Corrosion Science 208 (2022) 110623

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Integrating experiments, DFT and characterization for comprehensive

corrosion inhibition studies – A case for cinnamaldehyde as an excellent
green inhibitor for steels in acidic media
Dharmendr Kumar *, Venkata Muralidhar K , Vinay Jain , Beena Rai
Physical Sciences Research Area, TCS Research, Tata Consultancy Services Ltd., Hadapsar, Pune 411013, India

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

Keywords: We have investigated the corrosion inhibition mechanisms of TCA for steel in 1 M HCl. Gravimetric, electro­
Steel chemical and AFM studies confirm TCA’s high inhibition efficiencies. Partial desorption is observed in staged
Acid inhibition dilution studies. DFT computations indicate that the geometrically flat structure, π-electrons and unsaturated
Density functional theory
bonds lead to strong TCA-Fe interactions. However, interaction strength weakens with increasing coverage
Adsorption
Interfaces
indicating possible lateral repulsions. A holistic picture of inhibition mechanism comprising a strong, but
inhomogeneous chemisorbed monolayer on steel, coupled with weakly physisorbed layers is proposed.

1. Introduction CI’s for steel, having corrosion inhibition efficiencies exceeding 90 %

Acid well stimulation is an extensively used technique for enhancing
productivity of oil & gas wells. Generally, 5–28 % HCl is forced under
high pressures to dissolve the rocks in order to enlarge the existing flow
channels and open new ones to the wellbore. Tubular materials & other
equipment exposed to HCl can undergo severe corrosion under such
conditions. A variety of organic molecules including alcohols, alde­
hydes, amines, amides, thiourea derivatives, natural extracts, quinolone
derivatives, triazoles, pyridines etc. play a critical role for reducing the
severity of corrosion in these applications [1–4].
However, most of these corrosion inhibitors (CI’s) are found to be
toxic and non-biodegradable in nature [5]. Finšgar and Jackson [6] in
their review paper on corrosion inhibitors for steels in acidic media
mention that “Most of the developed corrosion inhibitors or their formula­
tions no longer meet the Oslo Paris Commission requirements because their
primary active ingredients may be harmful if discharged into the environ­
ment.” In the wake of increasingly stringent environmental norms,
especially for operations in the North Sea region, there is a need for
screening, design and deployment of more environmentally friendly, yet
efficient inhibitors.
Acetylenic alcohols, such as propargyl alcohol, although highly
efficient in their performance, even at high temperatures, tend to be
extremely toxic. Trans-cinnamaldehyde (TCA) (Fig. 1), on the contrary,
is a much greener alternative and has been known to be one of the best
[7]. It is found naturally in the bark of cinnamon trees and other species
of the genus Cinnamomum like camphor and cassia [8]. TCA is non-toxic
in nature and is used extensively in food and medicines [9]. Several
papers and patents have been published on TCA elucidating its efficacy
as CI for steels in acidic media [10–16]. Despite several studies reported
on TCA as a promising CI, the molecular level understanding of TCA
interaction with the steel surface is limited. This is imperative for
designing newer, more efficient and greener alternatives as CI’s for
steels.
In this work, we report the use of a multipronged experimental and
density functional theory (DFT) computational approach, coupled with
analyses of literature reported time-of flight secondary ion mass spec­
troscopy (ToF-SIMS) data, to comprehensively elucidate the underlying
mechanisms of TCA inhibition of steel corrosion at room temperature.
For instance, on the experimental front, apart from the conventional
weight loss, polarization, EIS techniques, we have performed staged
dilution studies in order to understand whether the interaction is via
physisorption or chemisorption. Similarly, on the DFT front, instead of
merely relying on simple quantum chemical descriptors, we have per­
formed detailed adsorption and coverage studies in order to bring out
the likely interaction and orientation of TCA on Fe-surface, and also, the
possibility (or lack) of formation of an adherent and cohesive protective
film. Besides, we are able to harmonize the experimental and compu­
tational results in order to establish the nature of the interaction – i.e.

* Corresponding author.
E-mail address: dharmendr.9@tcs.com (D. Kumar).

