweep rate (0.5 mVs−1). The
potentials were decreased towards the cathodic direction until it reaches zero and instantly
increased in the anodic direction with respect to OCP. The inhibition efficiency was calculated
from the following equation [32],
 icorr  - icorr '
IE(%) = ´ 100 - - - - - - - (2)
icorr 

where, icorr0 is the corrosion current density in absence of inhibitor and icorr’ is the corrosion
current density in presence of inhibitor.

2.3. Surface morphological studies

Steel specimens prepared as described earlier (Section 2.2) with a dimension of the 1 x 1
x 0.1 cms were embedded in concrete without and with plant extract for 120 days immersion
period. After that, steel specimens embedded in concrete were removed and washed well using
doubly distilled water and then properly dried. NanoSurf Easyscan2 instrument, USA model was
used to record the AFM images of embedded steel specimens.

2.4 Evaluation of compressive splitting tensile strengths of concrete

Compressive and splitting tensile strengths of the concrete used in the present study were
tested for the specimens of 100 x 200 mm size. The specimens were prepared by mixing a mass
of fine and coarse aggregates with water and cement. The mixing proportions of the concrete
specimens are given in Table 3A. Further, for a comparative study, some specimens filled with
100 ppm of plant extract. Then, the concrete specimens were prepared by mechanical mixing.
The specimens prepared were stored under water until the testing period. The experiments to
evaluate the flexural and compressive strengths were carried out using Universal Testing
Machine according to ACI committee 318, 2014 [33].

2.5. Computational study

The chemical reactivity of molecule can well be predicted by the use of DFT calculations
[25, 34-36]. Gauss View 5.0.8 has been used to visualize the complete optimized structure of
major ingredients of R. communis extract in the present study. The complete optimization of
molecules has been performed using 6-311G** basis set since, which is quite familiar in
predicting accurate geometries and electronic properties for a wide range of inhibitor compounds
[3, 4]. Quantum chemical parameters of major constituents of plant extract were computed using
DFT/B3LYP method with 321, 6-31G*, 6-311G** functional [37, 38].
3.0. Results and Discussions

3.1. Electrochemical Impedance Spectroscopy

Fig. 1A and B showed the nyquist plots obtained for reinforcing steel in concrete before
and after the addition of inhibitor in aqueous 3.5% NaCl test solution. Fig. 2A and B are the two
different equivalent circuit models which were adopted to obtain the EIS parameters for
reinforcing steel in concrete before and after the addition of various concentrations of plant
extract for different immersion periods [39]. Table 1A and B listed the parameters calculated
from nyquist plots are shown in Fig. 1A and B. The appearance of small loop in high-frequency
region of all the nyquist plots (Fig. 1A and B) for reinforcing steel in concrete before and after
the addition of different concentrations of inhibitor molecules revealed the characteristic time
constant of charge-transfer resistance (Rct) and the double-layer capacitance (Cdl) [40, 41]. The
appearance of semicircle indicated that, the electrode reaction is being controlled by the charge
transfer process. The literature [42] revealed that, the diffusion process of electrode might be
controlled by the transmittance of dissolved oxygen towards the electrode surface from the bulk
solution. The appearance of Warburg impedance (low frequency region) supported the
transmittance of dissolved oxygen towards the electrode surface. Absence of Warburg
impedance at lower frequencies for the concrete structures added with inhibitors, which
suggested that inhibitor molecules assembled more tightly on the surface of steel. The
transmittance of oxygen (diffusive) towards the electrode surface from the solution by diffusion
controlled process via thin layer formed over steel surface resulted in the observation of linear
low frequency region [43]. The precipitation of Ca(OH)2 and the assembly of inhibitor molecules
over the surface of the steel make the high frequency loop as free from the influence of reactions
occurred at electrode. Hence, there was no significant change observed in high frequency region.

The protective layer formation over the metal surface influenced charge transfer
resistance of corrosion reaction which further gave depressed non-uniform semicircles in nyquist
plots. This could be due to the non-homogeneity and rough surface of the solid electrode which
was known as dispersing effect [44]. In addition, adsorption of inhibitor molecules, porous layer
formation and active sites distribution on surface of solid electrode also contributed. Since, the
dispersing effect make the double-layer be deviated from its ideality, a constant phase element
(CPE) is frequently used instead of the capacitor in the equivalent circuit in order to minimize
the deviation of the impedance behavior of electrical double-layer [44].

