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FEM simulation of corrosion under macro-cell mechanism

Mehdi Attarchi (Methodology) (Investigation) (Writing - original

draft), Andrea Brenna (Conceptualization) (Supervision) (Writing -
review and editing), Marco Ormellese (Conceptualization) (Data
curation) (Writing - original draft)

PII: S0010-938X(20)32397-0
DOI: https://doi.org/10.1016/j.corsci.2020.109116
Reference: CS 109116

To appear in: Corrosion Science

Received Date: 26 July 2020

Revised Date: 6 November 2020
Accepted Date: 7 November 2020

Please cite this article as: Attarchi M, Brenna A, Ormellese M, FEM simulation of corrosion
under macro-cell mechanism, Corrosion Science (2020),
doi: https://doi.org/10.1016/j.corsci.2020.109116

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FEM simulation of corrosion under macro-cell mechanism

Mehdi Attarchia* mehdi.attarchi@polimi.it, Andrea Brennaa, Marco Ormellesea

a
Dipartimento di Chimica, Materiali e Ingegneria Chimica, “G. Natta”, Politecnico di Milano,
Via Luigi Mancinelli 7, 20131 Milan, Italy

*
Corresponding author, e-mail, Tel. +39 022 399 3118

Highlights:

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

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Defining new throwing power criteria for the active-passive metal in macro-cell corrosion
mechanism

 FEM modeling for macro-cell corrosion analysis with considering primary and secondary

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current distributions

 Proposing new and straightforward equation for calculating throwing power in the macro-
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cell condition
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Abstract:

In the present study, FEM simulations have been carried out to have an accurate estimation of
the electrical field in the presence of a macro-cell process, taking into account primary and
secondary current distribution to update present throwing power equations. The electrochemical
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boundary conditions were defined comprehensively, and simulations have been performed
changing water resistivity, geometry, and oxygen content. The studied systems are galvanic
coupling between a stainless steel-carbon steel and also a carbon steel-zinc. As a result, an
equation was proposed to predict the surfaces involved in the coupling to have an estimation of
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the corrosion rate.

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1. Introduction
Corrosion by a macro-cell mechanism is applicable in the study of localized corrosion, galvanic
corrosion, cathodic protection and other situation where the anodic and cathodic regions are
physically separated. In this respect, the macro-cell current passed through the electrolyte from
the anodic site to the surrounding cathodic surface [1]. The corrosion rate of the anodic zone is
proportional to the driving voltage, i.e., the difference in local free corrosion potential between the
anodic and cathodic sites, and increases as the cathodic-to-anodic surface ratio increases [2].
The involved surfaces, which may not be easily measured, can be estimated by the assessment
of the electric field established by the corrosion process. The maximum extension of the cathodic
surface is determined by the so-called throwing power, which is defined as the maximum distance
from the anodic zone reached by the macro-cell current. Throwing power could be calculated by
different approaches, depending on fixed boundary conditions. One basic approach is considering
primary current distribution and Ohm’s laws:

𝑉 = 𝐼𝑅 =  ∫ 𝑖𝑐 ∙ 𝑑𝐿 ≅ 𝑘 ∙ 𝑖𝑐 ∙ 𝐿 (1)

where ΔV is the ohmic drop (in V) in the electrolyte between anode and cathode (equal to IR,
where I is the macro-cell current and R the total electrical resistance), ρ is the resistivity of the
electrolyte (assumed homogeneous, in Ω m), ic is the average current density of the cathodic
process (in mA/m2), L the distance between anode and cathode (in m) and k a cell constant, which

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depends on the geometry of the system.