https://doi.org/10.1016/j.corsci.2022.110623
Received 12 May 2022; Received in revised form 24 August 2022; Accepted 29 August 2022
Available online 31 August 2022
0010-938X/© 2022 Elsevier Ltd. All rights reserved.
D. Kumar et al.
Fig. 1. Chemical structure of trans-cinnamaldehyde.
physisorption/chemisorption/physi+chemisorption.
We believe that such comprehensive studies are the need of the hour
to help unriddle scientific and industrial challenges pertaining to
corrosion inhibition.
2. Experimental studies
Corrosion inhibition characteristics of TCA were evaluated using
weight-loss tests, potentiodynamic polarization, electrochemical
impedance spectroscopy (EIS), potential for zero charge measurements
(PZC) and chronocoulometry on mild steel in acidic medium. In addi­
tion, staged dilution tests were conducted to understand the nature of
adsorption of TCA. All the tests were conducted at ~27 ◦ C in ambient
atmosphere. Ametek PARSTAT 1000 AC/DC Potentiostat was employed
for electrochemical tests on 1 cm2 area of mild steel using Ametek
K0235 flat cell with Pt mesh counter electrode, Ag/AgCl with Vycorr®
tip as reference electrode in 300 ml electrolyte. In addition, the influ­
ence of inhibitor on the roughness of the mild steel surface was studied,
using Atomic Force Microscope (AFM) from Asylum Research with
Olympus IX51 optical microscope and stand.
2.1. Materials
TCA (>99 %, CAS: 14371–10–9), procured from Sigma-Aldrich was
used as-received without any changes. Various concentrations of in­
hibitor were prepared from a stock solution of TCA in 99.9 % ethanol.
1 M HCl was used as blank test solution, serving as a reference for tests
with various concentrations of inhibitor. Mild steel IS2062 with the
composition as mentioned in Table 1, was used to evaluate the inhibitor.
Mild steel coupons were abraded/polished on emery papers of grits 80,
150, 240, 400 and 600. After polishing, the coupons were cleaned with
acetone, wrapped appropriately in paper and stored in a desiccator until
further use in electrochemical tests.
2.2. Weight-loss tests
Weight-loss tests were carried out using 100 ml 1 M HCl containing
various concentrations of TCA such as 100, 200, 500 and 1000 ppm. The
metal coupons were dipped in the test solution for 2 h for the study.
After the weight-loss tests, the samples were carefully removed from test
solutions and washed with distilled water, followed by air drying. The
corresponding weights of the coupons were measured before and after
the test to know the weight loss from each coupon.
2.3. Potentiodynamic polarization studies
Potentiodynamic polarization studies were carried out by sweeping
the potential at 1 mV/s scan rate between − 250 mV and + 250 mV
with respect to Open Circuit Potential (OCP).
Table 1
Composition of IS2062 mild steel used for experimental study.
Element C Si Mn P S
wt % 0.044 0.04 1.15 0.028 0.025
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Corrosion Science 208 (2022) 110623
2.4. Electrochemical impedance spectroscopy
EIS studies were carried out at OCP with a perturbation voltage of
10 mV between the frequencies 105 and 10− 1 Hz.
2.5. Potential for zero charge measurement
The potential for zero charge (PZC) was evaluated for each concen­
tration, from capacitance versus potential measurements, taken at an
alternating current of frequency 100 Hz, using Mott-Schottky module of
VersaStudio software of the same instrument as mentioned above.
2.6. Chronocoulometry
The chronocoulometry technique was carried out for each concen­
tration of TCA in 2 steps. In the first step, the potential was maintained at
+ 250 mV vs OCP for 100 ms, while in the second step, the potential was
maintained at − 250 mV vs OCP for 100 ms, with no intermediate delay
between the steps. The charge flow at the interface could be captured
using this technique for various concentrations of TCA including that for
the blank solution, at anodic/cathodic potentials.
2.7. Staged dilution tests
Initially, the weight-loss test was carried out using 100 ml 1 M HCl
solution containing 500 ppm TCA for 2 hrs. After 2 hrs, the 500 ppm
solution was removed without disturbing the coupon. And then, a
100 ml 1 M HCl solution with either of 0 and 50 ppm TCA was intro­
duced into the same beaker.
2.8. AFM studies
Roughness measurements were carried out in tapping or intermittent
mode using silicon tip. Measurements were carried out after tuning of
the tip, which resulted in the characteristic frequency of ~153.9 kHz.
3. Computational methodology
The TCA molecule created in Avogadro-1.2.0 [17] molecular editor
software was fully relaxed by keeping it in a 30×30×30 Bohr3 box using
DFT. For calculation of frontier molecular orbital energies, the TCA
molecule was optimized using NWChem 6.8 [18] computational
chemistry software. B3LYP exchange-correlation functional and the
6–311 + +G** basis set was used during minimization. The TCA ge­
ometry was deemed to be optimized if the force on each atom fell below
0.025 eV/Å.
Plane-Wave, spin-polarized DFT as implemented in the PWscf code
of Quantum Espresso-6.20 [19] was employed to investigate the
adsorption mechanism of TCA on Fe (001) surface. Per­
dew–Burke–Ernzerhoff (PBE) [20] parameterization of generalized
gradient approximation (GGA) was used for the exchange and correla­
tion potential. A kinetic energy cut off of 35 Ry and charge density cut
off of 300 Ry was used for all calculations. The van der Waals in­
teractions were accounted for using Grimme’s semi empirical correla­
tion (DFT-D3) [21] in-built in PWscf. The Fe unit cell was optimized and
a 5 × 4 supercell containing 5-layers was prepared and fully optimized
until the force on each atom fell below 0.0025 eV/Å. Owing to the large
system sizes, Brillouin zone integrations were limited to the gamma
point. More information on this section can be found in Kumar et al.
[22].
Cr Mo Ni Cu V Fe
0.051 0.001 0.001 0.052 0.011 Bal.
D. Kumar et al. Corrosion Science 208 (2022) 110623

Table 2
Results of weight-loss experiments.
Conc. (ppm) Corrosion Rate (cm/y) Inhibition Efficiency ( %)

Blank 1.24 –
100 0.37 70
200 0.29 77
500 0.13 89
1000 0.11 91

Fig. 3. Polarization curves for various concentrations of TCA.

