Sustainable Materials and Technologies 14 (2017) 1–10

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Sustainable Materials and Technologies

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

8-Hydroxyquinoline as an alternative green and sustainable acidizing MARK

oilfield corrosion inhibitor
I.B. Obota,⁎, N.K. Ankahb, A.A. Soroura,b, Z.M. Gasemb, K. Harunac
a
Center of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
b
Department of Mechanical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
c
Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

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

Keywords: Corrosion inhibition performance of an environmentally friendly compound, 8-hydroxyquinoline (8-HQ), on

Steel X60 steel was investigated in 15% hydrochloric acid (HCl), which simulate oil well acidizing environment.
8-Hydroxyquinoline Efficacy of the inhibitor was examined utilizing weight loss, potentiodynamic polarization (PDP), electro-
FT–IR chemical frequency modulation (EFM), linear polarization (LPR), and electrochemical impedance spectroscopy
Corrosion inhibitor
(EIS). Results show increased inhibitor efficiency with increase in concentration of 8-HQ and was further en-
hanced when iodide ions were added. The potentiodynamic polarization measurement illustrates the mixed type
behavior of 8-HQ. Scanning electron microscopy (SEM) with energy dispersive X-ray (EDX), and Fourier
transforms infrared (FT-IR) spectroscopy, were utilized to examine corrosion products and results indicate a
layer being formed on the X60 steel by 8-HQ that protects the steel from further corrosion.

1. Introduction quantities to a corrosive solution to impede the rate of corrosive attack

Production wells in oil and gas industries are continually exposed to
highly corrosive environments during stimulation treatments such as
acidization [1,2]. Acid treatment involves the application of con-
centrated acids to boost reservoir rock permeability and eliminate
formation damages [3]. The acid is introduced at high temperature
through the wellbore into the pores of the rock formation to enlarge
existing flow passages and open new ones to enhance the productivity
of wells. Acids used in stimulation treatments can be strong or weak
depending on the prevailing well conditions. Strong acids such as HCl,
HF, HCl and HF blends as well as weak acids such acetic and formic
acids are commonly used [4]. Among the various acids utilized in this
process, HCl is mostly preferred as the reaction products are water
soluble. The process is usually completed with 15–28% HCl [5]. During
these procedures, structural materials exposed to acid are corroded.
Such materials include well tubulars, mixing tanks, pipelines, casings
and tubing, as well as storage facilities, which are usually constructed
from carbon steel because its cheap and readily available [6]. Corrosion
of these structural materials may lead to compromised integrity of the
components [7], rupturing of pipes and spills, [8,9].
In order to control the corrosion of these structural materials, acids
employed in acidizing treatments need to be inhibited by effective
corrosion inhibitors. Corrosion inhibitor is a molecule added in minute
on the metallic materials [10]. Corrosion inhibitors offer surface pro-
tection by adsorption of their active functionalities on metal surfaces.
Conventional corrosion inhibitors such as chromate and arsenic com-
pounds are highly carcinogenic and therefore very unfriendly to the
environment. The environmental concerns of these toxic inhibitors are
the driving force towards continued research into more environmental
friendly corrosion inhibitors [11].
Several researchers investigated various types of corrosion in-
hibitors such as pyrazines, quinoline derivatives, amines aromatic al-
dehydes, plants extracts and quaternary salts [12–14]. Organic mole-
cules usually act as good corrosion inhibitor by adsorbing onto surface
of metals. S, O, P, N etc. can form coordination bonds with the surface
of metal due to the availability of lone electron pairs or pi-bonds
leading to adsorption [15].
Recently, several reports have been documented in the literature on
the use of quinoline derivatives as corrosion inhibitor in acidic media.
Compounds such as 5-Nitro-8-Hydroxy Quinoline [16], 3-formyl-8-hy-
droxy quinoline [17], 8-hydroxy-7-quinolinecarboxaldehyde [18], 5,5′-
(((2-hydroxypropane-1,3-diyl)-bis-(oxy))-bis-(methylene))-bis-(8-qui-
nolinol) [19], 5-(((1H–benzimidazol-2-yl) thio) methyl) 8-quinolinol
[20], 2-oxo-1,2-dihydroquinoline-4-carboxylic acid [21] have been re-
ported as effective corrosion inhibitors for steel in 1 M HCl. Among the
quinoline derivatives, 8-HQ was reported to be the most important

