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Available online at www.sciencedirect.com

www.jmrt.com.br

Original Article

Synthesis and evaluation of anticorrosion properties of

onion mesocarp-nickel nanocomposites on X80 steel in
acidic cleaning solution

Ekemini Ituen a,b,c,∗ , Ambrish Singh a,b , Lin Yuanhua a,b,∗ , Ruiyun Li b
a State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, Sichuan,
China
b School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China
c Emerging Materials and Energy Research Group, Department of Chemistry, University of Uyo, Uyo, Nigeria

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

Article history: New Ni-nanocomposites were synthesized from waste onion mesocarp extracts and
Received 9 September 2019 characterized by UV-Vis, FTIR, XRD, SEM/EDS, DLS and TEM techniques. Monodispersed non-
Accepted 6 January 2020 agglomerating colloidal nanoparticles with spherical shape and particle sizes of 30–50 nm
Available online xxx were obtained. The nanocomposites (Ni-OMNPs) exhibit O, N and C C sites which facilitated
their physisorption on X80 steel surface from aqueous 1 M HCl and efficient protection of the
Keywords: steel surface against corrosion in the acid solution. Ni-OMNPs inhibits X80 steel corrosion
Adsorption in 1 M HCl with 93.99 ± 2.10 % efficiency at 30 ◦ C and reduces surface pitting and roughness
Corrosion protection by 51.2 % and 52.3 % respectively. AFM, SEM, EDAX and FTIR techniques were used to check
Electron microscopy extent of surface protection and inhibitor-steel interaction mechanism. Compared to crude
Nanocomposites extract feedstock, Ni-OMNPs show higher corrosion inhibition and resistance to thermal
XRD. and biochemical degradation. Unlike the crude extract, inhibition efficiency of Ni-OMNPs
did not change considerably throughout 150 days of storage at different temperatures.
© 2020 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

scales. HCl is often used for industrial preparation of chlo-

1. Introduction
Hydrochloric acid (HCl) is one of the very important mineral
acids used extensively as industrial cleaning solution. Being a
heavy chemical, it has been used to clean the surfaces of var-
ious metals and alloys to remove rust, mineral deposits and
rine and chlorides, as component of pickling solution for steel,
for reduction of ores, chemical cleaning and processing, acid
treatment of oil and gas wells and in food processing [1]. The
required concentration of HCl varies from one purpose of use
to another. Since HCl is highly corrosive, depending on con-
centration and temperature, it can aggressively attack and

∗
Corresponding authors.
E-mails: ebituen@gmail.com (E. Ituen), yhlin28@163.com (L. Yuanhua).
https://doi.org/10.1016/j.jmrt.2020.01.017
2238-7854/© 2020 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).

