Results in Physics 13 (2019) 102116

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Results in Physics
journal homepage: www.elsevier.com/locate/rinp

A combined electrochemical and theoretical analysis of environmentally T

benign polymer for corrosion protection of N80 steel in sweet corrosive
environment
⁎
Ambrish Singha,b, , Neetesh Sonia, Yu Deyuana, Ashish Kumarc
a
School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China
b
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, Sichuan 610500, China
c
School of Mechanical and Civil Engineering, Lovely Faculty of Engineering and Technology, Lovely Professional University, Phagwara, Punjab, India

A R T I C LE I N FO A B S T R A C T

Keywords: The corrosion inhibition efficiency of aniline, formaldehyde and piperazine based polymer (ADPD) on N80 steel
Polymer in 3.5% NaCl solution saturated with carbon dioxide was investigated using electrochemical impedance spec-
DFT troscopy (EIS), potentiodynamic polarization, weight loss, scanning electrochemical microscopy (SECM), scan-
N80 steel ning electron microscopy (SEM) measurements, density functional theory (DFT) and molecular dynamics si-
EIS
mulation (MD). The adsorption of polymer onto N80 steel surface followed Langmuir adsorption isotherm
SECM
MD simulations
model. Potentiodynamic polarization study confirmed that inhibitor is mixed type with cathodic predominance.
SECM study reveals the current values decreases with the increasing concentration of polymer. SEM study
supports the smooth metal surface texture. DFT and MD calculations are in agreement with the experimental
findings.

Introduction properties and ability to form complex with iron ions [9].
The current effort aims the synthesis and assessment of corrosion
Carbon steel is widely used in petroleum industry due to their en- mitigation efficiency of polymer derived from aniline, formaldehyde
dearing properties such as hardness, durability, ductility and low cost. and piperazine (ADPD) on N80 steel in 3.5% NaCl solution flooded with
Nevertheless, they are very much prone to undergo corrosion in ag- carbon dioxide by means of weight loss, and electrochemical techni-
gressive media in which they are present i.e. high concentration of ques. The surface of steel samples was observed using SECM and SEM
chloride ions in presence of carbon dioxide [1,2]. Carbon dioxide forms measurements. The interaction of inhibitor molecules with the metal
carbonic acid (H2CO3) after reacting with water containing chloride surface was studied by MD simulation study.
ions and this weak acid causes the corrosion of carbon steel.
One of the most common and suitable way to overcome from cor- Experimental details
rosion problem without modifying corrosive environment is the use of
corrosion inhibitors. Chemical composition and preparation of N80 steel
Polymeric compounds enclosing heteroatoms (N, O, S), π-electrons
and phenyl rings provide the ability to adsorb onto the metal surface The steel samples of size 5.0 cm × 2.5 cm were used for weight loss
through adsorption. Polymeric compounds possess high molecular experiments and 2.0 cm × 1.0 cm for electrochemical experiments. The
weight that helps them to shield additional surface area of the metal surface was cleaned carefully, followed by abrading to a mirror finish.
and thus make them excellent candidates for corrosion inhibition.
Survey of literature reveals that a number of natural and synthetic Preparation of test solutions
polymers such water-based acrylic terpolymer, polyanthranilic acid,
chitosan, carboxymethyl cellulose, Gum Arabic have been stated as The corrosive medium (3.5 wt% NaCl) was prepared using analy-
corrosion mitigators [3–8]. The existence of a large number of free tical grade NaCl and double distilled water. The concentration ranges of
nitrogen atoms in the studied polymer assets their corrosion inhibition each tested inhibitor used in the course of the experiments were

⁎
Corresponding author at: School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China.
E-mail addresses: [email protected], [email protected] (A. Singh).

https://doi.org/10.1016/j.rinp.2019.02.052
Received 28 December 2018; Received in revised form 15 February 2019; Accepted 15 February 2019
Available online 21 February 2019
2211-3797/ © 2019 The Authors. 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/).
A. Singh, et al. Results in Physics 13 (2019) 102116

Fig. 1. Synthetic scheme of inhibitor.