⁎
Corresponding author.
E-mail address: obot@kfupm.edu.sa (I.B. Obot).

http://dx.doi.org/10.1016/j.susmat.2017.09.001
Received 11 August 2017; Received in revised form 12 September 2017; Accepted 30 September 2017
Available online 30 September 2017
2214-9937/ © 2017 Elsevier B.V. All rights reserved.
I.B. Obot et al. Sustainable Materials and Technologies 14 (2017) 1–10

immersed in inhibited acid solution for 10 s to remove the corrosion

products, thoroughly washed, cleaned, air dried, and reweighed. The
corrosion rates were calculated in mm/y and mpy using Eqs. (1) and (2)
respectively.

w × 87600
Corrosion rate(mm/year) =
d×a×t (1)

Fig. 1. Structures of 8-hydroxyquinoline.
chelating and outstanding complexing agent [22–25]. In most recent
studies, 8-hydroxyquinoline was reported to be mixed-type inhibitor on
aluminum corrosion and was also shown to form complexes with
copper and magnesium alloys [26]. Complexes are formed with the
dissolved metals during the inhibition process which in turn forms a
barrier that impedes further corrosion. This barrier blocks active sites
on the surface from further dissolution thereby inhibiting corrosion.
Though the inhibitive nature of 8-HQ was studied on magnesium,
copper and aluminum alloys corrosion in some recent studies, its effect
on carbon steel corrosion in oil well acidizing condition (15% HCl) has
not been investigated previously. The current research, therefore, in-
vestigates the inhibition effect of 8-hydroxyquinoline, (molecular
structure is shown in Fig. 1) on X60 steel in 15% HCl. Various techni-
ques such as weight loss, electrochemical frequency modulation (EFM),
linear polarization resistance (LPR), potentiodynamic polarization
(PDP) and electrochemical impedance spectroscopy (EIS) were utilized
in the work. FTIR, SEM and EDX were used to characterize the corro-
sion products formed.
2. Experimental
2.1. Materials
API X60 steel from a typical pipeline was used as coupons. Chemical
compositions of the specimen utilized are illustrated in Table 1. The
coupons utilized for weight loss tests were of the dimension 3 × 3 cm,
and the test coupons for the electrochemical measurements were cy-
lindrical with a 3.14 cm2 surface area. The test coupons were ground
using papers of grit sizes of 120, 240, 320, 400, 600 and 800. After
polishing, the coupons were rinsed in distil water, sonicated in acetone
and finally air drying was carried out prior to corrosion measurements.
Analytical grade HCl (Sigma Aldrich) was diluted to 15% HCl acid
using double distilled water. Four different concentrations (0.1, 0.2, 0.3
and 0.4 wt%) of 8-hydroxyquinoline (8-HQ) were prepared in 15% HCl.
And the concentrations of 8-HQ with added potassium iodide (KI) were
0.1 wt% 8-HQ + 0.005 wt% KI, 0.2 wt% 8-HQ + 0.005 wt% KI, 0.3 wt
% 8-HQ + 0.005 wt% KI and 0.4 wt% 8-HQ + 0.005 wt% KI for the
weight loss test.
3.45 × 106 × w
Corrosion rate(mpy) =
d×a×t (2)
where, w is weight loss (g), A is surface area exposed (cm2), t is ex-
posure time (h), and d is density (7.86 g/cm3).
Inhibition efficiency was evaluated from Eq. (3). Corrosion inhibitor
efficiency is a measurement of the effectiveness of the corrosion in-
hibitor.
CRo − CRi
%IE = × 100
CRo (3)
where CRo is corrosion rate of steel without inhibitor and CRi is cor-
rosion rate with inhibitor present.
2.2.1. Electrochemical measurement
In taking the various measurements, a setup consisting of counter
electrode (graphite), reference electrode (Ag/AgCl), and working elec-
trode (X60 steel) were assembled. The readings were carried out on
Gamry Potentiostat/Galvanostat/ZRA (Reference 3000) instrument.
EFM, PDP, LPR, and EIS, were utilized to investigate corrosion behavior
of X60 steel with and without different 8-HQ concentrations in 15%
acid.
EIS measurement was carried out within a frequency range of
100 kHz – 0.01 Hz and an amplitude of ± 10 mV after 3600 s open
circuit potential. For PDP measurement, the potential ranged between
− 0.25 V - +0.25 V vs. EOC and 0.125 mV/s scan rate. LPR measure-
ment was taken at Ecorr ± 10 mV and 0.25 mV/s scan rate. EFM was
conducted with a base frequency of 0.01, multiplier A = 2, B = 5,
cycle = 4 and amplitude = 10 mV. Data analysis and curve fitting was
done by Gamry EChem Analyst 5.5 software.
2.3. Characterization methods
2.3.1. FTIR
FTIR analysis of the pure inhibitor and that of the corrosion product
was performed using utilizing Shimadzu FTIR-8400S spectro-
photometer. The samples were prepared in potassium bromide.
Analysis of the samples was performed scanning through
400–4000 cm− 1 wave number range. FTIR was carried out on both
pure inhibitor and corrosion products on carbon steel coupon after
immersion in 0.4 wt% solution of 8-HQ with and without the addition
of KI in 15% HCl.

