J Bio Tribo Corros (2017) 3:54
DOI 10.1007/s40735-017-0115-y
Corrosion Inhibitive Behavior and Adsorption of Millet
(Panicum miliaceum) Starch on Mild Steel in Hydrochloric Acid
Environment
S. C. Nwanonenyi1 · I. O. Arukalam1 · H. C. Obasi1 · U. L. Ezeamaku1 · I. O. Eze1 ·
I. C. Chukwujike2 · M. A. Chidiebere3,4 
Received: 11 April 2017 / Revised: 17 October 2017 / Accepted: 18 October 2017
© Springer International Publishing AG 2017
Abstract  The performance of millet starch (MS) in
controlling the corrosion of mild steel in 0.5 M HCl solu-
tion at 30 ± 1 °C was investigated using potentiodynamic
polarization, gravimetric, thermometric and mathematical
simulation technique. Data obtained from gravimetric and
thermometric results revealed that MS inhibited corrosion
of mild steel in the acid solution and increase in inhibition
efficiency was concentration dependent for all the concentra-
tions of MS investigated. The mode of adsorption of MS on
the mild steel surface obeyed Langmuir adsorption isotherm.
The potentiodynamic polarization result indicates that MS
act as a mixed type inhibitor with absolute control on the
cathodic partial reaction. The thermodynamic parameters
(∆Hads, ∆Sads, ∆Gads and Ea) for the inhibition process were
calculated, and the results obtained supported the proposed
physical adsorption mechanism. The mathematical simula-
tion technique was used to evaluate the correlation between
the inhibition efficiency of MS and its electronic molecu-
lar structure. The results show that there is a satisfactory
agreement between mathematical simulation technique and
experimental data.
* S. C. Nwanonenyi
simeonnwanonenyi@gmail.com
1 Hence, it is practicable using different inhibitors to control
Department of Polymer and Textile Engineering, Federal
University of Technology, Owerri, Nigeria
2 Starch (bio-polymer) is a viable alternative and reliable
Department of Polymer and Textile Engineering, Nnamdi
Azikiwe University, Awka, Nigeria
3 exposing metals and their alloys to the aggressive environ-
Electrochemistry and Materials Science Research Laboratory,
Department of Chemistry, Federal University of Technology,
Owerri, Nigeria
4
Institute of Metal Research, Chinese Academy of Sciences,
Shenyang, China
Keywords  Corrosion · Mild steel · Inhibition efficiency ·
Mathematical simulation technique
1 Introduction
Steel and its alloys are advantageously employed in various
applications ranging from structural, industrial (chemical,
petrochemical, metallurgical), automotive to domestic appli-
cations. These wide range of applications are attributable to
some specific properties of steel and alloys [1] which include
high thermal, mechanical strength, conductivity, electrical
properties, and cost effectiveness. However, mild steel for
instance gradually fails to display these specific properties
optimally on exposure to aggressive service environment for
a longer range of time due to the resultant corrosion effect.
Hence, during corrosion process (acid or alkaline induced),
steel and alloys degrade or deteriorate because of reactions
with the surrounding environment. Some typical applica-
tions where acid solutions meet metals include textile dye-
ing, automobile batteries, coolants and cleaners, water treat-
ment, cleaning of oil and gas pipelines, oil and water drilling
operations, fruit and juice processing plants. The resultant
effects of exposing metals to harsh service environment lead
to failures of mechanical or physical properties, injuries to
human beings and the environment, cost and material loss.
or reduce these effects of corrosion on metals.
source of inhibitors for controlling unhealthy effects of
ment during service or maintenance. This behavior is likely
because its molecular and structural constituents serve as
media through which electrons transfer occurs between the
inhibitor and surface charges on the metal thereby leading
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to the formation of strong bond [2] that facilitates the pro-
cess of adsorption. The inhibition of the corrosive action of
metals in the aggressive environment by starch is possible
by either modifying the electrochemical process (oxidation/
reduction reaction) of the reaction or forming a passive layer
on corroding surface. Also, starch from various sources is
gaining wider acceptance as inhibitors for controlling metal
corrosion because of their ease of processing and conver-
sion, affordability, renewability and they do not pose a threat
to humanity and the environment. In the literature, many
scientific researchers have reported the use of both natural