Please cite this article in press as: Ituen E, et al. Synthesis and evaluation of anticorrosion properties of onion mesocarp-nickel nanocomposites
on X80 steel in acidic cleaning solution. J Mater Res Technol. 2020. https://doi.org/10.1016/j.jmrt.2020.01.017
JMRTEC-1272; No. of Pages 14
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degrade the surfaces it is meant to clean. Therefore, corrosion
inhibitors are often added to the acid solution to reduce corro-
sion rate while the acid still maintains its normal activity. The
use of corrosion inhibitors has proven a more effective, sim-
ple and practical method of reducing acid corrosion damage,
especially in the oilfield [2].
Corrosion inhibitors (CIs) are often added (in small quanti-
ties) to the acid solution. They inhibit corrosion by adsorbing
on the substrate (metals, alloys, etc) surface to form a protec-
tive thin film [3]. In selecting a suitable CI for a given purpose,
some factors such as efficiency at small concentrations, sta-
bility to varying operational temperatures, cost effectiveness,
low toxicity, environmental friendliness and shelf life are usu-
ally considered [4]. Green CIs derived from plant extracts
seem to offer combined advantage over many organic CIs with
regards to these considerations except that many extracts are
thermally and biochemically unstable, hence they would be
useful only for low temperature operations and may not be
stored for long time.
In recent researches, functionalization or modification of
plant extracts to enhance their stability/efficiency at elevated
temperatures and resistance to rapid biodegradation has been
attempted. Extracts have been mixed with additives such as
potassium iodide [5–7], zinc oxide and zinc salt [8–10], cerium
nitrate [11], praseodymium nitrate [12], acetylacetonate [13]
and sulphate ions [14] to enhance their performance by syn-
ergistic effects. Reaction between phyto-compounds in plant
extracts with metal salts could result in the formation of metal
ions complexes and/or nanoparticles (NPs) if appropriate con-
centrations of the feedstocks are selectively varied and other
conditions (such as temperature and pH) are favorable. In most
of these reports where metal salts were used to intensify the
efficiency of the CIs, the product formed were not NPs, or were
not characterized to confirm if they were in nanoscale.
Synthesis of plant nanocomposites/nanoparticles involves
a single step bio-reduction reaction which occurs within some
minutes, even at room temperature [15]. The main advantage
of bio-synthetic pathway for nanoparticles is that it can afford
large quantities of NPs which are non-toxic, inexpensive, clean
and ecofriendly, compared to other routes. Therefore, scien-
tists have exploited this prospect to fabricate biogenic NPs
for medical, pharmaceutical and agricultural purposes due
to their antimicrobial activities [16]. By far, silver nanoparti-
cles (AgNPs) have been extensively synthesized and applied
in these fields than NPs than other metal ions. They have
been established to exhibit antibacterial, antifungal, antipro-
tozoal and anticancer activities [17–21] because silver ions
can be slightly toxic to the target micro-organism thus reduc-
ing their growth/multiplication by tampering with their cell
membrane [15]. However, Ni nanocomposites, especially from
nickel nitrate and sulphate, are less toxic since the salts are
not carcinogenic. This provides a window of opportunities for
exploring eco-environmental applications of nickel nanoparti-
cles for various applications. The properties of biosynthesized
NPs would be expected to be different, depending on the
chemical composition of the extract. However, formation and
development of the nanoparticles would likely occur through
bio-reduction of the metal ion to the zero valency and com-
plexation (ligation) reaction of ligands in the extract with the
metal ion. Despite that many plant extracts have been estab-
Please cite this article in press as: Ituen E, et al. Synthesis and evaluation of anticorrosion properties of onion mesocarp-nickel nanocomposites
on X80 steel in acidic cleaning solution. J Mater Res Technol. 2020. https://doi.org/10.1016/j.jmrt.2020.01.017
lished to inhibit corrosion, just little has been done about
evaluating plant extract mediated NPs as CIs. The present
study aims to fill this gap and explore future research hori-
zon for in the field of corrosion protection since an avalanche
of plant materials exists for investigation.
From literature search, the use of plant extract mediated
nanoparticles as corrosion inhibitor only recently came into
limelight from reports by Essien and co-workers [22] and
Idrees and co-workers [23] using olive leaves and Sida acuta
extracts respectively. Sida acuta extract was used to mediate
the synthesis of AgNPs and the antimicrobial activity was
investigated. Passively, corrosion test was conducted by poten-
tiodynamic polarization measurements in 0.5 M H2 SO4 for 30
min. More emphasis was laid on biocidal activity of the NPs
rather than on acid corrosion inhibition. Olive leaves extract
mediated titanium NPs were intended to be use as adsorbents
for removal of heavy metal ions from waste water, therefore,
the particle properties were not wholesomely characterized.
Its electrochemical behaviour and potential anticorrosion
effect was tested and good efficiency was reported. Encour-
aged by the reasonably efficient performance, the present
study was designed to utilize extracts of some agro-wastes
in development of biogenic NPs for application as CIs for oil-
field pickling. Agro-wastes were selected because they can be
sustainably obtained (as long as food is consumed) and their
utilization has the potential to reduce environmental pollu-
tion, eliminate competition with food and create wealth from
wastes without competing with food production.
The gaps identified from the Sida acuta and olive leaves
extracts reports have been filled in the present study using
onion mesocarp extract and nickel salt. Laborious experi-
ments have been conducted to vary experimental conditions
and confirm if the nickel nanocomposites were actually
formed, the nature of their crystal structure, physicochemical,
electrochemical and optical properties, surface characteristics
and colloidal properties. The properties of the NPs formed are
compared to that of the crude extract precursor in most cases.
Corrosion tests were conducted using weight loss and elec-
trochemical techniques; corrosion products were subjected to
spectroscopic analyses and the surface of the protected steel
was analysed by combination of spectroscopic and micro-
scopic techniques.
Red onion mesocarp or peel is readily available, does not
need to be bought and can be sustainably supplied in large
quantity. Also, it has been reported that the peel extract con-
tains more compounds than the inner shells [24,25]. The
molecular structures of some of these compounds, as shown
in Supplementary material (SM 1), contain potential adsorp-
tion sites which is found in most reported efficient corrosion
inhibitors [26]. It has already been established that peels
extract of red onion can inhibit steel corrosion in various
media in previous reports [27–29], hence the present study
also builds on these reports. Since the efficiency of extracts
can be influenced by its source, solvent and extraction con-
ditions, we also tested our extract to confirm its potency.
In extension, characterization of the protected steel surface,
corrosion products and surface film, which were either inad-
equate or lacking in the previous reports cited, have been
carried out. With these, more understanding of the adsorp-
tion behaviour, crystalline properties, optical characteristics
JMRTEC-1272; No. of Pages 14
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and corrosion inhibition mechanism of phyto-mediated onion
mesocarp nanocomposites have been gained, documented
and discussed in this paper.
2. Materials and methods
2.1. Preparation of extract and nanocomposite
Red onion mesocarp was sourced from local market near
Southwest Petroleum University, Xindu, Chengdu in Sichuan
Province of China, and taken to our laboratory. The red meso-
carp were hand-picked to separate from mesocarp of white
and brown cultivars and remains of the fruit stalk, washed
thoroughly in double distilled water and spread to dry at
room temperature without direct sunlight. After drying, it
was ground into powder using electrical blender and stored
in sealed water proof bags.10 g of powder was soaked in 100
mL of double distilled water, warmed to 50 ◦ C for 3 h with
regular stirring, cooled and filtered. Filtrate was concentrated
using rotary evaporator and dried to powder in oven at 90 ◦ C
while the residue was dried in air and weighed to estimate
the amount of the extract recovered. 1.0 g of the extract was
prepared in 1 L of double distilled water. This solution was
labelled as 1 g/L OME (onion mesocarp extract).
The 1 g/L OME was mixed with 1 mM Ni(NO3 )2 in the
ration 1:1 and warmed at 40–50 ◦ C in water bath with con-
stant swirling until a firm colour change was observed which
signifies formation of NPs [30]. This was confirmed by UV-Vis
spectroscopic analyses and the resulting colloidal NPs solution
was labelled Ni-OMNPs. A portion of the colloidal Ni-OMNPs
solution was cooled to room temperature, centrifuged at 5000
rpm, filtered with ultrafine mesh to obtain a sol-gel matrix [30].
The sol-gel matrix was washed twice with deionized water,
air-dried and stored prior to use.
2.2. Characterization of Ni nanocomposites
The progress of formation/development of the NPs was moni-
tored using UV-2600 spectrophotometer (Shimadzu Enterprise
Management Co. Ltd., China) scanned in the range of 200−800
nm at different time intervals (minutes). Digital light scat-
tering (DLS) (Malvern Nano S) experiment was conducted in
triplicates to determine zeta potential, hydrodynamic size,
particle size distribution and polydispersity index of the NPs.
A drop of the colloidal solution was placed on a 1 cm x 1 cm
silicon tape mounted on a glass block and dried in oven at 40
◦ C, and the tape surface was scanned for particles morphology
and elemental composition by scanning electron microscopy
coupled with energy dispersive X–ray spectroscopy, SEM/EDS
(EVO MA 15 Zeiss, Carl Zeiss, Germany). The morphology and
particles shape and size were also confirmed by transmission
electron microscopy, TEM (Fei Technai G2F20) at accelerating
voltage of 300 kV. Crystal structure of the nanocomposites
were analysed by x-ray diffraction, XRD (DX-2700 Dandong
Haoyuan Investment Co. Ltd., Dandong) at 2  = 10 - 90◦ . The
crude extract and nanoparticles were also prepared into thin
films with KBr and analysed by Fourier transformed infra-
red spectroscopy, FTIR (WQF520 spectrophotometer, Beijing
Please cite this article in press as: Ituen E, et al. Synthesis and evaluation of anticorrosion properties of onion mesocarp-nickel nanocomposites
on X80 steel in acidic cleaning solution. J Mater Res Technol. 2020. https://doi.org/10.1016/j.jmrt.2020.01.017
3
Rayleigh Analytical Instruments Co. Ltd., China) in the range
of 400 – 4500 cm−1 .
2.3. Preparation of corrosion tests solutions and steel
specimens
The corrodent (1 M HCl) was prepared by dilution of analyt-
ical grade HCl (37 %) supplied by Chengdu Kelong Chemical
Reagent Factory, China. Different amounts (mL) of 1 g/L Ni-
OMNPs solution were added to 1 M HCl to prepare four
concentrations (v/v) of the NPs inhibitor solution between 5–20
% Ni-OMNPs. Also, 20 % v/v solution of 1 g/L OME was prepared
and used as control for assessing the NPs.
Different sizes of X80 steel coupons composed of (wt. %)
C (0.065), Si (0.24), Mn (1.58), P (0.011), S (0.003), Cu (0.01), Cr
(0.022), Nb (0.057), V (0.005), Ti (0.024), B (0.0006), Fe (balance)
were purchased from Shengxin Technology Co. Ltd, Xinyang,
China. Absolute ethanol was used to degrease the coupons
followed by polishing using silicon carbide abrasives of differ-
ent grades, and finished to mirror surface using 2000 grade.
Polished coupons were cleaned again with absolute ethanol,
rinsed in acetone to air-dry and stored in sealed water-proof
bags inside moisture-free desiccator until required. Coupons
for electrochemical tests were soldered to copper wire and 1
cm2 of the polished surface was exposed while the rest were
insulated using epoxy adhesives and similarly preserved.
2.4. Corrosion tests by weight loss experiment
The corrosion test was performed based on ASTM standard
(ASTM Committee G-1 on Corrosion of Metals of 2017). Pre-
weighed (polished) X80 steel specimens each of dimension 3
cm × 3 × 0.5 cm were immersed into the test solutions made
up of 1 M HCl without and with OME and different concen-
trations of Ni-OMNPs by suspension method and sealed to
exclude air. The containers were kept in water bath set to
30 ◦ C for 6 h after which they were retrieved and cleaned
[31], then weighed to determine the weight loss. Triplicates of
experiments were conducted and the mean weight losses (w
(g)) were determined and used to compute corrosion rate (CR,
mmpy) according to Eq. 1, given that A,  and t is the surface
area (cm2 ), density (gcm−3 ) and immersion time (h), respec-
tively. Percentage corrosion inhibition efficiency (IW , %) was
calculated using Eq. 2. The procedures were repeated for dif-
ferent temperatures (40, 50 and 60 ◦ C) in triplicates and only
the mean values are reported.
87600w
CR = (1)
At
 CRinh