For simple geometries, like pipes or plates, the throwing power, Lmax, could be extracted by solving

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Equation (1). The following expressions apply [3]:

𝑉 
𝐿𝑚𝑎𝑥 ≅ 𝑘√ (2)
  𝑖𝑐

𝐿𝑚𝑎𝑥 ≅ 𝑘
𝑉
  𝑖𝑐

-p (3)
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Equation (2) is applicable inside a pipe ( is the diameter) transporting a solution with resistivity
ρ. If the pipe is partially filled, the height of the solution must be considered instead of pipe
diameter. The same equation is still valid on flat surfaces in the presence of a thin electrolyte.
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Equation (3) is valid outside a pipe, or generally, in the presence of very wide electrolytes, i.e.,
structures buried in soil or immersed in seawater.

These equations are obtained by considering only the primary current distribution, i.e. they are
based on the solution of the Laplace equation and the Ohm’s law. In the above equations, the
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secondary current distribution, which considers the electrochemical relation at the metal surface
between the local current density and the local potential, namely the anodic and cathodic
overvoltages, is not included. The overvoltages are governed by the Butler-Volmer equation,
which is a non-linear equation. Generally, secondary distribution is more uniform than primary,
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because geometric factors determining the primary distribution are overlapped by overvoltage
effects that smooth current distribution [3]. The solution of the Laplace equation for secondary
current distribution is not always easy to achieve [4–8]. It is possible to use numerical method [9]
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such as finite element method (FEM) simulations to have an accurate estimation of the electric
field in the presence of a macro-cell corrosion process, taking into account overvoltages at the
electrodes [6,10–18]. Some equations in galvanic coupling are reported for specific cases, that
are a function of geometry, solution resistivity, solution height, and polarization resistance, but not
simple and generic [10,19–22]. However, in some cases, the linear current distribution is reported
[15, 23].

The purpose of the activity described in this work is to validate the above equations for calculating
the throwing power of corrosion systems with a macro-cell corrosion mechanism (solution height
between 0.01 to 5 m). Atmospheric corrosion and very thin layer electrolyte are not at the core of
this study. Two cases have been considered: 1) the galvanic coupling between stainless steel
(cathode) and a small carbon steel (anode) simulating localised corrosion, as pitting; 2) the
cathodic protection a carbon steel structure immersed in seawater by means of zinc anode. For
any simulation, electrolyte resistivity and geometry have been changed.

The boundary conditions have been completely defined, indicating the free corrosion potential of
the two metals, and the kinetic parameters of the anodic and cathodic processes (exchange
current density, Tafel slopes, oxygen diffusion limiting current density).

Using numerical simulation will give the possibility to define criteria for throwing power and
analyzing the macro-cell mechanism based on the parameter, which is not merely measurable in
the field. So, in this work, not only complete non-linear boundary conditions based on the

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secondary current distribution analysis in the macro-cell analysis are used, but it is also tried to
use the numerical simulation capacity in defining the new criteria in the development of macro-
cell mechanism analysis.

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2. Materials and Methods
As mentioned, two metal coupling would be studied: stainless steel-carbon steel and carbon steel-
zinc. The anodic material is carbon steel in the first case and zinc in the second one. Three main
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steps have been done in this research: (a) definition of boundary conditions, according to
laboratory tests; (b) FEM simulations and data analysis to extract a comprehensive and
straightforward equation to estimate the throwing power; (c) laboratory test to confirm simulation
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results.

2.1 Defining Boundary Conditions

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Laboratory polarization tests have been performed on carbon steel (grade API 5L X60 [24]) and
stainless steel (UNS S30400 [25]) samples immersed in a soil simulation solution (0.2 g/l NaCl +
0.2 g/l CaSO4.2H2O, resistivity 10 Ω m). Tested sample surface was 1 cm2. Tests were carried
out with three-electrode arrangement in standard 1 L cell, according to ASTM G61 [26]: platinum
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was used as counter-electrode, and a saturated silver / silver chloride (SSC) as the reference
electrode. After 1 h immersion, the free corrosion potential (OCP, Open Circuit Potential) has
been recorded. Then potential was increased from -1.0 V SSC up to some hundreds mV over the
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OCP, with a polarization scan rate 10 mV/minute. The cathodic branch was determined in a
separate test, scanning the potential from free corrosion potential to more negative values. The
extracted polarization graphs were fitted to Equation (4).