50–400 mg/L. Before the experiments, N2 gas was bubbled for 3 h in for 24 h. The subsequent equation was used to evaluate the corrosion
the corrosive solution in order to remove the oxygen. Then, the solution rate (CR) and inhibition efficiency (η%).
was deoxygenated by purging CO2 gas for 4 h. The specimens were then 8.76 × Δm
immersed into the solution while the CO2 gas-purging at a pressure of CR =
ρAt (1)
6 MPa was maintained to ensure a full saturation throughout the test.
−1
The electrochemical setup was sealed during the experiment. The pH of where CR be the corrosion rate (mmy ), Δm be the weight loss (g), ρ be
the corrosive medium was 4. The gravimetric tests were completed for the density (g cm−3), A be the exposed area (cm2) and t be the time (h),
24 h under static condition. respectively.

CR0 − CR ⎞
General procedure for inhibitor synthesis η% = 100 ⎜⎛ ⎟

⎝ CR ⎠ (2)
The synthesis of inhibitor was completed according to the reported where C0R
and CR are the corrosion rates evaluated from weight loss
literature method [10]. The synthesis scheme is shown in Fig. 1. The 8.76 × Δm
with and without inhibitor, CR = respectively.
developed polymer was characterized by 1H NMR and 13C NMR. The 1H ρAt
NMR and 13CNMR spectrum are included in the Supplementary file. Electrochemical
Autolab workstation was used to carry out all the electrochemical
Spectral analysis of polymer tests by means of a cell assembly with N80 steel as working electrode,
graphite rod as counter electrode and saturated calomel as reference
White color powder; 1H NMR (300 MHz, DMSO‑d6) δ (ppm): Signal electrode. The data obtained was analyzed with the help of Nova and
at 6.742–6.483 ppm is for aromatic protons. Peak at 2.342 represent Zsimpwin softwares. The working electrode altogether with the cell
methylene protons of piperazine. Signal at 4.897 and 3.518 is for assembly was immersed in the test solution for 30 min prior to each test
Ar–CH2–N and Ar–NH2 (primary amine group) groups respectively, to establish a stable potential. The electrochemical impedance spec-
13
C NMR, δ (ppm): Signals at 47.12, 51.62, and 55.28 ppm is for troscopy (EIS) was performed in the range of frequency 100 kHz to
Ar–CH2–Ar, Ar–CH2–N, and N–CH2–CH2–N group, respectively. Peak at 10 mHz at an amplitude of 10 mV. The Potentiodynamic polarization in
131.34 and 149.84 is for aromatic carbons attached to the methylene absence and presence of inhibitor was conducted at the potential range
(CH2) and NH2 groups respectively. of −250 mV to +250 mV vs OCP at a constant scan rate of 1 mV/s.

Corrosion evaluation methods Scanning electrochemical microscopy (SECM)

CHI900C workstation was used to conduct the SECM tests with the
Gravimetric tests three cell electrode assembly. All the tests were performed at room
In gravimetric tests samples were submerged in 3.5% NaCl solution temperature with and without inhibitor. To maintain a stable potential,

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A. Singh, et al. Results in Physics 13 (2019) 102116

