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Progress in Organic Coatings 131 (2019) 191–202

Contents lists available at ScienceDirect

Progress in Organic Coatings


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

Hybrid sol-gel coatings based on silanes-amino acids for corrosion T


protection of AZ91 magnesium alloy: Electrochemical and DFT insights
Habib Ashassi-Sorkhabia, , Saleh Moradi-Alaviana, Mehdi D. Esrafilib, Amir Kazempourc

a
Electrochemistry Research Laboratory, Department of Physical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
b
Laboratory of Computational Chemistry, Department of Chemistry, University of Maragheh, Maragheh, Iran
c
Young Researchers and Elite Club, Tabriz Branch, Islamic Azad University, Tabriz, Iran

ARTICLE INFO ABSTRACT

Keywords: In this research, hybrid organic-inorganic silica films were applied on the pre-treated AZ91 magnesium alloy by
Sol–gel coating using the dip coating technique. Inorganic precursor, tetraethylorthosilicate (TEOS), and the organic silane,
Amino acid methyltriethoxysilane (MTES), were used for providing a hybrid sol-gel thin-layer film. Different amino acids
Corrosion were incorporated into the coatings, and their corrosion inhibition performance was then investigated by using
Inhibitor
electrochemical techniques. The results indicate that the addition of L-Alanine, L-Glutamine, L-Methionine, and L-
Impedance
DFT calculation
Aspartic amino acids as green inhibitors with a concentration of 0.1, 0.5, 1.0, and 0.5 wt%, respectively to the
hybrid silane solution has outstanding inhibition performance. Furthermore, among the amino acids in-
vestigated, L-Aspartic exhibits the most improved corrosion resistance. The morphological characteristics of the
sol–gel coatings were analyzed by using scanning electron microscopy (SEM). The thickness evaluation of the
sol-gel coatings reveals that they are a thin layer with a thickness of about 250 nm. The hydrolysis of sol sample
was also characterized by Fourier transform infrared (FT-IR) spectroscopy. The corrosion protection behavior of
the coatings was evaluated by using electrochemical impedance spectroscopy (EIS) in 3.5% sodium chloride
solution. Finally, DFT calculations were performed to confirm and explain the results obtained from experi-
ments.

1. Introduction method [20,21]. Recent achievements in the sol-gel technology allow


successful fabrication of durable organic-inorganic sol-gel coatings
Magnesium is one of the most common elements on the earth with [22–24]. SiO2 thin films coated on ZE41 magnesium alloy using dif-
various applications [1–3]. Properties like low density, high strength to ferent concentrations of sol solutions at different densification tem-
weight ratio, and proven versatility make this material attractive for peratures produce coatings with improved corrosion resistance [25].
different purposes, such as automotive industries [4–6], processor Inhibitors are one of the commercial ways to protect metal surface
parts, cellular phones, aerospace engineering, and handheld tools [7]. against corrosion. Some organic compounds with special functional
In spite of these advantages, the low corrosion resistance of magnesium groups and structures are promising inhibitors. Mainly, they are com-
alloys limits their applications [8–10]. Hence, a large number of pounds containing nitrogen, oxygen, sulfur, phosphorus, and multiple
methods like chromate conversion coatings, anodizing, thermal bonds or aromatic rings in their structure. The number of lone pair
spraying, electroplating, chemical vapor deposition (CVD), and silica electrons and conjugated π-electrons in these functional groups is a key
coatings have been applied to improve the corrosion resistance of point that determines their effectiveness as an inhibitor. However, the
magnesium alloys [11–15]. Silica films prepared by the sol-gel process toxicity of these compounds is a concerning problem. Environmental
are widely accepted as environmentally friendly protective coatings for restrictions on the use of toxic compounds lead researchers to seek
magnesium and its alloys. This method provides a versatile route for the environmentally friendly alternatives. Amino acids are eco-friendly and
synthesis of silica compounds, which may be consisted of organic-in- non-toxic compounds, which are relatively cheap and easily prepared
organic groups [16–19]. Besides, high purity and homogeneity of the with a high purity. These compounds are used in living organisms as a
resulting coatings, operating at low temperatures, and having less toxic raw material for the production of protein [26–28]. L-Methionine is an
byproducts are considered as other beneficial properties of the sol-gel amino acid that was used as a corrosion inhibitor in 2007 by Oguzie and


Corresponding author.
E-mail addresses: habib.ashassi@gmail.com (H. Ashassi-Sorkhabi), moradi.saleh@hotmail.com (S. Moradi-Alavian), amirkazempour@ymail.com (A. Kazempour).