Table 3
Results of potentiodynamic polarization experiments.
Conc. Ecorr (mV) Icorr (mA/ βc (mV/ βa (mV/ IE ( %)
(ppm) cm2) dec) dec)

Blank -473.755 1.898 193.123 152.761 –

200 -454.663 0.0192 111.627 52.506 98.99
500 -481.579 0.0109 127.397 130.9 99.43
1000 -430.11 0.0120 193.792 76.563 99.37
Fig. 2. Temkin adsorption isotherm plot of TCA on steel surface in 1 M HCl.

ΔGads = -RT ln(55⋅5 Kads)

Different initial geometries of TCA were created on Fe (001) surface
in order to identify the most likely orientation of TCA on steel surface in
actual conditions. The molecular adsorption was carried out only on one
side of the Fe (001) surface and a vacuum of 26 Å was introduced be­
tween the slabs to avoid self-interaction.
Interaction energies between TCA and the Fe (001) surface were
calculated using the following correlation:
ΔEint = (Ecomplex - Eslab - N*Emol)/N
where Ecomplex, Eslab and Emol are the total energies of the TCA-Fe (001)
complex, Fe (001) slab system and the TCA molecule respectively, while
N is the number of TCA molecules.
4. Results and discussions
4.1. Experimental results
4.1.1. Weight-loss tests
Weight-loss tests were carried out to calculate the inhibition effi­
ciency (IE) at various concentrations of TCA, according to the following
formula:
[ ]
IE(%) = 1 −
corrosion rate with inhibitor
x 100
corrosion rate without inhibitor
From Table 2, it can be said that inhibition efficiency increases with
increasing concentration of TCA. During the weight loss tests, it has been
observed that the rapidity of bubble evolution decreased with increasing
concentration. This relates to the hydrogen evolution reaction at the
cathodic sites.
Based on these results, a plot of θ vs ln C (where C is the inhibitor
concentration and θ is the surface coverage or IE/100) was plotted as
shown in Fig. 2. The plot indicates that the adsorption of TCA on mild
steel in HCl follows the Temkin isotherm:
exp (− 2αθ) = KadsC
where Kads represents the equilibrium constant for adsorption.
From the obtained Kads value, the free energy of adsorption, ΔGads,
was calculated using the following equation:
Where R is the universal gas constant, and T is the absolute temperature
in Kelvin.
From the above expressions, we obtained a ΔGads value of
− 23.53 kJ/mol. The negative value indicates spontaneous adsorption.
Generally, values > − 20 kJ/mol are considered to represent a relatively
weaker physisorption of molecules on the metal surface, while values
< − 40 kJ/mol represent stronger chemisorbing molecules arising due to
sharing or transfer of electrons between the molecule and the metal
surface [23]. Based on the intermediate value of ΔGads so obtained, it
appears that interaction of TCA on mild steel is via both physical and
chemisorption. It must be pointed out that the inherent assumption for
computation of ΔGads that θ = IE/100 may not be necessarily valid as
shown by Walczak et al [24]. Consequently, the accuracy of ΔGads so
obtained is doubtful. Therefore, ΔGads may not be used as a sole and/or
reliable criterion for distinguishing between chemisorption and phys­
isorption, as has been discussed recently by Kokalj [25].
4.1.2. Potentiodynamic polarization
The potentiodynamic polarization experiments were carried out to
find the corrosion currents in various concentrations of the inhibitor,
which are equivalent to the corrosion rates. The resultant polarization
plots are given in Fig. 3 and were analyzed using VersaStudio to arrive at
corrosion currents with the help of Tafel regions. The respective results
shown in Table 3 confirm excellent inhibition efficiencies with the in­
hibitor at all the concentrations tested. The corrosion inhibition effi­
ciency at a particular concentration of inhibitor is calculated using the
below expression.
[
Icorr with inhibitor
]
IE(%) = 1 −
Icorr without inhibitor
x 100
The corrosion currents derived from polarization plots show that the
presence of inhibitor reduces the corrosion of mild steel by at least a
hundred times in 1 M HCl. There is a slight change in the cathodic
branch from 200 ppm to 500 ppm while it is more dominant in
1000 ppm. Similarly, such a change could be seen in the anodic branch
as well, suggesting the change in inhibition mechanism. The trends of
polarization curves suggest that, although 200 ppm is sufficient for good
inhibition, higher concentrations offer better shielding, evident from

