Corrosion Application Library Manual

Corrosion Module
Application Library Manual
CorrosionApplicationLibraryManual.book Page 1 Monday, April 13, 2015 5:05 PM
Corrosion Module Application Library Manual

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Solved with COMSOL Multiphysics 5.1
Ano de Fi lm R esi st an ce E ffec t on

Cathodic Corrosion Protection
Introduction
This example is an extension of the Corrosion Protection of an Oil Platform Using
Sacrificial Anodes model. The model exemplifies how the steel corrosion rate increases
over time due to build-up of a resistive film on the sacrificial anodes, formed by
reaction products.
Model Definition
The zinc dissolved on a sacrificial anode may react further to form various compounds.
One example is Zn(OH)2 formation according to
Zn Zn
Zn
2+
2+
+ 2e
+ 2H 2 O Zn(OH) 2 + 2H
2+
(1)
In marine saline environments, however, other products may also be formed, for
instance chloride and hydroxychloride compounds. This is not included in the model.
In this example we assume that 1% of the zinc ions dissolved precipitate as a dense film
on the zinc anode surface, resulting in a growing film resistance over time.
Constant molar mass, density and conductivity are ascribed to the species forming the
resistive film. Note however that in reality these may change over time due to changing
porosity of the depositing film.
The model also includes secondary current distribution electrode kinetics on the
protected steel structure, defining simultaneous metal dissolution and oxygen
reduction (mixed potential), in analogy with for instance the Galvanized Nail and the
Cathodic Protection of Steel in Reinforced Concrete examples.
The model is solved in a one year time-dependent simulation. The symmetry of the
model geometry has been considered in order to reduce the problem size, as shown in
Figure 1.
1 |
ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION
Figure 1: Model geometry. Symmetry was considered to reduce the model size.
Results and Discussion

Figure 2 and Figure 3 show the electrode potential vs SHE at the start of the
simulation and after one year, respectively. The potential on the steel structure is higher
at the end of the simulation, resulting in a reduced corrosion protection.
2 |
Figure 2: Potential vs SHE at t=0.
3 |
Figure 3: Potential vs SHE at t=365 days.

Figure 4 shows the resulting anode film thickness after one year. The film thickness is
fairly uniform.
4 |
Figure 4: Precipitated anode film thickness at t=360 days.

Figure 5 shows the steel corrosion current density for two points: one at the upper part
of one of the legs, and one at the inner bottom part of one of the legs. As can be seen
the corrosion rates increase significantly over time and approach the limiting current
density for oxygen (0.1 A/m2) used in the model.
5 |
Figure 5: Corrosion current density vs time.
Notes About the COMSOL Implementation

An External Corroding Electrode boundary node is used for the zinc anodes in order
to define the surface concentration of precipitated products, the film resistance
potential drop, and the zinc oxidation reaction.
Model Library path: Corrosion_Module/Cathodic_Protection/

anode_film_resistance
Modeling Instructions
From the File menu, choose New.
NEW
1 In the New window, click Model Wizard.
6 |
MODEL WIZARD
1 In the Model Wizard window, click 3D.

2 In the Select physics tree, select Electrochemistry>Corrosion, Deformed
Geometry>Corrosion, Secondary (corrsec).
3 Click Add.
4 Click Study.
5 In the Select study tree, select Preset Studies>Time Dependent with Initialization, Fixed
Geometry.
6 Click Done.
GLOBAL DEFINITIONS
Parameters
1 On the Home toolbar, click Parameters.
2 In the Settings window for Parameters, locate the Parameters section.
3 Click Load from File.
4 Browse to the applications Application Library folder and double-click the file
anode_film_resistance_parameters.txt.
GEOMETRY 1
Import 1 (imp1)
1 On the Home toolbar, click Import.
2 In the Settings window for Import, locate the Import section.
3 Click Browse.
oil_platform.mphbin.
5 Click Import.
6 Locate the Selections of Resulting Entities section. Select the Create selections check
box.
7 On the Geometry toolbar, click Work Plane.
Circle 1 (c1)
1 On the Work Plane toolbar, click Primitives and choose Circle.
2 In the Settings window for Circle, locate the Size and Shape section.
3 In the Radius text field, type 50.
7 |
4 In the Sector angle text field, type 90.

