metals

Article
Gallic Acid as a Potential Green Corrosion Inhibitor for
Aluminum in Acidic Solution
Przemysław Kwolek 1, * , Kamil Dychtoń 1 , Barbara Kościelniak 1 , Andrzej Obłój 1 , Agnieszka Podborska 2
and Marek Wojnicki 3

1 Department of Materials Science, Faculty of Mechanical Engineering and Aeronautics,

Rzeszow University of Technology, Żwirki i Wigury Street 4, 35-036 Rzeszow, Poland;
kdychton@prz.edu.pl (K.D.); b.koscielnia@prz.edu.pl (B.K.); obloja@prz.edu.pl (A.O.)
2 Academic Centre for Materials and Nanotechnology, AGH University of Science and Technology,
Mickiewicza Avenue 30, 30-059 Krakow, Poland; podborsk@agh.edu.pl
3 Faculty of Non-Ferrous Metals, AGH University of Science and Technology, Mickiewicza Avenue 30,
30-059 Krakow, Poland; marekw@agh.edu.pl
* Correspondence: pkwolek@prz.edu.pl; Tel.: +48-17-743-2376

Abstract: Plant extracts are intensively studied as green corrosion inhibitors of aluminum. Because these
extracts are complex systems, the influence of their individual constituents on the corrosion of alu-
minum should be determined. In this work, gallic acid was tested for the first time as a corrosion
inhibitor of aluminum in orthophosphoric acid aqueous solution. So far, its potential inhibiting
properties in acidic solutions were only suggested based on promising results obtained for various
plant extracts. Evaluation of the potential inhibiting properties of gallic acid was performed using
electrochemical methods. The corrosion potential, polarization curves, and impedance spectra of
aluminum in 0.5 M orthophosphoric acid, at T = 303 K, were determined. The corrosion potential,
corrosion current density, and corrosion rate of aluminum in orthophosphoric acid were equal to



−1.151 V vs. Ag|AgCl (3M KCl) reference electrode, 36 µA·cm−2 and 0.39 mm·year−1 , respectively.


These values did not change with the addition of gallic acid. The results obtained show that gallic acid
Citation: Kwolek, P.; Dychtoń, K.;
Kościelniak, B.; Obłój, A.; Podborska, does not inhibit aluminum corrosion. UV-Vis absorption spectra of gallic acid solutions and quantum
A.; Wojnicki, M. Gallic Acid as a mechanical calculations show that this organic compound did not adsorb onto the aluminum surface
Potential Green Corrosion Inhibitor under the studied conditions.
for Aluminum in Acidic Solution.
Metals 2022, 12, 250. https://doi.org/ Keywords: gallic acid; aluminum; corrosion inhibition; orthophosphoric acid; green corrosion inhibitor
10.3390/met12020250

Academic Editor: Robert Lindsay

Received: 29 December 2021 1. Introduction

Accepted: 26 January 2022
Aluminum alloys, due to their high strength-to-weight ratio, are commonly applied,
Published: 28 January 2022
especially in the aircraft industry [1]. Their applications usually require good corrosion
Publisher’s Note: MDPI stays neutral resistance. This is based on the natural ability of aluminum to form a compact layer
with regard to jurisdictional claims in of Al2 O3 . This protective layer becomes chemically unstable in acidic and alkaline so-
published maps and institutional affil- lutions and these environments are corrosive for aluminum and its alloys [2]. Thus,
iations. when aluminum is exposed to an acidic or alkaline solution, an efficient corrosion inhibitor
should be used. This problem is especially important in industrial processes, for instance,
during electrochemical etching and acid pickling of components made of aluminum al-
loys or when the anodic coating must be stripped off the substrate without dissolution of
Copyright: © 2022 by the authors.
the latter.
Licensee MDPI, Basel, Switzerland.
Probably the most effective inorganic inhibitor of aluminum corrosion in acidic solu-
This article is an open access article
tions is chromium trioxide CrO3 . For example, it is used during the gravimetric determi-
distributed under the terms and
conditions of the Creative Commons
nation of anodic coating’s weight. The coating is quickly dissolved in hot 0.5 M H3 PO4
Attribution (CC BY) license (https://
whereas the metallic substrate is efficiently protected with hexavalent chromium species [3].
creativecommons.org/licenses/by/
Among the less toxic inorganic corrosion inhibitors than CrO3 , probably the most important
4.0/). is sodium molybdate Na2 MoO4 . It efficiently protects aluminum of technical purity [4,5]

Metals 2022, 12, 250. https://doi.org/10.3390/met12020250 https://www.mdpi.com/journal/metals

Metals 2022, 12, 250 2 of 17

but is less effective for Cu-rich aluminum alloys [6]. Nevertheless, it is now recommended
inhibitor for anodic coating’s weight determination, together with CrO3 [7]. The vast
amount of organic corrosion inhibitors was also studied. This group contains amines, N-
heterocyclic compounds, azole, imidazole, and thiazole derivatives, polymers, organic dyes,
and Schiff bases. These compounds adsorb on the metal surface through the heteroatoms
N, S, O, and P, which serve as active centers for adsorption [8,9].
Another group of corrosion inhibitors called green inhibitors is attracting increasing
attention. This is partly because of the potential toxicity of many inorganic and organic
corrosion inhibitors but also due to the negative environmental impact of synthetic chem-
istry processes. On the contrary, green corrosion inhibitors are ecologically acceptable,
biodegradable, and renewable. Their most important drawbacks are a decreased inhibition
efficiency upon prolonged storage and a potential problem with reproducibility of the
inhibition efficiency. [10–13].
Green corrosion inhibitors that attract the greatest scientific attention are plant extracts,
natural oils, biopolymers, and drugs. Their influence on the corrosion of aluminum and its
alloys in acidic media is summarized in several extensive review articles [10–13]. Further
discussion will be restricted to plant extracts. Their main constituents are polyphenols,
terpenes, carboxylic acids, and alkaloids. There is a great deal of experimental evidence that
plant extracts act as corrosion inhibitors of aluminum and other metals [10]. Unfortunately,
many published corrosion studies do not identify which constituent of the extract is
responsible for corrosion inhibition. In fact, experimental studies, in which individual
components of plant extracts are applied as corrosion inhibitors, constitute a minority of the
available literature. To date, successful inhibition of corrosion of aluminum and its alloys
in acidic solutions was reported for rutin [14], tannin [15], quercetin [16], and derivatives
of baicalin [17].
Rutin, which belongs to the family of flavonoids, provided efficient corrosion protec-
tion for the 6063 aluminum alloy in 0.5 M HCl. Inhibition efficiency was greater than 90%
in the wide temperature range, between 303 and 333 K, when the rutin concentration was
40 ppm [14]. A slightly lower inhibition efficiency of 89% was obtained for the same alloy
in 0.5 M HCl when quercetin of 40 ppm was used as the corrosion inhibitor [16]. High
(>90%) inhibition efficiencies were reported for tannin. This polyphenolic biomolecule was
used as the corrosion inhibitor of the 7075 aluminum alloy in 0.1 M HCl. However, this time,
the corrosion inhibitor concentration was much higher, 14 g·dm−3 [15]. Baicalin, a flavone
traditionally used in Chinese medicine, was also regarded a promising green corrosion
inhibitor. Baicalin esters were applied as inhibitors of aluminum corrosion in 1.0 M HCl
because of the insufficient solubility of baicalin in water. These esters provided a high
inhibition efficiency, approximately 94%, when their concentration was 0.9 g·dm−3 [17].
Thus, still a lot of experimental work is needed in this field. It should focus on under-
standing the role of individual components of plant extracts in the corrosion mechanism.
Identification of the most efficient corrosion inhibitors in plant extracts is necessary for
their successful industrial application. In this work, 3,4,5-trihydroxybenzoic acid (Figure 1),
commonly known as gallic acid, was applied as a potential inhibitor of aluminum corrosion
in orthophosphoric acid aqueous solution. Gallic acid can be found in many plants and
foodstuffs, including tea [18,19]. It was a component of several plant extracts that inhibited
the corrosion of aluminum or its alloys in hydrochloric and sulfuric acid aqueous solutions.
These extracts were obtained from Morus nigra L. fruits [20], Phoenix dactylifera leaves [21],
Hemerocallis fulva leaves [22], areca nut [23], and areca flower [24]. In these works, gallic
acid was suggested to act as a corrosion inhibitor, but no direct evidence was provided; for
instance, a relatively high content of this compound was reported in the extract obtained
from Hemerocallis fulva leaves [22].
Metals 2022, 12, x FOR PEER REVIEW
Metals 2022, 12, 250 3 of 17