and synthetic polymers as materials for retarding the dis-
solution of metal in a harsh service environment [3–17] and
confirmed that inhibitive efficacy of polymers is dependent
on the molecular and structural constituents of polymers.
The mathematical simulation techniques provide a
detailed understanding of inhibition adsorption characteris-
tics of inhibitors at the molecular level to support the experi-
mental studies during the corrosion control using inhibitors.
Among the mathematical simulation techniques, density
functional theory (DFT) must be a valid tool in evaluating
corrosion inhibitive efficacy of different materials [18–20] to
(or “intending to”) predicting functional centers of adsorp-
tion and molecular species responsible for the interaction
between the inhibitor and surface charges on the metal.
This technique is feasible through the assessment of fron-
tier molecular orbital (FMO), the energy gap between the
molecular orbitals and chemical reactivity of the inhibitors
[21, 22].
The present research investigates the adsorption and cor-
rosion inhibitive behavior of MS on mild steel in the hydro-
chloric acid environment. Also, the correlation between the
inhibition effectiveness of MS and its molecular electronic
structure was investigated.
2 Materials and Methods
2.1 Material Preparation
3
The mild steel sheet was cut to 3 × 3 × 0.1 cm dimen-
sions using the mechanical press, and a small hole on one
side of the coupons produced to support the thread. The
metal coupons obtained were degreased in absolute ethanol,
washed with distilled water, dried in acetone and stored in
a desiccator. The acid used for the research was BDH grade
of hydrochloric acid (HCl). A blank acid solution of 0.5 M
HCl (aggressive medium) was prepared using double dis-
tilled water while inhibited solution (with a concentration
of 0.2–1.0 g/L) was obtained by dissolving the appropriate
amount of MS in one liter (1 L) of the blank acid solution.
The method described elsewhere [23] for extraction and pro-
cessing of MS was used.
13
J Bio Tribo Corros (2017) 3:54
2.2 Potentiodynamic Polarization Measurements
This was performed using PARC-263 Advanced Electro-
chemical system, electrolytic cell and computer display unit.
The cylindrical glass electrolytic cell consists of conventional
three electrodes; graphite rod (counter electrode, CE), satu-
rated calomel electrode (reference electrode, RE), a working
electrode (mild steel coupons covered in epoxy resin with a
surface area of 1 cm2 exposed to the test solution) and test
solution. The electrodes were connected to the electrolytic cell
through a luggin capillary of the electrochemical workstation.
All measurements were carried out in aerated and unstirred
solutions maintained at 30 ± 1 °C room temperature. The open
potential circuit (OCP) steady-state values obtained at the end
of 30 min of immersion before each measurement. Potentio-
dynamic polarization studies were performed in the potential
range ± 250 mV versus corrosion potential at a scan rate of
0.333 mV/s [24]. Power Suite software was used to extrapolate
the data. Each test was done in triplicates to verify the repro-
ducibility of the system.
2.3 Gravimetric Measurements
The prepared metal coupons were cleaned, weighed and
immersed completely in 250-mL capacity glass beakers contain-
ing 200 mL of test solutions with the aid of a glass rod and thread
and beakers kept at room temperature (30 ± 1 °C). For weight
loss determination, the metal coupons were retrieved from the
test solutions; metal dissolution was quenched to prevent further
corrosion reaction, washed with distilled water, dried in hot air
and reweighed at 24-h intervals gradually for 168 h. The weight
loss results were calculated as the difference between the final
weight at a given time and the initial weight. The recorded values
of weight loss were mean values of triplicate determination. The
corrosion rates of mild steel in 0.5 M HCl solution and inhibited
solutions calculated according to Eq. 1 [25] stated below:
[ ]
876000ΔW
Corrosion rate, CR(mm/year) = (1)
𝜌At
where ρ is the density of metal coupons (g/cm3), ΔW is the
weight loss in gram (g), A is the surface area of metal cou-
pon exposed to corrosion ­(cm2), and t is the time of exposure
(in h).
The percentage inhibition efficiency, %IE, was determined
using Eq. 2 [26] below:
[ ( )]
CRinh
%IE = 1 − × 100 (2)
CRblank
Also, the degree of surface coverage, θ, was determined
using Eq. 3 [27] below:
[ ( )]
CRinh
𝜃 = 1− (3)
CRblank
J Bio Tribo Corros (2017) 3:54 Page 3 of 11  54

