Review
ChemElectroChem doi.org/10.1002/celc.202300712
Corrosion Modeling of Aluminum Alloys: A Brief Review
A. Ruiz-Garcia,[a] V. Esquivel-Peña,[b] F. A. Godínez,*[c] and R. Montoya*[a]
Corrosion remains a critical concern in various industries,
particularly in applications involving aluminum alloys due to
their widespread usage as light structural materials. This work
provides a comprehensive overview of the recent advances in
modeling techniques for better understanding the corrosion
behavior of aluminum alloys. The present study encompasses
the state-of-the-art of computational approaches, highlighting
their strengths and limitations. Special attention is given to
transport models, galvanic couples, localized corrosion, and the
incorporation of different factors, such as pH variations, electro-
lyte thicknesses and dynamic electrolytes into corrosion models.
1. Introduction
Corrosion is a highly complex phenomenon from a technical-
scientific point of view and costly from an economic perspec-
tive. The latter is evidenced by the high costs associated with
corrosion problems in the transportation industry, one of the
most affected sectors by this issue. The aircraft sector estimated
that in the United States, the annual fee of the impact of
corrosion is in the order of $ 2.2 billion; of this amount, the item
that has the most significant effect is corrosion maintenance
with $ 1.7 billion.[1]
Many of the challenges in corrosion research are too
complex to be addressed by a single approach. Under this
scenario, computational corrosion analysis is increasingly
relevant, not as an isolated tool, but as an opportunity that
allows a deeper understanding of corrosion processes by
promoting a synergy between numerical-theoretical research
and electrochemical experimental techniques. Corrosion phe-
nomena can be described through different approaches, such
as deterministic models, artificial intelligence, empirical models,
[a] A. Ruiz-Garcia, Dr. R. Montoya
Unidad de Investigación y Tecnología Aplicadas, Facultad de Química,
Universidad Nacional Autónoma de México,
Apodaca, 66629, Nuevo León México
E-mail: rmontoyal@unam.mx
[b] Dr. V. Esquivel-Peña
Departamento de Química Analítica, Facultad de Química, Universidad
Nacional Autónoma de México,
Coyoacán, 04510, Ciudad de México
[c] Dr. F. A. Godínez
Unidad de Investigación y Tecnología Aplicadas, Instituto de Ingeniería,
Universidad Nacional Autónoma de México,
Apodaca, 66629, Nuevo León México
E-mail: fgodinezr@iingen.unam.mx
© 2024 The Authors. ChemElectroChem published by Wiley-VCH GmbH. This
is an open access article under the terms of the Creative Commons Attri-
bution License, which permits use, distribution and reproduction in any
medium, provided the original work is properly cited.
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Furthermore, the review delves into both bulk and atmospheric
corrosion models. On the other hand, this work also emphasizes
a clear differentiation between models designed for bare
aluminum alloys and those tailored for coated ones. Addition-
ally, it addresses certain challenges associated with the
experimental validation of such models. This review concludes
with perspectives on both sophisticated transport models to
bridge the gap between industrial and academic investigations,
as well as the integration of machine learning and artificial
intelligence techniques in corrosion modeling, offering promis-
ing directions for future research in this field.
molecular modeling, etc. In this review, we present a compila-
tion and critical analysis of relevant work related to mathemat-
ical modeling of aluminum corrosion and some of its alloys. It is
important to emphasize that we will focus on deterministic
continuum models, mainly those posed in terms of partial
differential equations (PDE’s). Applying numerical methods for
solving these types of equations has been a practice strongly
linked to the constant advances in computation; therefore, it is
not a new task, but with the advances in computational power,
numerical methods are capable of handling increasingly
complex scenarios.
The other modeling approaches cited above will be
discussed briefly. It is also worth mentioning that only models
where aluminum degrades in aqueous solutions have been
considered. The articles analyzed in Section 2 have been
classified into three main areas depending on the type/
mechanism of corrosion. This categorization is detailed in
Figure 1, which also highlights in red the main aspects
addressed in this review.
The paper likewise summarizes the state-of-the-art of
models formulated in terms of Laplace and Nernst-Planck
equations, as well as the numerical methods commonly used
for their solution. These equations are briefly described below.[2]
1.1. Mathematical equations and physical principles to model
corrosion phenomena
Corrosion modeling, in most cases, requires fulfilling two
important fundamental principles: electric charge and mass
conservation. The first is described by Gauss law (Equation 1),
whereas the latter by the Nernst-Planck equations (Equations 2
or 4, compact and expanded forms, respectively).
r � ðer�Þ ¼ 1 (1)
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@Ci X
n

¼ r � Ni þ Ri (2) zi Ci ¼ 0 (5)
@t i¼1

Ni ¼ Di rCi zi ui Ci r� þ Ci n (3)
For a stationary study, where concentration gradients are
@Ci not considered, and the electroneutrality criterion is assumed
¼ Di r2 Ci þ zi ui Fr � ðCi r�Þ n � rCi þ Ri
@t |fflffl {zfflffl } |fflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflffl} |fflffl {zfflffl } |{z} (4) (i. e., 1 = 0), the Equation 1 takes the form of the Laplace
Diffusion Migration Convection Reaction
Equation:

Where ɛ is the permittivity of the material (F/m), � is the r2 � ¼ 0 (6)

electric potential in the electrolyte (V), and 1 is the free charge
density (C/m3). In this approach, the electrolyte exhibits constant electrical
Under the assumption of a dilute solution and an incom- properties, i. e., a uniform ionic conductivity σs (S/m), and the
pressible electrolyte, the conservation of mass is defined current distribution in the electrolyte domain (i) obeys Ohm law
through (Equation 2). For a transient analysis, this equation in (Equation 7):
differential form relates the rate of change of the concentration
of species i (Ci) to the total flux of a dissolved species (Ni) and i¼ ss r� (7)
the homogeneous reactions (Ri). Ni include mass transport by
diffusion, convection, and migration (Equation 3). The other Thébault et al. classify the mathematical models for corro-
parameters for species i correspond to Di as the diffusion sion into two categories.[3] Potential models expressed in terms
coefficient (m2/s); zi as the charge number, ui as the mobility of of the Laplace equation (Equation 6) and transport models
the species (m2/V s) and ν as the fluid velocity (m/s). The formulated with the Nernst-Planck equations (Equation 2 to 4).