YCPE = Yo ( jw) n - - - - - - - (3)

1
Z CPE = - - - - - - - ( 4)
Yo ( jw) -n

where, Y0 is the magnitude of the CPE, ω is the angular frequency and n is the exponential term
of the CPE [41]. CPE is assumed as electrode surface irregularity at the metal-solution interface
which makes nyquist semicircles as depressed in their nature and is also acted as a capacitor with
irregular surface.

The introduction of R. communis extract into the admixture formed the protective layer
over the surface of reinforcing steel in concrete followed by decreased its capacitance, which is
clear from Tables 1A & B. There is an increase of Rct values with respect to increase in
concentrations of extract to the concrete has been observed. This might be caused by the
precipitation effect of solid Ca(OH)2 layer on increase of immersion time and the assembly of
protective layer at the steel/concrete interface by inhibitor molecules. The alkaline nature of
cement further led to the formation of passivity which also served as diffusion barrier. From the
results, it is clear that, R. communis extract inhibited the corrosion of steel embedded in concrete
effectively by diffusion controlled process and not by charge transfer process. Further, the
observation of increase in n values which could be due to the reduction of surface inhomogeneity
supported the inhibitive action of plant extract.

3.2. Potentiodynamic polarization

Fig. 3A and B projected the tafel plots obtained for steel reinforcing in concrete in
absence and presence of various concentrations and different immersion periods. Tafel
extrapolation method has been adopted for calculating the corrosion current densities (icorr)
values. The polarization parameters calculated from the tafel curves are presented in Table 2A
and B. After the introduction of plant extract into the concrete admixture, the resistance to the
diffusion of oxygen from the solution to the steel surface has been noted, which could be resulted
by the adsorption of inhibitor molecules over the surface of metal thereby acted as a barrier
between the solution and electrode surface [20]. Further, the decrease in icorr values with respect
to the addition of plant extract supported the protective layer formation by R. communis extract
on metal electrode surface (Table 2A and B) [17]. Increase in icorr values with increase in
immersion period has been observed in the present study. There has not been any particular trend
in variations in corrosion potential values observed in the present study which revealed that, R.
communis extract inhibited the corrosion in a mixed-mode manner [19]. Mixed-type inhibitive
action suggested that, both anodic and cathodic corrosion reactions have been controlled by
inhibitor molecules through the formation of protective layer on both the cathodic and anodic
active cites of electrode surface and acted as barrier on concrete/electrode surface interface [16].

There has been a quite agreement observed in both EIS and PDS results and which jointly
supported the validity of inhibitive action of R. communis extract by the protective layer
formation on the surface of steel reinforcing in concrete.

3.3. Adsorption isotherm

The anticorrosion potential of inhibitors could be well explained by evaluating the

adsorption characteristics of them over the surface of the electrode [15]. The surface coverage
values (θ), calculated from EIS data for various concentrations of R. commuis have been tried to
fit the most suitable adsorption isotherm. A linear fit having a correlation coefficient as almost
unity has been obtained when plotting (R2 = 0.9929) θ Vs log c confirmed the validity of Temkin
adsorption isotherm for the adsorption of the inhibitor molecules on reinforcing steel surface in
concrete (Fig. 4). The spontaneity of the adsorption of the inhibitor molecules on reinforcing
steel in concrete has been indicated from the observed Gibbs free energy (ΔG = -11624 kJ/Mol.)
and Kads (-1.645 kJ/Mol.) values [17].

3.4. Atomic force microscopy

To support the results of earlier studies and analyze the surface protection aided by the
inhibitors molecules at a nanoscale range, the AFM images of reinforcing steel in concrete
without and with of plant extract with a particular immersion period has been recorded. Fig. 5A
and B illustrates the recorded AFM images (two dimension) of reinforcing steel in concrete
without and with R. communis extract. It is clear from the figures that, the surface of reinforcing
steel in concrete without inhibitor has been severely damaged by the aggressive chloride ions
whereas the surface of reinforcing steel in concrete with inhibitor is highly protected and less
damaged due to the formation of protective layer by plant extract. Further, the observation of the
average surface roughness (Sa) values for embedded steel in concrete in absence and presence of
inhibitor as 119 and 19 nm, respectively, suggested the suppression in surface roughness (caused
by corrosion) on the introduction of 100 ppm of inhibitor to the concrete. This could be resulted
from the protective layer formation on steel surface which is confirmed from the results of EIS
measurements as the increase in n values with increase of concentration of inhibitor to the
admixture [16].

