Journal of The Electrochemical Society, 165 (10) C703-C709 (2018) C703

Ab Initio Monte Carlo Simulations of the Acidic Dissolution of

Stainless Steels: Further Insights into the Mechanisms
1,z
B. Malki, I. Guillotte,2 and B. Baroux3,∗
1 Simorg computing, 38028 Grenoble, France
2 Aperam Isbergues - Research Center, 62330 Isbergues, France
3 Laboratoire Science et Ingénierie des Matériaux et Procédés (SIMAP), Grenoble INP, Université de Grenoble
Alpes, 38402 Saint Martin d’Hères, France

Using Ab initio based Monte Carlo simulation techniques (AbMC), dissolution kinetics in acidic media was evaluated for different
stainless steels (SS) as a function of their chemical composition, with particular attention paid to the role of transition metals series
(TM). The elementary dissolution events at the atomic scale were treated as stochastic processes, from which dissolution probabilities
were deduced. Two determining factors emerge as critical for the control of dissolution kinetics: the bonding energy of an alloying
element in the SS matrix and its standard electrochemical potential. The first reflects the ability of an element to form stronger (Mo,
Nb, Ni etc.) or weaker (Cr, Cu, Sn etc.) bonding than Fe, and the second refers to its facility to dissolve under an applied potential.
High bonding energies and high standard potentials lead to a strong dissolution resistance (Mo), whereas low bonding energies and
low standard potentials induce high dissolution kinetics (Sn). The intermediate situations: high-bonding energy and low standard
potential (Nb) or low bonding energy and high standard potential (Cu) usually lead to moderate dissolution regimes with a strong
impact on the dissolution mechanisms.
© The Author(s) 2018. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.1321810jes]

Manuscript submitted April 30, 2018; revised manuscript received July 24, 2018. Published August 4, 2018.

In a recent paper, we developed a numerical approach (the details
of which are published elsewhere)1 that describes the dissolution pro-
cess of a metallic alloy by means of the Ab initio based Monte Carlo
simulation techniques (AbMC) method. We succeeded in formulat-
ing a general expression of the dissolution probability of any given
SS grade as a function of its chemical composition, crystallographic
microstructure and the environmental variables (pH and applied po-
tential). Our findings pointed out the effect of the chemical nature of
a dissolving atom and the number of its nearest neighbors. A critical
coordination number (CCN) was then defined, above which the dis-
solution probability of a surface atom is too low to contribute to the
dissolution rate. It was then shown that increasing the Cr content of
ferritic SS does not change the CCN, however, it makes the dissolution
process easier because of the low Fe-Cr bonding energy. The addition
of Mo was found to involve multiple CCN, belonging to different
crystallographic orientations, which also resulted in a substantial de-
crease of the dissolution kinetics. These results are consistent with
previous works2–9 that have also reported that the dissolution prob-
ability of various Tc base alloys depends strongly on Tc contents.
In these works, the most active surface atoms are found to act as a
site-blocking element at surface kinks and step-edges.
The present work seeks to extend our approach to both ferritic
and austenitic steels and to consider the effect of more transition or
post-transition alloying elements which, together with Fe, Cr and Mo
offer a large panorama of 3d TM (Fe, Cr, Ni, Mn and Cu) and 4d TM
(Mo, Nb and Sn) currently used in stainless steel making.
The interest of this work lies in the need to understand the role
of alloying elements in controlling dissolution kinetics, an issue of a
practical implication usually involved in picking and localized corro-
sion. The objective is to clarify the link that may exist between the
chemical composition of a given SS, its microstructure and the result-
ing dissolution kinetics and surface morphologies. The example of
localized corrosion of SS is worth noting in this respect, as the active
dissolution is known to be a critical step in the stabilization process
either in pitting or crevice corrosion.10 Therefore, understanding the
metallurgical factors controlling dissolution kinetics is a matter of
both practical and theoretical concerns. The findings may be used to
interpret the experimental measurements and develop more consistent
approaches for the prediction and the design of SS.11
∗ Electrochemical Society Member.
z
E-mail: Brahim.Malki@simorg-computing.fr
Physical Modeling and Computational Method
An overview of the AbMC simulation methodology.—The phys-
ical model used in our simulations is based on the transition state
theory (TST)12–14 with a view to formulating dissolution probabilities
at the atomic scale.15–18 These probabilities are then used to identify
all the possible dissolution events that may occur on the surface of a
given SS grade under given environmental conditions. At this stage,
we do not consider any passivation reaction, since we are interested in
very acidic dissolution conditions. We assigned to each surface atom
an activation energy that determines its dissolution probability as a
function of its surface position and the chemical composition of its
closest neighbors. In the presence of an applied potential ϕ (eV)
at the SS/electrolyte interface, the dissolution probability (ϑdiss ) of a
surface atom j of a Fe-xCr SS is given by:
    