migration term within the Nernst-Planck equations introduces � For the first case, it is possible to calculate the distribution of
as an unknown variable in Equation 1. The additional equation the electric current and potential in the electrolyte. In contrast,
to complete the system is given by the electroneutrality for the second case, the concentration of the chemical species
assumption: involved in the system can be predicted in addition to the

In 2017, Allan Ruiz obtained his Bachelor’s Dr. Francisco A. Godínez obtained a degree in
degree in Materials Engineering from the mechanical engineering from the Faculty of
School of Mechanical and Electrical Engineer- Engineering of the Universidad Nacional
ing at UANL (Mexico). In March 2020, he Autónoma de México and completed his
received his Master’s degree in Chemical Doctoral studies in Engineering at the same
Engineering at the National Autonomous university. In his Ph.D. he studied the sonolu-
University of Mexico (UNAM). Currently, he is a minescence phenomenon from different per-
Ph.D. candidate at the same institution, focus- spectives. He did a postdoctoral stay at the
ing his research on mathematical simulation Instituto de Investigaciones en Materiales
using the finite element method applied to developing studies of locomotion of magnetic
galvanic corrosion in the presence of alumi- robots in complex fluids to emulate the
num alloys. swimming of bacteria. He is currently working
on the development of bio-inspired robots to
Dr. Vicente Esquivel-Peña obtained his Ph.D.
produce cavitation to be used in various
in Chemical Sciences at the National Autono-
applications such as water disinfection, flow-
mous University of Mexico (UNAM) in 2020,
accelerated corrosion, and different mass
after which, in 2021, he joined the GRECCO
transfer processes.
group led by Prof. Montoya at UNITA-UNAM
as a postdoctoral researcher, developing a R. Montoya earned his Ph.D. in Engineering
low-cost method to detect aluminum in from the National Autonomous University of
galvanic pairs. Currently, he is an assistant Mexico (UNAM), after which, he got a post-
professor at the Analytical Chemistry Depart- doctoral position at the National Center for
ment in the Faculty of Chemistry, UNAM. His Metallurgical Research in Spain, where he
research focuses on designing sustainable combined mathematical simulation of electro-
nanomaterials based on cellulose for corrosion chemical processes with localized electro-
and environmental remediation applications. chemical techniques. In 2014, he secured a
postdoctoral position in the SURF research
group at the Free University of Brussels
modeling numerous electrochemical phenom-
ena. Currently, he holds the position of
Associate Professor at the Faculty of Chemistry
of the UNAM of Mexico, where he leads the
computational electrochemistry and corrosion
group (GRECCO).

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ChemElectroChem doi.org/10.1002/celc.202300712

Figure 1. Classification of computational corrosion models according to the type of prediction and scale.

current and potential. This categorization is indicated in Fig- non-polarizable metal surface (�l,bnd) or setting the concentra-
ure 1. tion of a species (cj), such as fixing the oxygen concentration
In a typical corrosion cell, three distinct boundaries can be (c0,k) at the air-solution interface. On the other hand, Neumann
clearly identified: one between the electrolyte and the external boundary conditions are applied in electrochemistry to describe
enviroment (normally a gas), another between the electrolyte the current or species flux that are independent of both
and non-active solid borders, and the third one between the potential and concentration, respectively. In instances involving
electrolyte and the surface of an active electrode. From the insulated borders, these conditions are homogenous, as
perspective of a boundary value problem, these boundaries indicated in the second row of Table 1. The third type of
should be described from a mathematical point of view. Table 1 boundary condition aids in specifying electrochemical phenom-
presents a summary of the boundary conditions most com- ena occurring at the metal/solution interface through electrode
monly used with both Laplace and Nernst-Planck equations. kinetics. The Robin condition establishes a relationship between
The primary boundary conditions used in corrosion model- current density and overpotential (η) at the boundary, which is
ing are Dirichlet (Type I), Neumann (Type II), and Robin (Type III). typically non-linear. This relationship is obtained experimentally
The Dirichlet condition allows us to specify the value of a field and can be adjusted to the different expressions detailed in
in a segment of the border of the computational domain. Table 2 written as i1 and i2, depending on the specific physical
Examples include defining the electrolyte potential (�l) on a case. It is crucial to note that these equations apply to both
models, only with the difference that in transport models such
terms must be specified as molar flux through Faraday laws. Ni,
Table 1. Some commonly employed boundary conditions in corrosion is determined from the normal component (n) of the flux
modeling encompass in both the potential and transport based
approaches.
vector, within this expression also involving the number of
participating electrons (n) and the stoichiometric coefficients, νj
Type Potential model Transport model
of the electrochemical reaction.