IW = 100 1 − (2)
CRHCl
where CRHCl and CRinh denote corrosion rate in the absence
and present of inhibitor.
To determine the effects of storage conditions on the effi-
ciency, freshly prepared solutions of OME and Ni-OMNPs were
stored under two conditions: (i) at room temperature in labo-
ratory cupboards and (ii) in refrigerator maintained at 10 ◦ C.
A 20 % v/v concentration of both solutions were prepared in 1
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M HCl and the anticorrosion efficiency was determined every for EIS (IEIS ), PDP (IPDP ), LPR (ILPR ) and EFM (IEFM ) using Eq. 3,4,5
30 days at 30 ◦ C and 60 ◦ C for 150 days. and 6, respectively.
R − R 
i b
2.5. Electrochemical measurements IEIS = 100 (3)
Ri
 
The three-electrode Gamry ZRA REF 1800–18042 electrochem- i
Icorr
IPDP = 100 1− (4)
ical workstation consisting of working electrode (X80 steel b
Icorr
specimens), counter electrode (platinium) and reference elec-
trode (saturated calomel electrode, SCE) was used for this
R − R 
Pi Pb
ILPR = 100 (5)
study. The three-electrode cell assemblage containing the test RPi
solution was allowed for 30 min. for corrosion to occur and  
stabilize the open circuit potential (OCP) before actual mea- i
Icorr
IEFM = 100 1− (6)
surements were made [32]. Input experimental parameters b
Icorr
were set at frequency range = 100 kHz - 10 mHz for electro-
chemical impedance spectroscopy (EIS), voltage range = −0.15 where R = Rf + Rct and Rb and Ri represent polarization
b
resistance without and with inhibitor respectively, Icorr and
V - + 0.15 V vs. OCP and scan rate = 0.2 mV/s for potentio-
i
Icorr represent corrosion current density without and with
dynamic polarization (PDP), frequency pair =2 Hz and 5 Hz;
base frequency =0.01 Hz and amplitude = 10 mV for electro- inhibitor, respectively RPi and RPb represent resistance polar-
chemical frequency modulation (EFM) and Ecorr = ±10 mV and ization without and with inhibitor, respectively and Rf and Rct
scan rate = 0.25 mV/s for linear polarization resistance (LPR) represents surface film resistance and charge transfer resis-
at room temperature (30 ± 2 ◦ C). Experiments were conducted tance, respectively.
in triplicates and average values of important parameters are
reported with errors. Gamry E-Chem software was used for 2.6. Corrosion products and surface analyses
data fitting and analyses. Inhibition efficiency was estimated
The morphologies, topographies and other surface features of
the retrieved steel coupons in both uninhibited and inhibited
solutions were investigated by SEM and AFM (Keysight Tech-
nologies 7500 America). Elemental composition of the steel
surface was determined by EDS. Thin coat formed on the sur-
face of the X80 steel coupon after immersion in the inhibited
solutions of OME and Ni-OMNPs gently scraped off and anal-
ysed by FTIR.

3. Results and discussion

3.1. Characterization of Ni nanocomposites

Absorption or radiation in the visible region by free elec-

Fig. 1 – (a) UV-Vis spectra during development of Ni-OMNPs
and (b) XRD diffraction pattern of OME and Ni-OMNPs.
trons often results in excitation and consequently, production
of plasmon at characteristic wavelengths, and spontaneous
emission of photons on return to the ground state [33]. For-
mation of Ni-OMNPs begins with bio-reduction reaction of
Ni2+ ions due to capping of OME ligands (phyto-compounds).
The colour of the mixture changed from light purple to dark
brown and this occurred at 150 min. at 40 ◦ C. The absorbance
also changed (Fig. 1a) to signify completion of complexation
reaction between the Ni salt and OME. The spectrum of the
OME shows two absorption peaks at 448 nm and 575 nm
attributed to absorption by the various chromophores in the
extract [34]. However, Ni-OMNPs absorb at a single wavelength
of 495 nm and this value falls within the range of bands pre-
viously reported for nickel NPs mediated by other extracts,
which indicates formation of Ni nanocomposite [35–37].
During formation of the nanocomposite, OME should act
as a catalyst that reduces the Ni2+ to zero valency. This should
be evident in coordination of OME ligands to the nickel atom.
The XRD pattern of the nanocomposite should therefore show
peaks characteristic of nickel crystal. Therefore, the XRD pat-
terns of the nanocomposite as well as the feedstock (extract)