2.2. Weight loss

Weight loss measurements were performed X60 steel coupons in
15% HCl with various 8-HQ concentrations for 24 h at 25 °C. During
weight loss measurement, each specimen was weighed prior to im-
mersion. The specimens were immersed in duplicates and average
weight loss was evaluated. After completion, specimens were retrieved,
2.3.2. SEM/EDX
Examination of morphological features was performed on the cou-
pons after immersion in 15% acid with various 8-HQ concentrations
after 24 h at 25 °C utilizing SEM at 20 kV. The associated EDX was used
to provide qualitative information about surface elemental composi-
tion.

Table 1
Chemical composition of the X60 steel specimen used for the experiment.

Element Fe Cr C Si Mn Cu Ni Mo Al Nb V

Composition (wt%) < 96.2 0.121 0.125 0.52 1.830 0.296 0.091 0.079 0.043 0.053 0.078

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I.B. Obot et al. Sustainable Materials and Technologies 14 (2017) 1–10

Table 2 of the metal and formation of more complete and stable surface film as
Weight loss results for X60 steel in 15% HCl with and without different concentrations of compared to 8-HQ alone [27,28]. It can be noted from Table 2 that 8-
8-HQ and with the addition of 0.005 wt% KI at 25 °C.
HQ + KI could provide good corrosion protection at 25 °C in 15% HCl
System/conc. of 8-HQ Weight loss Corrosion rate Efficiency up to the test duration of 24 h. Figs. 2 and 3 show the test specimens
immersed in 200 mL solutions before and after the test. No visible
(wt%) (g) mpy mm/y IE (%) pitting was seen on any of the coupons after the tests.
Blank 0.2110 128.63 3.2661 –
0.1 0.1134 69.13 1.7753 46.26 3.2. Electrochemical measurement
0.2 0.0991 60.41 1.5340 53.04
0.3 0.0850 48.65 1.2352 59.71 3.2.1. Electrochemical impedance spectroscopy (EIS)
0.4 0.0813 49.56 1.2414 61.47
Presented in Fig. 4(a) and (b) are Nyquist and Bode impedance
KI 0.0716 43.65 1.0530 66.07
0.1 + KI 0.0587 35.79 0.9086 72.18 curves, respectively, in 15% acid with various 8-HQ concentrations.
0.2 + KI 0.0405 24.69 0.6269 80.18 The Nyquist plot exhibits semicircular arc over the entire range of
0.3 + KI 0.0384 23.41 0.5944 81.80 frequency, this was attributed to transfer of charges that occurred in the
0.4 + KI 0.0353 21.52 0.5464 83.27 solution [29]. The imperfect semicircular nature of the capacitive arcs
could be ascribed to surface inhomogeneities and roughness of coupons.
The radius of the capacitive arc increased with increase in 8-HQ con-
3. Results and discussions
centration. This increase was marked with increasing inhibitor con-
centration, showing that, the inhibitor efficacy is in direct proportion-
3.1. Weight loss
ality to the concentration [30]. Increasing the concentration of the
inhibitor increases the rate of interaction between the N-atoms in 8-HQ
Corrosion rates and inhibitor efficiencies in an acidizing environ-
and the metal at the active sites leading to adsorption on the metal
ment (15% HCl) with different concentrations of 8-HQ was measured
surface [31]. This in effect suggests that, N- atoms formed coordination
with weight loss technique. The corrosion rates and inhibitor effi-
bond with the iron. The nitrogen atoms can also donate pi electrons to
ciencies are presented in Table 2. It is evident from Table 2 that, the
the surface of the metal thereby enhancing the adsorption on the sur-
corrosion rate significantly decreased from 128.63 mpy in the blank
face leading to higher potency of the inhibitor [32]. The stability of the