D� ¼ 0
@Ci
@t ¼ Di r2 Ci þ zi ui Fr � ðCi r�Þ þ Ri The kinetic expressions outlined in Table 2 are defined by
I. Dirichlet �l ¼ �l;bnd �l ¼ �l;bnd ; cj ¼ c0;k
the following terms: i0 denotes the exchange current, βa and βc
@� represent the anodic and cathodic Tafel slopes, respectively. R
II. Neumann @n ¼0 n � Nj ¼ 0
@� nj i
is the universal gas constant and T stands for the temperature.
III. Robin s @n ¼ i n � Nj ¼ Nj ; Nj ¼ nF
Furthermore, α corresponds to the charge transfer coefficient,

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Table 2. Equations commonly used to describe the electrode kinetics of an electrochemically active surface.
Kinetics expression type Equation
Anodic Tafel behavior i1 ¼ i0 � 10
Cathodic Tafel behavior i1 ¼ i � 10b
�0
Linearized Butler–Volmer i1 ¼ i0
ðaa þac ÞF
Butler–Volmer i1 ¼ i0 exp
Concentration dependent i1 ¼ i0 CR exp
either anodic (αa) or cathodic (αc). Finally, the incorporation of
the mass transport effect is achieved by considering the limiting
current (ilim). This variable may or may not be considered in the
local current, as illustrated in the third column of Table 2.
1.2. Different approaches in the application of model-solving
algorithms
The recent decades of technological progress and the increas-
ing power of central processing units (CPUs) have allowed the
simulation of more complex phenomena in less time and with
better resolution. These advances and sophisticated computa-
tional techniques such as the finite element method (FEM),
allow for more realistic descriptions of corrosive phenomena. In
parallel, other numerical procedures have been used for the
same purpose, among which the finite difference method
(FDM) and the boundary element method (BEM) stand out.[4–6]
Nevertheless, the notion of studying electrochemical sys-
tems from a mathematical point of view is not new but has
been around for more than 80 years. In the 1940s, decades
before the emergence of numerical methods, Kasper, in his
remarkable work on electrodeposition laid the foundations of
potential theory applied to electrochemical systems by analyti-
cally solving the Laplace’s equation for simple geometries.[7–11]
Cathodic protection and electrodeposition were also
studied theoretically through the Laplace’s equation in Wagn-
er’s work.[12,13] The conformal mapping transformation was used
to solve this equation. A significant result is the Wanger
dimensionless number, which relates the characteristic length
of the system to the polarization in metal electrodeposition
techniques.
Some years later, in a series of publications entitled
Mathematical Studies of Galvanic Corrosion,[14–19] Waber et al.
mathematically analyzed the galvanic corrosion phenomenon.
They studied a coplanar electrochemical system where the
electrodes are aligned parallel at the base of the cell. Through
the solution of the Laplace equation via Fourier series and
conformal mapping, they obtained the current distribution over
the electrodes and the electric potential distribution within the
electrolyte for different cases. The highlights of these works
were the influence of the electrode length, the consideration of
linear and equal boundary conditions, as well as the analysis of
the effect of the electrolyte thickness on the corrosion process.
Owing to the limitation of a primary current model, only
linearized polarization behaviors at the electrodes were consid-
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ilim
h
ba
h
c
�
RT h * i2 ¼ i1 i
1þki k
1
aa Fh � ��
ac Fh
lim
RT exp RT
aa Fh� ��
ac Fh
RT CO exp RT
ered in the aforementioned works. It was not until the mid-
1960s that Klingert et al.[20] proposed a numerical solution for
the Laplace equation using FDM to calculate the current
distribution in a two-dimensional cell. Another notable attempt
at numerical simulation through numerical techniques was in
1964 when R. N. Fleck developed a potential model solved with
FDM using the Fortran programming language, in which
nonlinear boundary conditions were considered.[21] Over the
following years, computational corrosion analysis using FDM
was successfully implemented in different studies where the
primary mechanism of action occurs in galvanic cells at the
macroscale level. This is demonstrated in the contributions of
Smyrl and Newman, Doig and Flewitt, and Strommen.[22–24]
In terms of numerical analysis of aluminum corrosion, the
pioneering efforts at modeling via Nernst-Planck equations the
degradation of this material were in the area of crevice
corrosion, which will be discussed in detail in Section 2.2.2.
These models were solved with FDM and the Crank-Nicolson
method.[25,26]
Over time, the progress of corrosion models goes hand in
hand with the development and maturity of FEM and BEM.
Since the 1980s, the advance of both techniques was roughly
parallel to each other. However, it was until a decade later that
the number of works using mathematical simulation to study
corrosive systems involving aluminum increased. These models
were focused on the study of cathodic protection (CP) systems,
either by implementing FEM or BEM.[27,28] The latter method is
even used in relatively recent research to evaluate the perform-
ance of aluminum anodes in a CP system.[29] It should be
pointed out that in this protection method, aluminum is the
sacrificial material, so its representation in the model formula-
tion was very simplistic. Commonly, a constant polarization as a
boundary condition on the surface of this material was used.
