Journal of Environmental Chemical Engineering: N.A. Odewunmi, S.A. Umoren, Z.M. Gasem
Journal of Environmental Chemical Engineering: N.A. Odewunmi, S.A. Umoren, Z.M. Gasem
Journal of Environmental Chemical Engineering: N.A. Odewunmi, S.A. Umoren, Z.M. Gasem
A R T I C L E I N F O A B S T R A C T
Article history: Three agro-waste products namely; watermelon rind extract (WMRE), watermelon seed extract (WMSE)
Received 19 June 2014 and watermelon peel extract (WMPE) were investigated for their corrosion inhibition potentials for mild
Accepted 19 October 2014 steel in HCl solution using electrochemical techniques at 25 C. All the extracts inhibited acid-induced
Available online 22 October 2014
corrosion of mild steel in the order WMSE > WMRE > WMPE. Corrosion inhibition effect was found to be
dependent on extracts’ concentrations. Inhibitive action of the extracts could be attributed to adsorption
Keywords: of the extracts’ components on mild steel surface by physisorption mechanism according to Langmuir
Watermelon
adsorption isotherm model and functions as mixed-typed inhibitors as revealed by potentiodynamic
Waste products
Mild steel
polarization studies.
Corrosion inhibition ã 2014 Elsevier Ltd. All rights reserved.
Acid corrosion
Introduction corrosion inhibition are scanty. For instance Noor [27] studied the
effect of aqueous extract of Fenugreek leaf (AEFL) and seed (AEFS)
The importance of mild steel cannot be under estimated in the on the corrosion of mild steel in HCl and H2SO4 solutions. Results
constructions and chemical industries based on their cost obtained showed that the seed extract was more potent than the
effectiveness and tremendous mechanical properties. Despite leaf extract in mitigating mild steel corrosion. This was attributed
the availability of mild steel, its poor corrosion resistance in acidic to the high concentration of the phytochemical constituents in the
media has been a major challenge to its application [1–3]. seed than in the leaf part of the plant. Similarly, Okafor et al. [28]
However, the use of corrosion inhibitors had been reported to reported on the inhibitive action of leaves (LV), seeds (SD) and a
be an efficient way of controlling its corrosion processes [4,5]. combination of leaves and seeds (LVSD) extracts of Phyllanthus
Most of the inhibitors used in the industries compose of amarus on mild steel corrosion in HCl and H2SO4 solutions by
some compounds that are toxic and have been presently facing hydrogen evolution and gravimetric methods. Inhibition efficien-
a lot of criticisms due to their threat to human and their cies were found to follow the trend LV > LVSD > SD. Corrosion
environments. Consequently, the use of natural products as inhibition of mild steel in 1 M H2SO4 by leaves and stem extracts of
corrosion inhibitors is in the fore front in the current trend of Sida acuta at different temperatures has been reported [29]. The
corrosion inhibition studies. The advocacy on the use of natural leaves extract was found to be a better inhibitor than the stem
products as corrosion inhibitors stemmed from the facts that extract.
they are cheap, renewable, readily available, ecologically There are few reports in the literature on the use of watermelon
acceptable and environmentally friendly. More so can be parts for corrosion protection. For example, the protection of zinc
obtained by simple extraction procedures. Corrosion inhibition in natural seawater by watermelon peel (WMP) [30] and mild steel
of metals and alloys using plant extracts as green inhibitors has by watermelon leaf [31] based on weight loss corrosion monitoring
been reported by many researchers [6–26]. technique have been reported. Previous reports had no informa-
Reports in the literature on the use of plant extracts as corrosion tion on the kinetics of the anodic and cathodic reactions of the
inhibitors are focused largely on single plant part (leaves, stems, corrosion phenomenon and how these were modified by the
barks, roots, fruits etc.). However, comparative studies on addition of the extracts of the watermelon waste products. Earlier,
utilization of extracts of various parts of a particular plant for we have reported on the corrosion inhibition effect of watermelon
rind extract (WMRE) for mild steel in HCl and H2SO4 solutions
using electrochemical techniques [32]. In an attempt to extend the
* [19_TD$IF]Corresponding author. Tel.: +966 13 860 7895; fax: +966 13 860 [20_TD$IF]3996. investigation to other watermelon waste products, the present
E-mail address: [email protected] (N.A. Odewunmi). paper reports on the corrosion inhibition effect of WMPE and
http://dx.doi.org/10.1016/j.jece.2014.10.014
2213-3437/ ã 2014 Elsevier Ltd. All rights reserved.