Figure
Figure1. Gallic acidacid
1. Gallic molecule.
molecule.
The aim of this work is the evaluation of gallic acid as the green corrosion inhibitor
The aim
for aluminum of orthophosphoric
in an this work is the evaluation
acid of gallic
aqueous solution. acid
This wasasnotthe green corrosion
performed yet
forthus
and aluminum
constitutesinthe
annovelty
orthophosphoric acidlack
of this study. This aqueous solution.determination
of experimental This was not of perfor
inhibiting properties of gallic acid in acidic solution is surprising, because
and thus constitutes the novelty of this study. This lack of experimental determin of the promising
results mentioned above obtained for plant extracts [20–24]. Furthermore, gallic acid was
inhibiting properties of gallic acid in acidic solution is surprising, because of the
already tested as a corrosion inhibitor of the 6061 aluminum alloy in an alkaline solution
ing results
(3.5% NaCl, pHmentioned abovehigh
= 12) and relatively obtained forefficiencies,
inhibition plant extracts [20–24].
between 72% andFurthermore,
96% were ga
was already
obtained [25]. Thetested as a corrosion
adsorption of gallic acidinhibitor of theoxide
onto aluminum 6061[26,27]
aluminum alloy in an alk
and an ultrathin
layer of Al
lution 2 O3 on
(3.5% Al substrate
NaCl, pH = were also relatively
12) and studied [28].high
Theseinhibition
studies show that gallic acid
efficiencies, between
adsorbs onto the oxidized aluminum surface. Gallic acid also enhances the dissolution of
96% were obtained [25]. The adsorption of gallic acid onto aluminum oxide [26,27
Al2 O3 at pH = 5, because of its ability to complex aluminum ions [26]. Thus, its application
inultrathin layer ofwhere
neutral solutions, Al2O 3 on Al substrate were also studied [28]. These studies sh
aluminum oxide protects the metallic substrate from corrosion,
isgallic
ratheracid adsorbs onto the oxidized aluminum surface. Gallic acid also enhances
unlikely.
solution
Corrosionof Al 2O3 atin
studies pHthis= work
5, because of its ability
were performed in 0.5to
Mcomplex aluminum ions [26].
H3 PO4 . Orthophosphoric
acid
application in neutral solutions, where aluminum oxide protectsindustry
at various concentrations is frequently used in the aluminum finishing the metallic s
for pickling [3], at 0.5 M concentration is used for gravimetric determination of anodic
from corrosion, is rather unlikely.
coating’s weight [7]. The potential green corrosion inhibitors were only rarely studied in
Corrosion
orthophosphoric studies
acid in Most
solutions. this ofwork were performed
the experimental work wasin 0.5 M H
performed in3PO 4. Orthoph
aqueous
acid at of
solutions various concentrations
hydrochloric is frequently
acid and sulfuric(VI) used in the aluminum finishing indu
acid [10].
pickling [3], at 0.5 M concentration is used for gravimetric determination of ano
2. Materials and Methods
ing’s weight [7]. The potential green corrosion inhibitors were only rarely studi
High purity aluminum, 99.999 wt.%, obtained from Sigma Aldrich® was used for
thophosphoric acid solutions. Most of the experimental work was performed in
the corrosion studies. These studies were carried out using electrochemical methods.
solutions
Working of hydrochloric
electrodes (WEs) for theacid and sulfuric(VI)
electrochemical acidwere
experiments [10].prepared according to
the following procedure. An aluminum slug of 6.35 mm in diameter and 12.7 mm in length
was screwed onto
2. Materials andtheMethods
thin aluminum alloy rod, acting as an electrical connection for the
electrode. The slug and the slug-rod connection were mounted in epoxy resin. The rod was
High
insulated frompurity aluminum,
the electrolyte using99.999 wt.%,tube.
a heat shrink obtained from area
The surface Sigma Aldrich
of the WEs waswas use
®

corrosion
0.32 2 studies.
cm . Before These studies
every experiment, the WEswere carried
were ground out using
with emeryelectrochemical
paper, grit 500 andmethod
1000, rinsed with demineralized
ing electrodes (WEs) for the water, and dried with experiments
electrochemical air. were prepared accordin
Corrosion studies were performed in 0.5 M H3 PO4 aqueous solutions, pH = 1.1. These
following procedure. An aluminum slug of 6.35 mm in diameter and 12.7 mm i
solutions contained different amounts of gallic acid (GA). Its concentration, CGA = 0, 1, 10,
was38screwed
and onto the85thin
mM. Concentrated, wt.%aluminum
orthophosphoricalloyacidrod, acting aspurity
of analytical an electrical connectio
was obtained
electrode.
from Chempur The
® slug and
, Poland. the
Gallic slug-rod
acid, connection
>98% purity, were
was obtained mounted
from Merck KGaA.in epoxy resin.
wasCorrosion
insulatedtestsfrom
werethe electrolyte
conducted using a heatglass
in the thermostated shrink tube. Thecell,
electrochemical surface
placedarea of
inwas
the 0.32
Faraday cage, at 303 K. The cell was filled with 100 cm 3 of the electrolyte. The
cm2. Before every experiment, the WEs were ground with emery paper
electrolyte was deoxygenated using Ar for 15 min prior to each experiment. Ar was also
and 1000, rinsed with demineralized water, and dried with air.
constantly applied over the electrolyte’s surface during the experiments. The corrosion
Corrosion
tests were conducted studies were performed
in electrolytes agitated within 0.5 M Hstirrer.
a magnetic 3PO4 aqueous solutions,
The agitation rate was pH = 1
solutions
300 contained different
rpm. Electrochemical corrosionamounts
tests were of gallic acid
conducted (GA).
in the Its concentration,
three-electrode system. cGA =
The counter electrode was made of platinum. Its surface area was 20 cm 2 . Ag|AgCl
and 38 mM. Concentrated, 85 wt.% orthophosphoric acid of analytical purity
(3M KCl) was used as a reference electrode (REF). Its potential was 0.210 V vs. the Standard
tained from Chempur , Poland. Gallic acid, >98% purity, was obtained from Merc
®

Corrosion tests were conducted in the thermostated glass electrochemical cel

in the Faraday cage, at 303 K. The cell was filled with 100 cm3 of the electrolyte. T
trolyte was deoxygenated using Ar for 15 min prior to each experiment. Ar was a
stantly applied over the electrolyte’s surface during the experiments. The corros
Metals 2022, 12, 250 4 of 17

Hydrogen Electrode (SHE). The reference electrode was placed in a Luggin probe with a
very short tip, filled with 0.5 M H3 PO4 solution. The impedance of such a setup was 500 Ω.
Electrochemical characterization of the Al-H3 PO4 -GA system was conducted using SP-
300 potentiostat (Bio-Logic SAS, Seyssinet–Pariset, France). This characterization included
open circuit potential (OCP), electrochemical impedance spectroscopy (EIS), chronoamper-
ometry (CA), and potentiodynamic polarization (PDP) measurements. First, the OCP was
measured for 3 h. Such a time was sufficient for the system to achieve its stationary state.
Then, impedance spectra and polarization curves were measured. Impedance spectra were
determined in the frequency domain between 200 kHz and 10 mHz. The root mean square
of the applied sinusoidal perturbation was 5 mV. All spectra were validated using KK Test
1.01 software. This software, developed by Bernard Boukamp [29,30], calculates Kramers–
Kronig transformation of the impedance spectra. Then the spectra were approximated
using electrical equivalent circuits. Applied circuits are discussed further in the text. The
approximation was performed using Zview 3.5d software (Scribner Associates, Southern
Pines, NC, USA). Relatively small values of the χ2 parameter, indicating good quality of the
approximation, were obtained. Parameter χ2 was calculated by the approximating software
as the square of the standard deviation between the measured and calculated data.
The anodic and cathodic polarization curves were obtained separately, starting from
the OCP, with the potential scanning rate 10 mV·min−1 . Manual ohmic drop correction
was applied to the registered polarization curves. The solution resistance necessary for this
calculation was determined from the EIS spectra. It was between 20 and 22 Ω.
Statistical analysis of some of the results was also provided. Uncertainty ∆x of an
experimentally determined physical quantity x was calculated using Equation (1):