3
D. Kumar et al. Corrosion Science 208 (2022) 110623

Table 4
EIS results for various concentrations of the inhibitor.
Conc. (ppm) Rs (Ω.cm2) Q-Y0 (x10− 4) ( (S-sec)n.cm2) Q-n Rct (Ω.cm2) L (H.cm2) RL (Ω.cm2) IE ( %) Cdl (µF/cm2)

Blank 3.726 6.913 0.897 29.62 441

200 3.472 0.615 0.858 227.5 8 11 86.98 30.3
500 3.512 0.263 0.772 795 11 25 96.27 8.4
1000 2.771 0.314 0.688 1230 35 65 97.59 7.17

Nyquist plots as in Fig. 4(a), i.e. interfacial behavior with the blank and
with the inhibitor respectively. Charge transfer resistance, Rct, was
considered to evaluate the inhibition efficiencies with various concen­
trations of inhibitor according to the following expression.
[ ]
Rct without inhibitor
IE(%) = 1 − x 100
Rct with inhibitor
The impedance due to constant phase element, Q is evaluated using
the following equation [26]:
1
ZQ =
Yo (jω)n
The double layer capacitance (pseudo-capacitance), Cdl, has been
calculated using the following expression [27]:
√ ̅̅̅̅̅̅̅̅̅̅
n
QRct
Cdl =
Rct
The Nyquist plots show a slight change in their appearance with
increasing concentrations of the inhibitor. The size of the inductive
portion in Nyquist plots with inhibitor is reducing with increasing in­
hibitor concentrations (inset in Fig. 4(a)), suggesting that the activity of
adsorption and desorption is decreasing as the concentration is
increased. The increasing Rct values suggest an increasing inhibition,
which is evident at 1000 ppm due to formation of a thick and strong
layer. This further supports the observations from polarization curves.
Also, there is a decrease in double layer capacitance, hinting better
protection or increased double layer thickness.
The Bode plot (Fig. 4(b)) shows increasing impedance with
increasing concentration of TCA, which is a sign of increasing protec­
tion. In addition, peaks of the phase angle curves are moving to higher
frequencies with concentration. For each of the concentrations 200 and
500 ppm, a single peak in phase angle curves is seen at intermediate
frequencies suggesting an incomplete protection [28]. However, with
1000 ppm concentration, two peaks (at 63.10 Hz and 3162.28 Hz) are
seen in phase angle response – the high frequency peak suggesting re­
gions with good protection while the low frequency peak (closer to the
peak of blank at 39.81 Hz) hinting the poorly protected regions i.e.
incomplete coverage. This is in line with the behavior of TCA inferred
and described in other sections i.e. staged dilution tests and the
adsorption isotherm.

4.1.4. Potential for zero charge and surface charge

Fig. 4. (a) Nyquist and (b) Bode plots showing the impedance response of mild
steel in various concentrations of TCA.
anodic branches of 500 ppm and 1000 ppm. The polarization curves
show that TCA is a mixed inhibitor for this steel.
4.1.3. Electrochemical impedance spectroscopy
Electrochemical impedance spectroscopy was carried out to under­
stand the corrosion inhibition by the inhibitor and respective inhibition
efficiencies were calculated and presented in Table 4. The circuits R(QR)
and R(Q(R(LR))) were used in ZSimpWin software for analyzing the
Fig. 5 shows the plots of absolute capacitance |C| versus potential,
obtained using Mott-Schottky test module of VersaStudio software by
scanning over various potentials at an alternating frequency of 100 Hz.
It can be inferred from Fig. 5(b) that the capacitance at PZC shows a
larger decrease from 200 ppm to 500 ppm while the decrease from
500 ppm to 1000 ppm is not much. From the polarization studies, it is
evident that there is considerable improvement in protection as we in­
crease concentration from 200 ppm to 500 ppm, while no such
improvement could be seen from 500 ppm to 1000 ppm. This implies
that 500 ppm concentration provides reasonable monolayer coverage
along with appropriate multilayer masking of uncovered empty spaces,
and is close to saturation point. A decrease in capacitance hints an in­
crease in the double layer thickness. This further supports the inference
drawn from anodic curves of polarization plots, that 200 ppm is not
sufficient for better shielding.

4
D. Kumar et al. Corrosion Science 208 (2022) 110623

Fig. 5. Absolute Capacitance |C| vs Potential plots from Mott-Schottky module, revealing PZC for a) blank test solution and b) 1 M HCl with TCA.