2.2 FEM Simulation

As previously stated, two galvanic couplings have been considered: stainless steel-carbon steel
and carbon steel-zinc. In both cases, the anode is a vertical electrode 0.01 m in height and the
cathode is a plate, the length varying from 1 m up to 300 m. The selected cathode length is long
enough to be considered as semi-infinite. In this circumstance, the potential of the cathode at the
end of the model is less than 0.1 mV different from its corrosion potential, so the macrocell current
can be considered zero. The height of the solution (H) changes is in the range of 0.01 m up to 5
m. In all the simulations, the width of the model is 2 m. The schematic arrangement of the system
is presented in Figure 1. The electrolyte resistivity changes from 0.2 Ω m (as seawater) to 100 Ω
m (simulating waters with low salinity, or soil). All these parameters were changed independently,
and all combined conditions were simulated.

The FEM simulations are performed using COMSOL 5.4® software. The mesh size in the
electrolyte changes from 0.03 to 1 m, depends on the geometry of the model. At the anode and
centerline of the cathode, for higher accuracy, the mesh size is set to 0.001 m. The mesh size
between anode and electrolyte and also the mesh size in between the cathode centerline and
electrolyte changes accordingly. The dimension of the simulated model is equal to the electrolyte
dimension in each case, Figure 1. For all the mentioned conditions, potential and current density

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profiles were extracted in the centreline of the cathode.

At the cathodic surface, the boundary condition defined by the lab tests have been imposed; in
both the considered galvanic couplings, hydrogen evolution reaction is not involved in the

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boundary condition of the model. Oxygen availability is an essential parameter for the cathodic
reaction, and it may vary in time. A stable condition is assumed in the present model, so the
stationary analysis has been done, and oxygen mass transport during the time and gradient are

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not explicitly implemented. In this circumstance, the effect of oxygen diffusion is a fixed value for
each condition, and it is considered in the model as the limiting current density (Equation 4). For
the oxygen diffusion limiting current densities, six values (10, 20, 50, 100, 200 and 300 mA/m2)
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have been taken into consideration in order to simulate slightly and well-aerated solutions. The
ranges of the main variables in the simulation model are presented in Table 1. The solution height
of the model is in the range of thick electrolyte.
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<Figure 1>
<Table 1>
Equation (4) is valid for every mesh surfaces at both anode and cathodic surface, so every
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element should follow this equation as a boundary condition. From a macroscopic point of view
and all elements beside each other, the whole surface function is different from Equation (4) and
more complex. FEM solves this overall complexity.
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2.3 Numerical validation of FEM Simulation

To validate the simulations, the local potential and current density were extracted at the anode
surface and at five points on the cathode surface. These extracted six points were superimposed
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on the defined boundary condition to verify if they were coherent. Moreover, the simulation was
validated, verifying that the total current released by the anode is equal to the total current
adsorbed by the cathode. The acceptable tolerance on the current balance is 0.1%. Checking
introduced boundary conditions, and the current balance was reported previously [27–29].

2.4 Experimental validation of FEM Simulation

Laboratory tests have been done to validate the simulation results. A UNS S30400 [25] (AISI 304)
stainless steel plate, 1 m long and 0.2 m wide, was used as a cathode and a carbon steel disk (1
cm in diameter) as an anode. The anode was fixed at one end of the plate. The height of the
electrolyte varies from 0.01 m up to 0.15 m. The resistivity of the solution varies from 10 to 870 Ω
m. Using the same experimental setup previously described, potentiodynamic tests have been
carried out in the same electrolyte of the potential profile test at different height and resistivity to
obtain the actual oxygen limiting current density.