t · sx
∆x = √ (1)
n

where sx represents the standard deviation of the average value of x and t is the Student
t-factor. It was equal to 2.7764 for 95% confidence level and the number of independent
experiments n = 5 [31].
The surface of corroded Al was examined with a Phenom XL scanning electron micro-
scope (Thermo Fisher Scientific Inc., Waltham, MA, USA). Prior microscopic examination,
the specimens freely corroded for 3 h in deaerated 0.5 M H3 PO4 solutions containing
CGA = 0 and 38 mM, T = 303 K. The Al/electrolyte surface to volume ratio was the same as
in the electrochemical experiments.
The chemical structure of the gallic acid molecule in acidic solution was proposed
from its UV-Vis absorption spectra; these spectra were determined experimentally as a
function of pH and calculated using the DFT method. Four solutions with the gallic acid
concentration equal to 0.65 mM were prepared. The first solution was obtained when
gallic acid was dissolved in deionized water. The pH of the obtained solution was 4.4. The
second solution was prepared in the same manner, but its pH was set at the level of 6.0
using 1 M NaOH solution. The third and fourth solutions were obtained when gallic acid
was dissolved in 0.5 M H3 PO4 and 0.1 M HCl, respectively. The absorption spectra were
measured on a Cary 60 UV-Vis spectrophotometer (Agilent Technologies Inc., Santa Clara,
CA, USA) in a 10 mm quartz cuvette. The aforementioned solutions were diluted 10-fold
with the appropriate diluent (water or mineral acid) before spectrophotometric analysis.
All quantum mechanical calculations were performed using the Gaussian 09 program
package. The molecular structures were optimized at the density functional theory (DFT)
level of theory using the Becke, 3-parameter, Lee–Yang–Parr (B3LYP) functional, with the
6–311G(d) basis set. Time-Dependent DFT (TD-DFT) was used for the calculations of the
UV-Vis spectra with the same basis. In addition, the solvation effect was accounted for
using the polarizable continuum model (CPCM) in all calculations. Charge distribution
and UV–Vis spectra were visualized using the GaussView5.0 program. All calculations
were supported by high-power computers in part by PL-Grid Infrastructure.
 distribution and UV–Vis spectra were visualized using the GaussView5.0 progra
calculations were supported by high-power computers in part by PL-Grid Infrastru

3. Results and Discussion

Metals 2022, 12, 250 5 of 17
3.1. Inhibiting Ability of Gallic Acid
The evaluation of the inhibiting ability of gallic acid was started from the deter
3. Results
tion of theand Discussion
aluminum corrosion potential. This was performed using the open circu
tential measurements. TheAcid
3.1. Inhibiting Ability of Gallic OCP vs. time dependencies were determined in deaerat
The evaluation of the inhibiting
M H3PO4 aqueous solutions containing ability of gallic
gallicacid was(Figure
acid started from the determination
2). OCP decreases immed
of the aluminum corrosion potential. This was performed using the open circuit potential
when aluminum is exposed to an acidic solution because this solution rapidly disso
measurements. The OCP vs. time dependencies were determined in deaerated 0.5 M
thin
H3 POlayer of Al2O3 formed on the aluminum electrode in air. Subsequent decrease
4 aqueous solutions containing gallic acid (Figure 2). OCP decreases immediately
OCP
whenisaluminum
much slower, andtoafter
is exposed circasolution
an acidic 3 h thebecause
stationary valuerapidly
this solution is reached. This
dissolves a corres
thin layer of Al O formed on the aluminum electrode in air. Subsequent
to the corrosion potential Ecorr and was calculated as the average of the OCP valu
2 3 decrease in the
OCP is much slower, and after circa 3 h the stationary value is reached. This corresponds to
tained during the last 5 min of the corrosion experiment. It can be concluded that
the corrosion potential Ecorr and was calculated as the average of the OCP values obtained
acid does
during thenot
lastinfluence
5 min of theEcorrosion
corr. To confirm this,Itacan
experiment. statistical analysis
be concluded of the
that gallic corrosion
acid does po
was
not conducted
influence Ecorr using Equation
. To confirm this,(1). The following
a statistical analysis of values were obtained:
the corrosion −1.151 ± 0
potential was
conducted using Equation (1). The following values
and −1.154 ± 0.009 V vs. REF for cGA = 0 and 38 mM, respectively. were obtained: − 1.151 ± 0.008 V and
−1.154 ± 0.009 V vs. REF for CGA = 0 and 38 mM, respectively.

Figure 2. Open circuit potential of aluminum immersed in deaerated 0.5 M H PO aqueous solution
3 4
Figure 2. Open circuit potential of aluminum immersed in deaerated 0.5 M H3PO4 aqueous s
as a function of initial concentration of gallic acid and exposition time; agitation rate 300 rpm,
as a function of initial concentration of gallic acid and exposition time; agitation rate 300 rp
T = 303 K.
303 K.
The potentiodynamic polarization method is commonly applied in corrosion studies.
It helps
Thetopotentiodynamic
understand the corrosion mechanism
polarization and offers
method the possibility
is commonly to estimate
applied the
in corrosion st
corrosion rate. In this work, the polarization curves were determined as a function of the
It helps to understand the corrosion mechanism and offers the possibility to estima
initial concentration of gallic acid, in 0.5 M H3 PO4 aqueous solutions (Figure 3a). The
corrosion rate. In this
anodic polarization curveswork,
have athe polarization
typical curves with
shape for aluminum werenodetermined as a[2].
linear part visible function
initial
Thus, concentration of gallic
only cathodic curves acid,
can be infor
used 0.5the
Mdetermination
H3PO4 aqueous solutions
of the corrosion(Figure
current 3a).
density. The kinetics of the anodic reaction, which is aluminum oxidation, does not depend
on the concentration of gallic acid.
The cathodic polarization curves describe mainly a hydrogen evolution process. They
exhibit a rather short linear part corresponding to about one decade of the current density.
This occurs between the overpotential η = −0.1 and −0.2 V. When the overpotential is more
negative than −0.2 V, the polarization curves deviate from linearity and reduction peaks
appear. These peaks correspond to the reduction of gallic acid. When its concentration
CGA = 1 mM, the maximum of the reduction peak is located at η < −0.5 V and is not
visible in Figure 3a. The peak positions are shifted in an anodic direction as CGA increases.
Gallic acid is not reduced when −0.2 V < η < 0 V, because all the polarization curves in
Figure 3a overlap with the one obtained at CGA = 0 mM. This also means that gallic acid
does not influence the cathodic process in the corrosion cell when aluminum corrodes at
the corrosion potential.
als 2022, 12, x FOR PEER REVIEW 6 of
Metals 2022, 12, 250 6 of 17

FigureFigure
3. Polarization curves
3. Polarization curvesofofaluminum:
aluminum: (a)(a) as as a function
a function of theofinitial
the initial concentration
concentration of gallic ac
of gallic acid;
(b) an(b)
example showing
an example showinghow howcorrosion current
corrosion current density
density was was determined;
determined; the indicates
the red line red linethe indicates
approximation
approximationof of
thethelinear partofofthethe
linear part polarization
polarization curve.curve. Experiments
Experiments were inperformed
were performed deaerated in dea
ated 0.5
0.5 M HH33PO
PO4 4aqueous
aqueous solutions
solutions with with an agitation
an agitation rate
rate of 300 rpm,ofT300 rpm,
= 303 K. T = 303 K.