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Fig. 2 – (a) SEM images of morphology and (b) EDS spectra showing elemental composition of the surfaces of (i) OME and (ii)
Ni-OMNPs.

were obtained and compared as shown in Fig. 1b. It can be
implied from the diffraction patterns that OME is amorphous
whereas Ni-OMNPs is highly crystalline with well resolved
peaks at 2 values corresponding to 27.70◦ (002), 32.16◦ (100),
38.04◦ (111), 46.16◦ (200), 64.46◦ (220) and 77.46◦ (222) crystal
planes as analysed using analysed using X-PERT HighScore
Plus software package (PANalytical). These reflections were
indexed to face-centred cubic (fcc) Ni◦ phase in accordance
with JCPDS Card No. 47-1049. The crystalline size (D) estimated
using Scherrer equation (Eq. 7) afforded values between 28.23
nm–44.82 nm [36]. Thus, XRD results confirm the crystalline
nature of synthesized Ni-OMNPs and the existence in nano
scale.
b
D=
Fw cos
where Fw is the full with of the peak and given scattering angle
of 2 ,  is the wavelength of the X-ray and b is a constant.
The elemental composition of the nanocomposite surface
was also characterized using EDS technique and the spectra
for both OME and Ni-OMNPs are shown in Fig. 2(b). Results
show that the surface of Ni-OMNPs contains some Ni whereas
the surface of OME does not. Also, Ni-OMNPs surface is richer
in N and O than that of the crude extract which could have
been made available by the capped phytocompounds. Since N
and O are electron rich sites, it can be predicted that the sur-
face of the nanocomposite exhibits higher electron cloud than
that of the extract. This would likely convey higher adsorp-
tive potential on the nanocomposites, which could make it
a more efficient adsorbent than the crude extract. The mor-
phology of the nanocomposites observed by SEM are shown in
Fig. 2(a). The particles were found to be free, distinct without
agglomeration and almost spherical in shape. However, some
traces of micro-scale organic ligands capped to the nanoparti-
cles were also visible. SEM results also confirm that particulate
nanocomposite was formed.
The particles shape, size and morphology were further
investigated by TEM technique and the results of obtained
images are shown in Fig. 3. It can be observed from the figure
that both at microscale (Fig. 3i) and nanoscale (Fig. 3ii), the
particles were all similar in shape and size, and distinct with-
out agglomeration. The size was determined to be 32.5 nm
and most of the particles were spherical in shape. However,
DLS measurement revealed that the particle sizes were dis-
tributed between 37.5 nm – 50.5 nm (Fig. 3iii) with the highest
(7)
number of the particles having sizes of 43.5 nm. The aver-
age zeta potential obtained from five runs was −43.64 ± 0.32
mV. The high negative value indicates that there was repul-
sion between the particles due to their net negative surface
charges, hence high stability and resistance to agglomera-
tion [37]. An average polydispersity index (PDI) of 0.23 ± 0.05
was obtained which indicates that the nanocomposites were
monodispersed in the colloidal solution [38]. This value of PDI
also indicates that the nanoparticles are very stable in the
colloidal system. It can also be observed that the size deter-
mined by XRD, TEM and DLS are all within nano-scale and
comparable.
The active functional groups present and/or involved in
the formation of the nanocomposite was probed by FTIR. It
has been reported that complexation and bio-reduction of

Please cite this article in press as: Ituen E, et al. Synthesis and evaluation of anticorrosion properties of onion mesocarp-nickel nanocomposites
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Fig. 3 – Morphology of Ni-OMNPs at (i) microscale; (ii) nanoscale as determined by TEM and (iii) particle size distribution of
Ni-OMNPs determined by DLS.

Fig. 4 – FTIR spectrum of (a) Ni-OMNPs, (b) OME and (c) pure Ni-OMNPs and its surface adsorbed film.

metal salts to nanoparticles is associated with changes in the
bending and stretching vibration pattern of associated func-
tional groups [39]. Previous reports have also suggested that
absorption wave numbers may decrease or increase in magni-
tude due to reduction of metal ion to zero valency [40]. In the
present study, the FTIR spectrum of the Ni NPs (Fig. 4) show
decrease in some wave numbers of absorption. The peak at
480 cm−1 shifted to 470 cm−1 ; 1100 cm−1 shifted to 1070 cm−1 ;
1440 cm−1 shifted to 1380 cm−1 and 2960 cm−1 shifted to 2930
cm−1 . However, the peak at 1610 cm−1 increased to1640 cm−1
while the broad peak around 3400−3500 cm−1 became a sharp
peak at 3410 cm−1 . These peaks are typical vibrational stretch-
ing of amine group in amides, amines, alkaloids and proteins
(1640 cm−1 ), C–H in methylene (2960 cm−1 ), CO in esters,
alcohols, ethers and carboxylic acids (1100 cm−1 ), OH in
flavonoids, polyphenols, alcohols, esters and carboxylic acids
(3400−3500 cm−1 ) and CC aromatic bonds (1440 cm−1 ). Thus,
these groups may be considered as active in the bio-reduction
process.
3.2. Anticorrosion efficiency
3.2.1. Weight loss
Weight loss provides a direct means of evaluating the effi-
ciency of an anticorrosion additive in a given aggressive
medium. After X80 steel was immersed in the different test
solution for 6 h, it was observed that the corroding solution
dissolved the steel faster without the inhibitor than when the
inhibitor is added. The loss in weight was far reduced with
the NPs compared to the crude extract. Thus, Ni-OMNPs was
highly efficient than OME indicating that corrosion inhibition
could be better obtained with reduced size to volume ratio
of the inhibitor. As the concentration of the NPs in the solu-
tion increases, the efficiency also increases. From the results
displayed in Table 1, it can be observed that an equivalent con-
centration of the extract (20 5v/v OME) was 70.30 % and 55.42
% efficient at 30 ◦ C and 60 ◦ C respectively, whereas 20 % v/v
Ni-OMNPs was 95.51 % and 95.44 % efficient at 30 ◦ C and 60 ◦ C,
respectively. Also, unlike OME, anticorrosion efficiency of Ni-
OMNPs initially increased as temperature increased, depicting

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Table 1 – Corrosion rate and inhibition efficiency of OME and Ni-OMNPs.