α j iN E b, i
j   α j z j ϕ j
ϑdiss, j = ϑo exp − exp −α j · p H exp −
kB T kB T
[1]
i
E b, j is the bonding energy of the surface atom with its
ith nearest neighbor, the pre-exponential factor given by ϑo =
Fe +x.E Cr )
kt k BhT exp( z.((1−x).E
2k B T
) relates the vibration frequency of the sur-
face atom and the average value of its chemical potential expressed
in terms of the chemical composition of Fe-Cr SS. Z , k B , T, h are
respectively the coordination number of the ferritic bcc structure, the
Boltzmann constant, the temperature and the Planck constant. kt is
a transmission coefficient related to the frequency of the vibrational
mode responsible for converting the activated complex to the product
in the TST. α j is the symmetry factor counting for the fraction of the
interfacial potential at the interface which helps to lower the energy
barrier and z j being the valence of the dissolving atom.
i
All E b, j energies are deduced from ab initio calculations. The
effective electrical potential ϕ j felt by a surface atom may depend
on the chemical composition of the surface,19 particularly for highly
alloyed surfaces. This effect was first neglected in the previous work1
and we will show in this work that this assumption, even if it remains
valid for high electrical fields (pickling and electropolishing regimes),
may not be appropriate for low fields (corrosion regime).
A simple MC scheme with a transition probability based on
Equation 1 is then used to obtain the dissolution dynamics of a
given SS microstructure. An iteration procedure is implemented in
the simulation in which the dissolution probability of a surface atom
is subjected to a MC decision process. For each step, a normalized