It should also be remarked that the BEM was the first
successful technique to quantitatively predict the performance
of galvanic couples in the presence of aluminum alloys. One of
the first approaches to studying this phenomenon dates back
to the late 1990s. In a study conducted by Bucaille et al., a
galvanic couple with technological relevance in the aeronautical
industry was considered (Al-4 %Cu and pure aluminum).[30] In
this work, the dissolution profiles at the anode were calculated
by solving the Laplace equation together with Butler–Volmer
kinetics as boundary conditions on the electrodes. In the 2000s,
the transport models reached a certain degree of maturity and
sophistication, specifically those that are solved by FEM. In the
field of coatings with aerospace applications (to be treated in
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further detail in Section 2.1.2), Wang et al. studied the effect of
an inhibitor on a scratch in an AA2024-T3 aluminum alloy
coated under atmospheric conditions.[31]
In addition to the exhaustive bibliographic analysis carried
out in this section, a bibliometric analysis of the literature
spanning the last decades was performed through network
maps using VOSviewer software. This map is shown in Figure 2.
A database containing 114 documents from the last 20 years
extracted from Scopus was used for its construction. The
database was meticulously adapted to the central subject of
the present review, employing search terms such as “modeling”,
“simulation”, “aluminum”, “aluminum alloys”, “numerical meth-
ods”, “FEM”, “FDM”, and “BEM”. A co-occurrence study analyzed
both the keywords the authors provided and the index of
articles. Keywords that occur at least three times were selected
as the most relevant, reducing keywords from 1531 to 137
when applying this selection criterion to create the correlation
map. The network map shows clusters in which closely related
concepts congregate within the dataset, distinguished by
various colors. As a prominent domain of study, the red color
cluster emphasizes the galvanic corrosion process studied
through FEM, while blue, green, and purple are clusters mostly
related to localized corrosion, stress corrosion cracking, and
aluminum corrosion present in the aircraft industry, respec-
tively. Other phenomena related to corrosion modeling of
aluminum alloys are also taken into account and will be
analyzed and classified in the following sections.
Figure 2. Visualization of networks in documents derived from co-ocurrence bibliometric analysis.
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2. Continuum modeling under aqueous
solutions
2.1. Galvanic corrosion: microscopic and macroscopic
Fuel-saving needs in the transportation industry promote the
adoption of lightweight materials. This strategy has been used
since the 1970s by the aeronautical industry but has gained
relevance in the automotive industry in recent years. The
materials most commonly used in modern automobiles are
advanced high-strength steels and aluminum alloys. The
application of such materials has brought new technological
challenges for this industry, among which galvanic corrosion
stands out. This problem occurs when dissimilar materials with
different oxidation potentials are in contact with a common
electrolyte, and the corrosion effect is exacerbated, to a greater
or lesser extent, depending on the type of predominant
atmosphere or meteorological circumstances (temperature,
relative humidity, electrolyte concentration, dew point, and
pollutants).
Specifically, this section will address the phenomenon of
galvanic corrosion from a numerical perspective.
In this regard, our research group has focused on studying
galvanic systems using both transport and potential models. In
Figure 3, a timeline illustrating our group scientific production
is shown, highlighting the different strategies for modeling
aluminum corrosion that have been implemented. Initially
(Figure 3a), a potential model was employed to examine a tri-
galvanic system used in the automotive industry: Zn –
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Figure 3. A diagram illustrating the scientific production of our research group over the past five years. This timeline showcases the key and significant
milestones achieved in each research article, offering a panoramic view of our contributions to the evolving landscape of corrosion modeling in aluminum
alloys.
Aluminum Alloy – Carbon Steel (Zn-AA-CS).[32] Due to the fact
that the couple AA-CS promotes the dissolution of the
aluminum alloy, the automotive industry proposed the place-
ment of a Zn washer between AA and CS to prevent AA
corrosion. For thin electrolytes (with a thickness of less than
800 μm according to Liu et al.), a dimension reduction was
conducted along the thickness of the electrolyte since the
potential gradient was considered negligible. In the case of
thick electrolytes (with thickness larger than 800 μm), the
boundary conditions were of Robin type on the borders of the
electrolyte in contact with the metallic surfaces. These con-
ditions expressed the current density as a function of the
potential by interpolating standard polarization curves.[33] In
contrast, for thin electrolytes, polarization curves obtained from
a rotatory disk electrode were applied to define the cathodic
behavior of each metallic material. In such a thin static
electrolyte, Oxygen is constantly supplied by the atmosphere,
and standard polarization curves cannot be applied. All
boundaries were considered insulated, and the contribution of
the polarization curves was included in the governing equation
as a source term divided by the thickness of the electrolyte.