where ­CRinh and C

­ Rblank = corrosion rates in the presence
and absence of inhibitor, respectively
2.4 Thermometric Measurements
This experimental technique was employed to monitor the
dissolution of metal in acid and compare the results obtained
with other known techniques. The process and equipment for
determining the dissolution of mild steel in 0.5 M HCl envi-
ronment using this technique have been reported by many
scientific researchers [28, 29]. The initial set temperature
was at 30 °C, and 100 mL volume of test solution maintained
in all experiments. The process of dissolution of mild steel
in control and inhibited solution at all concentrations was
monitored per minute at varying temperature using a ther-
mometer (0–100 °C) calibrated to the nearest ± 0.05 °C to
obtain the reaction number (RN). Hence, the reaction num-
ber (RN) was obtained according to Eq. 4 below:
( −1
) ( ) (corrosion potential (Ecorr), corrosion current densities (icorr),
Tm − Ti
RN ◦ C min = (4)
t
where Tm and Ti = the maximum and initial temperatures,
respectively, and t = time (min) taken to attain the maximum
temperature. The values obtained were mean values of trip-
licate determinations. The percentage inhibition efficiency
(%IE) was determined from the percentage reduction in the
reaction number according to Eq. 5 below:
RNaq − RNwi
( )
%IE = × 100
RNaq
where ­RNaq = reaction number in the absence of inhibitor
and ­RNwi = reaction number in the presence of the inhibitor.
2.5 Simulation
The mathematical simulations were performed using the
density functional theory (DFT) electronic structure pro-
grams ­D Mol 3 as contained in the Materials Studio 7.0
software program.
2.6 Scanning Electron Microscopy
The XL-30FEG scanning electron microscope was used to
study the surface morphology of the specimens after immer-
sion in 0.5 M HCl in the absence and presence of MS. The
specimens were then removed and cleaned with double
distilled water, dried in warm air and submitted for SEM
analysis.
3 Results and Discussion
3.1 Potentiodynamic Polarization Results
The experimental technique of potentiodynamic polarization
was used to investigate the mechanism of partial reactions
(anodic and cathodic) that occurs in corrosion of mild steel
and the influence of MS as inhibitor on either partial reac-
tion. Table 1 presents the results of polarization parameters
the cathodic (bc) and anodic (ba), Tafel slopes estimated
from polarization curves. Figure 1 illustrates the polarization
curves obtained from partial reactions of mild steel corro-
sion in a solution of 0.5 M HCl with and without the addi-
tion of MS. From the figure, the polarization curves revealed
that mild steel displayed active dissolution in 0.5 M HCl
solution without any sign of transition to passivation within
the studied potential range. Also, the presence of MS shifted
the Ecorr toward negative potential both at high and low MS
concentrations. This behavior served as evidence that MS
(5) retarded the releasing of hydrogen gas and anodic dissolu-
tion of mild steel, respectively, during the reaction process
with the evolution of hydrogen gas predominantly controlled
from the results of Ecorr. The change observed in the polari-
zation curves on the addition of MS reflects the behavior of
inhibition corrosion potential (Ecorr) of MS, and it is used
as criteria [29] to classify MS as cathodic, anodic or mixed
type inhibitor. In comparing the Ecorr value of inhibited and
blank solution, if the displacement is greater than 85 mV, the
inhibitor is regarded as either cathodic or anodic inhibitor
based on the direction of displacement, whereas it is a mixed
type inhibitor if it is lesser than 85 mV. The displacement
in Ecorr of inhibited and the blank solution did not show a

Table 1  Polarization System Ecorr [E vs. SCE (V)] Icorr (μA cm−2) IE (%) bc (mV dec−1) ba (mV dec−1)
parameters for mild steel
corrosion in 0.5 M HCl in the Blank − 405.76 703.24 – 127.03 93.34
absence and presence of MS
0.2 g/L MS − 435.06 204.23 70.96 84.51 67.45
0.4 g/L MS − 428.54 185.45 73.63 63.87 49.67
0.6 g/L MS − 423.76 152.47 78.37 54.78 33.45
0.8 g/L MS − 418.43 121.98 82.65 37.05 25.89
1.0 g/L MS − 412.36 97.87 86.08 31.23 19.34