https://doi.org/10.1016/j.porgcoat.2019.01.052
Received 18 June 2018; Received in revised form 8 December 2018; Accepted 28 January 2019
Available online 26 February 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.
H. Ashassi-Sorkhabi, et al. Progress in Organic Coatings 131 (2019) 191–202

co-workers [29]. In that work, the corrosion inhibition and adsorption stability of the magnesium and results in better adhesion of the sol-gel
behavior of L-Methionine together with iodide ions on mild steel in coating.
sulfuric acid were studied. They revealed that synergistic effect of io-
dide ions at static conditions plays an important role. Eddy [26] studied 2.3. Sol-gel coating preparation
three types of amino acids as inhibitors. The first type with heteroatoms
in their structures included cysteine (CYS), serine (SER), and amino A homogeneous, clear transparent solution was prepared by adding
butyric (ABU) acid. The results showed that the inhibition efficiency TEOS (Si(OC2H5)4) and MTES (CH3Si(OCH3)3) with a molar ratio of 2:3
depends on the type of heteroatoms so that oxygen¸ nitrogen, and sulfur to an acidic solution of nitric and acetic acids in 1:5 vol ratio with a pH
follow the order S > O > N to increase the inhibition ability. The adjusted on 4.5. After the hydrolysis of the initial mixture of the silane
second type of inhibitors with alkyl chains included threonine (THR), precursors in the acidic solution under stirring for 8 h at room tem-
alanine (ALA), and valine (VAL). The results obtained illustrated that perature, the 0.03 M ethanol (96%) solution was added to the mixture
the straight-chain amino acids have lower inhibition effect with respect and subsequently stirred for 4 h at 400 rpm by a magnetic stirrer. To
to the branched-chain amino acids. The more steric hindrance a investigate the inhibitive effect of amino acids, L-Glutamine, L-
structure has, the more inhibition effect it possesses. Finally, the third Methionine, L-Aspartic, and L-Alanine were added to the sol at various
type of amino acids with different aromatic rings namely as phenyla- concentrations as corrosion inhibitors. The pretreated AZ91 specimens
lanine (PHE), tryptophan (TRP), and tyrosine (TYR) manifested better were immersed in the prepared solutions for 3 min by dip coating with a
inhibition performance due to existing the electron-donating groups on speed of 10 cm/min. Then, the specimens were pulled out at the same
the ring. speed and dried at 60 °C for 30 min. Subsequently, the samples were
Apart from experimental studies, plentiful theoretical efforts have heated up to 150 °C in the furnace under a heating program of 3°/min
also been undertaken to understand the adsorption properties and for two hours.
corrosion inhibition mechanism of some organic molecules on different
metal surfaces [30–36]. In particular, density functional theory (DFT) 2.4. Sample characterization
has been found as a useful tool to study the inhibitor-metal interaction
and anti-corrosive mechanism based on different electronic/molecular MIRA3 FEG Tescan Field emission scanning electron microscope
properties and reactivity indices. There are numerous DFT studies (FE-SEM) equipped with a dispersive X-ray analyzer (EDX) was used to
[37–42] linking the corrosion inhibition efficiency with structural characterize the morphology of hybrid sol–gel coatings. The cross-sec-
parameters, such as the frontier molecular orbital energies and their tion of the coating was also assessed by LEO, VP 1430. Fourier trans-
energy gap, the charge transfer, and the absolute hardness η and softens form infrared (FT-IR) analysis was performed using a TENSOR27
σ. For instance, Eddy [27] found a strong relationship between the spectrometer (Brucker).
calculated molecular Fukui function and the experimental inhibition
efficiency of glutamine, asparagine, aspartic, and glutamic acids. Mi- 2.5. Electrochemical corrosion tests
lošev et al. [43] have attributed the better inhibition effectiveness of
cysteine compared to alanine to its smaller energy gap between the Electrochemical tests for corrosion and inhibition evaluation were
frontier molecular orbitals as well as smaller absolute hardness. carried out in stagnant 3.5% NaCl solution using an Autolab PGSTAT30
In this work, a silane-based film was coated on AZ91 magnesium potentiostat-galvanostat at room temperature by a three-electrode cell
alloy using a completely hydrolyzable tetraethylorthosilicate (TEOS) configuration. The coated specimens, Ag/AgCl (3 M KCl), and a pla-
precursor and a partially hydrolyzable precursor of methyltriethox- tinum rod were used as working, reference, and counter electrodes,
ysilane (MTES), as well as acetic and nitric acids as catalysts in the sol- respectively. The EIS tests were performed in a frequency range of
gel process. The prepared hybrid silica sol-gel coatings were examined 10 kHz to 0.1 Hz with an AC voltage of ± 5.0 mV. The real and ima-
as green coatings to increase the corrosion resistance of the magnesium ginary parts of the impedance data in the complex plane were analyzed
alloy. Subsequently, the effect of incorporation of several amino acids using the ZView® (II) software to determine the parameters of the
as corrosion inhibitors within the hybrid sol-gel coatings was in- proposed equivalent electrical circuit model.
vestigated. DFT calculations were also performed to understand the
mechanism of the adsorption of the studied amino acids on the Mg 3. Computational details
surface.
All spin–polarized DFT calculations were performed using the
2. Experimental DMol3 program [45,46]. The Perdew − Burke − Ernzerhof (PBE) [47]
functional within generalized gradient approximation (GGA) was em-
2.1. Materials ployed to describe the electronic exchange-correlation effects. The van
der Waals interactions were described using the empirical correction in
The chemical materials used were TEOS (98 wt%), MTES (98 wt%), the Grimme scheme [48,49]. A double numerical plus polarization
methanol (96 wt%), acetic acid (96 wt%), nitric acid (65 wt%), L- (DNP) was used as the basis set. The convergence tolerance of energy of
Glutamine (99 wt%), L-Methionine (99 wt%), L-Aspartic acid (99 wt%), 1.0 × 10−5 Ha, maximum force of 0.001 Ha/Å, and maximum dis-
and L-Alanine (99 wt%). All of the materials were purchased from placement of 0.005 Å were employed in all the geometry optimizations.
Merck Company. A smearing value of 0.005 Ha to the orbital occupation was employed
for all of the calculations to enhance SCF convergence. To obtain reli-
2.2. Substrate preparation and pretreatment able results, the real-space global orbital cutoff ; radius was set as high
as 4.6 Å.
The 1 × 1 cm2 samples were prepared from commercial AZ91 To model the Mg surface, a 8 × 8 supercell containing 128 atoms
sheets and polished by 500–3000 grade SiC papers. The samples were was considered. To avoid the interaction of this surface and its periodic
washed with distilled water and then degreased by acetone and washed image, we set the modulus unit cell vector along the z direction normal
with ethanol and eventually dried by air flow. Because of high activity to the sheet to be as large as 20 Å. The sampling of the Brillouin zone
of magnesium, cerium-lanthanum permanganate (CLP) conversion was done using a 3 × 3 × 1 Monkhorst–Pack grid. The adsorption
coating was applied on magnesium alloy prior to the sol-gel process energy (Eads) of each adsorbate was calculated as Eads = Eadsorbate/Mg -
according to the literature [44]. The CLP coating prevents the severe Eadsorbate - EMg, where Eadsorbate/Mg, Eadsorbate, and EMg are the total
corrosion of magnesium in the acidic sol. This pretreatment provides energies of the adsorbate/substrate complex, adsorbate, and substarte,