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 C704 Journal of The Electrochemical Society, 165 (10) C703-C709 (2018)
Figure 1. Typical microstructure used in the simulations; the different crystal-
lographic orientations of the grains makes it possible to emerge on the surface
a variety of atomic neighborhood configurations mapped in the figure by a
color coding (from 3 nearest neighbors to 6).
dissolution probability (NP ) is compared to a random number x taken
from between 0 and 1. Following an acceptance criterion (positive if
NP ≥ x), the dissolution is permitted or not. This procedure is repeated
several times until a complete dissolution of the atoms in the simu-
lation box is obtained. No surface relaxation is allowed between two
simulation steps since only nearest neighbors with fixed bonding en-
ergies are considered in the calculation of the dissolution probability.
Through this, it becomes possible to retrieve the dissolution kinetics
of any SS with a given chemical composition and microstructure as a
function of the applied potential and pH.
Monocrystalline and polycrystalline microstructures of up to half
million atoms were used in the simulations, see Figure 1. The poly-
crystalline structure was generated using the Voronoi tessellation
technique.20 Although these nanostructures are far from represent-
ing the practical reality of stainless steels, the variety of their crys-
tallographic orientations is expected to allow a thorough analysis of
their behavior. The chemical composition is defined by randomly dis-
tributing alloying elements in the simulation box, which means that
they are not necessarily at a thermodynamic equilibrium. Accordingly,
the dissolution probability of each surface atom is calculated using
Equation 1, and by changing the composition of a given SS one
changes only the neighborhood configurations of the atoms.
DFT calculations.—All the bonding energies used in the simula-
tions are calculated by means of Density Functional Theory (DFT)21 in
the generalized gradient approximation (GGA), with Perdew–Burke–
Ernzerhof (PBE) parametrization22 as the exchange-correlation func-
tional. This functional is known to give good results for bulk properties
when compared to experiments.23 The plane wave implementation in
the ABINIT package24–26 was used, employing the projector aug-
mented wave (PAW) method.27,28 The valence states for iron were
generated in the 3s2 3p6 3d6 4s2 configuration, whereas 3s2 3p6 3dx 4s2
and 4s2 4p6 4dx 5s2 were used for the 3d and 4d TM alloying elements,
x being the number of electrons in the d orbitals of the element. The
studied primitive cells contain up to 8 atoms.1 Different configurations
of chemical composition are used to determine the bonding energies
between alloying elements. Pure α-Fe, which is the basic structure of
ferritic SS, was studied in bcc ferromagnetic state (FM), while pure
γ-Fe which is the basic structure of austenite SS was considered in a
nonmagnetic state. The Monkhorst-Pack scheme29 based on a 14 × 14
× 14 k-points grid was used for the Brillouin zone integrals. Conver-
gence of the total energy to within 1 meV per atom was achieved with
a cutoff of 540 eV.30
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Table I. List of the used expressions to calculate the cohesive per
atom (E coh ) and the bonding energies (E Fe−Fe ) of pure α-Fe and
γ-Fe iron, ET (Fe), ET (Fe2) and ET (Fe4) are respectively the total
energy of an isolated Fe atom, the total energy of α-Fe and γ-Fe
primitive cells.
Pure α-Fe cell with 2 atoms Pure γ-Fe cell with 4 atoms
2E T (Fe)−E T (Fe2) 4E T (Fe)−E T (Fe4)
E coh = 2 E coh = 4
2E T (Fe)−E T (Fe2) 4E T (Fe)−E T (Fe4)
E Fe−Fe = 8 E Fe−Fe = 24
Results and Discussion
The bonding energies of some ferritic and austenitic SS.—Using
ab initio calculations, we evaluated the atomic bonding energies of
some ferritic and austenitic SS grades. A series of primitive cells
was used: bcc (α-Fe, α-FeX, α-Fe4 X2 ) and fcc (γ-Fe, γ-Fe3 X, γ-
Fe5 X3 ) where X is a 3d or 4d TM. The structure of each cell is
optimized using the relaxation technique where the obtained total
energies (E T ) are fitted using Murnaghan’s equation of state.31 The
cohesive and the bonding energies are then calculated using simple
algebraic relationships depending on the used primitive cells, see
Table I for the case of pure α-Fe and γ-Fe. Another way to calculate the
bonding energy is to use the supercell technique, i.e., a cell containing
few dozens of atoms in the middle of which an alloy element is
inserted, the whole structure is then relaxed. This second method gives
similar results to the previous one, we chose the least time-computing
option.
The obtained Fe-X bonding energies where X = Cr, Ni, Mn, Cu,
Nb, Mo, Sn and Si are shown in Figure 2, the special cases of Si and
Sn are added to the figures although they are not transition elements.
For the 3d TM, the results clearly show that the strength of the induced
chemical bonds is strongly dependent on the d-orbitals occupancy. Cr
and Ni which present partially filled orbitals exhibit slightly lower
values compared to Fe, whereas Cu with saturated orbitals sees its
bonding energy reduced by 30%. A focus should be placed on the
case of Mn, where a slight decrease in the bonding energy can be
noticed probably due to the half-filled composition of its d-orbitals.
For the 4d TM, the trend is slightly different, a substantial increase
in the bonding energies is obtained, peaking at Mo and Nb, followed
by a significant decrease when the 4d-orbitals are completely filled
(in the case of Sn for both ferritic and austenitic SS). These values
are by far the highest of all the metallic elements of the periodic
table, indicating the importance of the 4d elements in controlling the
chemical cohesion of SS.32
In addition, a detailed analysis of the electronic charge distributions
is carried out around some alloying atoms before and after the insertion
(see Figure 3). The purpose is to notice any variation likely to specify
the mode of formation of the resulting chemical bonds. For instance,
the insertion of Cr and Cu in an α-Fe matrix is accompanied by a
partial transfer of electrons from the matrix to the atoms (in blue in
Figure 3a), causing a change of the local electron density of the order of
0.05e− /Å3 . Regarding the electronic structure of the isolated Cu atom
(4s1 3d10 ), this transfer reflects the main contribution of the 4 s valence
electrons to the formation of the metallic bond. Since the 3d-orbitals
are filled, and hence thermodynamically stable, their influence is very
limited. Unlike Cu, the insertion of Sn leads to electrons transfer from
the Sn to Fe matrix (in red in Figure 3b). In this case, the electrons
of the 5p-orbitals (5s2 4d10 5p2 ) are those which contribute the most to
the formation of the chemical bond.
These effects can be correlated to the calculated cohesive energies
(Ecoh ) of some TM in their pure metallic state as reported in Table II.
One can easily see from these values that the value of Ecoh of 3d
TM increases as one progressively fills the d-orbital then decreases
to a half-filling (5 electrons), such as in the case of Mn. The relative
stability of its orbitals (probably of magnetic origin) prevents the d-
electrons from participating in the chemical bond, which explains the
weak calculated bonding energy. Therefore, Mn as an alloying element
 Journal of The Electrochemical Society, 165 (10) C703-C709 (2018) C705