[(Fig._2)TD$IG]
N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296 287
[(Fig._1)TD$IG]
WMSE and compares with that of WMRE for mild steel in 1 M HCl
as a corrosive medium at 25 C. UV–vis spectroscopy and
Attenuated Total Reflectance Fourier Transform Infrared
(ATR-FTIR) spectroscopy techniques were also employed to gain
insight into the possible corrosion inhibition mechanism.
Experimental
Materials preparation
The test solution was 1 M HCl prepared from A-R grade 37% HCl
(Sigma–Aldrich). Watermelon (Citrullus lanatus) was purchased in
the local market. The rind, seed and peel were separated from the
edible pulp, cut into pieces, sun dried and ground into powdery
form. Extracts of WMR, WMS and WMP were prepared by
weighing about 5.00 g portion of each watermelon parts in 1 L
of 1 M HCl, heat to boiling and allowed to boil for 10 min. The
solutions were cooled and then filtered with a sintered glass
Buchner funnel no. 36060 to obtain the stock solution. The
difference between the initial weight of the powdered materials
and the weight of the residue gave the amount of materials
extracted into the solution. Different concentrations of the extracts
(0.10–2.00 g/L) were prepared from the stock solution by dilution
with the corrodent (1 M HCl). All solutions were prepared with
double distilled water.
The mild steel chemical composition (weight %) used in the
experiment is: C, 0.15; Mn, 1.26; V, 0.017; Si, 0.035; S, 0.008; Cr,
0.036; Ni, 0.03; Al, 0.083; Cu, 0.038 and Fe (balance). The mild steel
was made into coupons of 3 cm 3 cm 0.25 cm dimension,
abraded with silicon carbide abrasive papers of different grades
(# 120–800), and rinsed with distilled water. The residue particles
from the grinding process were removed by sonication in ethanol
bath for 10 min, rinsed with ethanol and dried in warm air, and
then stored in the desiccator prior to use for corrosion measure-
ments.
Electrochemical measurements
SEM surface morphology efficiency (E) was calculated from the values of corrosion current
density in the absence (Icorr ) and presence (Icorr) of the inhibitors
The mild steel coupon (3 cm 3 cm 0.25 cm) surfaces were using Eq. (1) and the value obtained are listed in Table 1.
ground with silicon carbide paper of different grades (# 120–800)
Icorr Icorr
and polished to near mirror surface finished with a cloth sprayed E¼ 100 (1)
Icorr
with 1 mm diamond paste. The well surface treated mild steel was
rinsed with double distilled water, sonicated with ethanol bath for
10 min to remove polished residues and then placed in a desiccator.
The coupons were completely immersed in 1 M HCl without and [(Fig._3)TD$IG]
with 2.0 g/L of WMSE, WMRE and WMPE in a glass vessel at 25 C.
They were retrieved after 24 h of exposure, rinsed with distilled
water, dried in warm air and stored in desiccator before submission
for SEM surface examination. The surfaces of the mild steel
samples were examined with a Joel JSM-6610 LV scanning electron
microscope.
PDP measurements
Table 1
PDP data of mild steel in 1 M HCl in the absence and presence of different concentrations of WMRE, WMSE and WMPE.