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Fig. 1. SEM image (a) and EDX spectrum (b) of the AZ91 specimen prepared with the CLP conversion coating.

respectively. With this definition, a negative Eads value corresponds to absorption characteristic bands appeared in the FT-IR spectra indicate
an exothermic adsorption on the surface. The charge-transfer values the difference between the pure and hydrolyzed TEOS and MTES. In
were calculated using the Hirshfeld charge density analysis [50]. Fig. 2a, a strong band can be seen at 1082 cm−1 that is related to Si-O-C
bonds. Moreover, the stretching and vibrational bonds of C–H in
4. Results and discussion methoxy group are located at 2929 cm−1 and 2892 cm−1, respectively.
The CH3 bending vibrations for methoxy group appear at 1375-
4.1. Morphology and composition of the conversion coating 1450 cm-1 [52,53]. In Fig. 2b, the stretching vibration of Si-CH3 is seen
at about 780 cm−1, and the CeH stretching vibrations of the methyl
Fig. 1a shows the SEM image of the conversion coating applied on group appear at 2929 cm−1. Methyl bending vibrations appear at 1375
the AZ91 substrate. This figure illustrates an ununiformed coating with and 1450 cm−1. Additionally, the band appeared at 1469 cm−1 origi-
no significant changes on its surface. The presence of pores on the nates from the CH3 flexural vibrations. The CeC bond vibration occurs
surface causes to trap the silanes molecules and improve the adhesion at 1337 cm−1, and the stretching vibrations of CeH methylene and
of the sol-gel coating. The EDX pattern given by Fig. 1b depicts the CLP methyl groups appear at 2926 cm−1. Fig. 2c illustrates the stretching
coating applied on AZ91 by conversion coating and the percentages of vibrations of SieOeSi and CeOeC at 1053 cm−1 and 1120 cm−1, re-
elements existing in the coating. The anodic reactions consist of oxi- spectively. The broad absorption band around 3400 cm−1 is due to the
dation of magnesium (Eq. 1) and reduction of hydrogen ion in aqueous presence of OH groups even though Si−OH group may have a partial
solution (Eq. 2) are presented as follows [51] contribution to this bond. The band at 950 cm−1 indicates Si−OH
bending vibration, and the band of Si-CH3 group was found at about
Mg Mg 2 + + 2e (1) 770 cm−1 [54,55]. The existence of Si-O-Si group confirms the con-
densation inside the hydrolyzed sol (Eqs. 6 and 7). Furthermore, the
2H3 O+(aq) + 2e H2(g ) + 2H2 O (2)
appearance of a band at the region of 950 cm−1 is evidence of turning
If oxygen is dissolved in the solution, the cathodic reactions would methoxy group into Si−OH, indicating the hydrolysis of silanes (Eq. 5).
be initiated as below: These observations clearly demonstrate that the condensation process
and the hydrolysis step begin simultaneously [21,56].
O2(aq) + 2H2 O + 4e 4OH (aq) (3)
Si (OR) 4 + 4H2O → Si (OH) 4 + 4ROH (hydrolysis) (5)
The local pH increases as reaction (2) occurs. Permanganate is a
strong oxidizing agent that simultaneously oxidizes Ce3 + to Ce+4 and Si (OH) 4 + Si (OH) 4 → Si (OH) 3-O- (OH) 3Si + H2O (water con-
La+3 to La+4 (Eq. 4). densation) (6)