After a stabilization period of about a few hours, the potential profile on the stainless steel plate
has been measured, from a point very close to the anode up the end of the plate. The distance
between each two readings is 1 cm (Figure 2). As presented in Figure 2, the reference electrode
is placed near the surface (10 mm); after a few seconds of stabilization, the potential is recorded.
The reference electrode is moved from the anode all along the centreline of the cathode; potential
has been measured every 10 mm till the end of the plate. The test cell is transparent to check the

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possible trap of gas bubbles between the reference electrode tip and plate. The same geometry
of the cell is introduced to the software. Experimental profiles have been compared with simulation
results.

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<Figure 2>

3. Results
3.1 Definition of boundary condition

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Polarization tests performed on carbon steel and stainless steel samples immersed in a soil
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simulation solution are reported in Figure 3. Tests started after 1 h immersion, at a stable free
corrosion potential of about 0 V SSC and -0.65 V SSC for stainless steel and carbon steel,
respectively. A clear oxygen limiting current density is visible in the cathodic branch, at about 200
mA/m2 in both the cases. In the presence of stainless steel the anodic curve has a high slope,
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while in the case of carbon steel the typical active behaviour appears.

<Figure 3>
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The polarization graphs were fitted with the following equation:

2.3(𝐸−𝐸𝐶𝑜𝑟𝑟(𝐴𝑛.) )
( )
𝛃𝐴(𝐴𝑛.)
𝑖𝐴𝑛. = 𝑖0(𝐴𝑛.) ∙ 𝑒 − 𝑖𝐿(𝐴𝑛.)
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(4)
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2.3(𝐸−𝐸𝐶𝑜𝑟𝑟(𝐶𝑎.) ) 2.3(𝐸−𝐸𝐶𝑜𝑟𝑟(𝐶𝑎.) )
( ) ( )
𝛃𝐴(𝐶𝑎.) 𝛃𝐴(𝐶𝑎.)
𝑖𝐶𝑎. = −𝑖0(𝐶𝑎.) ∙ 𝑒 ⁄(1 + ‖𝑖0(𝐶𝑎.) ∙ 𝑒 ⁄𝑖𝐿(𝐶𝑎.) ‖)

The values and definitions of the mentioned parameters in Equation (4) are presented in Table 2
and Table 3. The oxygen limiting current density, iL, is fitted to 200 mA/m2. The cathodic Tafel’s
slope ranges from 100 to 200 mV/decade. For stainless steel, which is passive in the considered
electrolyte, for the sake of simplicity an anodic Tafel’s slope as high as 5 V/decade was
considered. In the case of carbon steel, the slope was fixed equal to 100 mV/decade. Anodic
Tafel’s slope for zinc is considered 20 mV/decade, which means its potential is quite constant
around corrosion potential, -0.93 V vs. SSC. A maximum 10 A/m2 anodic limiting current density
is considered for zinc.

Figure 3 also reports the potentiodynamic curves obtained at the selected boundary conditions.
A very good match is visible with experimental data.

<Table 2>

<Table 3>

3.2 Numerical validation of FEM simulation

Potential and current density profiles for all the conditions were extracted by FEM simulation. An

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example of simulation validation is presented in Figure 4. At points A, C1 to C3, the local potential
and current density is extracted. All the four points are perfectly overlapped to the imposed
boundary condition, confirming the validity of the FEM simulation. By increasing the distance from

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the anode, the current density at the surface of the cathode is reduced and the cathode potential
moves toward the free corrosion potential, which means the polarization effect of macro-cell is
reduced. The location of the extracted points on the graphs shows that in the close distance to

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the anode, C1, the cathode is in the oxygen diffusion control regime defined by the oxygen
diffusion limiting current density. By increasing the distance from the anode, from C1 to C3, the
cathodic activation polarization is dominant, and not affected by the diffusion contribution.
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<Figure 4>
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3.3 FEM simulation stainless steel – carbon steel