the tests were started after an immersion time of 30 min. that at particular temperature the corrosion rate decreases when in-
hibitor concentration increases and increases when temperature in-
Surface analysis (SEM) creases. Roughening of the steel sample reduces the adsorption ability
of the polymer at elevated temperatures [17]. The increase in inhibition
To detect the modifications at the metal surface before and after efficiency with inhibitor concentration is due to the more adsorption
corrosion they were exposed to ZEISS SEM machine. The surface was and surface coverage of metal.
analyzed at various regions of the metal surface using different mag-
nification levels. Prior to the test the N80 steel samples were submerged Activation and thermodynamic studies
in the test solution at room temperature for 24 h. Then the samples Arrhenius process is followed by the corrosion reaction of steel in
were cleaned by double distilled water followed by washing through acidic medium. So, as to obtain the activation energies (Ea) Arrhenius
sodium bicarbonate solution. The samples were then dried and further equation was used as included below.
exposed to the SEM tests. −Ea
log CR = + log λ
2.303RT (6)
DFT study
where R be the gas constant, T be the temperature, Ea signifies the
The inhibitor molecules were optimized using the DFT/ B3LYP basis activation energy and λ be the pre-exponential factor. The activation
set 6-31(d, p) as implemented in Gaussian 09 software [11]. DFT values energy (Ea) was acquired from slope of the Arrhenius plots as presented
related to the highest occupied molecular orbital (EHOMO), lowest un- in Fig. 3a and evaluated values are given in Table 1. The values of Ea are
occupied molecular orbital (ELUMO), and energy gap greater for inhibitor at different concentration. This is due to the for-
(ΔE = ELUMO − EHOMO) were evaluated. The corrosion occurs in aqu- mation of extraordinary energy shield for corrosion reaction to occur.
eous phase, so, it becomes obligatory to determine the quantum che- The enthalpy of activation (ΔH*) and entropy of activation (ΔS*)
mical calculation in aqueous phase in order to mimic the experimental were determined by the equation below.
conditions. Therefore, self-consistent reaction field (SCRF) theory and C R ⎞ ΔS∗ ⎞ ΔH ∗
polarized continuum model (PCM) was used to conduct all DFT calcu- log ⎛ R ⎞ = log ⎛
⎜ ⎟ +⎛ −⎛ ⎞
⎝T ⎠ ⎝ Na h ⎠ ⎝ 2.303R ⎠ ⎝ 2.303RT ⎠ (7)
lations in aqueous phase.
where h be the Planck’s constant and N be the Avogadro number, re-
MD simulations and radial distribution function spectively. The slope and intercept of log (CR /T) vs. 1/T graph (Fig. 3b)
was used to determine the ΔH* and ΔS* values and the evaluated values
All simulations were conducted using BIOVIA Materials Studio® are shown in Table 1.
commercial software [12]. The Fe (1 1 0) surface with a slab size of 5 Å The values of ΔH* are positive both with and without inhibitor
was selected for MD simulation owing to its high stability and its highly suggests that the formation of activated-complex is endothermic in
filled assembly. To ensure wide surface area for the steel and inhibitor nature and this in literature it represents that steel dissolution process is
to interact the tests were conducted in a box of size hindered [18]. The values of ΔS* without inhibitor is negative and with
24.82 × 24.82 × 35.69 Å3 with 9Cl−, 491H2O, 9CO32 − and inhibitor inhibitor is positive. The variation in ΔS* values correspond to the or-
molecules. The simulations were carried out at constant temperature dering and disordering of the inhibitors onto the electrode surface [19].
(303 K), a time step of 1 fs and 2000 PS simulation time to ensure an Table 1 suggests that that variation in the Ea and ΔH* values are in the
equilibrium state. Among the available functions COMPASS force field similar trend but the values of ΔH* are lower than those of Ea. So it can
was chosen to perform the energy minimization and MD calculation be said that the corrosion reaction consists of hydrogen gas evolution
processes [13]. The relation of the inhibitor molecules adsorbed on Fe and is connected with the reduction in overall volume of the reaction
(1 1 0) surface can be established using the subsequent equations [14]. [20].
Einteraction = Etotal − (Esurface + solution + Einhibitor) (3)
Adsorption isotherm
EBinding=− Einteraction (4) The adsorption of the inhibitor molecule on the steel surface is the
key to good protection from corrosion. Adsorption can be determined
where Etotal be the energy of the entire system, the Esurface + solution , be the
using different isotherms to get information’s about the steel-inhibitor
entire energy of Fe (1 1 0) and Einhibitor be the whole energy of inhibitor
interactions. Several isotherms including Langmuir, Temkin, Frumkin
molecules. The radial distribution function is demarcated by Hansen
were studied and the data was plotted using them. Out of all Langmuir
and McDonald as [15,16]:
provided the best fit for the experimental values of mass loss, im-
NA NB
1 1 δ(rij − r) pedance and polarization. The isotherm was plotted between Cinh/θ and
gAB (r ) =
〈ρB 〉local
×
NA
∑∑ 4π r 2 Cinh (Fig. 4) using the equation below and it gave a linear fit with
i∈A j∈B (5)
correlation coefficient (R2) values close to 1 [21–23].
where ρB local represents the particle density of B averaged over all shells
Cinh 1
around particle A. = + Cinh
θ K ads (8)
Results and discussion where Cinh be the concentration of inhibitor, Kads be the equilibrium
constant and θ be the surface coverage. The values of Kads were eval-
Gravimetric measurement uated from the reciprocal of the intercept and are given in Table 2. The
equilibrium constant (Kads) is correlated to the standard free energy of
Corrosion rates and efficiency of inhibition adsorption (ΔG0ads) using the equation below [24].
The calculation of corrosion in the form of mass loss of the sample o
ΔGads = −RT ln(1 × 106K ads) (9)
exposed in the corrosive media at definite time interval was in-
vestigated by gravimetric method. The effects of different concentration where T be the absolute temperature, R be the molar gas constant, and
of inhibitor on the corrosion mitigation property of N80 steel in the 1 × 10–6 be the concentration of water molecules. Generally, physical
temperature range of 303–353 K are shown in Fig. 2. Fig. 2a, b displays adsorption is seen in compounds with
figure of corrosion rate and inhibition efficiency versus inhibitor con- values of ΔG0ads up to −20 kJ mol−1 whereas, values greater than
centration respectively at different temperature. It could be observed −40 kJ mol−1 show chemical adsorption [25,26]. The adsorption of