4Ce 3 + + MnO4 + 8H+ + 2H2 O 4Ce 4 + + Mn(H2 O)63 + (4) Si (OH) 3 (OR) + R Si (OH) 4 → Si (OH) 3-O- (OH) 3Si + ROH (alcohol
condensation) (7)
Therefore, the three hydroxides Ce(OH)4 , La(OH)3 , and Mg(OH)4
form and deposit at the cathodic sites. By dehydrating the hydroxides,
CLP components which are metal oxides like magnesium oxide, cerium 4.3. Morphology of the coatings
oxide, lanthanum oxides, manganese dioxide, and manganese oxides
will form on the surface of magnesium alloy [44,51]. Cerium, lan- An optical microscope was used to characterize the surface ap-
thanum, and manganese element percentages are illustrated in the EDX pearance of the hybrid sol-gel coating applied on the substrate treated
spectrum, confirming the formation of these metal oxides. by the CLP conversion coating. The untreated substrate is also re-
presented in Fig. 3. This figure clearly shows that in the process of
4.2. FT-IR spectrum coating on the untreated substrate, hydrogen gas is released which
causes damage to the substrate surface and the coating. Fig. 4 shows the
Fig. 2a and b display the FT-IR spectra of pure TEOS and MTES, SEM images of the coating without inhibitor incorporation. Clearly, no
respectively. Fig. 2c also shows the FT-IR spectrum of the hydrolyzed cracks and pores are observed on the coating before exposure in the
TEOS and MTES, prepared in aqueous acidic solution. Several corrosive environment (see Fig. 4a), but after 12 h of immersion in

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Fig. 2. FT-IR analysis of the hybrid gel prepared with TEOS and MTES under acidic condition (a), pure TEOS (b), and pure MTES (c).

3.5% NaCl solution, pores appear on the coating (see Fig. 4b) due to the 4.4. EIS studies
cathodic reaction (Eq 2). Additionally, the SEM images of the coating
containing amino acids are shown in Fig. 5. Obviously, before immer- 4.4.1. Optimization of inhibitor content in the coatings
sion in the corrosive environment, the coating has a smooth, uniformed The EIS technique was used to study the corrosion protection
surface with white spots representing the inhibitor (see Fig. 5a). After properties of the prepared coatings. Fig. 7a shows the Nyquist plot of
immersion in 3.5% NaCl solution for 12 h, surprisingly, no pores are the untreated AZ91 (bare) and treated AZ91 with the CLP conversion
observed on the surface owning to the presence of amino acid in the coating. According to Nyquist diagrams, the CLP conversion coating
coating (see Fig. 5b). Amino acid molecules absorb to the active sites, illustrates a slight increase in the corrosion resistance of the AZ91 Mg
reduce the activity of the metal, and consequently prevent the cathodic alloy. When specimens are immersed in the corrosive solution with an
reaction. The AFM analysis along with the roughness data including acidic condition, the cathodic reaction (Eq. 2) releases hydrogen gas.
maximum profile peak height (Rp), maximum profile valley depth (Rv), This process would be intensified as heat treatment is applied for drying
root mean square (RMS) roughness (Rq), and average roughness (Ra) the coating. An increase in temperature will accelerate the cathodic
are available in Fig. 5c and d. Accordingly, it can be observed that the reaction and completely evaporate water and fabricate a porous sol-gel
surface of the coating is uniform. film. By applying the CLP conversion coating, the hydrogen gas release
The thickness of the coating was characterized by the cross-section can be delayed or stopped at the time of dip coating and heat treatment.
SEM image given in Fig. 6. This image illustrates three sections in which Fig. 7b depicts the Nyquist plots of the bare AZ91 and the untreated
the upper section is related to the hybrid sol-gel coating with the and CLP treated substrates coated by the sol-gel coating. It is clear that
thickness of about 250 nm, and the mid-section exhibits the CLP con- the sample treated with the CLP conversion coating has better corrosion
version coating with the approximate thickness of 600 nm. The thick- resistance than the untreated specimens. Despite the CLP conversion
ness of the sol-gel coatings reveals that it is a thin layer. coating possesses a thickness three times larger than that of the hybrid
sol-gel coating (see Fig. 6), it shows weaker anti-corrosion performance.
The maximum corrosion resistance of the coating is related to the hy-
brid sol-gel coating. This coating is reinforced when the CLP conversion
coating is applied before it. Therefore, we used the hybrid sol-gel

Fig. 3. Optical microscopic images of the surface appearance of the hybrid sol-gel coating applied on the substrate treated by CLP conversion coating (a) and
untreated surface substrate (b).