Potential and current density profiles were extracted for all the cases. The results of the current
density and potential in three solution resistivities (0.2, 10 and 100 Ω m) are presented in Figure
5.
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<Figure 5>

When the resistivity is 100 Ω m, the current density is reduced from 10 mA/m2, which is limiting
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the current density of the presented results of Figure 5, just after a few cm from the anode. For
lower resistivity, the falling-current-distance is high, but even for 0.2 Ω m solution resistivity and
after few meters, the current density is clearly dropped. After this fall from the limiting current
density, 10 mA/m2 here, the cathode surface as discussed in Figure 4 is in the activation
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polarization. So the length of the cathode that is under diffusion is affected by solution resistivity
[21]. The effect of solution resistivity will be analyzed in further sections.

As presented in Figure 5, by increasing the distance from the anode, cathode potential is
approaching to the free corrosion potential of the cathode, and the polarization effect of macro-
cell is reduced. In these circumstances, the current density is approaching the zero. Based on
Figure 5, solution resistivity is a factor that could change the profile of potential and current density
variation. Reducing solution resistance will increase current density and increase the affected
surface of the cathode.
3.4 FEM simulation carbon steel - zinc
Zinc is used as the galvanic anode in cathodic protection systems to protect carbon steel
structures, immersed in water or soil. In this arrangement, zinc works as anode and will corrode
under activation polarization. Carbon steel, the cathode, would be polarized: obviously, the
surface close to the anode is more polarized, and it will work in the diffusion polarization regime,
while the remote surface, not affected by the anode, will have a potential close to the carbon steel
free corrosion potential. In the present study, the well-known -0.85 V vs. CSE criterion
(corresponding to -0.73 V vs. SSC) [30] is used to define the protection level and so the cathodic
protection throwing power.

Figure 6 shows the extracted polarization profiles of carbon steel surface and the absorbed

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cathodic current density as a function of distance from the anode. Electrolyte height was 5 m and
resistivity was 0.2 Ω m. The six profiles refer to increasing oxygen limiting current density. The
dotted line represents the protection criterion level.

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Increasing the oxygen availability in solution leads to the reduction of the throwing power, the
surface has potential more negative than criteria, and in the same time, the higher current density

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will fall more rapidly to a value close to zero. It means the anodic current produced by zinc would
be consumed more rapidly at the cathode surface and the throwing power is then reduced.

<Figure 6>
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3.5 Experimental validation of FEM simulation
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Electrochemical parameters of the modelling were extracted from potentiodynamic polarization

and reported in Table 2 and Table 3. Other effective parameters are the height of the solution and
solution resistivity. The height of the solution may affect on the ORR liming current density, so it
is measured for all experiments separately. The combination of Table 2, 3, and 4 are imported to
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the simulation model as boundary conditions. Moreover, as mentioned in the experimental part,
the potential profiles at the center of the cell (Figure 2) are measured. The dimension of the FEM
model for the experimental validation is the same as Figure 2. For the condition of Table 4, both
simulation data with the mentioned boundary conditions and real measured potential at the
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centreline are presented in Figure 7. The measured potentials and simulated ones are close
enough, so the simulations are verified.
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<Table 4>

<Figure 7>

4. Discussion
The aim of this work is the estimation of the throwing power, a useful parameter in order to
estimate the surfaces involved in a galvanic coupling, pitting corrosion or cathodic protection
system. Once the surfaces are known, corrosion rate as well as anode consumption can be
estimated.
Laboratory tests, FEM simulation and mathematical solution of the primary current distribution
can be used to cope this aim.

4.1 Throwing power estimation

This throwing power could be calculated with four methods:

(a) Primary current distribution. As presented in Equation 2 and 3, it is possible to calculate

throwing power based on Ohm’s law. The main variables in these equations are the level
(height) of the electrolyte, free corrosion potential difference between cathode and anode,
solution resistivity, and oxygen diffusion limiting current density. This approach is
applicable if the macro-couple works in the limiting current density range.