adsorption was purely physisorption or chemisorption or a combination

of both. The hypothesis was that the corrosion rates will (not) change
significantly with lowering of inhibition concentration if TCA physisorbs
(chemisorbs) on the steel surface [29], while intermediate values would
obviously imply a combination of both physisorption and
chemisorption.
Three such experiments, each comprising of two stages each of 2 h
duration were performed. Table 5 indicates that with dilution, the
corrosion rate increases, implying that there is desorption to some
extent. The weight loss for the specimen in blank 1 M HCl solution
without any inhibitor is about 1.28 cm/y. However, as the Exp. No. 3 in
Table 5 suggests, after 2 h of such a test, the corrosion rate was merely
0.39 cm/y clearly indicating a combination of physisorption and
chemisorption. Such staged dilution tests, apart from throwing light into
the mechanism of adsorption, also can provide insights into the effects of
Fig. 6. Chronocoulometry results showing charge vs time plot.
varying inhibitor dosage, which is commonly seen in actual field con­
ditions. However, deeper studies are required to know the critical con­
Table 5 centration for sufficient first layer coverage and partitioning effects, that
Results of staged dilution tests. can provide precise control over inhibitor dosage.
Exp. Time per Inhibitor Inhibitor Average
No. stage in Concentration in Concentration in Corrosion 4.1.7. Atomic force microscopy
the Set 1st stage (ppm) 2nd stage (ppm) Rate (cm/y) Fig. 7(a)-(c) show the roughness plots in both 2D and 3D obtained
(hrs) from AFM studies and Table 6 further supports the above findings and
0 2 0 0 1.28 inhibition characteristics of TCA. AFM results show that there is an in­
1 2 500 500 0.13 crease in the roughness of the surface due to the action of 1 M HCl. The
2 2 500 50 0.17 roughness of the sample is almost retained in the case of inhibitor
3 2 500 0 0.40
(1000 ppm) along with 1 M HCl proving the efficient protection by TCA.

4.1.5. Chronocoulometry 4.2. Computational results

The charge versus time plot (Fig. 6) obtained from chronocoulometry
technique, clearly shows that with increasing concentration of TCA, the
magnitude of charge at the end of each step decreases. The amount of
charge flow at the interface due to anodic potential seems to match the
amount of reverse charge flow at the interface due to cathodic potential,
for 200 ppm and 1000 ppm cases. However, with blank solution and
500 ppm TCA, the reverse charge flow values due to cathodic potential
are higher than the charge flow values due to anodic potential. The
amount of charge flow (area under the curve) at the interface arrested
increased with increase in inhibitor concentration.
4.1.6. Staged dilution tests
The ambiguity in the values of ΔGads from the weight loss tests
necessitated staged dilution studies, in order to further understand if the
The DFT optimized structural parameters for TCA (Fig. 8(a)) were
found to match well with gas electron diffraction data of Egawa et al.
[30] (cf. Table S1, Supplementary Information). It is evident from Fig. 8
(b) and (c) that both the highest occupied molecular orbital (HOMO)
and lowest unoccupied molecular orbital (LUMO) are evenly distributed
on the entire TCA molecule hinting towards a flat adsorption geometry.
The computed HOMO, LUMO and HOMO-LUMO gap values using
NWChem 6.8 (Plane-wave/PBE) are − 6.96 eV (− 5.46 eV), − 2.52 eV
(− 2.96 eV) and 4.44 eV (2.50 eV), respectively. However, not much can
be concluded from these plots and values about the nature of the TCA-Fe
interactions per se and therefore, we resorted to explicit adsorption
studies.
Two stable adsorption geometries – flat and vertical, were identified

5
D. Kumar et al. Corrosion Science 208 (2022) 110623

Fig. 7. 2D & 3D Roughness profiles for 5 sq.μm area for sample that is (a) un-corroded/polished, (b) corroded with 1 M HCl without inhibitor, and (c) corroded with
1 M HCl in the presence of 1000 ppm inhibitor. Note – scales are different for (a), (b) and (c).