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Fig. 4. SEM images of the coated AZ91 sample with sol-gel before (a) and after (b) immersion in 3.5% NaCl solution for 12 h with various magnifications.

coating with a CLP conversion coating under it for further investiga- double-layer constant phase element and Rcorr represents metal corro-
tions. sion resistance or charge transfer resistance of the metal. The inductive
Fig. 8 shows the Nyquist plots of the hybrid sol-gel films containing loop appeared in the low-frequency range is related to the inductance
various amounts of amino acids (0.1, 0.5, 1.0, and 0.5 wt%). Two semi- (L) and resistance (RL) [57–59]. The equivalent circuit in Fig. 9a was
circles appeared in the plots are related to 2 specific time constants. The employed to fit the plots without inductance, and the equivalent circuit
high-frequency time constant corresponds to the capacitance and re- presented in Fig. 9b was used to fit the plots with an inductive loop.
sistance of the coatings. The time constant in intermediate frequencies The parameters obtained from analysis of the EIS data for the bare
is attributed to the double layer capacitance and charge transfer re- AZ91 and the untreated and CLP treated substrates coated by the sol-gel
sistance. An inductive loop observed in low frequencies is referred to coating are collected in Table 1. The parameters obtained from fitting
the initiation of local corrosion. The effect of amino acids added to the the Nyquist diagrams of the sol-gel coatings containing different con-
coating was investigated and their optimum contents were determined. centrations of amino acids are given in Table 2. According to this table,
Accordingly, the corrosion resistance enhances as the concentration of it is clear that by the formation of the defective coating, the corrosion
L-Alanine increases from 0.1 to 1.0 wt%, while in the concentration resistance decreases due to the shortage of inhibitors in the coatings.
higher than 1.0 wt%, the corrosion resistance decreases. Moreover, the Additionally, the corrosion resistance significantly reduces when the
performance of L-Aspartic acid in the coating is similar to L-Alanine. The aggregation of inhibitors occurs in the coatings owning to the high
best performance of L-Glutamine was achieved in 0.5 wt%, and L-Me- concentration of inhibitors. Therefore, determination and applying the
thionine follows the same pattern as L-Glutamine. optimum amount of an inhibitor is necessary.
The electrical equivalent circuits used to fit the Nyquist plots are
presented in Fig. 9. Due to the formation of an inductive loop in some 4.4.2. Effect of immersion time on behavior of the coatings
plots, the time constant related to inductance was ignored in this model. Fig. 10 illustrates the Nyquist plots for various immersion times of
The first time constant corresponds to the coating and is in accordance the coatings containing the optimum percentage (1.0 wt % L-Alanine,
with the loop at high frequencies in the charts. It consists of Rs, CPEcot, 0.5 wt% L-Glutamine, 0.5 wt% L-Methionine, and 1.0 wt% L-Aspartic) of
and Rcoat which represent the solution resistance, constant phase ele- the inhibitors in 3.5% NaCl solution. It can be concluded that L-Alanine
ment, and resistance of the coating, respectively. The loop located at and L-Glutamine give the maximum amount of total corrosion re-
intermediate frequencies is related to the double-layer. CPEdl represents sistance after 12 h, and then the corrosion resistance decreases. By

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Fig. 5. SEM images of the coating containing L-Glutamine inhibitor before immersion (a) and after exposure (b) in 3.5% NaCl solution for 12 h. AFM image of the
coating containing L-Glutamine inhibitor before immersion (c) and its typical roughness profile and table of roughness parameters (d).