It remains unclear why the reduction peak also appears when CGA = 0 mM. The
The anodic
following polarization
three explanationscurves have a typical
can be proposed. shape
The first one isfor
the aluminum
reduction of with no linear p
impurities
visible
from[2].theThus, only cathodic
electrolyte. curves acid
Orthophosphoric can applied
be used in for the determination
all experiments of the corrosi
was of analytical
current density.
purity The kinetics
and contained 0.00005of wt.the
% ofanodic reaction,
As, 0.00002 wt. % of which is aluminum
Cu, 0.00005 wt. % of Pb,oxidation,
and do
0.0005 wt. % of Fe.
not depend on the concentration This corresponds to the following
of gallic acid. concentrations of impurities in the
electrolyte: 29 µg·dm−3 of As, 11 µg·dm−3 of Cu, 29 µg·dm−3 of Pb, and 287 µg·dm−3
The cathodic polarization curves describe mainly a hydrogen evolution proce
of Fe. These are rather low values and probably do not affect the shape of the cathodic
Theypolarization
exhibit a rather curve. short linear
The other part corresponding
explanation is the reduction to of
about
oxygen. oneThedecade of the curre
electrolyte
density.
wasThisalways occurs between
thoroughly the overpotential
deoxygenated η = −0.1
with Ar before the and −0.2 V. When
experiments. Argon wasthe overpotent
also
applied
is more negativeto the than
electrochemical
−0.2 V, the cell over the electrolyte’s
polarization curves surface
deviateduring
fromthe experiments.
linearity and reducti
peaksNevertheless,
appear. These oxygen is produced on the counter electrode during cathodic polarization
peaks correspond to the reduction of gallic acid. When its concent
and may diffuse toward the working electrode and undergo reduction. The last explanation
tion cisGAthe= reduction
1 mM, the of H maximum of the reduction peak is located at η < −0.5 V and is n
3 PO4 , which is the most abundant in the studied system among the
visible in Figure
possible 3a. Thespecies.
electroactive peak The positions
possibleare shifted
reactions arein an anodic
listed in Table 1.direction
The drivingas force
cGA increas
Gallic acid is not reduced when −0.2 V < η < 0 V, because all the polarization
for these reactions is high because the reduction peak is centered at circa − 1.45 V vs. REF curves
Figure(Ag|AgCl
3a overlap (3M KCl)).
with the one obtained at cGA = 0 mM. This also means that gallic ac
does Table
not influence the cathodic process in the corrosion cell when aluminum corrodes
1. Standard electrode potentials of phosphorus-containing species in aqueous solutions,
the corrosion
data from [32]. potential.
It remains unclear why the reduction peak also appears when cGA = 0 mM. The f
Standard Electrode Potential
lowing three explanations Reaction can be proposed. The first one is the reduction of impurit
(V vs. Ag|AgCl (3M KCl))
from the electrolyte. + Orthophosphoric
−
H3 PO4 + 2H + 2e = H3 PO3 + H2 O acid applied in all −experiments
0.070 was of analyti
purity andH contained + 0.00005
− wt. % of As, 0.00002 wt. % of Cu, 0.00005 wt. % of Pb, a
−0.290
3 PO3 + 2H + 2e = H3 PO2 + H2 O
0.0005 wt. %H of Fe. This+ corresponds
− to the following concentrations−0.290
of impurities in t
3 PO3 + 3H + 3e = P + 3H2 O
electrolyte: 29 μg∙dm −3 of As, 11 μg∙dm−3 of Cu, 29 μg∙dm−3 of Pb, and 287 μg∙dm−3 of
P + 3H+ + 3e− = PH3 0.150
These are rather low values and probably do not affect the shape of the cathodic polariz
tion curve. TheTheTafelother explanation
extrapolation method iswas
theapplied
reduction of oxygen.
to determine The electrolyte
the corrosion was alwa
current den-
sity i and the Tafel slopes for the cathodic reactions
thoroughly deoxygenated with Ar before the experiments. Argon was also applied to t
corr (see example in Figure 3b). The
obtained Tafel slopes do not depend on CGA and are within the range between −166 and
electrochemical cell over the electrolyte’s surface during the experiments. Neverthele
−181 mV·dec−1 . These values are more negative than −120 mV·dec−1 obtained for alu-
oxygen is produced on the counter electrode during cathodic polarization and may d
fuse toward the working electrode and undergo reduction. The last explanation is the
duction of H3PO4, which is the most abundant in the studied system among the possib
electroactive species. The possible reactions are listed in Table 1. The driving force
 The Tafel extrapolation method was applied to determine the corrosion current den-
sity icorr and the Tafel slopes for the cathodic reactions (see example in Figure 3b). The
obtained Tafel slopes do not depend on cGA and are within the range between −166 and
Metals 2022, 12, 250 −181 mV∙dec−1. These values are more negative than −120 mV∙dec−1 obtained for aluminum 7 of 17

in acetic or sulfuric acid [33]. This means that when η is between −0.2 V and 0 V there is
an additional electrochemical process apart from hydrogen evolution. Corrosion current
minumare
densities in acetic or sulfuric
between 36 andacid [33]. This
49 μA∙cm means
−2 and dothat
not when η ison
depend between −0.2acid
the gallic V and 0 V con-
initial
there is an additional electrochemical process apart from hydrogen evolution. Corrosion
centration. These values correspond to linear corrosion rates between 0.39 and 0.53
current−1densities are between 36 and 49 µA·cm−2 and do not depend on the gallic acid
mm∙year . The corrosion rates are much lower when compared to those obtained for alu-
initial concentration. These values correspond to linear corrosion rates between 0.39 and
minum
0.53 mm·technical
of year−1 . Thepurity in 0.5
corrosion MH
rates 3PO4: 1.96 mm∙year−1 [5] and 2.56 mm∙year−1 [34].
are much lower when compared to those obtained for
The linear
aluminum corrosion
of technical rateindescribes
purity 0.5 M H3 POwell the studied−1system
4 : 1.96 mm·year
because
[5] and 2.56 mm·yearof the uniform
−1 [34].
character of the corrosion. This was confirmed microscopically (Figure
The linear corrosion rate describes well the studied system because of the uniform 4). SEM analysis
of the corroded
character aluminum
of the corrosion.specimens
This was did not reveal
confirmed any significant
microscopically influence
(Figure 4). SEM of gallic
anal- acid
on ysis of the corroded
the corrosion aluminum
process. specimens
The uniform did not
character reveal any issignificant
of corrosion related toinfluence
the highofpurity
of gallic acid onUsually
aluminum. the corrosion process. The
the corrosion uniform character
of aluminum alloys,of corrosion
even is related
in acidic to the has a
solutions,
high purity of aluminum. Usually the corrosion of aluminum alloys, even in acidic solu-
localized character, due to the presence of numerous intermetallic particles in their micro-
tions, has a localized character, due to the presence of numerous intermetallic particles in
structure [35].
their microstructure [35].

Figure 4. Scanning
Figure 4. Scanningelectron
electron microscopy (SEM)micrographs
microscopy (SEM) micrographs of corroded
of corroded aluminum:
aluminum: (a)= c0GA
(a) CGA = 0 mM;
mM;
(b) (b)
cGACGA
= 38= mM.
38 mM.Experiments
Experimentswere
were performed
performed inindeaerated
deaerated0.50.5
MH M3 PO
H34PO 4 aqueous
aqueous solutions
solutions with anwith an
agitation rate
agitation ofof300
rate 300rpm,
rpm,TT ==303
303 K.
K.

3.2. Corrosion Mechanism

Electrochemical impedance spectroscopy was used to provide a deeper understanding
of the system studied. First, the impedance spectra were recorded at the open circuit
potential, after 3 h of exposure of aluminum in the corrosive environment, as a function of
CGA (Figure 5 and Table 2). The impedance spectra for CGA = 1 and 10 mM are not shown,
because they are essentially the same as those obtained for CGA = 0 and 38 mM.
The impedance spectra were quantitatively analyzed using the electrical equivalent
circuits. The spectra recorded at OCP were approximated using the equivalent circuit
presented in Figure 6a. This circuit consists of resistors R1 –R4, constant phase elements
CPE1 , CPE2 , and the capacitor C1 . The physical meaning of R1 , R2 , and CPE1 is straightfor-
ward, while the interpretation of R3 , R4 , CPE2, and C1 is complicated and requires detailed
knowledge of the system studied.
Resistors R1 and R2 correspond to the solution resistance and the charge transfer
resistance, respectively. The latter takes into account both anodic and cathodic processes
because the spectra were recorded at the OCP. CPE1 corresponds to the double layer
capacitance. The electrical capacity of the double layer is usually not modeled using
the capacitor because it describes the idealized electrode/electrolyte interface with only
one time constant of the charge transfer process. In reality, there is always a certain
etals 2022, 12, x FOR PEER REVIEW 8 o
Metals 2022, 12, 250 8 of 17

3.2. distribution
Corrosion Mechanism
of these time constants. Thus, the constant phase element is typically used
to obtain the capacitance of the electrical double layer. The impedance of CPE is given
Electrochemical impedance spectroscopy was used to provide a deeper understa
by Equation (2) [36]:
ing of the system studied. First, the impedance 1 spectra were recorded at the open cir
ZCPE = (2)
potential, after 3 h of exposure of aluminum T ( jω in
) the corrosive environment, as a func
α

of cGA (Figure
where T is a5parameter
and Table 2). The impedance
corresponding spectra for
to the capacitance, α iscthe
GA = 1 and 10describing
parameter mM are not sho
because they are
the deviation essentially
from the purelythe same as
capacitive those ωobtained
behavior, for cfrequency,
is the angular GA = 0 and 38j mM.
and is the
imaginary number.

Figure 5. Impedance
Figure 5. Impedancespectra ofaluminum:
spectra of aluminum: (a) (a) recorded
recorded at OCPatand
OCP and subsequent
subsequent anodic polariza
anodic polarization;
(b) recorded
(b) recordedatatOCP andsubsequent
OCP and subsequent cathodic
cathodic polarization.
polarization. Continuous
Continuous lines
lines indicate indicate an app
an approxima-
tion of
mation of these
thesespectra using
spectra appropriate
using electrical
appropriate equivalent
electrical circuit. Experiments
equivalent were performedwere
circuit. Experiments in a perfor
deaerated 0.5 M H PO aqueous solution with an agitation rate of 300 rpm, T =
in a deaerated 0.5 M3 H34PO4 aqueous solution with an agitation rate of 300 rpm, T = 303 K. 303 K.