Numerical simulations of both models yielded significant in-
sights. Under thin films, the Zn washer provided temporary
protection for the aluminum alloy. Nevertheless, its high
corrosion rate led to rapid dissolution, limiting the protective
effect. Conversely, in the presence of thick electrolyte films, the
system could not fully shield the AA. However, the corrosion
rate was notably lower than in the thin film case after the
washer dissolution. A related study focused on the AA7075-CS
galvanic couple also considered thin electrolyte films.[34] This
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parallel work employed a mass transport model governed by
Nernst-Planck equations. In this case, the thin electrolyte was
again assumed as non-dynamic, and Oxygen was considered
abundant and constantly supplied from the atmosphere. In
such a study, a source term was formulated for both OH and
Al3 + species. In this study, an innovative experimental system
was utilized to validate the model (Figure 3b). A gel electrolyte
doped with thymol blue, coupled with a high-resolution
camera, facilitated the validation of alkaline fronts evolution
along the thin electrolyte (with a thickness of 50 μm) on the
steel surface. In 2021, another modeling contribution was
published for the same galvanic system.[35] This time, thin films
were not used, but instead, both dilute and concentrated
electrolytes were tested, and the system was again modeled by
using the Nernst-Planck equations. Although Nernst-Planck
approximations do not typically allow concentrated electrolytes,
the diffusion coefficients were expressed as empirical relations
dependent on the chloride concentration, and the results
demonstrated their good applicability. While numerical results
were more accurate for dilute electrolytes, the predictions for
concentrated cases were still reasonably close to reality. More-
over, this time, the propagation of the acidic front on top of the
aluminum alloy was validated (Figure 3c). Both experiments and
numerical predictions confirmed that the more diluted the
electrolyte, the more intense the acidification on the aluminum
side, as chloride ions compete with hydroxides to combine with
the coordination complexes from aluminum hydrolysis. These
findings emphasized the significance of utilizing proper kinetic
constants in the Nernst-Planck term of the homogeneous
chemical reactions. One year later, the galvanic study was
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conducted for a common couple extensively used in the
aerospace industry (AA2024/CFRP).[36] Similar to the previous
study, Nernst-Plank equations were employed to simulate the
electrochemical behavior of the system. However, this time, a
dynamic droplet of electrolyte was considered to mimic the
evaporation and condensation phenomena occurring during
atmospheric corrosion (Figure 3d). These phenomena were
simulated by accounting for the environmental humidity and
temperature. One of the key assumptions was that the base of
the droplet in contact with the metallic couple remained fixed
during the evaporation/condensation process. The droplet
followed a mathematical expression of an oblate shape during
evaporation and a prolate shape during the condensation
process. Regarding the numerical predictions, both the poten-
tial distribution and the evaporation rate were validated using a
Scanning Kelvin Probe (SKP) and a digital video camera. The
findings revealed no acidification on top of the aluminum alloy
for tiny systems (galvanic couples with metallic surfaces smaller
than 5 mm2). Finally, some months later, our most recent
transport modeling work was published.[37] Once again, Butler–
Volmer-type boundary conditions were applied. The diffusion
coefficient was considered as a function of the chloride
concentration, and a thick gel-electrolyte was utilized. Nonethe-
less, this time, to study real-world scenarios relevant to the
automotive industry, the investigation was extended to include
both a wrought aluminum alloy (AA7075-T6) and a cast
aluminum alloy (A380.0) coupled with carbon steel. Two
innovative experimental methodologies were successfully
tested to validate the potential distribution on the metallic
surfaces and the pH within the electrolyte (Figure 3e). The
numerical predictions showed excellent agreement with the
experiments. These findings provide strong evidence for the
considerable potential that hydrogel technology offers in
validating corrosion modeling works. Indeed, it was recently
proven that the evolution of aluminum ions (during the
corrosion of both wrought and cast aluminum alloys) can also
be visually tracked by incorporating appropriate chromophores
into gel electrolytes (Figure 3f).[38] It is important to point out
that all the transport models discussed above shared common
characteristics. Firstly, the boundary conditions were such that
only the anodic contribution of the corresponding Butler–
Volmer expression was used on the aluminum alloy surfaces.
Secondly, the convective term of the Nernst-Planck equation
was consistently neglected in all cases. Additionally, another
shared characteristic is that the aluminum alloys consistently
acted as the anode in the galvanic system. Finally, it is worth
noting that different software tools were used. Some of our
works involved the use of the commercial software COMSOL,
while others utilized a homemade code using both Python and
the FEniCS platform. This diversity in software enables the
expansion of capabilities in the field of modeling corrosion
phenomena. Both platforms have several advantages that can
be summarized as follows: On the one hand, COMSOL provides
a user-friendly graphical interface, making it accessible to users
with less programming experience. It also excels in simulating
complex phenomena, where multiple physical processes inter-
act, and offers a wide range of pre-built models, which can
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serve as a starting point for many simulations. On the other
hand, FEniCS is tightly integrated with Python, allowing users to
leverage the extensive palette of libraries and tools of Python.
Concerning the investigation of the microscopic scale, L. C.
Abodi et al. simulated the corrosion of the different phases
present in the microstructure of aluminum alloy 2024. By
applying the finite element method, it was possible to calculate
the potential in the electrolyte as well as the behavior of
chemical species involved in the system. It was possible to
numerically examine the pH distribution. In addition, the results
obtained were validated with the help of micropolarization
curves.[39]
In recent years, there have been some studies focusing on
the aircraft industry in order to avoid galvanic corrosion
between aluminum alloys and other materials such as steel or
magnesium alloys. In 2019, Snihirova et al. focused on the
development of a physico-chemical model based on mecha-
nistic and kinetics understanding of the corrosion process in
the galvanic couple.[40] The model was solved by FEM, and it
was validated using the Scanning Vibrating Electrode Technique
(SVET). In the simulation, the concentration of oxygen and pH
were calculated and validated with experimental data. This
model is able to reveal the localized corrosion related to the
heterogeneity of the aluminum microstructure and also high-
lights the major role of aluminum self-corrosion in galvanic
assemblies.
2.1.1. Bare system
2.1.1.1. Bulk conditions
As already mentioned, potential models involves solving the
Laplace equation (Equation 6) with the appropriate boundary
conditions, which generally represent the nonlinear electrode
kinetics. Their applications in the last ten years have been very
diverse, involving areas such as the oil and gas industry,
electrical, marine, automotive, aerospace, and materials science
engineering. Among them, one of the most important has been
the automotive industry; where, numerical simulations have
been used to analyze and predict corrosion in automotive
components, especially those exposed to harsh environments,
improving designs and materials to mitigate corrosion effects
on vehicles.[32,41]
In certain studies, the acidification of the electrolyte has
been theoretically demonstrated when there is localized
corrosion of aluminum or its alloys.[4,42] In these mathematical
models, homogeneous reactions have been considered, includ-
ing all the relevant chemical species in this corrosive process.