Faradic admittance on the localized corrosion points is more than the


rest of the film surfaces [57]. When the coated samples were immersed
in aggressive media at a certain time, the Nyquist charts began to shrink
(see Fig. 10). The semi circle in medium frequencies merged with a
semi circle in high frequencies. As a result, just two loops corresponding
to the capacitive and inductive phenomena can be seen. This integra-
tion begins after 12 h immersion in corrosion environment and in-
tensifies over the time. The inductive loop at low frequencies (ex-
tended) was shifted toward higher frequencies.
The plots fitted by the equivalent circuit are shown in Fig. 9, and the
obtained values of the parameters are given in Table 3. Water uptake by
the coatings at the specific time can be calculated from the following
equation [60]
(log(Ct )/log( 0 )
Water uptake(%)= × 100
log(80) (8)
which Ct is the coating capacitance at time t, and C0 is the coating
capacitance in initial moments of immersion into the corrosive en-
Fig. 6. Cross-section SEM image of the hybrid sol-gel coating on the surface of vironment. The capacitance of the coating in the corrosive medium can
AZ91 substrate pretreated by the CLP conversion coating.
be calculated from the following equation
Cc = (Y0 * R)1/ n / R (9)
passing 48 h of immersion, the lowest corrosion resistance was ob-
tained, but the coating still had its protective effects. On the other hand, where Cc is the capacitance of the coating, R is representative of the
the corrosion resistance of L-Methionine and L-Aspartic acid gradually resistance of the coating, Y0 and n are the parameters of the constant
decreases by exposing in aggressive media. phase element for the coating [61]. Normally, the capacitance values
In the first moments of immersion in the corrosive environment, the are used for predicting anti-corrosion performance of the coating. The
inductive loop can be attributed to initial stages of localized corrosion numerical values of capacitance (Cc) and water uptake are given in
so that by increasing the immersion time, the localized corrosion in- Table 3. It is revealed that the capacitance values of the coating in-
tensified and the inductive loop became more complete. Furthermore, crease due to the soaring water penetration. The lowest water

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Fig. 7. Nyquist plots of the substrate with CLP conversion coating treated and untreated bare (a) and the sol-gel coating on treated and untreated substrate (b).

penetration into the coatings is related to L-Aspartic acid and the Mg atoms of the surface and lone-pair electrons on the O and N atoms of
highest value of water penetration is related to the coating containing L- the amino acids. We note that for L-Methionine, our DFT calculations
Alanine. predict that the adsorption through the S atom is about 0.5 eV less fa-
vorable than that of via -COOH/-NH2 groups. The calculated adsorption
energies (Eads) are −1.62, −1.52, −1.51, and −1.12 eV for L-Aspartic,
4.5. Adsorption geometries and energies L-Methionine, L-Glutamine, and L-Alanine, respectively. These negative
Eads values clearly indicate that the adsorption of these species over the
In order to obtain additional information on the adsorption and Mg surface is energetically favorable. Notably, the magnitude of ad-
mechanism aspects of corrosion inhibition, we carried out DFT calcu- sorption energy increases in the sequence L-Alanine < L-Glutamine
lations to give models of amino acid absorption on the Mg surface. The < L-Methionine < L-Aspartic. This order reveals that L-Aspartic has
optimized adsorption configurations of the amino acids investigated on the strongest interaction with the surface and consequently the L-As-
the Mg surface are shown in Fig. 11. The corresponding adsorption partic@Mg (AZ91) system will be more stable than the others and then
energies are listed in Table 4. As it is clear from Fig. 11, all the studied exhibit the highest inhibition efficiency, being consistent with the ex-
amino acids adopt almost a perpendicular orientation over the Mg perimental results obtained herein. The lone pair electrons present on
surface, due to the more favorable electrostatic interaction between the

Fig. 8. Nyquist plots of the substrate with the sol-gel coating containing different contents of the amino acid inhibitors (a) L-Alanine, (b) L-Glutamine, (c) L-
Methionine, and (d) L-Aspartic acid in 3.5% NaCl solution.

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Fig. 9. The equivalent electrical circuit model used for fitting the impedance data. The circuit (a) was employed to fit the plots without inductance, and the circuit (b)
was used to fit the plots with an inductive loop.

Table 1
The EIS fitting parameters of different samples in 3.5% NaCl solution.
samples CPE-coat Rcoat (kΩ. cm2) CPE-ct Rcorr Rtotal RL L (kH. cm2) Fitting error
(kΩ. cm2) (kΩ. cm2) (kΩ. cm2)
Y0×10−6 n1 Y0×10−6 n2
(Ω-1 cm-2Sn) (Ω-1 cm-2Sn)

Bare 56.694 0.896 0.099 983.38 0.988 0.020 0.119 0.434 0.377 0.00262
CLP conversion coating 0.563 0.969 0.119 19.628 0.818 0.562 0.681 0.631 0.379 0.01052
Sol-gel on bare 0.912 0.863 0.464 8.118 0.658 2.788 3.252 5.667 6.003 0.00260
Sol-gel on CLP 0.641 0.835 8.068 3.944 0.989 5.772 13.840 10.510 10.788 0.00678

Table 2
The EIS fitting parameters obtained for the sol-gel coatings with different amounts of amino acids in 3.5% NaCl solution after 1 h immersion.
Inhibitor Percentage wt% CPE-coat Rcoat CPE-dl Rct Rtotal RL (kΩ. cm2) L (kH. cm2) Fitting error
(kΩ. cm2) (kΩ. cm2) (kΩ. cm2)
−6 −6
Y0×10 n1 Y0×10 n2
(Ω-1 cm-2Sn) (Ω-1 cm-2Sn)