Table 2. Averaged results of approximation of impedance spectra obtained in 0.5 M H3 PO4 at OCP
Table 2. Averaged
using results
equivalent circuit of approximation
from of impedance
Figure 6a: R1 is solution resistance;spectra obtained
T1 and α in 0.5 M H3PO4 at
1 are related to double
using equivalent circuit from Figure 6a: R is solution resistance; T and α
layer capacitance, R2 is charge transfer resistance; R3 , R4 , T2 , α2 , and C1 contribute1 to
1 1 are related to do
Faradaic
layerimpedance.
capacitance,
DataRpresented
2 is charge transfer
in this resistance;
table represent R3, R
average of4,five
T2,independent
α2, and C1 contribute to Faradaic
measurements; thus, im
ance.the χ2 values
Data presented in this
indicating tableof
goodness represent average
fit were not of uncertainties
provided; five independent
of fittedmeasurements;
parameters were thus, th
obtained
values from Equation
indicating goodness (1). of fit were not provided; uncertainties of fitted parameters were

R1
tained from Equation (1).
CGA T1 T2 C1
(mM) (Ω·cm2 ) (µF·sα−1 ·cm−2 ) α1 R2 (Ω·cm2 ) (µF·sα−1 ·cm−2 ) α2 R3 (Ω·cm2 ) (mF·cm−2 ) R4 (Ω·cm2 )
R16.9 ± 0.3 T161 ± 1 0.94 ± 0.01 723 ± 61 332 ± 69 α−1 0.82 ± 163 ± 25 R
413± 13 C1± 19
GA(mM)380 mM
mM 7.02 ± 0.2 17 ± 1 0.94 α
± 10.01 R 2 (Ω∙cm
647 ± 48
2) T 2 (μF∙s
358 ± 38 ∙cm
0.78
−20.06
± )
0.03 α 2 ± 21
164 45 ± 15
120
98 ± 9−2 R4 (Ω∙c
(Ω∙cm ) (μF∙sα−1∙cm−2) (Ω∙cm2) (mF∙cm )
0 mM 6.9 ± 0.3 16 ± 1 0.94 ± 0.01 723
The capacitance ± 61
of the electrode’s332 ± 69layer, C0.82
double ± 0.06 163 ± 25 41 ± 13
dl , can be calculated using Equation (3),
120 ±
38 mM 7.0 ± 0.2 17 ± 1 assuming
0.94 ±the 0.01 647distribution
surface ± 48 of358
time±constants
38 0.78
of the ± charge
0.03 164 ± 21process
transfer 45 [36]:
± 15 98 ±
 1−1/α
1/α 1 1
The impedance spectra were Cdl = Tquantitatively
1 + analyzed using the electrical (3) equiva
R1 R2
circuits. The spectra recorded at OCP were approximated using the equivalent circuit
sented in FigureR6a.
Elements 3 , RThis
4 , CPE 2 , and C
circuit 1 correspond
consists to the adsorption
of resistors of e.g., reaction
R1–R4, constant phase inter-
elements C
mediates and/or corrosion inhibitor as well as the formation of the protective layer onto
CPE2, and the capacitor C1. The physical meaning of R1, R2, and CPE1 is straightforw
aluminum. Impedances of these elements are related to the rate constants of the aforemen-
while theprocesses
tioned interpretation
and changes of inR3the
, Rsurface
4, CPE2, and C1 is complicated and requires deta
coverage in the case of both adsorption and the
knowledge
formationof
of the system studied.
the protective layer. These dependencies are complex and interrelated [36,37].
Resistors R1 and R2 correspond to the solution resistance and the charge transfe
sistance, respectively. The latter takes into account both anodic and cathodic proce
because the spectra were recorded at the OCP. CPE1 corresponds to the double layer
pacitance. The electrical capacity of the double layer is usually not modeled using the
pacitor because it describes the idealized electrode/electrolyte interface with only one t
Metals 2022, 12, x FOR PEER REVIEW 9 of 1

Metals 2022, 12, 250 9 of 17

1
ZCPE = (2
( j ) are provided in Table 2. This

The fitting results together with their statisticalTanalysis
analysis
where confirms that galliccorresponding
T is a parameter acid does not influence the corrosionαprocess
to the capacitance, of aluminum
is the parameter describin
in the orthophosphoric acid solution. Polarization resistance Rp , which is the sum of the
the deviation from the purely capacitive behavior, ω is the angular frequency, and j is th
four resistances, equals 1013 ± 97 Ω·cm2 and 936 ± 45 Ω·cm2 for CGA = 0 and 38 mM,
imaginary number.
respectively. This means virtually the same value of corrosion rate in both cases. The
The capacitance
same values of T2 , α2 , R3of
, Cthe electrode’s double layer, Cdl, can be calculated using Equatio
1 , and R4 obtained for CGA = 0 and 38 mM indicate that gallic
(3), assuming the surface distribution
acid molecules do not adsorb onto aluminum. of time constants
Therefore, theseofelements
the charge transfer
of the process [36
equivalent
circuit correspond to adsorption of reaction intermediates1−and/or 1/  the formation of the
1 1 
Cdl = T11/  +seems
protective layer. Adsorption of reaction intermediates  to be plausible only for the (3
cathodic process, where adsorbed hydrogen atoms  Rare
1 R2 
formed [36]. The charge transfer
relatedElements
to aluminumR3, Roxidation in acidic solutions is believed to be too rapid to observe
4, CPE2, and C1 correspond to the adsorption of e.g., reaction interme
the formation of any intermediates [38]. The protective layer that could be formed and
diates and/or corrosion inhibitor as well as the formation of the protective layer onto alu
dissolved simultaneously is Al2 O3 . This explains the lack of the linear part on the anodic
minum. Impedances of these elements are related to the rate constants of the aforemen
polarization curves in Figure 3a. Double layer capacitances also support the hypothesis
oftioned
partialprocesses
coverage ofand the changes
electrodein theAlsurface
with coverage in the case of both adsorption an
2 O3 , because they are smaller when compared
the formation of the protective layer.
to the typical value for metallic electrodes, 20 µF·cmThese dependencies
−2 [39]: C = 9.1
dl
are±complex
0.6 µF·cmand interrelate
−2 , and
[36,37].
9.6 − 2
± 0.3 µF·cm for CGA = 0 and 38 mM, respectively.

Figure
Figure 6. 6. Electrical
Electrical equivalent
equivalent circuits
circuits used used for approximation
for approximation of impedance
of impedance spectra:
spectra: (a) (a)at
recorded recorded
open
open circuit
circuit potential;
potential; (b) recorded
(b) recorded at η =at+0.1
η =V;+0.1 V; (c) recorded
(c) recorded at η = −at
0.1ηV.= −0.1 V.

The
The important question
fitting results arises as
together to why
with theirgallic acid does
statistical not adsorb
analysis onto aluminum.
are provided in Table 2. Th
Gallic acid is a weak acid with pK = − 4.152 [40]. This means that at
analysis confirms that gallic acid does not influence the corrosion process of aluminum i pH = 6.0 it is almost
completely (98%) dissociated. When the solution becomes acidic, gallic acid is protonated.
the orthophosphoric acid solution. Polarization resistance Rp, which is the sum of the fou
Thus, it was important to check whether at pH = 1.1 gallic acid exists as the neutral
resistances,
molecule or if equals
further 1013 ± 97 Ω∙cm
protonation
2 and 936 ± 45 Ω∙cm2 for cGA = 0 and 38 mM, respectively
is possible, e.g., of the oxygen from the carbonyl group.
This
The means virtually
protonation of gallictheacidsame value
can be of corrosion
studied using UV-Vis rate spectrophotometry
in both cases. The because
same values
it of T
α , R , C and R obtained for c = 0 and 38 mM indicate that
produces a bathochromic shift of the absorption bands. Gallic acid has two absorption bands
2 3 1, 4 GA gallic acid molecules do no
inadsorb onto aluminum.
the ultraviolet part of theTherefore, thesebands
spectrum. These elements of the to
are related equivalent circuit correspond
π → π* transitions [41]. t
At pH = 6.0, when
adsorption gallic acid
of reaction is almost completely
intermediates and/or the dissociated,
formationthese
of thebands are centered
protective layer. Adsorp
attion
212 ofand 259 nm.intermediates
reaction They are only seems
slightlytoshifted at pH =only
be plausible 4.4, where
for thecirca 64% ofprocess,
cathodic gallic wher
acid molecules are dissociated, and much stronger at pH = 1.1 (Figure
adsorbed hydrogen atoms are formed [36]. The charge transfer related to aluminum ox 7a). The absorption
spectra obtained for gallic acid dissolved in H3 PO4 and HCl at this pH are the same. This
dation in acidic solutions is believed to be too rapid to observe the formation of any inte
means that there are no specific interactions between gallic and orthophosphoric acids.
mediates [38]. Thespectrum
The absorption protective layer that
obtained could
in 0.5 M Hbe formed and dissolved simultaneously
3 PO4 can be compared with the one
Al2O3. This
calculated for explains the lackgallic
an undissociated of the linear
acid part using
molecule on thetheanodic
TD-DFT polarization
method (Figure curves
7b).in Figur
3a. Double layer capacitances also support the hypothesis of
Positions of absorption bands in both spectra are comparable. This, and agreement with the partial coverage of the elec
trode with
already Al2O3data
published , because
[41,42],they are smaller
strongly suggestwhen compared
that during to the typical
the corrosion value
tests, gallic for metall
acid
was in the form
electrodes, 20 of an undissociated
μF∙cm −2 [39]: Cdl = molecules.
9.1 ± 0.6 μF∙cmFor additional
−2, and 9.6confirmation,
± 0.3 μF∙cm−2the forUV-Vis
cGA = 0 and 3
mM, respectively.
 The absorption spectrum obtained in 0.5 M H3PO4 can be compared with the o
calculated for an undissociated gallic acid molecule using the TD-DFT method (Fig
7b). Positions of absorption bands in both spectra are comparable. This, and agreem
with the already published data [41,42], strongly suggest that during the corrosion te
Metals 2022, 12, 250 10 of 17
gallic acid was in the form of an undissociated molecules. For additional confirmation,
UV-Vis absorption spectrum of the gallic acid molecule with protonated oxygen at
fromabsorption
the carbonyl group
spectrum of was calculated.
the gallic This protonation
acid molecule with protonated process
oxygenproduces
atom fromathe strong ba
ochromic
carbonyl group was calculated. This protonation process produces a strong bathochromic an ad
shift of the absorption band centered at λ = 278 nm to λ = 341 nm, and
tional absorption
shift band also
of the absorption bandappears
centered atat 388 nm.nm
λ = 278 There
to λ =are
341no
nm,absorption bands at λ >
and an additional
absorption band also appears at 388 nm. There are no absorption
nm in the experimentally obtained spectra. Therefore, the oxygen atom from bands at λ > 320 nm the
in carbo
the experimentally obtained spectra. Therefore, the oxygen atom from the carbonyl group
group is not protonated at pH = 1.1.
is not protonated at pH = 1.1.