acid to 69.13 mpy when 0.1 wt% of the inhibitor was added. The effi-
metal complex formed can be ascertained in the extent of the corrosion
ciency of inhibition further increased with increasing inhibitor con-
inhibition process. Stable complexes are more protective. Inhibitor
centration until an optimum concentration was reached. Efficiency of
molecules generally suppress dissolution of the steel by forming metal
61.47% was achieved at 0.4 wt% concentration of the inhibitor alone.
complexes. The metal complexes adsorb to the surface and effectively
This can be attributed to the interaction of the inhibitor molecule and
isolating it from the corrosive media [33]. Differences in radii of ca-
the active sites on the metal surface. Metal atoms at the active sites
pacitive arcs of the Nyquist plot demonstrate that, 8-HQ influenced
form coordination bonds with lone electron pairs from nitrogen. Pi
corrosion rate by inhibition. The radius increases with increase in
electrons can also be donated to the metal surface by nitrogen atoms
concentration. This follows the same trend as efficiency of inhibition.
leading to enhanced adsorption and hence increased efficiency. It is
Thus, the larger the radius of the semi-circle, the higher the efficiency.
generally accepted that, at a given inhibitor concentration, the effi-
Double layer and film capacitances observed showed that corrosion
ciency decreases with increasing concentration of the acid. Similar
mechanism was mainly controlled by charge transfer processes. The
works on some quinoline derivatives in 1 M HCl by various authors
calculated EIS parameters obtained from Nyquist plot are presented in
showed inhibitor efficiencies between 84 and 91% [16,18,21]. Unlike
Table 3. The equivalent circuit employed in fitting the Nyquist plot is
the previous studies that were conducted in 1 M HCl, our work was
illustrated in Fig. 5. The accuracy of the fit was between 0.16 and
done in 15% HCl, it was therefore apparent that the efficiencies will not
1.5 × 10− 4 in all plots. The model utilized to fit the Nyquist plot in-
be same and it will rather decrease due to the high concentration of the
cludes Rs (solution resistance between working and counter electrodes),
acid. It was also observed from Table 2 that 0.005 wt% KI acted as a
Rf (film resistance), Rct (charge transfer resistance), CPEf (constant
corrosion inhibitor in 15% HCl. Efficiency of 66.07% was achieved by
phase angle element of film) and CPEdl (double layer constant phase
the addition of KI alone. But adding 0.005 wt% KI in combination with
angle element) as illustrated in Fig. 5. Inhibitor efficiency was eval-
different concentrations of 8-HQ led to significant improvement in the
uated from Eq. (4).
efficiency. It is worth noting that corrosion inhibitor efficiency of
83.27% was achieved by adding 0.005 wt% KI to the highest con- R
centration of 8-HQ investigated in this study. The increase in efficiency IE (EIS)% = ⎛1 − P ⎞ × 100
⎜ ⎟

⎝ RPI ⎠ (4)
upon adding KI may be attributed synergistic effect. This was exhibited
through co-adsorption of the iodide and 8-HQ molecule on the surface where Rp [sum of Rct and Rf] and RPI represent polarization resistances
without and with 8-HQ, respectively.

Fig. 2. Carbon steel coupons immediately after immersion in 15% HCl and the various concentrations of 8-HQ. (Note: 1000 ppm ~0.1wt%; 2000 ppm ~ 0.2 wt%; 3000 ppm ~ 0.3 wt%;
and 4000 ppm ~0.4 wt% of 8-HQ).