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A. Singh, et al. Results in Physics 13 (2019) 102116

(a) (b)
CR (mmy-1)

Ș %)
C. (mg/L)
C. (mg/L)
Fig. 2. a. Variation of weight loss with inhibitor concentration in different temperature. 2b. Variation of corrosion rate with inhibitor concentration at different
temperature. 2c. Variation of inhibition efficiency (η %) with inhibitor concentration at different temperature inhibitor. 2d. Variation of inhibition efficiency (η %)
with solution temperature at different concentration of inhibitor.

(a) (b)
log CR/T (mmy-1)
log CR (mmy-1)

[(1/T). 103] / K-1 [(1/T). 103] / K-1

Fig. 3. a. Arrhenius plot for N80 steel corrosion in the absence and presence of different concentrations of inhibitor. 3b. Transition state plot for N80 steel corrosion
in the absence and presence of different concentrations of inhibitor.

Table 1
Activation parameters obtained from weight loss measurements for APDP on
N80 steel in the 303–353 temperature range.
Inhibitor Concentration Ea Ea ΔH* ΔS*
[(C/ș ] (mg/L)

(mg/L) (kJ mol−1) (kJ mol−1) (kJ mol−1)

Blank 0 53.94 49.01 −52.08

APDP 50 89.25 84.76 51.90
100 97.73 93.25 76.60
200 109.08 104.60 109.54
400 121.55 117.09 145.92

the polymer on the steel surface was spontaneous as is evident from the
negative values of ΔG0ads (Table 2). The values of ΔG0ads are in the range
of −25.59 to −28.28 kJ mol−1suggesting that the adsorption followed
the mixed process by both physical and chemical reaction [27,28].

Electrochemical studies
C. (mg/L)
Electrochemical impedance study
Fig. 4. Langmuir’s isotherm plot for adsorption of inhibitor.
Electrochemical study is a common method used to determine the
corrosion rate at the steel/ solution interface. Is gives vital information
about the capacitive and resistive behaviour of the surface which fur-
ther helps to determine the exact mechanism of inhibitor action. The

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A. Singh, et al. Results in Physics 13 (2019) 102116