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(b) Modified primary current distribution. As discussed in Figure 4 and Figure 5, stainless steel
is working in the activation polarization regime. Therefore, the effective current density to
be used in the Equation 2 and 3 would not be the oxygen limiting current density, which is

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greater than the real adsorbed current. In a simplified approach it is assumed that just
10% of the limiting current density would be involved in the macro-cell circuit.
(c) Potential profile. The throwing power is assumed as the distance at which the potential of

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the polarised cathode approaches to its free corrosion potential. As a rule of thumb, a
difference in the potential of about 5 mV is considered as the minimum measurable
variation.
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(d) Passive current density. This method applies only in the presence of passive metal, as
stainless steel. It is based on the assumption that a passive metal may exchange a
minimum current equal to the passive current density. Accordingly, the throwing power is
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defined as the distance at which the cathodic current density equals the passive current
density. An example is presented in Figure 8. For the present case study, the criteria is a
passive current density of 1 mA/m2 at stainless steel surface, obtained as intersection of
the anodic branch in passive state and the cathodic branch. This criterion is more robust
than potential, but, as it is not possible to measure directly the current density at the
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surface, it needs a numerical modelling.

<Figure 8>
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4.2 Stainless steel – carbon steel macro-cell

The macro-cell between stainless steel and carbon steel could be representative of several
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industrial galvanic coupling systems, and also modelling of the localized corrosion propagation.
In this couple, carbon steel behaves as an anode, it corrodes and the produced anodic current is
consumed by cathodic processes at the cathode surface, which is stainless steel.

Applying criteria (a) and (b), the throwing power could be calculated from the defined boundary
condition, applying only the primary current distribution, without any polarization and FEM
modelling study. Criteria (c) and (d) need potential and current density profiles extracted by FEM
simulation, as the one shown in Figure 5.
Throwing power estimated with different criteria is presented in Figure 9. If the free corrosion
potential is used, instead of 5 mV of the present study, the throwing power could be one order of
magnitude higher and absolutely out of range.

As presented in Figure 9, modification in the primary current distribution and considering just 10
percent of the limiting current density could modify the calculated throwing power. The main
reason for using 10 percent is that the majority of the cathode surface is not in the diffusion control,
while it seems considering a fix ratio of the limiting current density as an estimation of effective
current density is not precise. When the limiting current density is low, bigger surface is under
diffusion control, so the modified primary current distribution equation could give a result close to
the passive current density, but by increasing limiting current density the activation polarization
become main polarization and the 10 percent modification could not be precise anymore.

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<Figure 9>

In order to obtain a better agreement with the simulation data, which were proofed by experimental

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results such as Figure 7, a new algorithm (Appendix A) has been proposed which correlates the
throwing power estimated by the simulation to the characteristic parameters, i.e. to driving force
(ΔV), the electrolyte height (H), the resistivity (ρ) and the cathodic liming current density,𝑖𝐿 . The

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relationship that best interpolates the data is:
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𝑉  𝐻 0.4 𝑉 𝐻
𝐿≅𝑘 ≈𝑘 √𝜌 (5)
0.6  𝑖𝐿 0.08 𝑖𝐿 0.08
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Where k is a constant. Increasing the cathodic Tafel slope from 0.1 to 0.2 V/decade of stainless
steel could reduce the power of the iL to approximately 0.05. This reduction is small, but even this
variation in the iL power, leads to a slight increase in the throwing power in the same condition.
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When the cathodic Tafel slope in the activation polarization is higher, the activation energy for the
reduction reaction at the cathode surface is higher, so with the same exchange current density
higher cathodic slope, for the same overvoltage, leads to lower cathodic reaction rate. Hence, an
increase in the cathodic Tafel slope makes activation polarization harder and increase the portion
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of the surface close to the anode that is under diffusion polarization. In both cases, different Tafel
slopes, the absolute value of the power of cathodic current density is low, which is in the
agreement of electrochemical analysis that shows a small portion of the cathode is in the diffusion
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control and throwing power do not affect from limiting current density so much.