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I.B. Obot et al. Sustainable Materials and Technologies 14 (2017) 1–10

Fig. 3. Carbon steel coupons 24 h after immersion in 15% HCl and the various concentrations of 8-HQ. (Note: 1000 ppm ~0.1 wt%; 2000 ppm ~ 0.2 wt%; 3000 ppm ~ 0.3 wt%; and
4000 ppm ~0.4 wt% of 8-HQ).

frequency and n is phase shift. Capacitance of the double layer (CPE)dl

values were evaluated from Eq. (6):
Yωn − 1
CPEdl =
sin n ( ( ))
π
2 (6)

As presented in Table 3, charge transfer resistance increased sig-

nificantly when inhibitor was added and continuously increased with
increasing concentration leading to enhanced inhibitor efficiency. This
behavior was assigned to surface film being formed. The surface film
protects by isolating the steel surface from corroding media thereby
impeding further charge and mass transfer. In addition, Yo for both the
film and double layer decreased with inhibitor concentration. Changes
in Rct and Yo values may be due 8-HQ molecules removing water on
steel surface subsequently reducing active sites necessary for corrosion
to occur [37]. There was no significant change in phase shift, n, values.
The stability of n for both the film and double layer indicates the me-
chanism of dissolution was controlled by charge transfer with and
without 8-HQ.

3.2.2. Potentiodynamic polarization measurements

In Fig. 6, X60 steel polarization curves in various 8-HQ concentra-
tions are illustrated. The respective electrochemical parameters were
acquired by extrapolating Tafel slopes to Ecorr. These parameters are
presented in Table 4. Inhibitor efficiency was evaluated from corrosion
current densities utilizing Eq. (7).

II ⎞
IE(PDP)% = ⎜⎛1 − corr
B ⎟
× 100
⎝ Icorr ⎠ (7)

Fig. 4. Impedance plots for X60 steel in 15% HCl without and with different con-
centrations of 8-HQ at 25 °C in (a) Nyquist and (b) Bode modulus.
CPE was used to accurately fit the curve instead of pure capacitor
[34,35]. The impedance of CPE was represented as [36]:
ZCPE = Y o−1 (jω)−n
where Yo is the magnitude of CPE, j is square root of −1, ω is angular
where IBcorr
is corrosion current density in blank and IIcorr
is corrosion
current density with an inhibitor present. The data listed in Table 4,
showed that, as the concentration of 8-HQ increased, Icorr, decrease.
Adding various 8-HQ concentrations causes slight alterations in the
cathodic Tafel slopes as illustrated in Fig. 6 indicating that the inhibitor
is a cathodic inhibitor. Considering the maximum change in Ecorr values
(5) was − 11 mV which was far less than the ± 85 mV showing that 8-HQ
can a mixed type inhibitor but predominantly cathodic inhibitor. This
suggests that 8-HQ does not interfere with only the hydrogen evolution

Table 3
Impedance parameters for X60 steel in 15% HCl without and with different concentrations of 8-HQ at 25 °C.

CPEf CPEdl

System/conc. Of 8-HQ (wt%) Rs Yo n1 Rf Yo n2 Rct Rp χ2 × 10− 4 IE

(Ω cm2) (μΩ sn cm− 2) (Ω cm2) (μΩ sn cm− 2) (Ω cm2) (Ω cm2) (%)

Blank 0.62 135.4 1.00 1.73 1529.0 0.62 20.35 22.08 0.33 –
0.1 0.73 205.5 0.94 3.81 1279.0 0.58 30.93 34.74 0.31 34.70
0.2 0.66 101.9 1.00 2.49 1348.0 0.63 40.04 42.53 1.55 49.17
0.3 0.47 98.20 1.00 3.21 829.1 0.66 45.64 48.85 0.16 55.41
0.4 0.42 85.09 1.00 3.60 816.6 0.66 58.37 61.97 0.23 65.13

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I.B. Obot et al. Sustainable Materials and Technologies 14 (2017) 1–10

Fig. 5. The equivalent circuit used to fit the Impedance spectra.

was inhibited by 8-HQ by impeding cathodic and anodic reactions.

3.2.3. Linear polarization resistance measurement

Linear polarization resistance measurement was conducted to
evaluate efficiency of inhibition by 8-HQ in 15% HCl. This is a non-
destructive technique that permits the measurement of corrosion rates
in real time. A small voltage value of 10 mV was chosen to avoid per-
manently disrupting the corrosion process, such that ensuing mea-
surement remains accurate. The linear relationship between E/I and
Icorr are valid at this small voltage value [39,40]. Polarization resistance
(Rp) and efficiency values obtained are illustrated in Table 4. Efficiency
of inhibition was calculated utilizing Eq. (8) [41].