Table 2 capacitive semi-circle at the higher frequency region (HF). But, adding
Thermodynamic parameters obtained from weight loss measurements for APDP up of different concentration of polymeric inhibitor (ADPD) affects the
on N80 steel in the 303–353 temperature range. shape and increase in the diameter of Nyquist plots is been observed
Inhibitor Temperature Kads ΔG°ads with an inductive loop at the low frequency. The phenomenon of in-
(K) (L/g) (kJ mol−1) crease in the diameter of capacitive loop is due to the increase in the
corrosion resistance property of N80 steel in presence of inhibitor,
APDP 303 55.34 −27.51
which is related to the adsorption of the inhibitor molecule on the N80
313 52.49 −28.28
333 16.45 −26.88 steel surface. The small inductive semi-circle can be endorsed to the
353 6.11 −25.59 layer equilibrium caused due to the corrosion process at the steel sur-
face containing polymer and its reactive products [29].
The figures obtained from the Nyquist plot were extrapolated with
impedance graphs of N80 steel in 3.5% NaCl solution with carbon di- the help of two circuits as shown in Fig. 5b, c. Randle’s circuit was used
oxide in the absence and presence of polymer is shown in Fig. 5a. The for the 3.5% NaCl figure without inhibitor as depicted in Fig. 5b. The
recorded Nyquist plot without inhibitor addition comprises of only one circuit includes Rs as the solution resistance, Rct as the charge transfer

(a)
-Z im (Ÿ cm2)

Z re (Ÿ cm2)

(b)

(c)
Fig. 5. a Nyquist plots for N80 steel in absence and presence of different concentration of inhibitor at 303 K. b, c. Equivalent circuit model used to fit the EIS data. 5d.
Bode (log f vs. log |Z|) and phase angle (log f vs. α◦) plots of impedance plots for N80 steel in absence and presence of different concentration of inhibitor at 303 K.

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A. Singh, et al. Results in Physics 13 (2019) 102116

(d)
-log |Z| (Ÿ cm2)

log i (A/cm2)
log f (Hz) E (mV vs. SCE)
Fig. 6. Potentiodynamic polarization curves for N80 steel absence and presence
(e) of different concentration of inhibitor at 303 K.

Table 4
Polarization parameters for N80 steel in the absence and presence of different
concentrations APDP.
Conc.(mg/L) Tafel data
-Į°

Ecorr Icorr ba −bc η

(V vs. SCE) (μA cm−2) (V d−1) (V d−1) (%)

Blank −0.684 102.7 147 104 –

APDP 50 −0.710 36.3 114 55 65
100 −0.723 17.1 99 52 83
200 −0.741 12.8 102 62 88
400 −0.721 7.2 95 42 93

Cdl = (Yo Rct1 − n )1/ n (11)

As can be observed from the Table 3 the values of Cdl reduces and
log f (Hz) Rct rises with the adding up of inhibitor. This phenomenon is related to
Fig. 5. (continued) the adsorption of inhibitor molecules on the steel surface that form a

Table 3
Electrochemical impedance parameters for N80 steel in absence and presence different concentration of APDP.
Solution Rs Rct n Y° −S Cdl L −α η%

2 2 −1 n 2 2 2
(mg/L) (Ω cm ) (Ω cm ) (Ω s /cm ) (μF cm ) (H cm )

Blank 9.6 128 0.755 298 0.496 50.2 – 32.1 –

APDP 50 8.5 507 0.793 238 0.622 47.5 67 43.3 75
APDP 100 9.2 1038 0.798 163 0.659 44.5 23 58.8 88
APDP 200 9.2 2167 0.844 101 0.734 39.5 79 61.5 94
APDP 400 7.9 2954 0.901 54 0.788 33.1 52 65.4 96

resistance and CPE as the constant phase element. In presence of in- shield and retards the corrosion reaction [35,36]. In absence of in-
hibitor the circuit could not fit appropriately so, inductance (L) was hibitor the value of n is 0.755 which represents a surface with rough-
added in the circuit to get the best fit parameters as shown in Fig. 5c ness while, the value of n increases in presence of inhibitor from 0.793
[30–33]. The CPE and impedance can be related as [34]: to 0.901 suggesting a better and smooth surface. This can be ascribed to
the adsorption of inhibitor on the steel surface that further increases its
ZCPE = Y o−1 (iω)−n (10) homogeneity [37,38].
Fig. 5d shows the Bode and phase angle figures for N80 steel in 3.5%
where Y0 be the magnitude of CPE, ω be the angular frequency, and n
NaCl solution with and without polymer at 303 K. At subordinate fre-
be an exponent to measure heterogeneity [34]. All the obtained para-
quencies the impedance value is enhanced in presence of polymer while
meters after fitting the circuit to the figures are listed in Table 3. The
it is seen to decrease in the absence of polymer. This occurrence can be
equation below was used to evaluate the double layer capacitance (Cdl)
endorsed to the formation of a protective barrier on N80 steel due to
[31]:

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A. Singh, et al. Results in Physics 13 (2019) 102116

(a)

(c)
Fig. 7. (continued)

figure for inhibited surface. This could be due to the adsorption of

polymer on the N80 steel surface that mitigates the corrosion reaction
[40]. The mechanism of corrosion process is not modified as is evident
by the similar shape of the polarization plots with and without polymer
indicating that the mitigation was achieved by blocking the active
centers on the steel surface. All the extracted kinetic parameters from
the polarization plots are shown in Table 4. The corrosion current
density (icorr) is quite enhanced for 3.5% NaCl solution (102.7 A/cm2),
while it is reduced (7.2 A/cm2 at 400 mg/L) in presence of polymer as is
indicated in the table. This phenomenon also supports the formation of
a protective shield by adsorption of polymer on the steel surface that
reduces the corrosion current density. Using the icorr values, inhibition
efficiency was calculated:

i corr(i) ⎞
(b) η% = ⎛1 −
⎜ ⎟ × 100
⎝ i corr ⎠ (12)
Fig. 7. A–d. SECM micrographs of N80 steel surfaces (a) blank 3.5% NaCl (b) at
50 mg/L (c) at 100 mg/L (d) at 200 mg/L (e) at 400 mg/L. where icorr be the current density for 3.5% NaCl and icorr(i) be the cor-
rosion current density for polymer, respectively.
adsorption of the polymer that protects the steel from the corrosive As can be noticed from the Table 4 that both the anodic and
media [39]. The values of the phase angle increases towards the more cathodic Tafel constants (βa, βc) show a slight variation signifying that
negative side from −32.10° (Blank) to −65.40° (at 400 mg/L) as can be the mechanism is intact with adding up of inhibitor. Although this
seen in Fig. 5e. This characteristic is seen for all potential inhibitors and phenomenon refers to the mixed mode of inhibitor action but, since the
it suggests the better inhibitive action of the studies polymer on the N80 Ecorr shift is more towards the negative direction with the addition of
steel surface. inhibitor it can be categorized as mixed type with predominantly
cathodic nature.
Potentiodynamic polarization
The potentiodynamic polarization method was employed to in- Scanning electrochemical microscopy (SECM)
vestigate the kinetics of cathodic and anodic region in 3.5% NaCl with Fig. 7 displays the 3D pictures of AC-SECM with and without dif-
carbon dioxide with and without polymer at 303 K. Fig. 6 includes the ferent concentration of inhibitor [41,42]. The platinum probe of the
obtained polarization plots with prominent anodic and cathodic re- machine recorded higher current for the N80 steel surface without in-
gions. A shift towards the lower current region is observed from the hibitor (surface acting as a conductor) as shown in Fig. 7a (x and y axis)

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A. Singh, et al. Results in Physics 13 (2019) 102116

(d) (e)
Fig. 7. (continued)

[43]. This may be due to the direct contact of the probe with the metal
surface. While, when the probe was brought close to the N80 steel
surface with adsorbed polymer a lower current was observed (surface
acting as insulator) as shown in Fig. 7b–e. This may be due to the
protective film of polymer on the steel surface which blocks the direct
contact of the probe with the metal [43].

Surface morphology analysis (SEM)