a) 3d TM in ferritic SS b) 4d TM in ferritic SS
1,5 1,6

Bonding energy Fe-X (eV)

Bonding energy Fe-X (eV) 1,1 1,2

0,8 0,8

0,4 0,4

0,0 0,0
Fe Cr Ni Mn Cu Fe Mo Nb Si Sn

c) 3d TM in austenitic SS d) 4d TM in austenitic SS
1,0 1,0

Bonding energy Fe-X (eV)

Bonding energy Fe-X (eV)

0,8 0,8

0,5 0,5

0,3 0,3

0,0 0,0
Fe Cr Ni Mn Cu Fe Mo Nb Si Sn

Figure 2. Histograms of the bonding energies of various TM in ferritic (a and b) and austenitic (c and d) stainless steels; individual bond energies are much lower
in austenitic system than ferritic one, but the high coordination number of fcc structure makes the cohesive energies of the two systems rather comparable.

will exhibit a strong tendency to dissolve unlike the rest of the 3d TM.
This effect cannot be found in 4d TM due to the large spatial extent of
the 4d-orbitals (far beyond the first nearest neighbors), which forces
the electrons to always participate in the formation of the chemical
bond.
Dissolution mechanisms in FeCr based ferritic steels.—In this
section, we examine the role of some alloying elements in the disso-
lution mechanisms of both ferritic and austenitic SS. The influence of
alloying elements on the dissolution probability is analyzed on both a
metallurgical and an electrochemical level. The metallurgical level is

a) b)

Cr Cu
Fe

0.05e -Å-3
Figure 3. Projected electronic density around some alloying
elements (Cr, Cu, Mo and Sn) obtained by subtracting electronic
(100) charges before and after their insertion in a α-Fe matrix; these
changes in the partial charges around an element (negative in
c) d) blue and positive in red and of the order of 0.05e− /Å3 ) reflect the
mode of formation of the chemical bond of the given element.