⎛ RpB ⎞
IE(LPR)% = ⎜1 − I ⎟ × 100
⎝ Rp ⎠ (8)

Fig. 6. Potentiodynamic polarization plots for X60 steel in 15% HCl without and with
different concentrations of 8-HQ at 25 °C.
but also interferes with the anodic reaction [38]. Inhibitor efficiency
increasing with concentration indicates that, inhibition actions are as a
result of adsorption on the surface. The inhibitor is adsorbed onto the
surface thereby blocking further corrosion reaction. The observed de-
crease in corrosion current densities, Icorr, with increased concentration
of 8-HQ in Table 4, indicates increased protection of X60 steel surface.
The inhibitor also forms metal complexes with the dissolve metal in-
hibiting the anodic dissolution and consequently increasing the Tafel
slopes for the reaction. This is an indication that, the corrosion process
where RBpis the polarization resistance with no inhibitor present and RIp
is polarization resistance with an inhibitor present. The values pre-
sented in Table 4 indicate increasing polarization resistance with an
increase in concentration. Relative to the uninhibited acid, the polar-
ization resistance values increased upon adding an inhibitor. This be-
havior corroborates the fact that 8-HQ impedes corrosion of steel in this
high acidic environment. At an inhibitor concentration of 0.4 wt%,
polarization resistance value of 62.8 Ω cm− 2 was obtained. This con-
trasts with the polarization resistance value of 20.1 Ω cm− 2 obtained in
the uninhibited solution. This indicates a clear inhibition of the cor-
roding steel in the aggressive 15% acid. It is apparent that PDP and LPR
values are in perfect agreement. Both show similar trends in decreased
corrosion rates and increased inhibition efficiencies with increasing
inhibitor concentrations [42].

Table 4
Potentiodynamic polarization (PDP) and linear polarization resistance (LPR) parameters for X60 steel in 15% HCl without and with different 8-HQ concentrations at 25 °C.

PDP method LPR method

System/conc. 8-HQ (wt%) Ecorr Icorr βa βc CR IE Rp CR IE

(mV vs. Ag/AgCl) (A/cm2) (mV/dec) (mV/dec) (mpy) (%) (Ω cm2) (mpy) (%)

Blank −428 768 67.8 114.1 224.6 – 20.1 379.0 –

0.1 −434 608 76.3 119.4 177.6 20.80 33.5 227.6 39.9
0.2 −435 536 81.0 135.9 156.7 30.23 41.9 181.6 52.1
0.3 −437 364 71.7 120.7 106.3 52.67 51.9 146.6 61.3
0.4 −439 316 75.5 128.5 92.24 58.93 62.8 121.3 67.9

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I.B. Obot et al. Sustainable Materials and Technologies 14 (2017) 1–10

Fig. 7. Intermodulation Spectra for X60 steel in 15% HCl without and with different concentrations of 8-HQ at 25 °C.

Table 5 intermodulation spectra for X60 steel with various 8-HQ concentrations
Electrochemical frequency modulation parameters for X60 steel in 15% HCl in the ab- in 15% HCl at 25 °C. The response of the current consists of frequencies
sence and presence of 8-HQ at 25 °C.
that are multiples, differences, and sums of the two-frequency inputs.
System/ Icorr βa βc CF–2 CF–3 CR IE
The two-frequency inputs were very small and were multiples of a base
conc. 8- (μA cm− 2) (mV dec− 1) (mV dec− 1) (mpy) (%) frequency used throughout the duration of the test. The smaller fre-
HQ (wt%) quency must be at least a factor of two lower than the highest. The
current response between peaks was very small. Corrosion parameters
Blank 1305.0 100.5 146.0 1.97 3.67 381.4 –
0.1 847.0 104.4 128.3 2.03 2.25 247.5 35.1
illustrated in Table 5 were calculated utilizing Eqs. (9)–(13) [46,47];
0.2 709.9 105.4 124.0 2.09 2.90 207.5 45.6
0.3 591.9 103.3 122.6 2.06 3.89 173.0 54.6
Iω2
Icorr =
0.4 496.0 104.7 124.0 2.09 3.26 144.9 62.0 48(2I3ω Iω − I2ω ) (9)