The N80 steel surface was exposed to SEM tests and the results are
displayed in Fig. 8a–e. The steel surface without polymer was very
rough, damaged and with visible cracks (Fig. 8a). This took place due to
the attack of aggressive media on the steel directly. The surface of the
steel with polymer covering was smooth and less damaged (Fig. 8b–e).
This can be ascribed to the good inhibitive effect of the polymer Fig. 7. (continued)
forming a protective shield on the steel surface and not allowing the
aggressive solution to break through and attack the steel. phase. As can be observed from the table that the EHOMO in case of
neutral inhibitor is more as compared to protonated one so, the pro-
Density functional theory (DFT) analyses tonated form has less electron donation tendency than the neutral form.
The ELUMO values for protonated inhibitor are more positive than the
Global reactivity neutral inhibitor therefore, neutral form has lower ability to accept
The optimized neutral and protonated forms of the studied in- electron than the protonated form. Energy gap (ΔE) is one of the im-
hibitors along with the highest occupied molecular orbital (HOMO), portant parameter to define the adsorption tendency of the inhibitor
and the lowest unoccupied molecular orbital (LUMO) are represented in molecules on the steel surface. Now, as can be seen that the value of ΔE
Fig. 9. EHOMO signifies the electron donating ability of the inhibitor as is lower in case of neutral form of inhibitor that suggests the greater
per the frontier orbital theory. So, higher the EHOMO values, better is the ability to adsorb on the steel surface in the neutral form. The ability of
electron donation to the suitable acceptor sites. On the other hand, the inhibitor to adsorb increases with decrease in the energy gap.
ELUMO signifies the electron accepting ability of the inhibitor molecules. According to Fig. 9, the distribution of HOMO and LUMO regions in
This implies that lower the value of ELUMO, more available tendency to neutral and protonated inhibitor forms are opposite to each other in
accept electrons [44,45]. Table 5 shows the computed parameters for other words the neutral HOMO regions are almost similar to protonated
the neutral as well as protonated form of the inhibitor in the aqueous

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A. Singh, et al. Results in Physics 13 (2019) 102116

(a) (b)

(c) (d)

(e)

Fig. 8. a–d. SEM micrographs of N80 steel surfaces (a) blank 3.5% NaCl (b) at 50 mg/L (c) at 100 mg/L (d) at 200 mg/L (e) at 400 mg/L.

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A. Singh, et al. Results in Physics 13 (2019) 102116

(b)
(a)

(c) (d)

(e) (f)
Fig. 9. Optimized geometries (a) Neutral (b) Protonated. 9c. d. Frontier molecular orbital’s of neutral inhibitor (c) HOMO (d) LUMO. 9e. f: Frontier molecular
orbital’s of protonated (e) HOMO (f) LUMO.

Table 5
Calculated quantum chemical parameters of ADPD.
Inhibitors EHOMO ELUMO ΔE
(eV) (eV) (eV)

ADPD −4.787 0.0527 4.839

ADPD+ −4.875 0.779 5.654

LUMO and neutral LUMO regions are almost similar to protonated

HOMO. In both neutral and protonated inhibitor forms HOMO and
LUMO are dispersed on the NH2 and phenyl groups.

MD simulations and radial distribution function

Despite many studies on CO2 corrosion have been conducted, a

slight exploration has been done to the computational simulation of the
corrosion inhibition process. The inhibitor-steel interactions are be-
lieved to be affected at the molecular levels. So, the molecular dynamic
simulations have been computed on neutral and protonated forms of
the inhibitor molecule in presence of a simulated electrolyte aiming to
mimic the experimental conditions as much as possible. Herein, an
important difference that sets our model more suitable is the inclusion
of carbonate into the simulated solution which makes the estimation of
the interactions between tested inhibitor and steel surface more in-
Fig. 10. a. Side and top views of the adsorption of the neutral inhibitors on the
formative. All the computations were run till the structures reached an
Fe (1 1 0) surface in solution. b. Side and top views of the adsorption of the
equilibrium, then, the interaction energies were estimated by calcu- protonated inhibitors on the Fe (1 1 0) surface in solution.
lating the single point energies of all system constituents [46]. The
obtained equilibrium configurations of neutral and protonated forms of
inhibitor molecule on the Fe (1 1 0) surface in solvent are shown in
Fig. 10.

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A. Singh, et al. Results in Physics 13 (2019) 102116

2.0 interactions [50].