3.5 Compressive and splitting tensile strengths of concrete

The compressive (30 and 120 days) and splitting tensile (30 days) strengths observed
(ACI committee 263, 1997) concrete mortars [45] without and with 100 ppm of R. communis
extract by following ACI standard is given in Table 3B. Table 3B revealed the influence of the
plant extract on compressive and splitting tensile strengths of concrete with the addition various
concentrations of (25-100 ppm). It could be noted from the table that, increase of the strengths of
concrete has been observed after the introduction of plant extract. However, negligible amount of
decrease of compressive and splitting tensile strengths has been observed at 100 ppm. But, there
has not been any change in strengths observed beyond 100 ppm, i.e. saturated condition. The
increase of compressive and splitting tensile strengths indicated the reduction of porosity in
concrete which further suppressed the penetration of aggressive chloride ions thereby increased
the lifetime followed by decreased the corrosion reinforcing steel in concrete [1, 46].

3.5. Quantum chemical calculations

To elucidate the reactive center of the inhibitor molecule, there should be a consideration
about the distribution of frontier molecular orbital and Fukui indices. It is well known that,
electronic charge of molecules can induce the electrostatic interactions. Literature revealed the
influence of local electron densities as charge in many chemical reactions [1, 28]. Pearson
explained the magnitude of electronic hardness (η) and softness (s) in his hard–soft–acid– base
principle (HSAB) earlier in reactivity theory through the HSAB principle [47-49]. Quantum
chemical parameters described earlier have been calculated by DFT method. The representations
of electronegativity (c), global hardness (h), softness (s) and chemical potential (CP), were
calculated in expressions of IP and EA from following equations [50-52]

IP = - E - - - - - - - (5)
HOMO

EA = - E - - - - - - - (6)
LUMO

η, µ and χ can be calculated by from the following equation (Koopman’s theorem) [50]

IP + EA
c= - - - - - - - (7 )
2

E HOMO + E LUMO
CP = - - - - - - - (8)
2

IP - EA
h= - - - - - - - (9)
2

The s is defined as the inverse of the η (8).

1
s = - - - - - - - (10)
h

The electrophilicity index (ω) formula is

c2
w= - - - - - - - (11)
2h

In addition, he explained the nucleophilicity (ɛ) as the multiplicative inverse of

electrophilicity (e=1/w). The electrons transmitted towards the metallic surface from the inhibitor
molecules (DN) and back donation (DE back donation) have been calculated by the expressions of
hardness (h) and electronegativity (c) from the following equations,

c Fe - c inh
DN = - - - - - - - (12)
2(h Fe + h inh )

h
DE = - inh - - - - - - - (13)
back - donation 4
 where cFe and hinh are the electronegativity of iron and inhibitor molecules, respectively.
cFe is the hardness iron whereas hinh represents chemical potential of inhibitor molecule. The
fractions [1, 2 & 25] of theoretically calculated electrons transfer values are cFe = 7.0eV and hFe =
0. FMO stated that, the transfer of electrons could be attributed to the interaction between
HOMO and LUMO (Fig. 6) of reacting species. HOMO energy is directly linked to the
ionization potential and is a measure of the molecule towards electrophilic attack. The LUMO
energy is associated with the electron affinity and revealed the ability of the molecule to be
attacked by nucleophiles. Exact hardness and softness are significant properties to evaluate the
molecular stability and reactivity.

In general, molecules having lesser DE (HOMO-LUMO) values will have greater

electron-donating ability and which could be acted as good inhibitors. From the results observed
in the present study, it seems to be all the three inhibitor molecules (1, 2 & 3) can serve well as
corrosion inhibitors.

The global electrophilicity index, (ω) is the measure of ability of the inhibitor molecules
to accept electrons. The values obtained in the present study showed that, the inhibitor molecules
present in the plant extract could also inhibit the corrosion by accepting electrons from metal
ions too [1, 2]. The anti-corrosion potential of the plant extract is confirmed from the chemical
parameters (c, ω,e, ΔN and ΔEback-donation) listed in Table 4.