5 Locate the Rotation Angle section. In the Rotation text field, type 180.
6 Right-click Component 1 (comp1)>Geometry 1>Work Plane 1 (wp1)>Plane
Geometry>Circle 1 (c1) and choose Build Selected.
7 Click the Zoom Extents button on the Graphics toolbar.
Extrude 1 (ext1)
1 On the Geometry toolbar, click Extrude.
2 In the Settings window for Extrude, locate the Distances from Plane section.
3 In the table, enter the following settings:
Distances (m)
92
4 In the Model Builder window, right-click Extrude 1 (ext1) and choose Build Selected.
5 Click the Transparency button on the Graphics toolbar.
Difference 1 (dif1)
1 On the Geometry toolbar, click Booleans and Partitions and choose Difference.
2 Select the object ext1 only.
3 In the Settings window for Difference, locate the Difference section.
4 Find the Objects to subtract subsection. Select the Active toggle button.
5 Select the objects imp1(6), imp1(33), imp1(2), imp1(8), imp1(31), imp1(17), imp1(1),
imp1(12), imp1(3), imp1(22), imp1(24), imp1(4), imp1(35), imp1(30), imp1(27),
imp1(34), and imp1(28) only.
6 Right-click Component 1 (comp1)>Geometry 1>Difference 1 (dif1) and choose Build
Selected.
DEFINITIONS
Difference 1
1 On the Definitions toolbar, click Difference.
2 In the Settings window for Difference, type Anodes in the Label text field.
3 Locate the Geometric Entity Level section. From the Level list, choose Boundary.
8 |
4 Locate the Input Entities section. Under Selections to add, click Add.
5 In the Add dialog box, select Import 1 in the Selections to add list.
6 In the Selections to add list, select Import 1.
7 Click OK.
8 In the Settings window for Difference, locate the Input Entities section.
9 Under Selections to subtract, click Add.
10 In the Add dialog box, select Import 1(41) in the Selections to subtract list.
11 In the Selections to subtract list, select Import 1(41).
12 Click OK.
Union 1
1 On the Definitions toolbar, click Union.
2 In the Settings window for Union, type Cathode in the Label text field.
5 In the Add dialog box, select Import 1(41) in the Selections to add list.
6 In the Selections to add list, select Import 1(41).
7 Click OK.
Union 2
2 In the Settings window for Union, type All electrodes in the Label text field.
5 In the Add dialog box, In the Selections to add list, choose Anodes and Cathode.
6 Click OK.
CORROSION, SECONDARY (CORRSEC)
Electrolyte 1
1 In the Model Builder window, expand the Component 1 (comp1)>Corrosion, Secondary
(corrsec) node, then click Electrolyte 1.
2 In the Settings window for Electrolyte, locate the Electrolyte section.
3 From the l list, choose User defined. In the associated text field, type sigma_sea.
9 |
External Corroding Electrode 1