The result of the FEM simulation and the proposed new equation for four different sets of data
are presented in Figure 10. In most of the cases, Equation 5 shows a good fit with the throwing
power data obtained from the simulations. Some small discrepancies are apparent in some cases
in low solution resistivity or high solution resistivity, Figure 10 (c) and (d), but is in the acceptable
range.

<Figure 10>
4.3 Carbon steel – zinc macro-cell
In the coupling carbon steel and zinc, the throwing power has been calculated with two
approaches:

(a) Primary current distribution: As discussed in Equation 2 and 3, the primary current
distribution may use to calculate throwing power.
(b) Potential analysis: protection potential criteria could be considered as criteria for
calculating the throwing power of anode.

The comparison between the two approaches are presented in Figure 11. In some cases the
primary current distribution could predict the throwing power very good, but in some others, there
is some order of discrepancies.

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<Figure 11>

If the simulation result with potential criteria is fitted to the model of equation 5, in the simplified
approach only changes are the power of limiting current density, iL, to -0.7 (Appendix A). The

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relation between throwing power and height of the solution and solution resistivity remain similar
to Equation 5 (√𝐻 ⁄𝜌), which was reported from direct measurement on low level of solution too

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[18]. This means for the carbon steel-zinc that the criteria is a potential that is in the range of
diffusion polarization, the effectiveness of limiting current density is higher than stainless steel-
carbon steel that is mostly is under activation polarization control.
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5. Conclusions
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Two types of galvanic coupling are studied. For active anode-passive cathode the new criteria
based on the passive current density is defined and successfully used for calculating throwing
power. For both passive current density in active anode-passive cathode and potential criteria in
active anode-cathode the new simple equation based on solution resistivity, solution height,
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potential difference and limiting current density is proposed and validated. In both cases, throwing
power is proportional to √𝐻 ⁄𝜌 and the power of 𝑖𝐿 would be different in two systems. Power of 𝑖𝐿
for active anode-passive cathode is low, so it is not effective in this condition. However, in active
anode-cathode with potential criteria this power is between -0.7 to -1.2 and limiting current density
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is an important parameter.

Author Contribution Statement

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Mehdi Attarchi: Methodology, Investigation, Writing- Original draft

Andrea Brenna: Conceptualization, Supervision, Reviewing and Editing

Marco Ormellese: Conceptualization, Data curation, Writing- Original draft

Appendix A
The throwing power for the stainless steel and carbon steel is extracted from the current density
profile of the simulation. In this respect, the throwing power is the distance that the local current
density equal to the passive current density, which is 1 mA/m2 (Figure 8). For carbon steel and
zinc couple, the throwing power is the distance that the potential of the steel reaches to -0.73 V
(vs. SSC). So, after running the simulation, the throwing power for each simulation is extracted
and used for fitting to the best power equation.

For finding the best fitting, error function should be minimized, so defining the error function has
a key role. Two suitable equations are:

𝐸𝑟𝑟𝑜𝑟 = ∑𝑛𝑖=1(𝑋 − 𝐿)2 (A1)

𝐸𝑟𝑟𝑜𝑟 = ∑𝑛𝑖=1((𝑋 − 𝐿)/𝐿)2 (A2)

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Where X is a calculated value from the new equation and L is the real value from the simulation.
In this circumstances minimizing the A1 will leads to minimizing the error, especially in a range
that the real value high. But using equation A2, a normalized error distribution is considered in

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the whole range of variables, so from the A2 equation the importance of centimetre and meter
range is the same and just the percentage of deviation is important.

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With assumption the constant value for the K and power of ρ and H, the power of iL would be in
accordance of Table A1.