3.6. Mechanism of inhibition

The steel embedded in hydrated cement is automatically protected from corrosion due to
high alkaline nature which readily formed the passive films on steel surface in case of absence of
aggressive anions [6]. Hence, the embedded steel in concrete is physico-chemically protected by
concrete covers itself due to the high alkalinity. But, the presence of aggressive chloride ions can
effectively diminish the passivation of reinforcing steel in concrete to its extension even in high
alkalinity. This led to the depassivation stage and induces the active dissolution of metal [7]. The
reaction of chlorides with ingredients of cement is not completely occurred and is complicated.
Hence, chloride ions present in lower concentration will not induce corrosion much greater, but
higher concentration of chloride ions throws the reinforcing steel in concrete to high risk of
corrosion. The addition of R. communis extract attracts the excess chloride ions and bound to
them since they have positively charged in the hydrated form. By this way, the corrosion of
reinforcing steel due to the presence of chloride ions might be reduced or controlled.

R. communis contains ricinine, N-methyl recinine and ricinoleic acid [21, 22] etc. (Fig.
6). The perusal of literature showed that the organic compounds comprising heteroatoms,
electron rich functional groups, π-electrons in double as well as triple bonds and aromatic rings
could make bonds with metal atoms effectively [15-18]. The heteroatoms such as O and N in a
molecule in addition to π- electrons can effectively influence the adsorption on metal. In aqueous
solutions, there may be a possibility of existence of two types of species viz., as either neutral or
protonated molecules (cations). The results of the present study obviously confirmed the
inhibitive action of R. communis extract against the corrosion of reinforcing steel in concrete.
However, it is quite complicated to predict the exact molecule responsible for the inhibitory
effect of the plant extract since, the extract contains several numbers of organic molecules. It
could be attributed to the synergistic effect of each and every phytoconstituent of R. communis
extract.

There might be a possibility of two types of adsorption of extract molecules on

reinforcing steel in concrete which includes (1) the electrostatic interaction between protonated
form of inhibitor molecules and pre-adsorbed chloride ions on reinforcing steel surface and (2)
aromatic ring π-electrons adsorption over the embedded steel surface.

At first, the negative charge (cathodic) on embedded steel surface has been formed by the
adsorption of chloride ions present in NaCl solutions and later the positively charged protonated
form of inhibitor molecules are adsorbed on the embedded steel surface. The anodic sites of
metal might be protected by the adsorption of electrons around N, O atoms and aromatic rings
over the surface of the steel and prevent dissolution of steel. By these ways R. communis fruit
extract might be acted as mixed type inhibitor against the corrosion of embedded steel in
chloride media [52]. The mode of inhibitive action of the extract has been already confirmed
from potentiodynamic polarization technique is validated here.

4.0. Conclusions

The introduction of R. communis extract to the embedded steel in concrete in NaCl

markedly reduced the corrosion. The inhibition of corrosion of reinforcing steel in concrete in
NaCl solution through the formation of surface protective film has been confirmed by the results
of EIS measurements and supported by the AFM analysis. The results obtained from PDS
revealed the mixed type inhibition mode of plant extract which includes the modification of the
reactions of both cathodic as well as anodic sites of reinforcing steel in concrete. R. communis
extract molecules have been adsorbed on the reinforcing steel by following Temkin adsorption
model. The increases in compressive and splitting tensile strengths have been obtained after the
addition of the R. communis extract into the concrete. The results of DFT indicated that, the
presence of major ingredients might be the main reason for the inhibitive of R. communis extract.
The outcome of present study leads to the development of cheaper and greener concrete
structures those do not harmful to the environment and also longer lasting.

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 Figure Captions

Fig. 1. A) Nyquist plots of embedded steel in concrete without and with various
concentrations of R. communis after 30 days
B) Nyquist plots of embedded steel in concrete without and with R. communis
after 30 and 120 days
Fig. 2. Equivalent circuits
Fig. 3. A) Tafel plots of embedded steel in concrete without and with various
concentrations of R. communis after 30 days
B) Tafel plots of embedded steel in concrete without and with R. communis
after 30 and 120 days
Fig. 4. Temkin isotherm of R. communis on embedded steel in concrete
Fig. 5. AFM images of the embedded steel specimens in
a) NaCl and b) NaCl with 100 ppm of inhibitor
Fig. 6.
1. The x) optimized molecular structure, y) HOMO and z) LUMO of
ricinine
2. The x) optimized molecular structure, y) HOMO and z) LUMO of
N-methyl ricinine
3. The x) optimized molecular structure, y) HOMO and z) LUMO of
ricinoleic acid
 Tables