Figure 7. Absorption
Figure 7. Absorptionspectra of aqueous
spectra of aqueous solutions
solutions of gallic
of gallic acid:
acid: (a) (a) measured
measured experimentally
experimentally as a
function of pH,
function cGACGA
of pH, = 65 μM;
= 65 µM;(b)
(b) obtained using
obtained using quantum
quantum mechanical
mechanical calculations.
calculations.

Adsorption onto a metallic electrode is related to the electrical charge of both coun-
Adsorption onto a metallic electrode is related to the electrical charge of both co
terparts. The sign of the electrical charge on aluminum depends on its potential in the
terparts. The sign
electrolyte. ofwork,
In this the electrical
the corrosioncharge
processonwas
aluminum depends
studied mainly at theon its potential
corrosion po- in
electrolyte. In average
tential. Its this work, thecirca
value, corrosion
−1.15 Vprocess
vs. REF,was studied
is more mainly
negative whenatcompared
the corrosion
to pot
the average
tial. Its potential of zero charge
value, of aluminum,
circa −1.15 V vs. REF,−0.73isVmore
vs. REF [43]. Thewhen
negative value of corrosion to the
compared
potential is between the potentials of anodic and cathodic areas in the corrosion cell. This
tential of zero charge of aluminum, −0.73 V vs. REF [43]. The value of corrosion poten
means that, under studied conditions, at least the anodic areas are negatively charged.
is between the potentials
The electrical ofcathodic
charge at the anodic areas
and cannot
cathodic areas ininthe
be deduced thiscorrosion
manner; it cell. This me
can be
that,positive
under of studied
negative.conditions, at least
The interaction theacid
of gallic anodic
with areas are negatively
the metallic charged.
surface is possible via The e
trical charge at the cathodic areas cannot be deduced in this manner; it can be8.positive
hydroxyl or carbonyl groups. All of them are negatively charged as is shown in Figure
Thus, the
negative. Theprobability
interactionof adsorption
of gallic of gallic
acid acidthe
with on the anodic surface
metallic areas of the corrosion cell
is possible via hydro
is low and the anodic process in the corrosion cell is not inhibited. In fact, there is an
or carbonyl groups. All of them are negatively charged as is shown in Figure 8. Thus,
overall positive charge at the benzene ring, but it apparently does not facilitate adsorption
probability of adsorption
on anodic areas of gallic
of corroding acid on
aluminum. the anodic
Further areas
studies, e.g., of local
with the corrosion cell is low a
electrochemical
methods, are necessary to explain why gallic acid does not adsorb at the cathodic areas
in the corrosion cell. Adsorption of the neutral molecule should be possible at a potential
close to the potential of zero charge [44]. Adsorption of gallic acid onto aluminum oxide is
possible at pH = 1.1, because the oxide surface is positively charged then [45].
The negatively charged surface of aluminum attracts cations from the electrolyte.
These are, in addition to hydronium, aluminum complexes such as [AlPO4 H2 ]2+ and
[AlPO4 H]+ . Their presence in the solution at pH = 1.1 can be suggested based on thermo-
dynamic calculations (Figure 9). Complexes of gallic acid with aluminum are not formed
because they are less stable than complexes with phosphate anions [40,46]. This confirms
the results of corrosion experiments. The formation of stable complexes of aluminum with
gallic acid would result in an increased corrosion rate.
 charge at the benzene ring, but it apparently does not facilitate adsorption on anodic a
of corroding aluminum. Further studies, e.g., with local electrochemical methods, are
essary to explain why gallic acid does not adsorb at the cathodic areas in the corro
cell. Adsorption of the neutral molecule should be possible at a potential close to the
Metals 2022, 12, 250 tential of zero charge [44]. Adsorption of gallic acid onto aluminum oxide 11 ofis
17 possib

pH = 1.1, because the oxide surface is positively charged then [45].

Figure 8. Electrical charge distribution in gallic acid molecule; C, O, and H atoms are depic
grey, red, and white balls, respectively.

The negatively charged surface of aluminum attracts cations from the electr
These are, in addition to hydronium, aluminum complexes such as [AlPO4H2]2
[AlPO4H]+. Their presence in the solution at pH = 1.1 can be suggested based on the
dynamic calculations (Figure 9). Complexes of gallic acid with aluminum are not fo
because they are less stable than complexes with phosphate anions [40,46]. This con
the results of corrosion experiments. The formation of stable complexes of aluminum
gallic
Figure 8.acid
Figure wouldcharge
Electrical
8. Electrical resultdistribution
charge in an increased
distribution in gallic corrosion
in gallic
acid acid rate.
molecule;
molecule; C,HO,atoms
C, O, and and are
H depicted
atoms are
as depicte
grey,grey,
red,red,
andandwhite
white balls,
balls, respectively.
respectively.

The negatively charged surface of aluminum attracts cations from the electro
These are, in addition to hydronium, aluminum complexes such as [AlPO4H2]2+
[AlPO4H]+. Their presence in the solution at pH = 1.1 can be suggested based on ther
dynamic calculations (Figure 9). Complexes of gallic acid with aluminum are not form
because they are less stable than complexes with phosphate anions [40,46]. This confi
the results of corrosion experiments. The formation of stable complexes of aluminum w
gallic acid would result in an increased corrosion rate.

Figure 9. Speciation diagram for Al-H PO -GA-H O system. Calculations were performed for 0.5 M
3 4 2
Figure 9. Speciation diagram for Al-H 3PO4-GA-H2O system. Calculations were performed for
H3 PO4 aqueous solution. Total aluminum concentration of 5 mM was obtained from corrosion rate,
H3PO4 aqueous solution. Total aluminum concentration of 5 mM was obtained from corrosio
assuming t = 3 h, the total gallic acid concentration was 38 mM. Stability constants for complex ions
assuming t = 3 h, the total gallic acid concentration was 38 mM. Stability constants for comple
are from [40,46].
are from [40,46].
Impedance spectra recorded at the OCP characterize both anodic and cathodic pro-
cesses in the corrosion cell. These processes were studied separately using the following
methodology. First, aluminum corroded freely at the OCP for 3 h, and the impedance spec-
trum was recorded. Subsequently, the working electrode was polarized either −0.1 V or
+0.1 V vs. OCP. The constant potential was then held for 1 h, and the impedance spectrum
was recorded. This procedure was carried out for CGA = 0 and 38 mM, and again, there was
no influence of gallic acid on the studied processes (Figure 5a,b, Tables 3 and 4).
Figure 9. Speciation diagram for Al-H3PO4-GA-H2O system. Calculations were performed for 0
The impedance spectrum characterizing the anodic processes, i.e., obtained at η = +0.1 V,
H3PO 4 aqueous solution. Total aluminum concentration of 5 mM was obtained from corrosion
consists of two time constants (Figure 5a) and was approximated with the electrical equiva-
assuming t = 3 presented
lent circuit h, the totalingallic
Figureacid
6b. concentration
This circuit canwas 38 mM.
describe the Stability constants
passivation process for
[37],complex
are from
where[40,46].
R3 and C1 correspond to the formation of the protective layer. The impedances
of these two elements depend on the charge transfer resistance and describe how the
electric current changes when the surface is gradually covered with the protective layer
Metals 2022, 12, 250 12 of 17

or when the resistivity of this layer increases. When the electrode potential is below the
active-passive transition potential R3 has a positive value and dissolution of the protective
layer prevails. Nevertheless, a certain deviation from the Tafelian behavior is visible in the
polarization curve. The higher the value of R3 , the more significant this deviation is. The
active-passive transition occurs when R3 goes to infinity. When the metal is in the passive
state, R3 is negative [37].