6
D. Kumar et al.
Table 6
Roughness values from AFM Analysis.
Sample Average Roughness, Ra (nm) RMS Roughness, Rq (nm)
Uncorroded 29.095 34.734
Blank 88.771 117.808
Inhibited 32.035 38.729
in the explicit DFT adsorption studies and are shown in Fig. 9 along with
their corresponding adsorption energies. The top panel shows the opti­
mized DFT structures while the bottom panel shows the dispersion-
corrected DFT-D3 structures. Two things can be inferred from these
results:
a. The magnitudes of interaction energy values are significantly higher
for the flat configuration.
b. With dispersion corrections (DFT-D3), the interaction strengthens
drastically for the flat configuration (ΔEint = − 1.96 eV), while not so
much for the vertical configuration (ΔEint = − 0.23 eV).
These differences in the Eint values between the flat and vertical
configurations can be explained by analyzing the optimized structures.
At the outset, it is evident that the geometrically flat structure of TCA,
coupled with the presence of π-electrons and unsaturated bonds (C– –C
and C– O) in its structure providing a large number of electrons to the
– Δρ(r)
partially filled d-orbitals of Fe, facilitate the strong adsorption of TCA on
Fe surface. Besides, the strong interactions induce the sp2 to sp3 rehy­
bridization of the electronic structure of the ring C-atoms as evidenced
by the shifting of all the attached H-atoms above the ring plane. [31].
Without DFT-D3, the flat adsorption geometry shows formation of
several Fe-C/O bonds. The average Fe—C (dFe—C) bond length is ~
2.16 Å which is close to the sum of the covalent radii of Fe and C i.e. rcv
= 1.32 (rFe) + 0.76 (rC) = 2.08 Å [32]. Thus, there is possibly strong
coordinate covalent bonding between surface Fe and C-atoms of TCA.
The coordinate covalent bond formation is also possibly present be­
tween Fe and O-atoms in both flat and vertical adsorption geometries.
The computed Fe—O bond lengths (1.98 Å, 1.92 Å) are close to the sum
of the covalent radii of Fe and O (rcv = 1.32 (rFe) + 0.66 (rO) = 1.98 Å).
[32,33].
With dispersion corrections (DFT-D3), the TCA molecule in flat
configuration comes further close to the Fe (001) surface, thus reducing
the average Fe-C/O bond lengths besides facilitating the formation of
Fig. 8. (a) Optimized molecular structure, (b) HOMO and (c) LUMO plots of TCA (Atom legends: red = O, yellow = C and aqua = H).
7
Corrosion Science 208 (2022) 110623
additional Fe—C bonds. This explains the significant strengthening in
Eint for this configuration with inclusion of DFT-D3. On the contrary, for
the vertical configuration, there continues to be only one Fe-O bond
between the Fe (001) surface and the TCA molecule, thus explaining its
weaker Eint values.
The reduced distances notwithstanding, it is evident that the spatial
configurations for both flat and vertical adsorption geometries remained
almost unaffected due to dispersion corrections, which is consistent with
similar findings for other molecules by Bedolla et al. [34] and Kumar
et al. [22].
It must be mentioned that computations for adsorption of protonated
TCA (likely under acidic conditions), also indicate similar optimized
structures implying that the adsorption mechanism essentially remains
same as that of the neutral molecule (Cf. Supplementary Information
(section B)).
(Blue and red regions indicate charge depletion and accumulation
respectively). Iso-surface value: ± 0.003 eV/Å3.
In order to further understand the nature of the surface-adsorbate
interactions, the electron density difference and projected density of
states (PDOS) have been plotted in Fig. 10 for the DFT-D3 optimized
geometries.
The computation of the electron density difference (Δρ) was based
on the following expression:
= ρtotal (r)– ρsurface (r) − ρinhibitor(r)
where ρtotal, ρsurface and ρinhibitor represent electron densities of Fe-TCA
complex, the isolated Fe (001) surface and the isolated TCA molecule,
respectively.
The blue and red regions in the electron density difference plots
(upper panel) show charge depletion and accumulation respectively. On
comparing the flat and vertical adsorption configurations, it is evident
that the former shows extensive charge localization between the mole­
cule and the surface, possibly, due to the strong interaction of the
delocalized π-electrons of the aromatic ring as well as the unsaturated
C–– C/C– – O bonds in TCA with the surface Fe-atoms. Whereas, in case of
the latter, the charge localization is mostly confined to the interacting
surface Fe and O-atoms of the TCA molecule thus indicating compara­
tively weaker interactions.
Fig. 10 (lower panels) show the PDOS of TCA/Fe (001) system after
the interactions. Only bond-forming atoms were considered for the
plots. A reduced broadening of 0.1 eV was used for these PDOS calcu­
lations. In the flat adsorption geometry, almost all the C and O atoms are
D. Kumar et al.
Fig. 9. Optimized adsorption geometries of TCA on Fe (001) surface along with their adsorption energies. Upper panel: DFT and Bottom Panel: DFT-D3 results. All
indicated bond-lengths are in Å units.
making chemical bonds with Fe (001) surface while only the O-atom is
making chemical bond in case of the vertical adsorption geometry. After
adsorption the molecular peaks broaden because of hybridization of the
Fe-3d orbitals with the 2p-orbitals of the interacting C and O-atoms in
the molecule. In case of the flat adsorption geometry, the spread is in the
entire range of Fe-3d states. However, for the vertical adsorption ge­
ometry, the spread is not continuous suggesting that a flat orientation of
TCA on the Fe-surface is more favored electronically.
Bader charges (Table 7) were calculated for the DFT-D3 optimized
flat configuration using the algorithm developed by Henkelman’s group
[35] by generating charge densities with the projector-augmented-wave
(PAW) potentials [36] and 800 Ry kinetic energy cutoff for charge
density. As evident from Table 7, there is an overall charge transfer from
the metal surface to the molecule. The C16 atom of carbonyl (C– – O)
group receives the maximum electrons i.e., − 0.765e while O atom
donates 0.181e electrons possibly indicating their predominant role in
the strong TCA-Fe interactions.
4.3. Harmonizing experimental and computational results
From the intermediate magnitude of ΔGads (reported in the weight
loss section), the Bode plots, and the staged dilution studies, it appears
that TCA is interacting via both physi+chemisorption on the steel
8
Corrosion Science 208 (2022) 110623
surface. Whereas, the DFT optimized geometries, PDOS, and the large
perturbation of electronic structure in the electron density difference
plots, indicate that the molecule is chemisorbed. In order to arrive at a
definitive and consistent explanation of the underlying inhibition
mechanism, we have performed extensive coverage studies of TCA (at
coverages ranging from 0.042 to 0.125 ml) on Fe (001) surface using
DFT. This is because corrosion inhibition is not only dependent on strong
inhibitor adsorption, but also on the compactness of packing of the
molecules on the metal surface. [37].
The optimized structures at each coverage are shown in Fig. 11. The
interaction strength weakens with increasing coverage almost linearly
by ~0.50 eV across the tested coverage range indicating possible lateral
repulsions between adjacent molecules (Fig. 12). This validates the
Temkin adsorption isotherm model for TCA adsorption, as this model
allows for a linear decrease in the heat of adsorption with coverage [38]:
ΔHads = ΔH◦ ads - rθ
where ΔH◦ ads is the heat of adsorption at near-zero coverages and r is the
Temkin parameter.
However, as per Kokalj [39], ΔEint is not a good measure for
comparing the stabilities at different coverages. The adsorption surface
free energy γads, i.e., ΔEint normalized to a unit surface area, as a func­
tion of molecular chemical potential (Fig. 13) is a much better measure.
D. Kumar et al. Corrosion Science 208 (2022) 110623