Test 30 ◦ C 40 ◦ C 50 ◦ C 60 ◦ C
solution
CR (mmpy) Iw (%) CR (mmpy) Iw (%) CR (mmpy) Iw (%) CR (mmpy) Iw (%)

Blank 12.22 ± 0.31 – 18.75 ± 1.17 – 30.40 ± 2.05 – 52.63 ± 2.82 –

20 % v/v OME 3.63 ± 0.11 70.3 ± 0.8 6.17 ± 0.62 67.1 ± 0.2 11.78 ± 1.26 61.2 ± 0.5 23.46 ± 1.01 55.4 ± 0.6
5 % Ni-OMNPs 1.43 ± 0.08 88.3 ± 0.3 2.02 ± 0.21 89.2 ± 0.6 3.03 ± 0.13 90.0 ± 0.3 6.12 ± 0.22 88.4 ± 0.3
10 % Ni-OMNPs 1.20 ± 0.07 90.1 ± 0.4 1.49 ± 0.14 92.0 ± 1.0 2.09 ± 0.06 93.1 ± 0.4 5.28 ± 0.17 89.9 ± 0.2
15 % Ni-OMNPs 0.76 ± 0.12 93.8 ± 0.7 1.10 ± 0.12 94.1 ± 1.3 1.30 ± 0.05 95.7 ± 0.8 3.13 ± 0.11 94.1 ± 0.7
20 % Ni-OMNPs 0.55 ± 0.07 95.5 ± 1.1 0.58 ± 0.08 96.9 ± 0.8 0.65 ± 0.08 97.8 ± 1.1 2.40 ± 0.06 95.4 ± 0.8

Fig. 5 – Stability of (a) OME preserved at room temperature (b) Ni-OMNPs preserved at room temperature (c) OME preserved
at 10 ◦ C in refrigerator and (d) Ni-OMNPs preserved at 10 ◦ C in refrigerator.

excellent stability and resistance of the nanocomposite to the efficiency of OME declined significantly, especially at 60
thermal degradation compared to the extract. ◦ C, whereas Ni-OMNPs was fairly stable and efficient through-

out the storage duration of 150 days. It was also observed that
storage temperature had some effects on the stability and effi-
3.2.2. Stability of Ni-OMNPs
ciency of OME but negligible effect on the nanocomposite. For
Many plant materials reported to inhibit corrosion in acidic
OME, low storage temperature enhanced stability perhaps due
media often yield decreased efficiency at increased tem-
to reduced biochemical activity. To the best of our knowledge,
peratures [41,42] due to thermal degradation. Also, being
this is the first time the effects of storage/preservation temper-
bio-based, they may be susceptible to microbial or biochemical
ature on inhibition efficiency has been reported for a bio-based
degradation, making it difficult to store them for longer time
corrosion inhibitor. Therefore, with this interesting result, we
without decline in efficiency. In this study, we sought to find
have designed further studies to extensively investigate this
out if chemical treatment of extracts to nanocomposites could
aspect using various range of storage temperatures and longer
improve their stability to biodegradation and increase their
observation time.
storage time. Results obtained (Fig. 5) reveal that after 60 days,

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Fig. 6 – (i) Arrhenius and (ii) transition state plots for the corrosion of X80 steel in 1 M HCl without and with OME and
Ni-OMNPs additives.
Table 2 – Activation parameters deduced from Arrhenius
and transition state plots.
Test solutions Ea (kJ) H∗ (kJ)
Blank 40.04 −37.82
20 % OME 51.90 −49.31
5 % Ni-OMNPs 53.14 −56.17
10 % Ni-OMNPs 58.98 −59.07
15 % Ni-OMNPs 71.07 −66.30
20 % Ni-OMNPs 76.02 −73.38
3.2.3. Kinetics and thermodynamics studies
Corrosion inhibitors for steel are believed to act by adsorp-
tion mechanism [43]. This involves adherence of the inhibitor
molecules on the surface of the steel driven by either phys-
ical or chemical interactive forces. The nature of the force
can be predicted from treatment of surface coverage data as
a function of concentration based on plots called adsorption
isotherm. Since the concentration of the nanoparticles were
not measured in molar terms, adsorption isotherms could not
be determined for this inhibitor. Rather, plots from linearized
Arrhenius kinetic equation (Eq. 8) and transition state thermo-
dynamic equation (Eq. 9) were constructed as shown in Fig. 6
to determine some activation parameters (Table 2) for explain-
ing the adsorption process [44]. Apparent activation energy
(Ea ), enthalpy change (H∗ ) and entropy change (S∗ ) were
deduced for the acid solution with and without the inhibitors.
Results reveal that Ea was higher in the presence of the
inhibitors, especially Ni-OMNPs, indicating that the inhibitors
increased the energy threshold for ease of corrosion. This
implies that their adsorption conveyed corrosion resistance
on the surface the steel surface. Inhibitors that cause increase
in Ea as their concentrations increase have been reported to
have adsorbed via physical interactive forces or physisorption
[45]. Also, negative enthalpy changes obtained indicates spon-
taneous adsorption and the magnitudes fall within the range
assigned to physical adsorption mechanism. The entropy val-
ues obtained indicate that the activated complex stage was
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dominated by association of molecules of inhibitor on the
surface, rather than dissociation [46].
S∗ (kJ)
Ea
logCR = logZ − (8)
0.27 2.303RT
0.28
0.33
  R   S*   H* 
CR
0.34 log( )= log + − (9)
T Nh 2.303R 2.303RT
0.37
0.40
where CR is the corrosion rate, Z the Arrhenius pre-
exponential or frequency factor, R is the universal gas
constant, N is Avogadro’s number, h is Planck’s constant, T
is absolute temperature, H∗ and S∗ is the enthalpy and
entropy change of activation respectively.
3.3. Electrochemical measurements
3.3.1. EIS measurements
Experimental values were used to construct OCP, Nyquist,
Bode and phase angle plots shown in Fig. 7(a), (b) and (c),
respectively, for some of the solutions tested. For the OCP vs
time plot, fairly stable potential was obtained after 300 s for
most of the solutions. The Nyquist curves yielded depressed
imperfect semi-circular over the entire frequency range which
indicates that corrosion in all the solutions occur via the same
charge transfer mechanism [47]. Imperfection in shapes could
be due to roughness of the surface of the steel coupons used
[32,47]. For each of the semicircles, the diameter increases as
concentration of Ni-OMNPs increases. This also corresponds
to increase in charge transfer resistance [48] and inhibition
efficiency, implying that the efficiency of the inhibitor could
be directly proportional to Ni-OMPNs concentration. Increase
in charge transfer resistance demonstrates that more species
of inhibitors were adsorbed on the surface as concentration
increases. The adsorbed species form a film with resistance
denoted with Rf and the values of Rf increases as concen-
tration increases. This can be attributed to increase in local
dielectric/insulation in the vicinity of the surface as a result
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Fig. 7 – (a) OCP vs. time (b) Nyquist (c) Bode modulus and phase angle (d) Tafel plots for the corrosion of X80 steel in 1 M HCl
without and with OME and different concentrations of Ni-OMNPs.