Table 3. Results of approximation of impedance spectra obtained in 0.5 M H3 PO4 at OCP prior
anodic polarization, using equivalent circuit from Figure 6a: R1 is solution resistance; T1 and α1 are
related to double layer capacitance, R2 is charge transfer resistance; R3 , R4 , T2 , α2 and C1 contribute
to Faradaic impedance; uncertainties of fitted parameters were obtained from fitting software, χ2
values indicate goodness of fit.

CGA T1 T2 C1
(mM) χ2 R1 (Ω·cm2 ) (µF·sα−1 ·cm−2 )
α1 R2 (Ω·cm2 ) (µF·sα−1 ·cm−2 )
α2 R3 (Ω·cm2 ) (mF·cm−2 ) R4 (Ω·cm2 )

0 mM 0.00014 7.0 ± 0.1 15.2 ± 0.2 0.94 ± 0.01 721 ± 13 308 ± 39 0.83 ± 0.05 150 ± 14 59.7 ± 3.6 136 ± 6
38 mM 0.00039 7.2 ± 0.1 15.8 ± 0.2 0.94 ± 0.01 672 ± 17 321 ± 39 0.74 ± 0.05 191 ± 19 40.9 ± 3.5 101 ± 5

Table 4. Results of approximation of impedance spectra obtained in 0.5 M H3 PO4 at η = +0.1V vs.
OCP using equivalent circuit from Figure 6b: R1 is solution resistance; T1 and α1 are related to double
layer capacitance, R2 is charge transfer resistance; R3 and C1 contribute to Faradaic impedance;
uncertainties of fitted parameters were obtained from fitting software, χ2 values indicate goodness
of fit.

T1 C1
CGA (mM) χ2 R1 (Ω·cm2 ) α1 R2 (Ω·cm2 ) R3 (Ω·cm2 )
(µF·sα−1 ·cm−2 ) (mF·cm−2 )
0 mM 0.00053 6.9 ± 0.1 14.3 ± 0.1 0.94 ± 0.01 721 ± 2 12.1 ± 0.3 374 ± 6
38 mM 0.00053 7.1 ± 0.1 15.4 ± 0.1 0.94 ± 0.01 743 ± 2 12.1 ± 0.4 353 ± 8

It can be observed that R3 = 374 Ω·cm2 , obtained for the anodically polarized electrode
(Table 4), and this is significantly higher than both R3 = 150 Ω·cm2 and R4 = 136 Ω·cm2
obtained at the OCP (Table 3). Thus, anodic polarization enhances the formation of the
protective layer. This should decrease the double layer capacitance of the electrode because
the dielectric permittivity of Al2 O3 is lower when compared to that of water. This seems to
occur in the studied system. Cdl decreases from 8.6 to 7.8 µF·cm−2 when CGA = 0 mM and
from 9.3 to 8.2 µF·cm−2 when CGA = 38 mM. These, however, are small differences, and
further statistical analysis is necessary to prove it. The protective layer is simultaneously
formed and dissolved in an orthophosphoric acid solution, and either the surface coverage
or the film thickness is insufficient to induce the active–passive transition. Gallic acid does
not influence the passivation process; therefore, virtually the same values of C1 and R3
were obtained for CGA = 0 and 38 mM.
The impedance spectrum characterizing the cathodic processes consists of the three
time constants, with the inductive loop at the low-frequency range (Figure 5b). The
impedance spectrum was approximated using the electrical equivalent circuit presented in
Figure 6c. This circuit consists of resistors R1 –R4 , constant phase elements CPE1 and CPE2
as well as the inductor L1 . Resistors R1 and R2 correspond to the solution and the charge
transfer resistance, respectively. The constant phase element CPE1 represents the double
layer capacitance. Resistors R3 and R4 , CPE2 , and L1 can be related to the adsorption of
two different species [47].
The results of approximation of the impedance spectra obtained at OCP and sub-
sequent cathodic polarization are presented in Tables 5 and 6 respectively. Cathodic
polarization caused a very small change in the double layer capacitance. Cdl decreased
with polarization from 8.5 to 8.2 µF·cm−2 when CGA = 0 mM and from 9.9 to 9.2 µF·cm−2
when CGA = 38 mM. On the contrary to the anodic polarization, the cathodic one caused
a significant decrease in charge transfer resistance (R2 in all equivalent circuits). This is
Metals 2022, 12, 250 13 of 17

understandable because cathodic polarization should facilitate charge transfer from the
electrode to hydrogen ions in the electrolyte. More interesting is the nature of the inductive
loop appearing upon cathodic polarization. The most important cathodic process in the
studied system is hydrogen evolution. Typically, this process is modeled with a simple
equivalent circuit, such as presented in Figure 6b [36]. This might suggest that the inductive
loop corresponds to the adsorption process that is not related to hydrogen evolution. It has
already been mentioned that there is more than one cathodic process in the system studied.
The following possibilities were proposed: reduction of impurities from the electrolyte,
oxygen generated at the counter electrode, and orthophosphoric acid. The latter seems to
be the most plausible. That is because the first two of them should be diffusion-controlled
due to the low concentration of either impurities or oxygen in the electrolyte. Diffusion
processes, contrary to adsorption, do not manifest in the impedance spectra in the form of
the inductive loop [36].

Table 5. Results of approximation of impedance spectra obtained in 0.5 M H3 PO4 at OCP prior
cathodic polarization, using equivalent circuit from Figure 6a: R1 is solution resistance; T1 and α1 are
related to double layer capacitance, R2 is charge transfer resistance; R3 , R4 , T2 , α2 and C1 contribute
to Faradaic impedance; uncertainties of fitted parameters were obtained from fitting software, χ2
values indicate goodness of fit.

CGA T1 T2 C1
(mM) χ2 R1 (Ω·cm2 ) (µF·sα−1 ·cm−2 )
α1 R2 (Ω·cm2 ) (µF·sα−1 ·cm−2 )
α2 R3 (Ω·cm2 ) (mF·cm−2 ) R4 (Ω·cm2 )

0 mM 0.00016 6.8 ± 0.1 15.0 ± 0.1 0.94 ± 0.01 739 ± 9 308 ± 23 0.79 ± 0.03 186 ± 11 40.2 ± 2 117 ± 2
38 mM 0.00017 6.8 ± 0.1 17.1 ± 0.2 0.94 ± 0.01 667 ± 8 373 ± 28 0.80 ± 0.03 160 ± 9 39.5 ± 2 105 ± 3

Table 6. Results of approximation of impedance spectra obtained in 0.5 M H3 PO4 at η = −0.1V

vs. OCP, using equivalent circuit from Figure 6c: R1 is solution resistance; T1 and α1 are related to
double layer capacitance, R2 is charge transfer resistance; R3 , R4 , T2 , α2 and L1 contribute to Faradaic
impedance; uncertainties of fitted parameters were obtained from fitting software, χ2 values indicate
goodness of fit.

CGA T1 T2
(mM) χ2 R1 (Ω·cm2 ) (µF·sα−1 ·cm−2 )
α1 R2 (Ω·cm2 ) (µF·sα−1 ·cm−2 )
α2 R3 (Ω·cm2 ) L1 (H·cm2 ) R4 (Ω·cm2 )

0 mM 0.00017 6.7 ± 0.1 15.0 ± 0.2 0.94 ± 0.01 484 ± 16 619 ± 74 0.59 ± 0.05 2447 ± 331 4576 ± 652 166 ± 21
38 mM 0.00032 6.8 ± 0.1 17.1 ± 0.2 0.94 ± 0.01 470 ± 7 616 ± 53 0.69 ± 0.04 2310 ± 157 5040 ± 426 125 ± 10