L-Alanine 0.1 0.084 0.973 6.418 4.924 0.987 2.897 9.315 3.075 4.398 0.04623
0.5 1.453 0.823 8.109 4.685 0.846 6.909 15.018 22.394 42.200 0.00109
1.0 0.023 0.782 10.193 5.462 0.671 10.149 20.342 —————— —————— 0.00110
5.0 0.543 0.800 5.674 3.830 0.958 5.368 11.042 7.406 8.942 0.00989
L-Glutamine 0.1 1.222 0.829 6.340 5.912 0.975 3.503 9.843 12.410 38.152 0.00280
0.5 0.075 0.939 10.960 1.627 0.978 13.896 24.856 16.309 28.108 0.00616
1.0 0.062 0.981 2.649 9.952 0.902 0.054 2.703 2.010 3.706 0.04722
5.0 0.077 0.989 4.558 31.370 0.844 2.156 6.714 2.308 2.425 0.07338
L-Methionine 0.1 0.043 0.995 13.439 6.807 0.997 7.404 20.843 6.752 9.356 0.06240
0.5 0.084 0.982 25.592 0.867 0.987 20.132 45.724 33.024 22.470 0.03395
1.0 0.089 0.979 4.142 5.523 0.997 2.486 6.628 3.040 4.440 0.03914
5.0 0.167 0.981 0.397 5.927 0.729 4.769 5.166 15.759 16.492 0.00315
L-Aspartic acid 0.1 0.093 0.929 14.116 1.605 0.985 12.174 26.290 34.722 22.239 0.00789
0.5 0.207 0.937 4.055 4.541 0.810 4.082 8.137 6.913 5.255 0.01461
1.0 0.419 0.830 30.932 2.520 0.712 54.485 85.417 —————— ——————— 0.01423
5.0 0.231 0.816 17.572 2.233 0.979 9.074 26.646 19.633 22.590 0.01778

heteroatoms can be shared in the orbital of substrate metal and form an surface. For the all complexes studied, it is found that the chemisorp-
insoluble complex, resulting in the protection of the surface from ag- tion of amino acid leads to the flow of a sizable electron density from
gressive species. [62] Inspection of the four amino acids also indicates the surface into the adsorbed molecule. Such a charge-redistribution
that some heteroatoms on their structure relax toward the outside with effect is largest for L-Aspartic, while smallest for L-Alanine. It is also
respect to the surface. The number of these heteroatoms as well as their noted that the obtained sequence for the qCT values (L-Alanine < L-
electronegativity and their vertical distance from the surface affect the Glutamine < L-Methionine < L-Aspartic) is in good agreement with
adsorption energy and therefore the inhibition efficiency. According to the inhibition efficiency of these species, demonstrating that the
Fig. 11, the aforementioned heteroatoms of L-Aspartic are closer to the charge-transfer between the adsorbed molecule and surface plays an
metal surface than L-Glutamine and L-Methionine, resulting in its higher important role in the corrosion inhibition process. To further explore
adsorption energy. Besides, the adsorption of these molecules leads to the effects of adsorption of the amino acids on the electronic structure
the displacement of the Mg atoms in the first layer with respect to the of the Mg surface, the partial density of states (PDOS) analysis was
clean surface. As evident from Table 4, the maximum vertical dis- performed on the optimized adsorption configurations shown in Fig. 12.
placement increases as L-Alanine < L-Glutamine < L-Methionine < As evident, there are some important orbital interactions between the
L-Aspartic, which is consistent with the obtained Eads values for these Mg atoms of the surface and each amino acid, especially L-Aspartic, L-
molecules. Methionine, and L-Glutamine. Such orbital interactions can be mainly
Table 4 also gives the calculated Hirshfeld charge-transfer values attributed to the Mg-2 s states of the surface and empty 2π* state of the
(qCT) due to the adsorption of different amino acids over the Mg carboxyl group in the amino acids. In all the considered models, this

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Fig. 10. Nyquist diagrams obtained at different immersion times in 3.5% NaCl solution for the coatings with the optimum amounts of the amino acids (a) L-Alanine,
(b) L-Glutamine, (c) L-Methionine, and (d) L-Aspartic acid.

Table 3
The EIS fitting parameters for the sol–gel coatings with the optimum amounts of various amino acids at different exposure times in 3.5% NaCl solution.
Inhibitor Time (h) CPE-coat Rcoat CPE-ct Rct RL (kΩ.cm2) L (kH.cm2) Capacity (μF) water-uptake% Fitting error
(kΩ.cm2) (kΩ.cm2)
Y0×10−6 n1 Y0×10−6 n2
(Ω-1cm-2Sn) (Ω-1cm-2Sn)