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 54   Page 4 of 11
Fig. 1  Polarization curves of mild steel corrosion in 0.5  M HCl in
the absence and presence of MS
meaningful change from our results. Therefore, MS is clas-
sified as a mixed type inhibitor.
3.2 Gravimetric Measurement Results
3.2.1 Weight Loss
The dissolution of mild steel coupons in 0.5 M HCl solu-
tion in the absence and the presence of varying concentra-
tions of MS at 168 h was determined at room temperature
(30 ± 1 °C). Figure 2 shows a representative plot of weight
loss of mild steel coupons against time in the absence and
presence of MS at 30 ± 1 °C. It depicts that loss of mate-
rial (metal coupons) in acid-induced solution increases with
time, but predominantly controlled by the presence of MS.
This is an indication that MS acted as an effective inhibitor
for control of mild steel in 0.5 M HCl solution.
3.2.2 Corrosion Rate
Table 2 shows the effects of varying different concentra-
tions of MS in controlling the corrosion rate of mild steel
in a solution of 0.5 M HCl after 168 h of exposure. Data
in Table 2 revealed that rate of corrosion of mild steel in
0.5 M HCl solution reduced with time. Thus, an indica-
tion that the potency of diluted acid solution reduces with
time or that corroded surface formed a stable surface which
prevented the diffusion of diluted acid solution within the
metal surface. The presence of MS is seen to reduce the
rate of corrosion of mild steel at all concentrations stud-
ied, indicating retardation of the metal dissolution process.
Hence, the improved inhibiting effect with increasing MS
13
J Bio Tribo Corros (2017) 3:54
Fig. 2  Weight loss against time for mild steel corrosion in 0.5 M HCl
in the absence and presence of different concentrations of MS
concentration suggests a dependence of the inhibitory action
on the amount of inhibiting species available in the system.
3.2.3 Inhibition Efficiency
The effectiveness of MS in reducing the dissolution of
mild steel in 0.5 M HCl was determined by comparing the
corrosion rates of mild steel in the blank acid and inhib-
ited solutions, respectively, and expressed as a function
of the inhibition efficiency (%IE). Figure 3 presents the
relationship between the inhibition efficiency and different
concentrations of millet starch in 0.5 M HCl at 30 ± 1 °C.
It is evident that a corresponding increment occurred
between the inhibition efficiency and inhibitor concen-
tration. Hence, a maximum inhibition efficiency value of
91.78% attained at the highest concentration (1.0 g/L) of
MS (Table 2). However, inhibition efficiency decreases
with time, an indication that the efficacy of the starch as a
corrosion inhibitor is time dependent.
3.3 Thermometric Result
The thermometric method is of considerable importance
in corrosion measurement because it provides a sensi-
tive testing method in the corrosion studies and helps in
determining the corrosion behavior of many metals and
alloys in various aggressive service environments by the
introduction of reaction number. Table 3 presents the cal-
culated values of reaction number (RN) and percentage
reduction in the RN for mild steel dissolution in 0.5 M
HCl containing different concentrations of MS obtained
from the thermometric measurement. The data obtained
J Bio Tribo Corros (2017) 3:54 Page 5 of 11  54

Table 2  Calculated values System Corrosion rate (mm/year) Inhibition efficiency (%) Surface coverage (θ)
of corrosion rate (mm/year),
inhibition efficiency (%) and 24 h 72 h 120 h 168 h 24 h 72 h 120 h 168 h 24 h 168 h 72 h 120 h
surface coverage (θ) for mild
steel in 0.5 M HCl in the Blank 38.33 20.76 12.92 9.98 – – – – – – – –
absence and presence of MS 0.2 g/L 6.91 4.18 3.34 2.92 81.97 79.87 74.15 70.74 0.82 0.80 0.74 0.71
from weight loss measurement 0.4 g/L 5.63 3.61 2.85 2.62 85.51 82.61 77.94 73.75 0.85 0.83 0.78 0.74
at 30 ± 1 °C
0.6 g/L 4.43 3.04 2.47 2.35 88.44 85.36 80.88 76.45 0.88 0.85 0.81 0.76
0.8 g/L 3.74 2.34 1.90 1.72 90.24 88.73 85.29 82.26 0.90 0.89 0.85 0.82
1.0 g/L 3.15 2.12 1.59 1.53 91.78 89.79 87.69 84.67 0.92 0.90 0.88 0.85

of an optimum concentration of MS. The micrograph as

received specimen shown in Fig. 4a appears very smooth.
However, in the uninhibited solution (Fig. 4b), a rough sur-
face was observed due to the effective dissolution of mild
steel in this environment, while in the presence of MS the
roughness reduced significantly (Fig. 4c). This scenario
shows an evidence of adsorbent species on the mild steel
surface, thus confirming the adsorption of MS constituents
on the mild steel surface.