Table 3 – EIS parameters for corrosion of X80 steel in 1 M HCl without and with OME and different concentrations of
Ni-OMNPs at 30 ◦ C.
Test Rs CPEf CPEdl
solution (˝cm2 )

n1 Rf (˝cm2 ) n2 Rct (˝cm2 ) R (˝cm2 ) 2 (x10−4 ) IEIS (%)

Blank 0.84 ± 0.12 0.87 1.6 ± 0.2 0.71 130.7 ± 1.4 132.3 ± 1.7 0.12 –
20 % OME 0.87 ± 0.14 0.89 14.1 ± 0.3 0.67 610.1 ± 3.6 624.2 ± 3.1 0.10 78.8 ± 0.4
5 % Ni-OMNPs 0.86 ± 0.13 0.92 16.9 ± 0.2 0.73 1365.8 ± 2.6 1382.7 ± 3.3 0.46 90.3 ± 0.5
10 % Ni-OMNPs 0.90 ± 0.14 0.96 21.1 ± 0.4 0.74 1983.5 ± 4.8 2004.6 ± 5.6 0.35 93.3 ± 0.3
20 % Ni-OMNPs 1.01 ± 0.15 0.99 33.6 ± 0.5 0.78 2821.1 ± 8.3 2854.7 ± 7.8 0.28 95.4 ± 0.4

of increased adsorption of the inhibitor. Adsorption of the
inhibitor results in displacement of water molecules and chlo-
ride species from the surface and consequently, reduction in
the active corrosion sites and decrease in corrosion rate. Anal-
yses of results was achieved by fitting using the equivalent
circuit model embossed in Fig. 7 (b). The circuit includes the
solution resistance (Rs ), charge transfer resistance (Rct ), con-
stant phase element of the adsorbed film (CPEf ) and double
layer (CPEdl ) with phase shifts n1 and n2 , respectively. The con-
stant phase elements provide accurate fit instead of a pure
capacitor. The fits yielded accuracy between 0.10 and 0.46 ×
10−4 for all the curves. The values of n has been attributed
to surface inhomogeneity or roughness of the steel elec-
trode [49]. As n increases, it signifies that surface roughness
decreases because the adsorption of inhibitor on the steel sur-
face reduces corrosion [50]. The value of n also increases as
concentration of inhibitor increases, demonstrating that bet-
ter anticorrosion effect is obtained with increasing inhibitor
concentration. The values of resistances obtained for the trip-
licate experiments were comparable with errors ranges that
supports reliability of the obtained results. The maximum
error in the inhibition efficiency values calculated was ± 4.3 %
(Table 3).

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Table 4 – PDP and EFM parameters for the corrosion of X80 steel in 1 M HCl without and with OME and different
concentration of Ni-OMNPs at 30 ◦ C.
Test PDP parameters EFM parameters
solutions
−Ecorr (mVSCE ) Icorr (Acm−2 ) ˇa (mV/dec) ˇc (mV/dec) IPDP (%) Icorr (Acm−2 ) ˇa (mV/dec) ˇc (mV/dec) CF-2 CF-3 IEFM (%)

Blank 51.2 ± 0.12 1028.1 ± 3.6 155.7 138.4 – 801.3 ± 1.3 129.7 108.9 1.997 2.972 –
20 % OME 48.3 ± 0.11 243.7 ± 2.2 161.2 139.7 76.3 ± 0.4 214.7 ± 1.1 132.8 112.6 1.986 2.894 73.2 ± 0.3
5 % Ni-OMNPs 47.2 ± 0.12 116.2 ± 1.4 167.5 143.1 88.7 ± 0.2 143.4 ± 0.8 139.4 109.8 2.012 2.887 82.1 ± 0.4
10 % Ni-OMNPs 46.9 ± 0.10 89.4 ± 0.9 178.1 145.7 91.3 ± 0.3 105.8 ± 0.7 144.3 113.7 1.964 2.906 86.8 ± 0.6
20 % Ni-OMNPs 44.8 ± 0.11 43.2 ± 1.1 187.4 151.2 95.8 ± 0.6 76.1 ± 1.2 148.1 119.6 2.110 3.054 90.5 ± 0.6