1 On the Physics toolbar, click Boundaries and choose External Corroding Electrode.
2 In the Settings window for External Corroding Electrode, type Zinc Anodes in the
Label text field.
3 Locate the Boundary Selection section. From the Selection list, choose Anodes.
Surface Properties 1
1 In the Model Builder window, expand the Component 1 (comp1)>Corrosion, Secondary
(corrsec)>Zinc Anodes node, then click Surface Properties 1.
2 In the Settings window for Surface Properties, locate the Corroding Species section.
3 In the Mccorr text field, type M_ZnOH2.
4 In the ccorr text field, type rho_ZnOH2.
Electrode Reaction 1
1 In the Model Builder window, under Component 1 (comp1)>Corrosion, Secondary
(corrsec)>Zinc Anodes click Electrode Reaction 1.
2 In the Settings window for Electrode Reaction, type Zn Oxidation in the Label text
field.
3 Locate the Model Inputs section. In the T text field, type T.
4 Locate the Equilibrium Potential section. In the Eeq text field, type Eeq_Zn.
5 Locate the Electrode Kinetics section. From the Kinetics expression type list, choose
Anodic Tafel equation.
6 In the i0 text field, type i0_Zn.
7 In the Aa text field, type A_Zn.
8 Locate the Stoichiometric Coefficients section. In the nm text field, type 2.
9 In the ccorr text field, type -lambda.
Zinc Anodes
(corrsec) click Zinc Anodes.
2 In the Settings window for External Corroding Electrode, click to expand the Film
resistance section.
3 Locate the Film Resistance section. From the Film resistance list, choose Thickness and
conductivity.
4 From the s list, choose Total electrode thickness change (corrsec/ede1/sp1).
5 In the film text field, type sigma_ZnOH2.
10 |
Electrolyte-Electrode Boundary Interface 1

1 On the Physics toolbar, click Boundaries and choose Electrolyte-Electrode Boundary
Interface.
2 In the Settings window for Electrolyte-Electrode Boundary Interface, locate the
Boundary Selection section.
3 From the Selection list, choose Cathode.
1 In the Model Builder window, expand the Electrolyte-Electrode Boundary Interface 1
node, then click Electrode Reaction 1.

2 In the Settings window for Electrode Reaction, type Steel Oxidation in the Label
text field.
4 Locate the Equilibrium Potential section. In the Eeq text field, type Eeq_Fe.
6 In the i0 text field, type i0_Fe.
7 In the Aa text field, type A_Fe.
1 On the Physics toolbar, click Attributes and choose Electrode Reaction.
2 In the Settings window for Electrode Reaction, type Oxygen reduction in the Label
text field.
4 Locate the Equilibrium Potential section. In the Eeq text field, type Eeq_O2.
Cathodic Tafel equation.
6 In the i0 text field, type i0_O2.
7 In the Ac text field, type A_O2.
8 Select the Limiting current density check box.
9 In the ilim text field, type ilim_O2.
11 |
Initial Values 1
1 In the Model Builder window, expand the Study 1 node, then click Component 1
(comp1)>Corrosion, Secondary (corrsec)>Initial Values 1.
2 In the Settings window for Initial Values, locate the Initial Values section.
3 In the phil text field, type -Eeq_Zn.
MESH 1
Size
1 In the Model Builder window, under Component 1 (comp1) right-click Mesh 1 and
choose Edit Physics-Induced Sequence.

2 In the Model Builder window, under Component 1 (comp1)>Mesh 1 click Size.
3 In the Settings window for Size, locate the Element Size section.
4 Click the Custom button.
5 Locate the Element Size Parameters section. In the Maximum element size text field,
type 10.
6 In the Minimum element size text field, type 0.5.
7 In the Curvature factor text field, type 0.9.
8 In the Resolution of narrow regions text field, type 0.5.
9 Click the Build All button.
STUDY 1
Step 1: Current Distribution Initialization

1 In the Model Builder window, under Study 1 click Step 1: Current Distribution
Initialization.
2 In the Settings window for Current Distribution Initialization, locate the Study
Settings section.
3 From the Current distribution type list, choose Secondary.
Step 2: Time Dependent, Fixed Geometry

1 In the Model Builder window, under Study 1 click Step 2: Time Dependent, Fixed
Geometry.
2 In the Settings window for Time Dependent, Fixed Geometry, locate the Study
Settings section.
12 |
3 From the Time unit list, choose d.