Mo Sn

-0.05e -Å-3

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 C706 Journal of The Electrochemical Society, 165 (10) C703-C709 (2018)

Table II. Calculated cohesive energies of some transition metals. icantly high for Cr, which is enhanced by the slight decrease in the
induced bonding energies (Figure 2). The result is a multiplication of
3d TM Ti V Cr Mn Fe Ni Cu Zn the initiation sites extended to higher coordinated atoms up to CN = 6
within the (110) dense planes, as shown in Figure 4b. These findings
Ecoh (eV) 4.9 5.2 4.1 2.8 4.4 4.5 3.3 1.4 illustrate the strong oxidability of Cr which will readily form a passive
4d TM Zr Nb Mo Ag Cd Sn film provided that the pH and potential conditions are fulfilled.
Ecoh (eV) 5.4 7.5 7.9 6.8 1.2 2.9 In general, one would expect antagonistic effects from the alloying
elements depending on the polarization level. This is the case for Cu
Table III. Standard potentials of some transition metals. for instance, which exhibits weak bonding energies (see Figure 2) and
element Fe Cr Ni Cu Mn Mo Nb Sn Si hence a certain tendency toward bond breakdown, however, its high
E0 (V/SHE) −0.45 −0.75 −0.25 0.34 −1.14 −0.20 −1.09 −0.14 −0.80 standard potential is likely to reduce the dissolution probability. This
effect is also evident for Sn but to a lesser extent. On the contrary, Nb
with its tendency to form strong bonds has, nonetheless, a very low
represented by the pre-exponential term of Equation 1, where the effect standard potential. A compensating effect is therefore expected in this
of bonding energies was previously demonstrated. The electrochemi- case.
cal level refers to the effect of an electrical field at the SS/electrolyte To better illustrate these effects, here is a detailed simulation of
interface on the magnitude of the energy barrier that a surface atom the acid dissolution of a ferritic Fe20Cr4Cu SS at pH 0 (Figure 5). To
must cross to dissolve toward the electrolyte. The expression ϕ j of carry out the study, we used to analyze first the metallurgical contri-
Equation 1 includes a reference to the standard potential of a given bution alone by setting ϕ j = 0 eV for all elements of the SS (Figure
alloying element j, from which the local electrical potential is defined. 5a). Then, we added the electrical contribution in a second step (Fig-
We use the standard potential of each alloying element at pH 0 as a ure 5b). As shown by the inserted current transients in Figure 5a, the
reference for ϕ j overpotentials33 (see Table III). metallurgical effect of Cr and Cu is revealed by the acceleration of the
These two critical aspects concerning the role of alloying elements dissolution dynamics due to the high dissolution probabilities induced
are illustrated in the dissolution patterns obtained for pure α-Fe and by their weak bonding energies. This is reflected in the dissolution
α-Fe17Cr monocrystalline structures at pH 0 and ϕ Fe = 0 eV (see patterns by an increase in the density of the initiation sites, extended
Figure 4). In the absence of alloying elements, such as in the case to higher coordinated atoms. Considering the electrical contribution
of pure iron, the dissolution proceeds along the most densely packed of alloying elements (ϕ Fe = 0 is set only for Fe), a significant de-
planes (110) in blue in Figure 4a (for more details see our previous crease of the dissolution currents is obtained, likely due to the high
paper).1 The most active neighborhood configuration that governs the standard potential of Cu. Some of the initiation sites are pinned on
experimentally observed dissolution kinetics is found to be the 4 near- the surface by Cu atoms during the dissolution process, leading to
est neighbors system (with a CN = 4, i.e. kink atoms). Conversely, in a rapid depletion of less coordinated atoms. This surface-blocking
the presence of alloying elements, this primary dissolution mechanism scheme is comparable to that observed for Mo but with a rather dif-
undergoes significant changes depending on the nature of the alloying ferent mechanism.1 At the macroscopic level, this behavior results in
element and the applied potential, Figure 4b illustrates the effect of a gradual shift of the equilibrium potential toward higher values,34 a
Cr. Regarding the applied potential (ϕ Fe = 0 eV which implies that fact that is not explicitly integrated in our simulation.
ϕCr = +0.3 eV), the dissolution probability is found to be signif-
Dissolution mechanisms in FeCrNi based austenitic stainless
steels.—The purpose of this section is to investigate the effect of
before dissolution after dissolution
some alloying elements on the acidic dissolution mechanisms of Ni-
a) Pure α -Fe bearing austenitic SS. The transition from a bcc (8 NN) to fcc (12
NN) structure substantively changes the neighborhood configuration
of surface atoms. For a Fe18Cr8Ni SS, for example, there are up to
450 neighborhood possibilities. An immediate consequence is that the
(110)
resulting dissolution probability spectrum will extend to several crys-
(110)
tallographic systems, and this will necessarily affect the dissolution
kinetics.
Figure 6 shows the average dissolution probability of a Fe18Cr8Ni
(110)
polycrystalline structure at two different polarization levels: a)
ϕ Fe = 0 eV and b) ϕ Fe = +0.4 eV, along with the corresponding
dissolution patterns. It appears from this result that the acid dissolu-
b) Fe17Cr SS
tion of austenitic SS is more complex than that of ferritic SS, since
it involves several critical coordination numbers at the same time. At
low polarization levels (corrosion regime), the initiation sites are lo-
calized on the edge of the (111) dense planes having 5NN and 6NN
as the CCN, whereas for high polarization levels (pickling regime)
7NN/(111) system and higher dominate the dissolution dynamics.
This complex distribution of the dissolution probability is expected
to generate different dissolution kinetics depending on the chemical
composition of a surface and the crystal orientation.35,2,36
In addition, the role of alloying elements can be regarded as similar
to that of ferritic SS with, however, more complex antagonist effects.
Figure 7 shows the dissolution probability obtained at a high applied
potential ϕ Fe = 0.45 eV of some austenitic SS selected to illustrate
Fe Cr sites with CN = 6
the role of Cr, Ni, Nb, Cu and Sn. As is expected, the beneficial effect
Figure 4. Dissolution patterns of: (a) a pure monocrystalline α-Fe and (b) a
of the Nb, which is a priori similar to Mo from a metallurgical point of
ferritic Fe17Cr SS in highly acidic conditions (pH 0 and ϕ Fe = 0) before view (Figure 1), is somewhat canceled out by the electrical effect due
and after few iterations of simulation; the most active sites in α-Fe are those to its low standard potential (Table II). In the case of Cu and Sn, which
localized on the edge of the (110) dense planes. The addition of Cr will increase both induce weak chemical bonds, the metallurgical effect is stronger
the number of initiation sites localized even in the (110) planes. for Cu than for Sn. A deactivation of several dissolution systems of