Iω2 Uo
3.2.4. Electrochemical frequency modulation βa =
Electrochemical frequency modulation is a type of nondestructive 2I2ω + 2 3 2I3ω Iω − I22ω (10)
method that gives corrosion current directly without resorting to Tafel
extrapolation. Sine waves with two frequencies that are different are Iω2 Uo
βc =
simultaneously used in the cell [43–45]. Fig. 7 illustrates 2 3 2I3ω Iω − I22ω − I2ω (11)

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I.B. Obot et al. Sustainable Materials and Technologies 14 (2017) 1–10

where I is instantaneous current density, ω is frequency, and U0 is

amplitude.
Table 5 illustrates the parameters obtained at various 8-HQ con-
centrations. Corrosion current density decrease as the inhibitor con-
centration increases. Also, efficiency increased with increasing 8-HQ
concentration. This confirms that, 8-HQ effectively decreases the cor-
rosion rate in the 15% acid. This observation was further authenticated
by approximately equal values of the experimental CF values with the
theoretical values of 2 and 3. Inhibitor efficiency (IE(EFM)%) presented
in Table 5 was calculated utilizing Eq. (14).

II ⎞
%IE(EFM ) = ⎜⎛1 − corr
B ⎟
× 100
⎝ Icorr ⎠ (14)

where IBcorr and IIcorr are corrosion current densities without and with an
inhibitor, respectively.

3.3. Surface characterizations

Fig. 8. FTIR spectra of pure 8-HQ, 0.4 wt% 8-HQ, 0.4 wt% 80HQ + KI in 15% HCl after
immersion of X60 steel. 3.3.1. FTIR
FTIR was utilized to probe the mechanism of interaction and the
functional groups that took part in the adsorption process of 8-HQ on
Iω2 ± ω1
Casaulity factor (2) = =2 the surface. Fig. 8 shows FTIR results obtained on the pure inhibitor (8-
I2ω1 (12)
HQ), the inhibitor concentration with the highest efficiency (0.4 wt% 8-
HQ), and the inhibitor concentration with the highest efficiency in
Iω2 ± ω1 combination with KI (0.4 wt% 8-HQ + KI). The peaks in the pure in-
Casaulity factor (3) = =3
I3ω1 (13) hibitor at 1571–1508 cm− 1 was assigned to CeN ring stretching and

Fig. 9. SEM micrograph of (a) Polished X60 steel sample, (b) X60 Steel sample immersed in 15% HCl blank after 24 h (c) X60 Steel sample immersed in 0.4 wt% 8-HQ in 15% HCl after
24 h, (d) X60 Steel sample immersed in 0.4 wt% 8-HQ in 15% HCl with added KI after 24 h.

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I.B. Obot et al. Sustainable Materials and Technologies 14 (2017) 1–10

Fig. 10. EDX spectra of X60 steel specimens (a) polished (b) After immersion in 15% HCl without inhibitor (c) with 0.4 wt% 8-HQ (d) with 0.4 wt% 8-HQ + KI.

Table 6 24 h are illustrated in Fig. 9. The result shows that the polished X60
Elemental composition of the X60 steel specimen before and after immersion in 15% HCl steel specimen (Fig. 9(a)) was considerably smooth with no corrosion.
in the absence and presence of 8-HQ at 25 °C. The X60 Steel sample immersed in 15% HCl blank after 24 h (Fig. 9(b))
Element Mirror X60 immersed X60 immersed X60 immersed in
shows a highly corroded surface. However, upon adding 8-HQ, there
polished X60 in blank in 0.4 wt% 8-HQ 0.4 wt% 8-HQ was a marked reduction in the corrosion of the coupon. The specimen
steel + KI immersed in 0.4 wt% 8-HQ (Fig. 9(c)) was relatively smooth compared
to that in the 15% HCl blank. Additionally, specimen immersed in the
wt% wt% wt% wt%
inhibitor solution containing KI (Fig. 9(d)) showed relatively less pits as
Fe 98.54 88.47 85.80 93.58 compared to that of 0.4 wt%. This demonstrates that addition of in-
Mn 0.93 0.95 1.25 0.73 hibitor reduced corrosion that occurs in the uninhibited solution.
Si 0.53 – – 0.57 EDX was utilized to extract information regarding the surface ele-
O – 9.17 11.19 4.38
mental composition. Fig. 10 illustrates the EDX spectrum of X60 steel
Cl – 1.41 1.75 0.74
specimens 24 h immersion with and without an inhibitor. The EDX
spectrum for an uncorroded polished X60 steel specimen (Fig. 10(a))
was shifted to higher values of 1633 cm− 1 for both 0.4 wt% 8-HQ, and shows the characteristic peak of iron which is the major constituent
0.4 wt% 8-HQ + KI. The peak at 1370 cm− 1 was ascribed to in-plane element in X60 steel specimen. In 15% HCl (blank), the EDX spectrum
OeH bends [48] and diminished for both 0.4 wt% 8-HQ, and 0.4 wt% illustrated in Fig. 10(b) shows the characteristics peak of iron and small
8-HQ + KI. The peak at 1284 cm− 1 was ascribed to in-plane OeH peaks characterizing chloride and oxygen; these peaks represent cor-
deformations. The peak at 1087 cm− 1 was ascribed to CeO stretching. rosion products (chloride and oxide). Peaks of Fe are largely suppressed
The peaks at 694, 632, 463 and 406 cm− 1 were ascribed to out of plane relative to coupons immersed in the blank acid with 0.4 wt% 8-HQ
OeH bonds. The presence of eOH, eC]N, and eC]Ce and aromatic alone (Fig. 10(c)) and 0.4 wt% 8-HQ with KI (Fig. 10(d)). This clearly
ring provide active sites for inhibitor interaction with surface of steel. indicates metal complex formation on the surface (Table 6).