The most important result of these works is that more realistic
pH maps are obtained by taking into account the chemical
reactions in the model approach. Additionally, the studies agree
with the fact that the acidification process is due to the
hydrolysis of the Al3 + ion and the consequent formation of
intermediate aluminum compounds.
Recently, Kadowaki et al. investigated the effect of NaCl
concentration over the galvanic and self-corrosion of the
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AA6016/SM490 couple using experimental data and FEM
simulations performed on the COMSOL Multiphysics software.[43]
The Nernst-Planck equations were used, and the boundary
conditions were established with potentiodynamic polarization
experiments. The study concluded that the corrosion behavior
of the AA6016/SM490 couple changed with varying NaCl
concentrations. Galvanic corrosion was predominant at high
concentrations, and pits appeared on both surfaces after
galvanic corrosion. In contrast, at lower concentrations, self-
corrosion of SM490 played a more significant role due to
changes in the anodic and cathodic reactions. These observa-
tions are in good agreement with Scanning Electron Microscopy
(SEM) and Energy-Dispersive X-ray Spectroscopy (EDXS) results.
On the other hand, the results obtained by Montoya et al.
establish that at low NaCl concentration, the acidification over
the aluminum alloy surface is faster and more drastic because
the competition between the Cl and OH ions enhance the
hydrolysis of Al3 + ions in the electrolyte.[35] It is well known that
pits appeared when the pH decreases; this may explain the
formation of pits over both surfaces of the galvanic couple and
the predominance of self-corrosion observed by Kodowaki
et al.[43]
2.1.1.2. Thin films
Palani et al. studied the galvanic corrosion between a galvanic
system characteristic of the aircraft industry by applying a
numerical and experimental approach.[44] The galvanic system
was constituted by a carbon fiber reinforced polymer (CFRP)
and 2024 aluminum alloy in a coplanar arrangement. This
system is subjected to a micrometric electrolyte. In the
numerical study, they proposed a potential model with a source
term added to the governing equation, thus reducing a
geometric dimension of the problem. The calculations were
obtained with the software Elsyca Galvanic Master which works
with FEM, and the numerical results were validated with Zero
Resistance Ammetry (ZRA) measurements. The most important
contribution of this work is that the model is applicable to thin
electrolyte layers.
A 1D model solved in COMSOL Multiphysics was recently
presented.[45] In such a model is grounded on the mechanistic
principles of corrosion, specifically employing the Nernst-Planck
equations to investigate the galvanic coupling between a 1050
aluminum alloy and 416 L stainless steel under atmospheric
conditions with a NaCl electrolyte. Moreover, the model
incorporates empirical data to enhance the accuracy of its
predictions. As a result, it achieves a more precise simulation of
pitting initiation, pitting propagation, and galvanic current
under various environmental conditions. It is worth noting that
the transport model was calibrated rather than validated.
Consequently, the numerical simulations of the distribution of
the corrosion products could not be independently verified.
Nevertheless, notable results were obtained, particularly regard-
ing pH, wherein the surface of the aluminum alloy showed an
acidity of approximately four pH units, aligning with the
numerical and experimental findings of our research group.[35]
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2.1.2. Coated systems
Stewart’s Ph.D. dissertation led to a homemade code called
CREVICER, which uses FEM.[46] This program was subsequently
adapted in the early 2000s to study the behavior of corrosion
inhibitors contained in coatings of various kinds. These systems
are typically used in the aircraft industry to protect particular
aluminum alloy structures such as AA2024-T3. Once the coating
is damaged, the substrate is exposed and interacts galvanically
with its environment. Mathematical models of transport and
potential have been proposed for the study of both organic,
and metallic coatings.[31,47,48] For the three previous cases,
sodium chloride (NaCl) electrolytes of micrometric thickness
(approximately 100 microns) are used, representing the atmos-
pheric corrosion conditions to which the structures are
subjected under operating conditions.
Wang and Presuel-Moreno developed transient models
involving 12 and 10 chemical species, respectively, including
those associated with the inhibitor chemical species. The
objective of these models was to evaluate both the chemical
(environmental) and physical conditions such as pH, chloride
concentration, scratch size, and electrolyte thickness under
which the coatings enhanced corrosion protection.[31,48]
In aerospace coatings, there is a promising trend in using
magnesium-rich primers (MgRP) to protect aluminum alloys
such as AA2024-T351. Recently, employing finite element
analysis applied with commercial software such as COMSOL
Multiphysics®, the behavior of these primers has been inves-
tigated under different physical, chemical, and electrochemical
factors such as electrolyte concentration, electrolyte layer
thickness, humidity, and wet/dry cycling; or by examining the
effect of pH on the electrochemistry of the system as well as
the chemical reactions in the electrolyte and the solubility of
the inhibitor products.[49,50]
2.2. Localized corrosion
As discussed throughout this revision, different types of
corrosion can occur in aluminum and its alloys depending on
different causes, such as the medium, or factors related to the
material, such as the complex microstructure of the alloys.