Fe-Neutral Fe-Protonated The RDFs results are graphically represented in the Fig. 11, from
which we can easily observe that the first prominent peak for both
forms are observed, situated at distances less than 3.5 Å. These results
1.5 are important and an interesting point that emerges from this data is
2.9
that both inhibitor forms seem to be effective in inhibition of steel
corrosion.
g(r)

1.0 3.3
Mechanism of polymer interaction

The mechanism of adsorption of polymer onto the steel surface

0.5 consists of three adsorption modes in presence of carbonic acid. First
mode of adsorption includes chemical bond formation in case of neutral
form of inhibitor. This adsorption consists of sharing of extra pair of
electrons present on the O, N, to the empty d- orbital of iron and also
0.0 donor-acceptor interactions between π- electrons of benzene ring and
0 2 4 6 8 10 12 vacant d-orbitals of iron. The second mode suggests that, in acidic
X (Angstrom) medium steel surface bears positive charge [51,52], thus, it becomes
difficult for protonated inhibitor forms to adsorb on the steel surface
Fig. 11. RDFs of neutral and protonated forms of tested corrosion inhibitors
because of the electrostatic repulsion. However, the degree of hydration
adsorbed on the Fe (1 1 0) surface in solution.
of chloride ions are small, so they can easily convey additional negative
charges towards the interface and favor more adsorption of the posi-
tively charged molecules through electrostatic exchanges between the
positively charged molecules and negatively charged steel surface. The
third mode includes back-donation of electrons from occupied iron
orbitals to the vacant anti-bonding orbital’s present in the inhibitor
molecules. All the three adsorption modes are shown in Fig. 12.

Conclusions

(1) The developed polymer derivative considerably enhanced the cor-

rosion mitigation effectiveness of N80 steel in 3.5% NaCl saturated
with carbon dioxide.
(2) Potentiodynamic polarization measurement established that ADPD
molecules successfully.
(3) reduce corrosion reaction and characterized into mixed type cate-
gory with dominantly cathodic.
(4) The adsorption of inhibitor followed Langmuir isotherm prototype.
Fig. 12. Mechanism of corrosion inhibition. (5) SEM and SECM pictures suggests the adsorption of polymer onto
the steel surface.
(6) DFT computation reveals that neutral inhibitor has more electron
As can be seen from the results in Fig. 10 that both forms of the
donation ability than the protonated form.
polymer adsorbed on the surface of Fe (1 1 0) with a parallel mode.
(7) MD outcomes suggests that neutral form of inhibitor has more
Interestingly, the whole inhibitor molecule adsorbed on the steel sur-
binding energy than protonated form.
face, indicating that there are more adsorption centers. It is believed
that this parallel disposition can enhance the inhibitive effects of the
said compound, this is because parallel adsorption can ensure more Declaration of interest
surface coverage, thus prevent steel surface from corrosion. The binding
(interaction) energies of inhibitor achieved under equilibrium state for None.
neutral and protonated forms are 675.760 kJ/mol (−675.760 kJ/mol)
and 601.088 kJ/mol (−601.088 kJ/mol) respectively. The results show
that the collaboration between inhibitor molecule and steel is robust Acknowledgements
and steady in neutral form than that in protonated form [47]. This can
be endorsed to the strong solvation of polymer in the water solvent Dr. Ambrish Singh is grateful for the Sichuan 1000 Talent Fund and
which opposes adsorption [48]. The adsorption takes place through financial assistance provided by the open fund of southwest petroleum
more than one centers as is evident from the magnitude of the binding university (No. X151518KCL30).
energies for the tested inhibitor molecule [48,49].
To allow for further insights into the extent of adsorption in both Author Contributions
inhibitor forms, we computed a RDF as a significant means for struc-
tural depiction. Here, the total radial dissemination function was The concept and design was prepared by Dr. Ambrish Singh. The
evaluated for both forms using MD computations. Whether the inter- experiments were carried out by Dr. Ashish Kumar, and Neetesh Soni.
actions of an inhibitor with iron atoms are meaningful can be judged by The characterizations were done by Yu Deyuan. The rewriting of DFT
comparison of the first prominent peaks in the RDF curves. The peak of computations was done by Dr. Ashish Kumar and Dr. Ambrish Singh.
1–3.5 Å indicates a smaller bond length that is correlated to chemi-
Further, Dr. Ambrish Singh interpreted and prepared the final draft of
sorption, whereas, peaks longer than 3.5 Å indicates the physical
the paper.

11
A. Singh, et al. Results in Physics 13 (2019) 102116

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