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 Journal of The Electrochemical Society, 165 (10) C703-C709 (2018) C707

(a) Metallurgical effect of Cu (b) Electrochemical effect of Cu

6000 6000

Dissolution rate atom/iteration

Dissolution rate atom/iteration
5000 5000

4000 4000
Fe
3000 3000

2000 Cr 2000

1000 1000
Cu Fe
Cr
0 Cu
0
0 50 100 150 200 0 50 100 150 200
Iterations Iterations

Fe Cr Cu sites with CN = 6

Figure 5. Dissolution patterns and the corresponding current transients of Fe17Cr4Cu SS in acidic media (pH 0) and the corresponding corrosion patterns: (a)
ϕ j = 0 for all elements and (b) ϕ Fe = 0 for Fe only; the effect of Cr and Cu is revealed by the acceleration of the dissolution rate due to the weak bonds
induced by Cu.
1 1
10 10
CCN > 5 0 CCN > 6
0 10
10
Dissolution probability

Dissolution probability

-1 -1
10 10
-2 -2
10 10
-3
10
-3 10
-4
10
-4 10
-5
10
-5 10
-6
10
-6 10
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12
Coordination Coordination

Figure 6. Calculated dissolution probability of a polycrystalline Fe18Cr8Ni SS in very acidic media and the corresponding corrosion patterns: a) ϕ Fe = 0 eV
and b) ϕ Fe = 0.4 eV ; depending on the applied potential the dissolution mechanism may involve multiple crystallographic systems at the same time.