Usually, there is no predominant form of corrosion in these
materials; nonetheless, localized corrosion is one of the most
severe forms of corrosion that can attack aluminum and its
alloys. The three main types of localized corrosion discussed in
this section are pitting, intergranular, and crevice. The first two
occur at the microscale and are strongly related to the passive
layer and the different intermetallic particles (IMPs) that
constitute the material (heterogeneities in the
microstructure).[51] In contrast, crevice corrosion is mainly
promoted when there are occluded areas of stagnation of the
electrolyte solution (geometrical factors). Although morpholog-
ically, there are apparent differences between the types of
localized corrosion, the electrochemical mechanism is similar in
all of them. Specifically for pitting and crevice corrosion,
numerical and phenomenological models have been imple-
© 2024 The Authors. ChemElectroChem published by Wiley-VCH GmbH

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ChemElectroChem doi.org/10.1002/celc.202300712
mented to simulate the local dissolution process. In this field,
transport models are the most relevant ones. Therefore, they
are the ones that will be addressed in detail, mainly those
solved with numerical methods.
2.2.1. Pitting corrosion
A work made by Onishi in 2012 presented a numerical method
for localized corrosion in materials that exhibit a passive layer.
He introduced electromigration, diffusion, and moving bounda-
ries and used the Finite Volume Method (FVM) complemented
with the voxel method. The FVM was used to satisfy the mass
conservation, and the voxel method led to an update in the
boundaries of hollows without the need of remeshing the
domain in each iteration.[52] The above method provides a good
idea of how the materials that present a passive oxide layer on
their surface behave and how a pitting study could be
performed on them. In addition to the FVM, alternative
approaches known as autonomous models have been used to
investigate pitting corrosion in aluminum alloys. Notable
examples include Cellular Automata (CA) techniques, Peridy-
namic (PD) formulations, and Phase-Field (PF) models. These
methods allow for the simulation of the initiation, growth, and
diverse physicochemical phenomena. However, it is pertinent
to note that these methodologies extend beyond the primary
scope of this study. L. Yin et al.[53–56] in their remarkable work
made significant contributions to the field of pitting corrosion
by investigating this phenomenon in AA7075 driven by micro-
galvanic effects using the Finite Element Method (FEM). The
Arbitrary Lagrangian-Eulerian Formulation (ALE) method was
integrated to address mesh movement considerations. The
blocking effects of deposited corrosion products,[53] the effect of
porosity,[54] as well as geometric[55] and chemical effects[56] were
analyzed in a transport model that considers chemical species
from aluminum hydrolysis in an aqueous medium containing
NaCl.
Guseva et al. subsequently published a paper in which they
modeled the time-dependent pitting mechanism.[57] In this work
they used a piece of Aluminum 2024 focusing the study on the
corrosion that occurs inside the material due to the alloying
elements. The model simulated a capillary to mimic the
localized corrosion and to follow in a transient and stationary
manner the point dissolution of the material. This was one of
the most relevant works on this topic because they took into
account hydrolysis reactions and the formation of Al and Mg
species that are formed during this process.
Xiao and Chaudhuri solved the Nernst-Planck equation and
also considered surface reactions in a sodium chloride environ-
ment varying in concentration. The partial differential equations
were solved using COMSOL® software supplemented with
moving boundaries using MATLAB®.[58] This was one of the first
works where the pitting evolution is shown considering the
internal phases of the material, as well as a 3D model.
A variation of the FEM method is the so-called extended
finite element method (XFEM) developed in 1999 which
approximates the solution of a complex system, with localized
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features, in differential equations with discontinuous functions.
In 2016 Duddu et al. used this method to model pitting and
crevice corrosion.[59] In this work they solved the Nernst-Planck
equation by including diffusion coefficients as well as species
concentrations, further complementing the method by adding
moving boundaries as well as the evolution of near surfaces.
The modeling was developed using COMSOL® software, obtain-
ing promising results but leaving as an open issue the study of
models with concentrated electrolytes, as well as the incorpo-
ration of chemical reactions and the processes occurring at
both the anode and cathode.
2.2.2. Crevice corrosion
In 1982 Alkire and Siitari developed the first numerical model
for aluminum crevice corrosion in NaCl solutions.[25] They used a
FDM technique, based on their previous experimental observa-
tions, to propose fundamental equations that allow the
prediction of crevice corrosion in realistic conditions.[60] Their
findings applied to well-controlled crevice geometries, but the
model could not address the conditions needed for local
passivity breakdown and the accumulation of chloride ions.
Nevertheless, in a further article, Hebert and Alkire determined
that no accumulation of chloride ions is needed before
breakdown.[26] However, oxygen consumption, rapid acidifica-
tion, and the increase in aluminum oxidized species in crevice
solution eventually trigger breakdown, a critical concentration
of Al(III) species of 2 mmol/L must be reached, and the pH
dropped to values around 3–4 inside the crevice.[61] In order to
obtain those results, diffusion and migration fluxes for both
homogeneous and heterogeneous reactions were added to the
previous model solving the Nernst-Planck equations.
In 1995 Li and Ferreira developed experimental work and a
transport model to explain the chemical and electrochemical
dissolution mechanism for the initiation of localized
corrosion.[62] Consistent with previously described works, the
most critical circumstances to start crevice corrosion are the
potential drop and the acidification inside the crevice. They
found that in the presence of chloride ions, the pH decreases
more due to the formation of chloride-metal complexes during
metal hydrolysis (i. e., Al(OH)Cl2 and Al(OH)2Cl). They concluded
that the breakdown of the passive film follows a mechanism of
acid-aided complexing dissolution without charge transfer
across the interface (chemical reactions). In 2004 Vankeerber-
ghen used FEM to develop a model that allowed to predict the
ratio between the square of the crevice’s length to its gap
needed to reach the Al(III) critical concentration.[63] This work
extends the concept of a critical characteristic crevice dimen-
sion to a critical crevice geometry, facilitating the evaluation of
component designs for susceptibility to crevice corrosion once
the operative mechanism is identified. It is also important to
note that the onset of crevice corrosion is linked to a critical
potential drop or a critical species concentration.