Fig. 10. Electron density differences (upper panels) and density of states projected to TCA molecule and Fe (lower panels) for the DFT-D3 optimized flat and vertical
adsorption configurations in Fig. 9.

This γads is given by:

Table 7
Computed Bader charges on isolated (initial) and adsorbed (final) TCA molecule γads ≈ n(ΔEint -μ)/A
for the flat orientation.
Where, n is the number of TCA molecules adsorbed on the supercell
S. No. Atom Initial Final Change having area A. As evident from Fig. 13, in the chemical potential range μ
1 C -0.087 -0.146 -0.059 ϵ [− 3.89, − 3.54], the lowest monolayer coverage (1/24) is thermo­
2 C 0.078 -0.205 -0.282 dynamically most stable among the studied coverages while stability
3 H -0.014 0.058 0.072
decreases with increase in coverage, thus, further confirming the
4 H 0.062 0.079 0.017
5 C -0.056 -0.279 -0.223 intermolecular repulsions between adjacent molecules.
6 H 0.074 0.113 0.039 Interestingly, Kovač and Finšgar [40] using sophisticated ToF-SIMS
7 C -0.055 -0.204 -0.148 imaging have shown that the distribution of TCA molecules on the
8 H 0.064 0.087 0.023 steel surface is not homogeneous (as opposed to the more efficient
9 C -0.006 -0.227 -0.221
10 H 0.062 0.072 0.010
propargyl alcohol), thus leaving some places prone to corrosion attack.
11 C -0.037 -0.077 -0.040 This further substantiates our DFT coverage studies results which indi­
12 C -0.008 -0.234 -0.226 cate the possibility of lateral repulsion by adjacent molecules. Besides,
13 H 0.053 0.086 0.033 this also possibly explains why CO acts as an intensifier for TCA inhi­
14 C -0.063 -0.217 -0.154
bition of steel corrosion in HCl at room temperatures, as reported by
15 H 0.047 0.030 -0.018
16 C 1.645 0.879 -0.765 Cabello et al. [10] as the relatively smaller CO molecules can go and
17 H 0.037 0.087 0.050 chemisorb on the vacant spaces between adjacent TCA molecules and,
18 O -1.795 -1.614 0.181 thus, offer a more compact protective layer against ingress of corrosive