3.5 Adsorption and Thermodynamic Considerations

Inhibitors of organic origin contribute immensely in con-

trolling or inhibiting the corrosion of metals in aggressive
solution via adsorption mechanism. During corrosion inhi-
bition process, organic inhibitor separated the real metal/
Fig. 3  Variation of inhibition efficiency with different concentrations corrodent interface via layer formation and adsorbed on the
MS at different time metal surface. Hence, this inhibitor shields the metal sur-
face from direct attack of the corrosive agent in the solution
and further reduces metal dissolution. The adsorption route
Table 3  Calculated values of reaction number (RN) and percentage regarded as displacement process between the organic inhib-
reduction in RN for mild steel dissolution in 0.5  M HCl containing itor in the aqueous solution ­[Inh(sol)] and water molecules
different concentrations of millet starch obtained from thermometric
adsorbed on the metal surface [χH2O(ads)] is shown below
measurement
according to Eq. 6 [8]:
System Reaction number (RN) % Reduction in RN
(°C min−1) (> inhibition effi- Inh(sol) + 𝜒H2 O(ads) ↔ Inh(ads) + 𝜒H2 O(sol) (6)
ciency)
where χ is the number of water molecules are placed by
Blank 0.36 – one molecule of adsorbed inhibitor. Hence, the displace-
0.2 g/L 0.18 50.00 ment reaction process protects the metal surface from cor-
0.4 g/L 0.13 63.89 rosion damage. The increase in inhibition efficiency by MS
0.6 g/L 0.09 75.00 determined by weight loss method with an increase in the
0.8 g/L 0.07 80.56 inhibitor concentration indicates that adsorption of MS on
1.0 g/L 0.04 88.89 the mild steel surface at higher concentration leads to greater
surface coverage. The data of the degree of surface coverage
(θ) determined from weight loss measurement were fitted
using the thermometric technique (Table 3) is in line with to different isotherms (Temkin, Freundlich and Langmuir),
the traditional method [30]. and the best fit obtained from the value of linear correlation
co-efficient (R2) is used to determine the mode of inhibition
3.4 Scanning Electron Microscopy adsorption. Thus, the generalized expressions for each of the
adsorption isotherms used are stated below [31];
Figure 5 presents the SEM micrographs of mild steel speci- In𝜃 = InKads + InC (Freundlich) (7)
mens immersed in 0.5 M HCl in the absence and presence

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 54   Page 6 of 11 J Bio Tribo Corros (2017) 3:54

Fig. 4  SEM images of mild steel surface after 24-h immersion at 30 °C in 0.5 M HCl a As received, b without MS and c with 1 g/L MS

Fig.  5  a Plot of Langmuir adsorption of MS on mild steel in 0.5 M HCl solution at 30 ± 1 °C. b Plot of Freundlich adsorption of MS on mild
steel in 0.5 M HCl solution at 30 ± 1 °C. c Plot of Temkin adsorption of MS on mild steel in 0.5 M HCl solution at 30 ± 1 °C

Table 4  Calculated values of Langmuir isotherm adsorption param-

exp (−2a𝜃) = Kads C (Temkin) (8) eters for mild steel corrosion

C 1 Time (h) R2 Slope Kads ∆Gads (KJ mol−1)

( )
𝜃
=
Kads
+ C (Langmuir) (9)
24 0.99 1.05 23.04 − 17.90
where θ is the degree of surface coverage,  α = molecular 72 0.99 1.07 20.88 − 17.66
interaction parameter whose value depends on the type of 120 0.99 1.08 13.85 − 16.63
molecular interactions in the adsorption layer and the degree 168 0.99 1.11 11.64 − 16.19
of homogeneity of the surface, C, is the inhibitor concen-
tration and Kads = adsorption–desorption equilibrium con-
stant. The plot of (C/θ) against C is shown in Fig. 5a for mild steel surface. The Kads value (23.04) obtained at the end
Langmuir adsorption of millet starch on mild steel surface in of 24 h is higher than those obtained at other time intervals,
0.5 M HCl. The plots obtained are linear plot and correlation thus suggesting that there is more efficient adsorption and
co-efficient (R2) at all concentrations being 0.99 (Table 4). better inhibition efficiency at the 24-h time interval. The
Hence, the adsorption of millet starch followed Langmuir Kads values of some inhibitors tested under similar condition
adsorption because the value of correlation co-efficient, R2 as available in the literature are referenced [17, 32–35] to
(0.99) obtained from the plots is very close to unity. Thus, justify that Kads of MS is very efficient. From the intercepts
suggesting that adsorption sites on the mild steel surface are of the straight lines in Fig. 5a, Kads was calculated, and it is
uniformly distributed and energetically identical and that related to the standard free energy of adsorption (∆Gads) by
maximum number of adsorbed molecules per site is one, the equation shown below:
implying a case of monolayer adsorption (i.e. homogene- ( )
1 ΔGads
ous surface). Also, the plots for the Freundlich and Temkin Kads = exp − (10)
adsorption isotherms are shown in Fig. 5b, c respectively. 55.5 RT
The values of Kads obtained from Fig. 5a are positive and where T is the absolute temperature, R is the universal gas
decrease with increasing time (shown Table 4). Positive val- constant, and Kads is the equilibrium adsorption constant.
ues of Kads confirmed adsorption of MS constituents on the