© 2024 The Authors. ChemElectroChem published by Wiley-VCH GmbH

Review
ChemElectroChem doi.org/10.1002/celc.202300712
3. Perspectives and Conclusions
The increasing significance of aluminum alloys in outdoor
applications, such as aerospace and construction, is expected to
lead to a higher demand for modeling efforts focused on
atmospheric corrosion issues of aluminum alloy components in
the foreseeable future. Regarding deterministic models, mainly
dynamic electrolytes (with transitions between thin and thick
films) will be taken into account, involving condensation and
evaporation phenomena. This entails considering both the
Nernst-Planck and heat transport equations, along with phys-
icochemical boundary conditions. Climatological factors such as
temperature, humidity, wind rate, and atmospheric chemical
composition should also be integrated into these works. As
computational power continues to advance, the next gener-
ation of modeling investigations holds the potential to
seamlessly integrate the Navier-Stokes equations within the
electrolyte. This significant development addresses previously
overlooked internal convective effects within the electrolyte
during the corrosion of aluminum alloys, especially in the
context of evaporation and condensation phenomena. These
advancements are anticipated to bridge the gap between
academic and industrial investigations, where the last have
traditionally relied heavily on accelerated tests in salt fog
chambers. On the other hand, model validation and calibration
are crucial for ensuring precision and trustworthiness. Compar-
ing models with proper experimental data refines parameters
and assumptions, enhancing their reliability. Current trends in
literature indicate that models in aluminum alloy corrosion
studies are progressively validated using data obtained from
three specific types of experiments: localized electrochemical
tests, the use of doped gel electrolytes (particularly for models
focused on transient phenomena over short durations), and
atmospheric tests for long-term predictions. Nonetheless, it is
clear that fundamental electrochemical research still remains
necessary in furnishing key kinetic constants. The perspectives
in corrosion modeling cover various aspects and research areas
that are in constant evolution. In the realm of aluminum and its
alloys, there are emerging trends that deserve attention in the
coming years. Notably, atomic, and molecular modeling
techniques play a pivotal role in studying corrosion inhibitors
commonly used in aeronautical applications. Herein, strategies
such as Density Functional Theory (DFT), quantum molecular
dynamics, and classical molecular dynamics (MD) have been
effectively employed, all directed toward the exploration of the
interactions between the chemical structure of organic mole-
cules and the metallic surface.[64–66] Another relevant trend
involves modeling based on artificial intelligence, a technology
that is currently present in many areas of knowledge, and in a
wide range of applications. In the context of corrosion, machine
learning techniques using artificial neural networks have been
employed to predict the lifespan of materials and structures.
These methods have been strengthened with the help of big
data and deep learning.[67] This progress has led to improved
pattern recognition and more accurate predictions of corrosion
in aluminum.[68,69] Beyond detection and classification tasks,
there are other AI issues which are worth exploring with the
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numerical simulation of corrosion processes in mind. The
implementation of neural networks to solve the Nerst-Planck
equation has already yielded some encouraging results high-
lighting the advantages of deep learning as a mesh-free
method; however, there are difficulties in terms of stability and
convergence that further research will need to improve.[70] The
most recent tendency focuses on the development and
implementation of hybrid methods in which the advantages of
more traditional techniques such as FEM (versatility, accuracy,
efficiency) and those based on neural networks (computational
speed) can be exploited.[71,72] Regarding the corrosion area, such
hybrid models have been recently implemented into the
examination of galvanic couples in the presence of aluminum
alloys. Specifically noteworthy are the works that combine finite
element models with machine learning.[73,74] This integration
symbolizes so far, the most comprehensive approach to address
multiscale aluminum corrosion, which has the potential to
produce substantial advances in the accuracy and predictive
capability of models applied to different industries. Lastly, a
potentially promising direction for the field is the application of
fractional calculus, which is a powerful tool of widespread use
for describing dynamic processes of diverse nature.[75] Never-
theless, there are still few works that have studied the Nerst-
Planck equation with non-integer order derivatives. Of partic-
ular interest will be the further development of anomalous
diffusion models using fractional time and/or space
derivatives.[76,77]
Acknowledgements
The authors are thankful to the UNAM-DGAPA-PAPIIT IG100623
and IN103124 programs for their support. A. R.-G. extends his
gratitude to CONAHCYT for the doctoral fellowship. V. E.-P.
expresses his gratitude to the SIJA-DGAPA-UNAM program.
Conflict of Interests
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
Keywords: aluminum alloys · computational chemistry ·
corrosion · electrochemistry · corrosion models
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Manuscript received: November 25, 2023
Revised manuscript received: February 2, 2024
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REVIEW
This work provides a comprehensive A. Ruiz-Garcia, Dr. V. Esquivel-Peña,
overview of the recent advances in Dr. F. A. Godínez*, Dr. R. Montoya*
modeling techniques for better under-
1 – 12
standing the corrosion behavior of
aluminum alloys. The present study Corrosion Modeling of Aluminum
encompasses the state-of-the-art of Alloys: A Brief Review
computational approaches, highlight-
ing their strengths and limitations.
Transport models receive especial
attention and certain challenges asso-
ciated with the experimental valida-
tion of such models are also
described.