3.3.2. Potentiodynamic polarization
Displayed in Fig. 7(d) is the Tafel plot for the corrosion of X80
steel in 1 M HCl without and with OME and different con-
centrations of Ni-OMNPs. The plots show both cathodic and
anodic components of the corrosion current function with
respect to corrosion potential. Compromise potential (Ecorr )
between both components and the corresponding current
(Icorr ) were obtained by extrapolation of the Tafel slopes and
given in Table 4. The Tafel anodic (ˇa ) and cathodic (ˇc ) con-
stants were also obtained for all the test solutions. Results
show Icorr that decreases on addition of the inhibitor. This
implies that current circulation through the electrode sur-
face reduced perhaps due to insulating effect of the adsorbed
inhibitor film. The inhibition efficiency (calculated from the
relative reduction in current density) increased as Ni-OMNPs
concentration increased. Addition of the inhibitor resulted
in alterations in the anodic slopes and displacement in Ecorr
by a maximum of −6.33 mV. Because this displacement is
not up to ±85 mV which is the benchmark for categorizing
an inhibitor as cathodic or anodic, Ni-OMNPs can be consid-
ered as mixed type inhibitor which exhibits dominant anodic
influence [51]. In other words, Ni-OMNPs acts by interfering
with not only the anodic half reaction (oxidative dissolution
of Fe) but also with cathodic (hydrogen release) half reac-
tion. Formation of metal complexes between the inhibitor
and the surface species could have resulted in inhibition
of the anodic dissolution reaction and thus increased the
Tafel slopes obtained. Both ˇa and ˇc increased on addition
of inhibitor and with increasing concentration of Ni-OMNPs,
which supports that the bio-composites inhibits both anodic
and cathodic reactions. The slightly higher displacement in
ˇa than ˇc substantiates dominance of anodic influence by the
inhibitor.
3.3.3. Linear polarization resistance
LPR experiment was conducted so as to support the results
of inhibition efficiency obtained with EIS and PDP measure-
ments. The lowest average value of polarization resistance (Rp )
from the triplicate measurements was obtained with the blank
solution as 103.7 ± 0.6 cm2 , just as charge transfer resis-
tance in EIS measurement was lowest in the uninhibited acid
solution. On addition of the inhibitor, the Rp values increased
and with increase in Ni-OMNPs concentration till it reaches an
average of 2693.5 ± 4.3 cm2 corresponding to an inhibition
efficiency of 96.1 ± 0.4 % for 20 % Ni-OMNPs. For pure OME, the
Rp = 488.1 ± 2.6 cm2 corresponding to efficiency of 78.7 ± 0.5
%. For the solutions with 5 % and 10 % Ni-OMNPs, the Rp values
were 989.4 ± 2.7 cm2 and 1416.2 ± 3.2 cm2 corresponding
to efficiency of 89.5 ± 0.5 % and 92.7 ± 0.6 %, respectively. The
obtained inhibition efficiencies are comparable with PDP and
EIS measurements.
3.3.4. Electrochemical frequency modulation
EFM spectra parameters were obtained from analyses of exper-
imentally generated intermodulation spectra for the different
test solutions and displayed in Table 4. Results show similar
trends for Icorr , ˇa , ˇc and IEFM as PDP measurements except
that the values and inhibition efficiencies were comparatively
lower. This could be due to shorter exposure time associ-
ated with fast EFM measurements. In addition, the causality
factors, CF-2 and CF-3 obtained were very proximate to the
theoretical values of 2 and 3 respectively which is indicative
of good accuracy and reliability of EFM results.
3.3.5. Comparison of Ni-OMNPs efficiency from various
techniques
As expected from experimental results, there were slight dif-
ferences in the inhibition efficiency of Ni-OMNPs measured
by the various techniques used. The mean and standard devi-
ation of the efficiency for the acid inhibited by the highest
concentration of the nanocomposite was evaluated at 30 ◦ C
and found to be 93.99 and 2.32, respectively. Therefore, the
efficiency of Ni-OMNPs at 30 ◦ C can be approximated as 93.99
± 2.32 %. This corresponds to a standard error of mean (SEM)
of Sx = √S = 1.04, where S is the standard deviation. Also, at 95
N
%, 1.96 Sx confidence level, the error margin was found to be
93.99 ± 2.03 (±2.10 %), indicating good accuracy of efficiency
results obtained from the different techniques.
3.4. Surface protection of steel
The extent of surface protection of X80 steel in the aggres-
sive acid solution was investigated by SEM and AFM. Presented
in Fig. 8 are the SEM micrographs of the X80 steel surface in
blank and inhibited 1 M HCl solution after six hours of immer-
sion. Inspection of the 2D images reveals that the surface
of the steel without the inhibitor experienced severe dam-
ages due to excessive corrosive attack. However, addition of
Ni-OMNPs reduced this corrosive damage and the extent of
protection was better than when the crude OME was applied.
From nano-micro scale examination by AFM, the X80 steel
surface morphologies/topographies were obtained (Fig. 9) at
3D level as well as the 2D amplitude (b) images. Similar to
SEM observation, the specimen immersed in the uninhibited
acid exhibited very high surface roughness, having many pits
due to severe damage caused by rapid corrosive acid attack.
However, in the presence of Ni-OMNPs, pitting was reduced

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Fig. 8 – Top: SEM micrographs and; Bottom: EDS profiles of X80 steel corrosion after 6 h of immersion in (i) 1 M HCl (ii) 1 M
HCl + OME and (iii) 1 M HCl + Ni-OMNPs.
and corrosive damage was very mild demonstrating the high
surface protective effect of the nanocomposite.
In addition to the morphological images, AFM tests
afforded root mean square (RMS) height parameters which are
used to further characterize the protected and unprotected
surfaces. RMS height parameters are known to be highly sen-
sitive to surface deviations with respect to the mean line [52].
Sv represents the deepest pit from the mean line and the val-
ues were found to be 238 nm and 116 nm in the presence and
absence of the nanocomposite respectively. This implies that
addition of the nanocomposites reduced pitting by 51.2 %. The
highest peak (Sp) were found to be 356 nm in the blank acid
but reduced to 268 nm when Ni-OMNPs were added, corre-
sponding to 24.7 % reduction in peak heights by addition of
the nanocomposite. Such reduction in peak heights and pit
depths are clear evidences of efficient corrosion protection. In
addition, RMS height (Sq) was 58.4 nm and 33.6 nm without
and with inhibitor, also portraying efficient peak height reduc-
tion (42.5 %) and anticorrosion effect of Ni-OMNPs. From the
skewness parameter (Ssk < 0) and kurtosis parameter (Sku >
3) obtained without and with the nanocomposite, it could be
inferred that in the absence of inhibitor, height distribution is
more skewed below the mean plane, and that spike in height
distribution is reduced in the presence of the inhibitor [53]. The
parameter commonly used to estimate the roughness of the
surface is the arithmetic mean height (Sa). This value in the
blank was 71.7 nm, but decreased to 34.2 nm when Ni-OMNPs
were added corresponding to 52.3 % reduction in degree of sur-
face roughness. The implication of the parameters discussed
is that addition of Ni-OMNPs impeded the attack of the steel,
hence steel surface was relatively smooth with minor pits and
reduced surface degradation, and in overall, confirms efficient
anticorrosion effect of Ni-OMNPs. On the other hand, the fol-
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11
lowing parameters were obtained for OME: Sq = 51.1 nm, Sv =
222 nm, Sp = 284 nm, Sa = 52.6 nm, Ssu = −0.247 and Ssk = 5.06,
which depict less surface protection compared to Ni-OMNPs.
3.5. Inhibitor-steel surface interaction mechanism
For Ni-OMNPs to inhibit corrosion of steel in the acidic solu-
tion, there may have been adsorptive interaction between
species of its compounds and Fe on the steel surface. There-
fore, the corrosion products on the steel surface after were
carefully scrapped and analysed by FTIR. Also, without scrap-
ping, the elemental composition at the surface was checked by
EDS. The essence of these checks was to compare if the surface
properties are different after corrosion in the test solutions
and to use the difference to explain the possible mechanism of
interaction between the inhibitor and steel surface. The FTIR
spectra obtained is shown in Fig. 4 (c) and the EDS spectra in
Fig. 8 (bottom).
3.5.1. FTIR analyses
We initially assumed that if the corrosion product species
scrapped from the steel surface after 6 h of immersion is
related to Ni-OMNPs, the FTIR spectrum will show some sim-
ilarities with that of the pure Ni-OMNPs. Other researchers
have previously reported that there could be changes in
intensity of transmittance, shift in vibrational frequencies cor-
responding to some groups or some peaks could disappear
after adsorption [54]. These changes were also observed in our
present study. For instance, the peak at 3410 cm−1 assigned to
OH stretching vibrations became less prominent (low inten-
sity) and shifted to 3420 cm−1 ; the peak at 2930 shifted to
2950 cm−1 ; the intensity of peak at 1640 cm−1 was reduced
after adsorption; and the peak at 1100 cm−1 reduced in inten-
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Fig. 9 – (a) 3D images and (b) amplitude images of X80 steel corrosion after 6 h of immersion in (i) 1 M HCl (ii) 1 M HCl + OME
and (iii) 1 M HCl + Ni-OMNPs obtained by AFM.