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J Bio Tribo Corros (2017) 3:54 Page 7 of 11  54

The negative values of ∆Gads implied strongly adsorption
of MS on the mild steel surface, spontaneous adsorption
process and favorable from the thermodynamics point of
view. Also, the value of ∆Gads is used to predict whether
the adsorption process occurred by physical adsorption or
chemical adsorption. Hence, the ∆Gads value < − 20 kJ/mol
depicts physical adsorption and is linked to an electrostatic
interaction between inhibitor molecules and charges on the
metal surface, whereas the ∆Gads value more than − 40 kJ/
mol shows chemical adsorption and involves charge sharing
or transfer from the inhibitor molecules to the metal sur-
face to form a coordinate covalent bond [36]. On this note,
the values of ∆Gads obtained in this study suggest physical
adsorption.
3.6 Temperature Effect and Kinetic Studies
Figure 6 and Table 5 present the effect of temperature on
corrosion rate and corrosion inhibition process of mild
steel in a solution of 0.5 M HCl in the absence and pres-
ence of MS investigated using weight loss measurement
technique for 4 h in the temperature range of 308–338 K.
It is evident from the data in Fig. 6 and Table 5 that corro-
sion rate is temperature dependent, but the presence of the
inhibitor decreased the corrosion rate. The behavior can be
attributed to the fact that increases in temperature speed
up the rate of reaction, diffusion, and ionization of reactive
species in the reaction. On the other hand, the reduction in
the corrosion process observed in the presence of MS may
be due to adsorption of MS constituents on the mild steel
surface. This action further retards the dissolution pro-
cess by displacing more of corrosion agents at the reactive
sites on the metal surface and thus reduced the corrosion
rate. Furthermore, the decrease in %IE, observed with an
increase in temperature, is an indication that desorption of
MS constituents on the metal surface occurred at elevated
temperature, and the reduction in %IE, with the rise in
temperature, suggesting physical adsorption mechanism.
The relationship between the corrosion rate and temper-
ature in corrosion process is determined from Arrhenius
equation stated below:
( ) ( )
CR2 Ea 1 1
log = − (11)
CR1 2.303R T1 T2

where ­CR1 and ­CR2 represent the corrosion rates at tem-

peratures T1 and T2, respectively. R is the universal gas con-
stant. Ea is apparent activation energy (Ea) for the corrosion
process in absence and presence of different concentrations
MS. Table 6 displays the calculated values of Ea obtained.
The relationship between the energy of activation of the test
solutions and temperature dependence of the inhibition effi-
ciency of an inhibitor as seen in Eq. 10 is grouped into three
as stated below:

i. Eainh solution < Eablank, %IE increases with increase

in temperature (chemical adsorption)
ii. Eainh solution > Eablank, %IE increases with decrease
in temperature (physical adsorption)
iii. Eainh solution = Eablank, %IE does not change with
temperature variations.
Fig. 6  Corrosion rate against temperature for mild steel corrosion in
0.5 M HCl in the absence and presence of different concentrations of
MS

Table 5  Calculated values Conc Corrosion rate (mm/year) Inhibition efficiency (%) Surface coverage (θ)
of corrosion rate (mm/year),
inhibition efficiency (%) and 30 °C 40 °C 50 °C 60 °C 30 °C 40 °C 50 °C 60 °C 30 °C 40 °C 50 °C 60 °C
surface coverage (θ) for mild
steel corrosion in 0.5 M HCl Blank 29.42 33.53 46.28 62.79 − − − − − − − −
in the absence and presence of 0.2 g/L 17.62 20.93 32.39 53.25 40.10 37.58 30.01 15.19 0.40 0.38 0.30 0.15
different concentration of MS 0.4 g/L 7.54 18.05 27.73 49.20 74.37 46.17 40.08 21.64 0.74 0.46 0.40 0.23
from weight loss measurement
at different temperatures 0.6 g/L 7.05 16.30 24.33 46.93 76.07 51.39 47.43 25.26 0.76 0.51 0.47 0.25
0.8 g/L 5.26 14.35 21.98 44.45 82.21 57.20 52.51 29.21 0.82 0.52 0.53 0.29
1.0 g/L 4.40 12.94 19.19 41.57 85.04 61.41 58.54 33.80 0.85 0.61 0.59 0.34

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Table 6  Calculated values of activation energy, enthalpy of adsorp-

tion and entropy of adsorption for mild steel corrosion presence of
different concentrations MS in 0.5 M HCl at 30–60 °C