An additional corrosion experiment was performed to verify whether the inductive

loop is related to the presence of orthophosphoric acid in the studied system. During this
experiment, aluminum corroded freely in a 0.1 M HCl aqueous solution for 5 h. Then, the
impedance spectrum was recorded. Subsequently, the electrode was polarized cathodically
vs. OCP, η = −0.1 V. The potential was held for 1 h and the impedance spectrum was
recorded (Figure 10).
The impedance spectrum obtained at the cathodic polarization can be approximated
using the equivalent circuit from Figure 6b, which is typical for hydrogen evolution [36]
(results in Table 7). This confirms the assumption that the inductive loop obtained in
0.5 M H3 PO4 at η = −0.1 V (Figure 5b) is related to the adsorption of a reduced form of
orthophosphoric acid.
It is also interesting to compare the impedance spectra obtained at the OCP in 0.1 M
HCl and 0.5 M H3 PO4 . The former exhibit the inductive loop at the low frequencies,
thus the equivalent circuit from Figure 6c was applied (Table 8). Similar spectra were
recorded for iron in an acidic solution, at the potential below the active-passive transition
potential [37]. Because the data points at the low frequencies are scattered and their number
is too small a reliable determination of R4 was not possible. Nevertheless, this value is very
high. This fact, together with the high value of the charge transfer resistance, R2 , indicates
that at the same pH, orthophosphoric acid is much more corrosive than hydrochloric acid.
This, in turn, can be related to the formation of stable aluminum complexes in the H3 PO4
aqueous solution.
Metals 2022, 12, x FOR PEER REVIEW 1
Metals 2022, 12, 250 14 of 17

Figure 10. Impedance spectra of aluminum in 0.1 M HCl aqueous solution recorded at OCP and
Figure 10. Impedance spectra of aluminum in 0.1 M HCl aqueous solution recorded at O
subsequent cathodic polarization. Continuous lines indicate an approximation of these spectra using
subsequent cathodic polarization. Continuous lines indicate an approximation of these spe
appropriate electrical equivalent circuit. Experiments were performed in deaerated, agitated solutions
ing appropriate electrical equivalent circuit. Experiments were performed in deaerated, agita
with an agitation rate of 300 rpm, T = 303 K.
lutions with an agitation rate of 300 rpm, T = 303 K.
Table 7. Results of approximation of impedance spectra obtained in 0.1 M HCl at η = −0.1V vs. OCP
usingTheequivalent circuit from
impedance spectrum R1 is solution
Figure 6b:obtained resistance;
at the T1 and
cathodic α1 are related can
polarization to double
be approxi
layer capacitance, R2 is charge transfer resistance; R3 and C1 contribute to Faradaic impedance;
using the equivalent circuit from Figure 6b, which is typical for hydrogen evolutio
uncertainties of fitted parameters were obtained from fitting software, χ2 values indicate goodness
(results
of fit. in Table 7). This confirms the assumption that the inductive loop obtained
M H3PO4 at η = −0.1 V (Figure 5b) is related to the adsorption of a reduced form of
R1 T1 R2 C1 R3
χ2
phosphoric acid. α1
(Ω ·cm2 ) (µF·sα−1 ·cm−2 ) (Ω·cm2 ) (µF·cm−2 ) (Ω·cm2 )
0.00075 6.5 ± 0.1 16.0 ± 0.2 0.96 ± 0.01 2853 ± 68 55.0 ± 11 629 ± 67
Table 7. Results of approximation of impedance spectra obtained in 0.1 M HCl at η = −0.1V v
using equivalent circuit from Figure 6b: R1 is solution resistance; T1 and α1 are related to
Table 8. Results of approximation of impedance spectra obtained in 0.1 M HCl at OCP, using
layer capacitance, R2 is charge transfer resistance; R3 and C1 contribute to Faradaic impedan
equivalent circuit from Figure 6c: R1 is solution resistance; T1 and α1 are related to double layer
certainties
capacitance,of
R2fitted parameters
is charge were obtained
transfer resistance; R3 , R4 , T2 ,from
α2 andfitting software,
L1 contribute χ2 values
to Faradaic indicate good
impedance;
fit. 2
uncertainties of fitted parameters were obtained from fitting software, χ values indicate goodness
of fit.
T1
T1 χ2 R1 (Ω∙cm2)2 T2 α1 R2 (Ω∙cm2) 2 C1 (μF∙cm −2)
χ2 R1 (Ω·cm2 ) (µF·sα−1 ·cm−2 )
α1 R2 (Ω·cm ) (μF∙s ∙cm ) α2
α−1 −2
(mF·sα−1 ·cm−2 ) R3 (Ω·cm2 ) L1 (H·cm ) R4 (Ω·cm2 ) (Ω
0.00093 6.5 ± 0.1 17.0 ± 0.2 0.00075
0.95 ± 0.01 6.5 ± 0.1
2856 ± 101 16.0
2.2 ±±
0.60.2 0.220.96
± 0.04 ± 0.01 2853 ±30335
11377 ± 1736 68± 5218 55.0n.d.± 11 62

4. Conclusions
It is also interesting to compare the impedance spectra obtained at the OCP in
HCl andThe corrosion
0.5 M H3behavior
PO4. Theofformer
aluminum in orthophosphoric
exhibit the inductiveacid loopwasatstudied
the lowinfrequencie
the
presence of gallic acid as a potential corrosion inhibitor using electrochemical methods.
the equivalent circuit from Figure 6c was applied (Table 8). Similar spectra were rec
A relatively low value of corrosion potential of aluminum, −1.151 ± 0.008 V vs. REF,
for
was iron in an This
obtained. acidic solution,
value did not at the potential
change belowof
with the addition the active-passive
gallic transition po
acid to the corrosive
[37]. BecauseGallic
environment. the data points
acid also at the
did not low
affect the frequencies areand
kinetics of anodic scattered
cathodicand theirinnumber
reactions
the corrosion cell. Consequently, virtually the same corrosion
small a reliable determination of R4 was not possible. Nevertheless, rates were obtained
this in the is ver
value
solution without and with gallic acid: CGA = 38 mM, 0.39 and 0.40 mm·year−1 , respectively.
This fact, together with the high value of the charge transfer resistance, R2, indicat
Thus, this organic compound does not act as a corrosion inhibitor in the system studied.
atImpedance
the samespectra
pH, orthophosphoric
analysis confirms thisacid is much
conclusion. more corrosive
Polarization resistancesthan
were hydrochlori
equal
This, in±turn,
to 1013 can
97 and 936be± related to=the
45 for CGA formation
0 and of stable aluminum complexes in the
38 mM, respectively.
aqueousIt was also shown that there are two cathodic processes in the corrosion cell. The main
solution.
process is hydrogen evolution; the other one is presumably the reduction in phosphorus-
containing species. Anodic processes in the corrosion cell involve aluminum oxidation and
Table 8. Results of approximation of impedance spectra obtained in 0.1 M HCl at OCP, using
alent circuit from Figure 6c: R1 is solution resistance; T1 and α1 are related to double layer
tance, R2 is charge transfer resistance; R3, R4, T2, α2 and L1 contribute to Faradaic impedance
tainties of fitted parameters were obtained from fitting software, χ2 values indicate goodnes
Metals 2022, 12, 250 15 of 17

the formation of a protective layer, most probably aluminum oxide. The latter is chemically
dissolved, and thus the specimen cannot be passivated. Again, gallic acid inhibited neither
aluminum oxidation, nor the protective oxide layer dissolution.
The aim of this work was to verify whether gallic acid is capable of inhibiting alu-
minum corrosion in orthophosphoric acid aqueous solution. Electrochemical characteriza-
tion of the Al-H3 PO4 -GA system clearly shows that gallic acid does not act as a corrosion
inhibitor under the conditions adopted in this work. This occurs because the organic
molecules do not adsorb on the surface of aluminum. This is related to the net negative
electric charge located at the possible adsorption sites of gallic acid, hydroxyl or carbonyl
groups, and negatively charged surface of anodic areas in the corrosion cell. The sign
of the electrical charge located at the cathodic areas in the corrosion cell remains un-
known. Inhibiting effect of the plant extracts containing gallic acid was observed in HCl
and H2 SO4 solutions. The corrosion potential of aluminum or its alloys was then circa
0.25–0.65 V higher than reported in this study. This may facilitate the adsorption of the
organic molecules. Verification of this hypothesis requires additional corrosion studies.
Another possibility is that gallic acid simply does not act as the corrosion inhibitor in the
aforementioned extracts.
The experimental results presented in this work show that systematic studies on
the influence of the individual constituents of plant extracts on aluminum corrosion are
necessary. The plant extracts are very complex, multicomponent systems, where some
antagonistic or synergistic effects between constituents can occur. Thus, in our opinion, the
promising results obtained using plant extracts are just the first step toward more detailed
corrosion studies.

Author Contributions: Conceptualization, P.K.; methodology, P.K.; formal analysis, P.K.; investiga-
tion, P.K., K.D., B.K., A.O., M.W., A.P.; writing—original draft preparation, P.K.; writing—review and
editing, P.K., M.W.; supervision, P.K. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was partially funded by National Science Centre, Poland, grant number
2016/23/D/ST5/01343.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on reasonable request
from the corresponding author.
Acknowledgments: This research was supported in part by PL-Grid Infrastructure. DFT calcula-
tions were performed at the Academic Computer Centre CYFRONET AGH within computational
grant LIIPS3.
Conflicts of Interest: The authors declare no conflict of interest.

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