Extracts Concentration (g/L) Ecorr (mV/SCE) Icorr (mA/cm2) ba (mV/dec) bc (mV/dec) CR (mpy) E (%)
Blank 1 M HCl 487.60 226.00 97.05 125.00 131.50 –
From Table 1, it is observed that inhibition efficiency Bode modulus plots which also increases as the concentration of
increased with increasing concentration of the three watermel- the extracts increases. The adsorption of some components such as
on waste products extract studied. Also, the order of corrosion tannins, flavonoids, polyphenols, saponnins and citrulline on the
inhibition efficiency for the highest concentration (2.0 g/L) of mild steel surface could be responsible for the corrosion inhibition
the extracts studied is WMSE (83.67%) > WMRE effects of the extracts. It has been reported that watermelon rind
(79.36%) > WMPE (72.42%). and seed contain majorly citrulline in addition to tannins,
flavonoids, polyphenols, saponins [38,39]. The adsorptions of
EIS measurements these compounds through the aromatic ring and the heteroatoms
(N, O) onto the mild steel surface could prevent the attack of
The kinetics of the electrochemical processes and capacitive corrosive ions in the solution by creating a barrier for mass and
behaviors at 1 M HCl/steel interface in the presence and absence charge transfer. Corrosion inhibition efficiency (E) from the
of WMRE, WMSE and WMPE were characterized with EIS impedance spectroscopy measurements were estimated by
measurements. Figs. 4–6 show the (a) Nyquist, (b) Bodes’ comparing the charge transfer resistance with (Rct) and without
modulus and (c) phase angle plots for WMRE, WMSE and (Rct ) WMRE, WMSE and WMPE using the expression given in
WMPE respectively. The shape of the impedance plot remains Eq. (2):
the same in spite of addition of different concentrations of
Rct Rct
WMRE, WMSE and WMPE which indicates similar corrosion E¼ 100 (2)
Rct
mechanism of the mild steel in HCl medium in the absence and
presence of the extracts. Also the diameter of the semi-circle in
the Nyquist plots increases as the concentration of the extracts The double layer capacitance Cdl, values (Table 2) obtained at
increased. The Bode phase angle plots of all the extracts show the maximum frequency (fmax) of the imaginary component of the
just one relaxation process which correspond to one semi-circle impedance using Eq. (3) was observed to decrease with the
capacitive loop in the Nyquist plots over the range of the introduction of the extract into the acidic medium. This can be
studied frequencies. This behavior is attributed to a time attributed to the displacement of water molecules by the adsorbed
constant in an electrochemical system [34]. It is also observed species of the extracts onto the mild steel surface, as a result lead to
in the phase angle plots that the phase angle maxima of all the decrease in the dielectric constant due to the increase in double
extracts’ concentrations as well as the blank solution are less layer thickness [40], thereby protect the surface of the mild steel
than 90 . The semi-circles of the Nyquist plots are depressed from acid attack.
with the center under the real axis. Many reasons including
1
surface roughness, inhomogeneity in the dielectric material and C dl ¼ : (3)
2pf max Rct
so on have been attributed to such impedance behavior of the
interface as revealed by the Nyquist and Bode phase angle plots
[35]. A constant phase element (CPE) should be introduced to The reduction in the Cdl value as the double layer thickness
replace a true capacitor in the equivalent circuit to account for increases can also be linked to the Helmholtz model (Eq. (4)).
these effects in order to estimate the impedance parameters
ee0 A
[36,37]. The enumerated characteristics of the EIS plots for mild C dl ¼ (4)
d
steel electrode in 1 M HCl with and without WMRE, WMSE and
WMPE, lead to the consideration of the equivalent circuit where the dielectric constant of the medium is e, vacuum
shown in Fig. 7 to fit the EIS experimental data to generate the permittivity is e0,A is the exposed area of the electrode and d is
impedance parameters of interest listed in Table 2. the thickness of the protective layer. The corrosion inhibition
The intercept of the semi-circle in the low and high frequency efficiency of 83.35%, 85.96% and 79.52% are obtainable for
region on the real impedance axis were assigned to the charge WMRE, WMSE and WMPE respectively which follow the trend
transfer resistance (Rct) and solution resistance (Rs) respectively. (WMSE > WMRE > WMPE) obtained in the PDP results.