System Ea (KJ mol−1) ∆Hads (KJ mol−1) ∆Sads (KJ mol−1)

Blank 0.38 19.048 − 173.784

0.2 g/L 0.55 28.662 − 146.629
0.4 g/L 0.94 48.435 − 86.968
0.6 g/L 0.95 48.652 − 86.936
0.8 g/L 1.06 54.985 − 68.273
1.0 g/L 1.12 57.573 − 61.129

Also, this relationship is used to interpret the form of

adsorption mechanism that occurs during metal corrosion
process [37]. It is evident in Table 6 that activation energy
of inhibited solution is higher than that obtained from blank
solution, thus indicating that the corrosion of mild steel
is inhibited by MS and also suggests physical adsorption
mechanism. Hence, the group (ii) is applicable. The increase
in activation energy values in the presence of MS indicates
the high inhibiting action of MS, the presence of electro-
static interaction between MS and surface charge on the mild
steel. Obviously, the action is related to increasing number
of blocked active corrosion sites which enhances the activa-
tion energy of the corrosion process.
An estimate of enthalpy of adsorption, ∆Hads and entropy
of adsorption, ∆Sads were obtained from the transition state
equation stated below:
) [ ( ) ( ΔS )]
(
CR R ΔHads
log = log + ads
− tained. Also, increase in inhibition efficiency with increase
T hN 2.303RT 2.303RT
(12)
Figure 7 gives the plot of log (CR/T) versus 1/T with
slope equal to −  ∆H ads/2.303R and intercept equal to
log[(R/Nh) + ∆Sads/2.303R], from which ∆Hads and which
∆Sads are determined. Table 6 shows the results of ∆Hads
and ∆Sads obtained. The values of ∆Hads obtained are posi-
tive, thus indicating an endothermic nature of the reaction
process. It also reflects that degree of surface coverage
decreases with a rise in temperature, thus suggesting the
physisorption mechanism. The values of entropy change
were found to be high and negative; revealing the degree of
disorderliness of adsorption of the inhibitor on the mild steel
surface. The negative values of entropy change are an indi-
cation that MS molecules freely move in the bulk solution,
adsorbed in an orderly manner onto the mild steel surface
resulting in a decrease in entropy.
3.7 Inhibition Mechanism
The interaction existing between the functional groups pre-
sent in the polymer structure and charge on the metal surface
Fig. 7  Plot of Log(CR/T) and 1/T for mild steel corrosion in 0.5 M
HCl in the absence and presence of different concentrations of MS
is responsible for the formation of protective layer or film
that controls the corrosion of metal surface. The functional
groups are adsorption centers, and adsorption occurs by
either physical or chemical adsorption mechanism through
monolayer or double-layer mode. Availability of multiple
functional groups within the polymer structure increases
the potency of inhibitor in blocking corrosion sites on the
metal surface or altering the electrochemical reaction of the
corrosion process, but the exact impact of the individual
functional group on inhibition process could not be ascer-
in concentration suggests an increase in surface area cover-
age and enhanced protection due to more adsorption on the
metal surface. The corrosion inhibitive effect of MS can be
linked to the presence of two glucose polymers. However,
in acidic media, starch is hydrolyzed partially into simple
sugar (glucose) whereby some of the glycosidic bonds are
broken down into glucose units. In the presence of glucose
molecules, two glucose polymers may interact with a charge
on the corroding surface, forming organometallic [Fe-Inh]
complex. The inhibiting performance of such complex
formed could be dependent on their stability and solubil-
ity in acid solution with respect to time, temperature, and
concentration.
3.8 Mathematical Simulation Studies
Density functional theory (DFT) was the mathematical
simulation technique employed to investigate the correla-
tion between the inhibitive efficacy of MS and its molecular
electronic structure at the molecular level. This technique
is an acceptable tool [38, 39] for assessing the theoretical
inhibitive performance of varied materials and also serves