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 C708 Journal of The Electrochemical Society, 165 (10) C703-C709 (2018)

Fe20Cr18Ni Fe20Cr18Ni4Cu
1 1
10 10
0 CCN > 6 0
CCN > 3
10 10

Dissolution probability
Dissolution probability
-1 -1
10 10
-2 -2
10 10
-3 -3
10 10
-4 -4
10 10
-5 -5
10 10
-6 -6
10 10
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12
Coordination Coordination

1
Fe20Cr18Ni4Nb Fe20Cr18Ni4Sn
10 1
10
0
CCN > 5 CCN > 5
10 0
10
Dissolution probability

Dissolution probability
-1 -1
10 10
-2 -2
10 10
-3 -3
10 10
-4 -4
10 10
-5 -5
10 10
-6 -6
10 10
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11
Coordination Coordination

Figure 7. Dissolution probabilities of different austenitic SS grades selected as best illustrating the role of Cr, Ni, Nb, Cu and Sn obtained at pH 0 and highly
applied potential ϕ Fe = 0.45 eV.

low coordination is then obtained (CCN >3 for the F20CrNi84Cu,
resulting in a slowing down of dissolution and a completely different
surface morphology.
Conclusions
In this work, we carried out MC simulations of the acidic dissolu-
tion of various stainless steels grades with the aim to investigate the
effect of their chemical composition and/or crystallographic structure
on the dissolution kinetics. Using ab initio calculations, we first eval-
uated the bonding energies induced by alloying elements for different
solid solutions (ferritic and austenitic). It was found that all the va-
lence orbitals (s, p and d) of a given alloying element contribute to
the chemical bonding, though there is a predominance for d-orbitals
depending on their occupancy state. 3d transition metals are found to
generate bonding energies comparable to Fe-Fe ones (in the case of
Cr, Ni, Ti and V), or even smaller (in the case of Cu and Zn) due to the
fully saturated 3d-orbitals. Note that Mn represents a singularity in
this series since it tends to form weak bonds with all the other elements
due to the half-filled state of its d-orbitals. By contrast, 4d transition
metals systematically generate strong bonding energies (in the case
of Mo, Nb, Zr and W), except when one approaches orbital saturation
(in the case of Sn, Cd, In etc.). We believe that this wide variety of
bonding energies in SS has a substantial impact on the dissolution
mechanisms of both ferritic and austenitic SS.
Through a series of simulations conducted on several SS grades,
we found that the role of the alloying elements should be considered
at two different levels:
- A first (metallurgical) level in which the bonding energy of an
alloying element directly controls the dissolution probability of its
surrounding atoms. Strong chemical bonding will tend to block
the surface from dissolution (Mo, W etc.), whereas weak bonding
will enhance the dissolution rates by activating highly coordinated
sites, increasing thereby the density of the initiation sites. This
effect is embodied in the pre-exponential term of the phenomeno-
logical law of dissolution.
- A second (electrochemical) level related to the thermodynamic
equilibria of a given chemical element in aqueous media. The
higher the standard potential of an alloying element, the lower
its dissolution probability, and this is likewise reflected in the
exponential term of the dissolution law.
From this perspective, the dissolution mechanisms of both ferritic
and austenitic SS can be regarded as governed by the combination of
these two aspects and a wide variety of situations was found:
- High bonding energies with high standard potentials (Mo): this
configuration offers the highest dissolution resistance. One would
expect similar behavior from W.
- High bonding energies but low standard potentials (Nb): a drop in
the dissolution resistance is obtained.
- Low bonding energies with high standard potentials (Cu): this is
reflected in a selective dissolution of the SS due to the blocking
effect of Cu atoms on the surface.

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 Journal of The Electrochemical Society, 165 (10) C703-C709 (2018)
These findings remain the same in the case of austenitic SS, though
with, higher degrees of complexity, with the crystallographic structure
itself exhibiting little influence on the dissolution ability.
ORCID
B. Malki https://orcid.org/0000-0002-2605-1565
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