The corrosion inhibition effectiveness of WMRE, WMSE and WMPE The same order of corrosion inhibition efficiency was observed
can also be interpreted in the real impedance values axis of the in the LPR experiment where the polarization resistance (Rp) using
290 N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296
[(Fig._4)TD$IG] [(Fig._5)TD$IG]
Fig. 4. Impedance plots for mild steel in 1 M HCl in the presence and absence of Fig. 5. Impedance plots for mild steel in 1 M HCl in the presence and absence of
different concentrations of WMRE; (a) Nyquist, (b) Bode modulus and (c) Bode different concentrations of WMSE; (a) Nyquist, (b) Bode modulus and (c) Bode
phase angle. phase angle.
Eq. (5) was utilized to estimate the data shown in Table 3. where Rp and Rp represent the polarization resistance in the
presence and absence of WMRE, WMSE and WMPE respectively.
Rp Rp
E¼ 100 (5) The Rp increases as the concentration of the extracts increases in
Rp
the same way as the other electrochemical measurements
N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296 291
[(Fig._6)TD$IG]
observed trend is not clear, the differences in the phytochemical
composition and the amount of the materials extracted into the
solution may not be ruled out.
Adsorption isotherm
[(Fig._7)TD$IG]
Fig. 6. Impedance plots for mild steel in 1 M HCl in the presence and absence of
different concentrations of WMPE; (a) Nyquist, (b) Bode modulus and (c) Bode
phase angle.
Table 2
EIS data of mild steel in 1 M HCl in the absence and presence of different concentrations of WMRE, WMSE and WMPE.
Extracts Concentration (g/L) Rs (V/cm2) Rct (V/cm2) Yo (mV Sn/cm2) Ceff (mF/cm2) Cdl (mF/cm2) n u E (%) x2 104
Blank 1 M HCl 4.13 73.14 154.60 58.32 87.19 0.90 – – 0.24
WMRE 0.10 5.02 179.70 89.43 28.30 55.85 0.89 0.59 59.30 10.51
0.50 5.06 253.20 94.14 26.60 50.85 0.87 0.71 71.11 5.74
1.00 6.63 339.90 78.92 17.00 47.10 0.86 0.78 78.48 9.66
2.00 4.23 439.20 94.89 23.80 57.28 0.87 0.83 83.35 3.54
WMSE 0.10 6.17 272.50 96.98 19.00 47.10 0.85 0.73 73.16 8.65
0.50 4.08 306.90 99.00 17.10 52.20 0.84 0.76 76.17 3.84
1.00 5.88 433.20 79.66 11.50 37.00 0.83 0.83 83.12 6.33
2.00 9.15 520.80 78.30 11.30 38.40 0.83 0.86 85.96 2.78
WMPE 0.10 3.94 201.10 133.90 31.35 63.80 0.86 0.64 63.63 2.84
0.50 13.37 289.60 81.45 13.55 44.30 0.84 0.75 74.74 6.84
1.00 4.50 273.90 102.80 20.33 46.80 0.85 0.73 73.30 6.60
2.00 14.49 357.10 79.59 15.04 44.80 0.85 0.80 79.52 6.75
Table 4
Comparison of inhibition efficiency of the electrochemical techniques data of mild steel 1 M HCl in the absence and presence of different concentrations of WMRE, WMSE and
WMPE.
[(Fig._8)TD$IG] [(Fig._9)TD$IG]
Fig. 8. Langmuir adsorption isotherms for the WMRE, WMSE and WMPE in 1 M
HCl on mild steel.
Surface morphology
Fig. 9. UV–vis absorption spectra of solutions of extracts without mild steel, mild
Table 5
steel in 1 M HCl and mild steel 1 M HCl with 2.0 g/L concentration of extracts; (a)
Langmuir adsorption isotherms for WMRE, WMSE and WMPE in 1 M HCl on mild
WMRE (b) WMSE and (c) WMPE.
steel.
[(Fig._1)TD$IG]
Fig. 11. SEM images of unexposed and exposed mild steel in 1 M HCl in the presence and absence of extracts for 24 h at room temperature. (a) Unexposed mild steel, (b) 1 M
HCl, (c) 1 M HCl with 2.0 g/L WMRE (d) 1 M HCl with 2.0 g/L WMSE and (e) 1 M HCl with 2.0 g/L WMPE.
N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296 295
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