9
D. Kumar et al.
Fig. 11. Optimized structures of TCA on Fe (001) surface at various coverages (a) 0.042 (1/24), (b) 0.050 (1/20), (c) 0.062 (1/16), (d) 0.083 (1/12), (e) 0.100 (2/
20), and (f) 0.125 (2/16) ML.
Fig. 12. Effect of TCA coverage (in ML) on the magnitude of interaction en­
ergy, |Eint| (eV).
species.
Additionally, Kovač and Finšgar in the same paper [38] also inves­
tigated in detail, using ToF-SIMS, the thermal stability of TCA on steel
and showed that the TCA molecules remain stably adsorbed till ~100 ◦ C
and only at higher temperatures do these molecules start to desorb. This
clearly indicates that TCA is strongly chemisorbed on the steel surface,
thus, substantiating our DFT adsorption studies, as physisorbed mole­
cules are supposed to desorb rapidly with increase in temperature.
Thus, based on detailed experiments, DFT calculations, and SIMS
data from literature, a holistic picture (Fig. 14) of the room temperature
inhibition mechanism of TCA emerges out suggesting a strong, but
inhomogeneous chemisorbed monolayer on steel, coupled with weakly
physisorbed layers, susceptible to desorption under dynamic conditions.
Our work thus establishes that an integrated approach combining ex­
periments, characterization techniques (such as ToF-SIMS) and DFT
10
Corrosion Science 208 (2022) 110623
Fig. 13. Adsorption surface free energies, γads, as a function of TCA chemical
potential, μ, for the structures shown in Fig. 11.
adsorption/coverage studies can significantly help in establishing the
underlying adsorption mechanism of a given corrosion inhibitor mole­
cule and also possibly, expedite the screening/design of novel inhibitors.
It must be mentioned that the inhibition mechanism of TCA for steels
in HCl at high temperatures is via a combination of TCA chemisorption
and film-forming polymerization reactions. However, it has been shown
by Growcock and Lopp [13], that the former is usually responsible for
the major inhibiting effect and the polymer film is probably anchored to
the surface via adsorbed TCA and serves as a diffusion barrier to enhance
the inhibition. Therefore, our work provides important insights into the
principal mechanism of inhibition at both low as well as high
D. Kumar et al.
Fig. 14. Schematic of the proposed room temperature inhibition mechanism by
TCA on steel.
temperatures – strong chemisorption of TCA molecules on Fe (001)
surface due to formation of a plethora of Fe-C/O bonds facilitated by a
flat adsorption geometry. Owing to the computational challenges asso­
ciated with modeling polymer film-formation via DFT, we have not
taken it into account in this work. However, work is in progress to
capture this via more computationally efficient ReaxFF and classical
molecular dynamics techniques.
5. Conclusion
We have comprehensively investigated the mechanisms underlying
the excellent corrosion inhibition of TCA for mild steel in 1 M HCl using
a combination of experimental and DFT techniques. The following are
some of the salient conclusions from our work:
• Gravimetric, electrochemical and AFM studies confirm the excellent
corrosion inhibitive nature of TCA.
• The polarization curves show that TCA is a mixed inhibitor for this
steel.
• The trends of polarization curves suggest that, although 200 ppm is
sufficient for good inhibition, higher concentrations offer better
shielding, evident from anodic branches of 500 ppm and 1000 ppm.
This was further corroborated by EIS, Mott-Schottky and chro­
nocoulometry techniques.
• Partial desorption in staged dilution studies performed by reducing
TCA concentration from 500 ppm to 0 ppm, indicate that TCA acts
by a combination of physi and chemisorption.
• Two stable adsorption geometries – flat and vertical, were identified
in the explicit DFT adsorption studies on Fe (001) surface. The
significantly stronger interaction energies for flat configuration
suggest this to be the preferred orientation under actual conditions.
• The geometrically flat structure of TCA, coupled with the presence of
π-electrons and unsaturated bonds (C– – C and C–– O) in its structure
providing a large number of electrons to the partially filled d-orbitals
of Fe, facilitate the strong adsorption of TCA on Fe surface as
confirmed by the electron density difference and PDOS plots.
• Bader charge calculations indicate there is an overall charge transfer
from the metal surface to the molecule with the C atom of the
carbonyl (C–– O) group receiving the maximum number of electrons,
thus, possibly indicating its predominant role in the strong TCA-Fe
interactions.
• DFT coverage studies of TCA (at coverages ranging from 0.042 to
0.125 ML) on Fe (001) surface show that interaction strength
weakens with increasing coverage indicating possible lateral re­
pulsions between adjacent molecules.
11
Corrosion Science 208 (2022) 110623
Based on detailed experiments, DFT calculations, and SIMS data
from literature, a holistic picture of the room temperature inhibition
mechanism of TCA emerges out suggesting a strong, but inhomogeneous
chemisorbed monolayer on steel, coupled with weakly physisorbed
layers, susceptible to desorption under dynamic conditions.
CRediT authorship contribution statement
Dharmendr Kumar: Conceptualization, Methodology, Software,
Formal analysis, Investigation, Validation, Data curation, Writing –
original draft preparation, Software, Writing – review & editing, Su­
pervision. Venkata Muralidhar K: Conceptualization, Methodology,
Software, Formal analysis, Investigation, Validation, Data curation,
Writing – original draft preparation, Software, Writing – review &
editing, Supervision. Vinay Jain: Conceptualization, Methodology,
Software, Formal analysis, Investigation, Validation, Data curation,
Writing – original draft preparation, Software, Writing – review &
editing, Supervision. Beena Rai: Project administration, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical or time limitations.
Acknowledgements
The authors thank Mr. K. Ananth Krishnan - Chief Technology Officer
at Tata Consultancy Services (TCS), for the funding and encouragement
towards this research. The help offered by Prof. Suvarna Datar at DIAT,
Pune, for the AFM studies is also gratefully acknowledged.
Appendix A. Supplementary information
Comparison between computed and experimental bond-lengths/
angles, effect of Protonation on TCA adsorption, Bader charge analysis
of adsorbed protonated TCA, and Adsorption Surface Free Energies are
presented in Supplementary Information.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.corsci.2022.110623.
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