13
J Bio Tribo Corros (2017) 3:54 Page 9 of 11  54
as a guide for a practical approach to experimental corro-
sion work. To determine the correlation between inhibi-
tive efficacy of MS and its molecular structure, energies
of frontier molecular orbitals (HOMO orbital and LUMO
orbital) and energy gap between the LUMO and HOMO
(ΔE = ELUMO − EHOMO) [40] were investigated. Figure 8
presents the geometrically optimized structure of glucose,
HOMO and LUMO orbitals, Fukui functions, and the total
electron density determined from the simulations. The tran-
sition of electrons which brings about the adsorption process
is due to an interaction existing between the frontier orbit-
als of reacting species, according to the frontier molecular
orbital theory of chemical reactivity. HOMO energy char-
acterizes the susceptibility of the molecule toward attack
by electrophile, corresponds to a tendency for electron
acceptance and is directly related to the ionization poten-
tial, whereas LUMO energy defines the susceptibility of the
molecule toward attack by a nucleophile, corresponds to a
tendency for electron donation and is directly related to the
electron affinity. High values of EHOMO (less negative) indi-
cate the great ability of a molecule to give out electrons to an
appropriated acceptor with empty molecular orbital which
facilitates the adsorption process, and it indicates superior
performance of the corrosion inhibitor. Lower values of
ELUMO indicate the stronger electron-accepting ability of the
Fig. 8  Electronic properties of glucose molecule: a optimized struc-
ture, b electron density, c HOMO orbital, d LUMO orbital, e electro-
philic attack ­(F−) and f nucleophilic attack (­ F+) (C, gray; H, white; O,
molecule [41, 42]. Similarly, low values of the energy of the
gap, ΔE will provide good inhibition effectiveness, since
there is a reduction in the energy required in removing an
electron from the last occupied orbital. The calculated values
of EHOMO and ELUMO for starch molecule were − 0.5991 and
− 0.0842 eV, respectively. High values of EHOMO indicate
a greater disposition of a molecule to donate electrons to a
mild steel surface. Hence, the ∆E value (0.5149 eV) from
our result shows that glucose unit of a starch molecule has a
high reactivity toward adsorption on the mild steel surface.
The range of ∆E is in line with the result obtained elsewhere
[43].
The electronic structure of starch, distribution of fron-
tier molecular orbital and Fukui indices were assessed to
establish the active adsorption sites or centers as well as
local reactivity of the inhibiting molecules. The simula-
tions were done with the density functional theory (DFT)
electronic structure programs D ­ Mol3 and analyzed using
a Mulliken population analysis. Such electronic param-
eters for the simulation include restricted spin polarization
local correlation density functional form which uses the
DND basis set as the Perdew–Wang (PW). Local reac-
tivity regarding nucleophilic and electrophilic behavior
was analyzed using the Fukui indices to assess the active
regions (Fig. 8). The site for the nucleophilic attack is the
red). The blue and yellow isosurfaces depict the electron density dif-
ference: the blue regions show electron accumulation, while the yel-
low regions show electron loss (Color figure online)
13
 54   Page 10 of 11
area where the value of F­ + is maximum which corresponds
to the HOMO locations. Also, the site for the electrophilic
attack is the area in which the value of ­F− maximum which
corresponds to LUMO locations. In the geometrically opti-
mized structure of glucose molecule, the HOMO orbital is
dominated by the aromatic nucleus and hydroxyl groups
which are the regions of maximum electron density, often
the site at which electrophiles attack, and thus, represents
the active centers, with the ability to bond to the metal
surface. The LUMO orbital is dominated by the methyl
hydroxy group, hydroxyl groups and partially seen in the
aromatic nucleus. It represents the site at which nucleo-
philic attack occurs. The above explanations suggest that
MS possessed excellent inhibiting potential. Hence, this
agrees with the experimental findings.
4 Conclusion
1. MS was found to be a suitable inhibitor for corrosion of
mild steel in 0.5 M HCl environment.
2. Inhibition efficiency (%) of MS increased with an
increase in concentration and with a decrease in tem-
perature.
3. The adsorption of the MS on mild steel surface fol-
lowed Langmuir adsorption isotherm. Thus, indicating
a homogeneous layer of adsorption on the mild steel
surface.
4. Activation energies were higher in the presence of MS,
thus indicating physisorption. This trend of inhibition
mechanism observed agreed with the values of the heat
of adsorption obtained. Also, the adsorption process was
spontaneous and exothermic with a decrease in entropy
of the system from a thermodynamic point of view.
5. The mathematical simulation technique using density
functional theory (DFT) revealed that parameters asso-
ciated with the optimized structure of MS molecule con-
firmed its inhibitive potentials.
Acknowledgements  The contribution of Electrochemistry and Mate-
rials Science Research Laboratory, Federal University of Technology,
Owerri, Nigeria and Institute of Metal Research, Chinese Academy of
Sciences, Shenyang, China in making this research successful is highly
appreciated. Also, the authors are grateful to Ezeh Comas, Okoro Chin-
weike and Adika Precious for their assistance in carrying out some
measurements.
Compliance with Ethical Standards  18. Khaled KF (2010) Corrosion control of copper in nitric acid
Conflict of interest  On behalf of all authors, the corresponding au-
thor states that there is no conflict of interest.
13
J Bio Tribo Corros (2017) 3:54
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