3.3.2. SEM/EDX 4. Mechanism of inhibition of 8-HQ on steel

SEM micrographs of polished X60 steel specimens prior to immer-
sion and those immersed in 15% HCl blank with and without 8-HQ for The inhibition mechanism can be explained based on the inhibitor

8
I.B. Obot et al.
adsorption onto surface of the steel. Adsorption of organic compounds
usually works by both physical or chemical processes and sometimes
both processes of adsorption on the surface of the steel. Numerous
factors such as inhibitor charge, molecular structure and the surface of
the metal determine the adsorption process. 8-HQ contains functional
groups such as aromatic ring, OH and eN]Ce that act as centers of
adsorption during the inhibitor adsorption process.
To positively illustrate the mechanisms of inhibition of 8-HQ in HCl,
a model was proposed as shown in Fig. 11. As can be observed from
Fig. 11, the inhibitor was protonated in HCl and was subsequently
adsorbed on the steel through electrostatic interaction. The protonated
N atoms are attracted to the Cl−. This inhibitor-Cl− interactions leads
to adsorption on the surface [49]. This process reduces hydrogen evo-
lution by competing with the hydrogen ions for electrons on the steel
surface. After H2 evolution, inhibitor returns to its neutral form with
free lone electron pairs [50]. The process is achieved without altering
the hydrogen evolution mechanism [51]. Another possible mode of
adsorption can be due to the interaction of unshared electron pairs of
nitrogen atom and vacant d orbital of Fe atoms and there can be donor-
acceptor interactions between the pi electrons of the aromatic ring. The
protonated sites of the inhibitor may adsorb on the steel through a
synergistic effect with pre-adsorbed Cl− as well.
5. Conclusion
Corrosion of X60 steel was monitored in laboratory simulated well
acidizing fluid with and without different concentrations of 8-HQ to
investigates its inhibition effects. The following conclusions were
drawn:
(i) 8-HQ functioned as an effective corrosion inhibitor for the corro-
sion of X60 steel in 15% acid.
(ii) Efficiency increased with increasing 8-HQ concentration and
adding KI further increases inhibitor efficiency.
(iii) 8-HQ is as a mixed type inhibitor and protects by forming a surface
film through adsorption. The functional groups present in 8-HQ
form corrosion inhibitive layer by complexation with iron ions
present on the X60 steel surface.
Acknowledgment
The authors gratefully acknowledge the support received from King
Abdulaziz City for Science and Technology (KACST) for funding this
work under the auspices of National Science Technology and
9
Sustainable Materials and Technologies 14 (2017) 1–10
Fig. 11. Schematic illustration of the adsorption mechanism of 8-
HQ on steel surface in 15% HCl.
Innovation Plan (NSTIP) grant No. 14-ADV2448-04. Also, the support
provided by the Deanship of Scientific Research (DSR) and the Center of
Research Excellence in Corrosion (CORE-C), at King Fahd University of
Petroleum & Minerals (KFUPM) are gratefully acknowledged.
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