L-Alanine 1 0.023 0.782 10.193 5.462 0.671 10.149 ———— ———— 0.002 ———— 0.00110
12 0.221 0.826 4.928 5.922 0.685 13.900 ———— ———— 0.049 70.88 0.00067
24 3.296 0.568 7.027 6.503 0.860 8.308 50.680 28.786 0.188 101.49 0.00083
48 3.182 0.662 4.378 6.410 0.987 2.365 10.818 9.532 0.359 116.25 0.00144
L-Glutamine 1 0.075 0.939 10.960 1.627 0.978 13.896 16.309 28.108 0.047 ————— 0.00616
12 0.169 0.971 10.834 1.551 0.986 13.472 30.365 13.713 0.142 24.70 0.00668
24 1.933 0.672 1.429 0.145 0.983 10.229 15.373 11.821 0.311 42.93 0.00334
48 1.055 0.932 0.407 3.593 0.751 3.538 4.894 4.022 0.599 57.89 0.00169
L-Methionine 1 0.084 0.982 25.592 0.867 0.987 20.132 33.024 22.470 0.046 ————— 0.03395
12 0.074 0.984 4.516 4.489 0.577 31.092 58.837 43.470 0.065 7.66 0.00289
24 0.967 0.830 9.809 5.552 0.967 9.243 49.046 22.967 0.372 47.51 0.00175
48 2.287 0.745 4.191 9.113 0.970 2.532 42.887 30.354 0.466 52.62 0.00091
L-Aspartic acid 1 0.419 0.830 30.932 2.520 0.712 54.485 ————— ————— 0.182 ————— 0.01423
12 0.804 0.791 28.528 5.502 0.756 37.055 ————— ————— 0.295 12.28 0.00114
24 0.944 0.873 3.626 3.108 0.762 11.963 20.523 9.527 0.404 19.50 0.00923
48 1.324 0.811 4.758 8.307 0.803 6.066 42.925 20.288 0.435 21.20 0.00136

orbital mixing occurs mainly below the Fermi level of the surface (see isosurfaces as well as their energies of the isolated amino acids. It is
Fig. 12). Interestingly, the strong chemisorption of L-Aspartic, L-Gluta- seen that the HOMO of L-Alanine, L-Aspartic, and L-Glutamine mole-
mine, and L-Methionine results in a partial occupation of 2π* state of cules is mainly localized on the N atom, being attributed to the lone-
the carboxyl group and therefore its large stabilization. pair electrons over this atom. However, in the case of L-Methionine, one
The frontier molecular analysis is also adopted as a useful tool to can see a relatively large contribution of the S atom in the corre-
illustrate the chemical reactivity of inhibitor molecules towards the sponding HOMO. On the other hand, the LUMO state of these molecules
surface. In particular, the energy gap between the highest occupied has mainly 2π* characteristic which is chiefly localized over the car-
molecular orbital (HOMO) and lowest unoccupied molecular orbital boxylic group. The calculated HOMO-LUMO energy gaps (in eV) are in
(LUMO) is viewed as a good global index to predicts the inhibitive ef- the order of 3.86 (L-Methionine) < 4.00 (L-Aspartic) < 4.39 (L-Gluta-
ficiency of the adsorbed molecules. Fig. 13 shows the HOMO and LUMO mine) < 4.40 (L-Alanine). From the point of view that the HOMO-

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Fig. 11. Optimized adsorption configurations of the amino acids on the Mg (AZ91) surface.

Table 4 performance of these species, such as solvent effect, inhibitor-metal


Calculated adsorption energy (Eads, eV), maximum displacement of Mg atoms in surface bonding, and the solubility of inhibitor, which should be con-
the first layer due to the adsorption of amino acid (h, Å), and Hirshfeld charge- sidered during the DFT calculations.
transfer value from the surface into the adsorbed molecule (qCT, e).
amino acid Eads h qCT 5. Conclusions
L-Alanine −1.12 0.12 0.034
L-Aspartic −1.62 0.32 0.481 Crack-free silica films based on TEOS and MTES were developed by
L-Glutamine −1.51 0.30 0.440 the sol-gel method to protect magnesium from corrosion. Amino acids
L-Methionine −1.52 0.31 0.453 were added to the coatings as green corrosion inhibitors. The results
revealed that the presence of amino acids in the coatings enhances the
corrosion resistance. The SEM images indicated that unlike the coating
LUMO energy gap is generally considered to exhibit the chemical re-
without amino acids, the coatings containing amino acids show no
activity of the inhibitor molecules toward the substrate surface, the
crack and pores after immersion in the corrosive medium. The most
observed sequence is not in agreement with the obtained experimental
improved performance belonged to the coatings with 1 wt% of L-
inhibitive efficiency of the molecules. This clearly indicates that there
Aspartic acid. This observation originates from the L-Aspartic acid
should be other competitive effects influencing the inhibition
structure with three active adsorption sites that allows it to absorb on

Fig. 12. PDOS analysis of the amino acid/Mg complexes: (a) L-Alanine, (b) L-Aspartic, (c) L-Glutamine, and (d) L-Methionine. The 2π* state of the carboxyl group of
the amino acid is depicted in each figure.

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Fig. 13. Frontier molecular orbitals, their energies, and gaps (in eV). The isosurface value for the HOMOs and LUMOs is 0.02 au.

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