<Table A1>
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References

[1] P. Pedeferri, Corrosion Science and Engineering, Springer International Publishing, 2018.
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FIGURE CAPTION

Figure 1: Schematic arrangement of the simulated system.

Figure 2: Picture of laboratory test set up for validating the simulation.

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Figure 3: Laboratory test results and selected boundary condition for iL = 200 mA/m2 (a) stainless steel

and (b) carbon steel.

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Figure 4: Example of simulation results in respect to the polarization profile.

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Figure 5: (a) potential and (b) current density profiles for different solution resistivity. (Stainless steel-

carbon steel couple, H=0.1 m, iL=10 mA/m2, and βC = 0.2 V/decade)

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Figure 6: (a) Potential profile (b) Current density profile for carbon steel-zinc couple (H = 5 m, and ρ = 0.2
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Ω m).

Figure 7: Potential profile for the conditions mentioned in Table 4 with superimposed FEM simulation
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results.

Figure 8: Passive current density definition on the defined boundary conditions.

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Figure 9: Calculated throwing power based on four different criteria (Stainless steel-carbon steel couple,
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H=0.01 m, ρ=100 Ω m, and βC = 0.2 V/decade).

Figure 10: Throwing power from passive current density and equation 5.

Figure 11: Throwing power vs. limiting current density for carbon steel-zinc couple (a) H = 0.1 m and ρ =

0.2 Ω m, and (b) H = 1 m and ρ = 100 Ω m.

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Figure 2
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Figure 3
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Figure 4
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Figure 5
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Figure 6
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Figure 7
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Figure 10
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Figure 11
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Table 1: Main variable of FEM simulations.

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Parameter Description Qty.

H Height of the solution 0.01-5 m
ρ Solution resistivity 0.2-100 Ω m
iL Limiting current density for ORR 10-300 mA/m2
 Table 2: Extracted boundary condition parameters for FEM simulations for stainless steel-
carbon steel macro-cell couple
Parameter Description Qty.
βA (An.) Anode-Anodic Tafel’s slope 100 mV/decade
i0 (An.) Anode-Anodic reaction exchange current density 20 mA/m2
ECorr (An.) Anode-Corrosion Potential -0.6/-0.7 V vs. SSC
iL (An.) Anode-ORR limiting current density 200 mA/m2
βC (Ca.) Cathode-Cathodic Tafel’s slope 100 and 200 mV/decade

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i0 (Ca.) Cathode-Anodic reaction exchange current density 1 mA/m2
ECorr (Ca.) Cathode-Corrosion Potential of Anode 0 V vs. SSC

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iL (Ca.) ORR limiting current density of Anode 200 mA/m2

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Table 3: Extracted boundary condition parameters for FEM simulations for carbon steel-zinc
macro-cell couple
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Parameter Description Qty.

βA (An.) Anode-Anodic Tafel’s slope 20 mV/decade
i0 (An.) Anode-Anodic reaction exchange current density 400 mA/m2
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ECorr (An.) Anode-Corrosion Potential -0.93 V vs. SSC

iL (An.) Anode-ORR limiting current density 200 mA/m2
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βA (Ca.) Cathode-Anodic Tafel’s slope 100 mV/decade

βC (Ca.) Cathode-Cathodic Tafel’s slope 100 mV/decade
i0 (Ca.) Cathode-Anodic reaction exchange current density 100 mA/m2
ECorr (Ca.) Cathode-Corrosion Potential of Anode -0.4 V vs. SSC
iL (Ca.) ORR limiting current density of Anode 200 mA/m2
 Table 4: Laboratory variable for potential profile measurement.
H (m) ρ (Ω m) iL (mA/m2)
Test (a) 0.01 10.7 225
Test (b) 0.05 11.7 170

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Table A1. Power of iL in the equation 5 for two different error functions.

Error function Error function

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A1 A2
Stainless steel-carbon steel -0.05 to -0.08 -0.23
Carbon steel-zinc -0.7 -1.2

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