Table 1A. Nyquist parameters of R. communis on embedded steel in NaCl

Conc. of Rct Cdl

Concrete Time (days) n % of IE
Inhibitor (ppm) Ω cm-2 mFcm-2

30 0 52 248 0.6235 -
Blank
120 0 38 347 0.6812 -

30 100 99 204 0.7984 47

R. communis
120 100 295 187 0.8257 87

Table 1B. Nyquist parameters of various concentrations of R. communis on embedded steel

in NaCl

Conc. of Inhibitor Rct Cdl

S. No. n % of IE
(ppm) Ω cm-2 mFcm-2

1. 0 52 248 0.6235 -

2. 25 69 225 0.7256 25
3. 50 74 216 0.7478 30

4. 100 99 204 0.7984 47

 Table 2A. Tafel parameters of R. communis on embedded steel in NaCl

Conc. of
Time ba bc Ecorr Icorr % of
Concrete inhibitor
(days) mVdec-1 mVdec-1 mV μAcm-2 IE
(ppm)
30 0 188 190 -0.751 663 -
Blank
120 0 190 185 -0.628 1239 -

30 100 180 184 -0.602 318 52

R. communis
120 100 197 205 -0.612 260 79

Table 2B. Tafel parameters of various concentrations of R. communis on embedded steel

in NaCl

Conc. of ba bc Ecorr Icorr

S. No. % of IE
inhibitor (ppm) mVdec-1 mVdec-1 mV μAcm-2

1. 0 188 190 -0.751 663 -

2. 25 194 193 -0.774 418 37

3. 50 194 189 -0.768 385 42

4. 100 180 184 -0.692 318 52

Table 3A. Mixing proportion for concrete specimens

S. No. Sample W/B Water Cement FA CA R.C S.P

(ppm) %
1 Plain 0.31 161.2 520 805.1 914.3 0 0.6
2 RC1 0.31 161.2 520 805.1 914.3 25 0.6
3 RC2 0.31 161.2 520 805.1 914.3 50 0.6
4 RC3 0.31 161.2 520 805.1 914.3 75 0.6
5 RC4 0.31 161.2 520 805.1 914.3 100 0.6

Table 3B. Mechanical properties of concrete specimens

Splitting
Tensile
Compressive strength
S. No. Sample Strength

30 Days 90 days 30 Days

1 Plain 90.5 101.6 4.61
2 RC1 90.5 101.8 4.76
3 RC2 91.4 102.1 4.84
4 RC3 92.2 102.6 4.94
5 RC4 89.4 99.6 4.21
Table 4. Quantum chemical parameters calculated using DFT method for a) ricinine, b) N-methyl ricinine and
c) ricinoleic acid

Methods Inhibitor HOMO(eV) IP LUMO(eV) EA DE η (eV) s c ω e ΔN ΔE( back- Donation)

B3LYP/321 1 -8.70 8.70 -1.57 1.57 -7.13 3.57 0.28 5.13 3.70 0.27 3.32 -0.89
2 -6.19 6.19 -2.04 2.04 -4.15 2.07 0.48 4.12 4.09 0.24 2.99 -0.52
3 -3.67 3.67 -1.48 1.48 -2.19 1.09 0.91 2.57 3.02 0.33 2.42 -0.27
B3LYP 1 -8.90 8.90 -1.36 1.36 -7.54 3.77 0.27 5.13 3.49 0.29 3.53 -0.94
/6-31G* 2 -6.45 6.45 -2.28 2.28 -4.17 2.09 0.48 4.37 4.58 0.22 2.74 -0.52
3 -3.76 3.76 -1.59 1.59 -2.17 1.09 0.92 2.67 3.29 0.30 2.35 -0.27
B3LYP 1 -6.55 6.55 -2.36 2.36 -4.19 2.10 0.48 4.46 4.74 0.21 2.67 -0.52
/6-311G** 2 -6.68 6.68 -2.51 2.51 -4.17 2.09 0.48 4.59 5.06 0.20 2.51 -0.52
3 -4.04 4.04 -1.85 1.85 -2.19 1.09 0.92 2.94 3.97 0.25 2.22 -0.27
 Highlights
· Green approach for control the corrosion of reinforced steel in concrete has been proposed.

· R. communis extract has been used as a natural admixture successfully for the development sustainable concrete with excellent

mechanical properties.

· Mechanism of inhibitive action of R. communis extract has been proposed and correlated its anti-corrosion potential with the

presence of major ingredients.

Figures

Figure 1A
Figure 1B

Figure 2
Figure 3A
 Figure 3B

2
0.55 R = 0.9929; Slope = 0.00269

0.50

0.45

q
0.40

0.35

20 30 40 50 60 70 80 90 100 110

Log C

Figure 4
Figure 5
Figure 6