sity and also shifted to 1070 cm−1 for the surface adsorbed
complex film. This demonstrates the likelihood of O H and
NH groups of the Ni-OMNPs being involved in the interac-
tion with the surface species. As a support to this likelihood,
these sites have been reported to be active adsorption sites in
many efficient organic [55] and plant extract-based corrosion
inhibitors [56]. In addition, the peaks at 1380 cm−1 , 1260 cm−1
and 810 cm−1 were of higher intensity compared to that of the
pure Ni-OMNPs. These peaks, which are sharp and medium
in intensity, can respectively be assigned to O H bending of
phenolics, C N stretching or CO stretching and CC bend-
ing (disubstituted alkenes or vinylidene) vibrations.1 The CN
stretching vibration at 1260 cm−1 could have also resulted
from interaction between N sites from the inhibitor and C
atoms present in the X80 steel.
When the differences in spectral properties of the adsorbed
complex is simply changes in intensity or vibrational fre-
quency, the mechanism can be associated with physical
adsorption. Physical adsorption does not involve formation of
1
https://www.sigmaaldrich.com/technical-
documents/articles/biology/ir-spectrum-table.html
actual chemical bonds, which could result in disappearance of
some peaks and appearance some new peaks, which is associ-
ated with chemical adsorption. Thus, adsorption of Ni-OMNPs
occurred by physisorption mechanism involving electrostatic
interaction between negatively charged Ni-OMNPs species (as
described by DLS results) and positively charged Fe ions on the
steel surface [43].
3.5.2. EDS analyses
Results obtained from EDS analyses also supported FTIR find-
ings. The weight and atomic percentages of the elements
checked are embedded in the EDS spectra presented in Fig. 9.
Going from the elemental composition of the surface retrieved
from the uninhibited acid solution to that inhibited by Ni-
OMNPs, the percentages of C, N and O increase while that
of Fe decreased. These increase (%) could have resulted from
adsorptive interactions of C C, CO, CN, OH and NH
groups with the surface (as earlier seen from FTIR results)
resulting masking the amount of Fe ‘seen’ on the surface [57].
The percentages of C, N and O were higher in Ni-OMNPs than
OME implying that more of these sites were present and/or
adsorbed with nanocomposite compared to the crude extract.
Also, Cl atoms initially seen on the surface for the blank was

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due to formation of chlorides between HCl and Fe, but on
adsorption of the inhibitors, the percentage of Cl reduced per-
haps due to replacement by inhibitor molecules. Additionally,
the surface of steel retrieved from the solution inhibited by
Ni-OMNPs also had some traces of ligated Ni atoms.
3.6. Environmental concerns
Since Ni is a heavy metal, this raises environmental on the
toxicity of the nanocomposite. Ni is naturally available in the
earth’s crust, hence is expected to be parts of composition
of food and water, however, in very trace amounts. Expo-
sure to Ni in water or the environment has been limited to
an ambient value of 100 ␮g/L by the US Environmental Pro-
tection Agency (EPA). In the body, the EPA reference dose
(RfD) of 0.02 mg/kg of body weight. Hardly can these bench-
references
marks be passed; common exposures to nickel include from
excessive tobacco smoking, from stainless cooking and eat-
ing utensils, contact with nickel containing jewellery, or in
air around sewage sludge incineration, and oil and coal com-
bustion sites. Even at that, these exposures are commonly
very low. Therefore, the amount of Ni ion in Ni-OMNPs pre-
pared was determined by AAS following procedures reported
by Muhammadi and co-workers [58]. Results show that the
amount was 26.3 ␮g/L in the stock solution and 4.8 ␮g/L in the
20 % v/v Ni-OMNPs solution. These quantities are far below
the safe dosage, indicating that the nanocomposite devel-
oped from this study is eco environmental. It is worth noting
that nickel sulphate has not been recorded to be carcinogenic.
However, high exposure to nickel ions has been associated
with mild gastrointestinal disorders, dermatitis to pulmonary
fibrosis and renal oedema according to US-EPA.
4. Conclusion
Aqueous onion mesocarp extract-mediated nickel nanocom-
posites (Ni-OMNPs) were synthesized, characterized and
evaluated as corrosion inhibitor additive in 1 M HCl solution.
Ni-OMNPs was an efficient inhibitor of X80 steel corrosion at
30–60 ◦ C. Formation of nanocomposite occur at 150 min and at
50 ◦ C with the formation of plasmon at 495 nm. The nanocom-
posites are crystalline and composed fcc particles of Ni◦ phase
with dominant Ni (111) orientation based on XRD diffraction
pattern. Ni-OMNPs surfaces are negatively charged with high
electron cloud due to abundance of O, N sites, conveying high
adsorption capacity on the particles. Ni-OMNPs are spheri-
cal in shape with sizes between 37.5 nm – 50.5 nm and are
monodispersed in colloidal aqueous solution without agglom-
eration. Ni-OMNPs was 95.51 % and 95.44 % efficient at 30
◦ C and 60 ◦ C respectively, whereas equivalent concentration
of the crude extract was 70.30 % and 55.42 % the respec-
tive temperatures. The nanocomposites were more thermally
and biochemically stable and could be stored for longer time
than the crude extract. Ni-OMNPs works as mixed type corro-
sion inhibitor with anodic predominance and corrosion in the
presence of Ni-OMNPs occur by charge transfer mechanism.
Addition of Ni-OMNPs to 1 M HCl effectively protects the steel
surface against excessive corrosive damage and reduces sur-
face roughness by 52.3 %. Action of Ni-OMNPs is attributed to
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13
collective physisorption of its phytocompounds, which needs
to be further characterized in future studies.
Conflict of interests
The authors declare no conflict of interests
Appendix A. Supplementary data
Supplementary material related to this article can be found,
in the online version, at doi:https://doi.org/10.1016/j.jmrt.
2020.01.017.
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