4 In the Times text field, type 0 10 20 30 range(60,60,300) 365.
5 On the Home toolbar, click Compute.
RESULTS
Data Sets
1 On the Results toolbar, click More Data Sets and choose Solution.
2 On the Results toolbar, click Selection.
3 In the Settings window for Selection, locate the Geometric Entity Selection section.
4 From the Geometric entity level list, choose Boundary.
5 From the Selection list, choose Anodes.
10 From the Selection list, choose All electrodes.
3D Plot Group 3
1 On the Results toolbar, click 3D Plot Group.
2 In the Settings window for 3D Plot Group, type Potential vs SHE in the Label
text field.
3 Locate the Data section. From the Data set list, choose Study 1/Solution 1 (4).
4 Click to expand the Title section. From the Title type list, choose Manual.
5 In the Title text area, type Potential vs SHE (V).
6 Locate the Plot Settings section. Clear the Plot data set edges check box.
Potential vs SHE
1 Right-click Results>Potential vs SHE and choose Surface.
2 In the Settings window for Surface, locate the Expression section.
3 In the Expression text field, type 0 - phil.
4 On the Potential vs SHE toolbar, click Plot.
13 |
7 In the Model Builder window, click Potential vs SHE.

8 In the Settings window for 3D Plot Group, locate the Data section.
9 From the Time (d) list, choose 0.
3D Plot Group 4
1 On the Home toolbar, click Add Plot Group and choose 3D Plot Group.
2 In the Settings window for 3D Plot Group, type Oxide layer thickness in the
Label text field.
3 Locate the Data section. From the Data set list, choose Study 1/Solution 1 (3).
Oxide layer thickness

1 Right-click Results>Oxide layer thickness and choose Surface.
2 In the Settings window for Surface, click Replace Expression in the upper-right corner
of the Expression section. From the menu, choose Model>Component 1>Corrosion,

Secondary>corrsec.sbtot - Total electrode thickness change.
3 Locate the Expression section. From the Unit list, choose m.
4 On the Oxide layer thickness toolbar, click Plot.
1D Plot Group 5
2 In the Settings window for 1D Plot Group, type Local corrosion current
density in the Label text field.
3 Click to expand the Title section. From the Title type list, choose None.
4 Click to expand the Legend section. From the Position list, choose Middle right.
Local corrosion current density

1 On the Local corrosion current density toolbar, click Point Graph.
2 Select Point 18 only.
3 In the Settings window for Point Graph, click Replace Expression in the upper-right
corner of the y-axis data section. From the menu, choose Model>Component
1>Corrosion, Secondary>Electrode kinetics>corrsec.iloc_er1 - Local current density.
4 Click to expand the Legends section. Select the Show legends check box.
5 From the Legends list, choose Manual.
14 |

Legends
Top of leg
7 Right-click Results>Local corrosion current density>Point Graph 1 and choose

Duplicate.
8 In the Settings window for Point Graph, locate the Selection section.
9 Select the Active toggle button.
11 Locate the Legends section. In the table, enter the following settings:
Legends
Bottom of leg
12 On the Local corrosion current density toolbar, click Plot.
15 |
16 |
Atmospheric Corrosion
Introduction
Atmospheric corrosion may occur when thin films of liquid water, in the range of up
to hundreds of micrometers, forms on metal surfaces in contact with humidified air.
The thickness of the film depends on the relative humidity of the surrounding air, but
also on factors such as surface roughness and the presence of particles, especially salt
crystals. The thin film of moisture acts as electrolyte, and may cause various corrosion
phenomena, such as galvanic corrosion of a bimetallic element or crevice corrosion.
This tutorial model studies atmospheric galvanic corrosion as a function of the relative
humidity of the surrounding air and salt load (NaCl) on a bimetallic aluminum alloy
steel surface. It is assumed that the electrolyte film solution is in equilibrium with solid
salt particles, distributed uniformly over the surface at a given load.
The example uses parameter data from Ref. 1, Ref. 2, and Ref. 3.
Model Definition
The model geometry is shown in Figure 1.
Air at given relative humidity
Thin film electrolyte
Aluminum alloy
(metal oxidation)
Varying thickness
Steel (oxygen reduction)
Figure 1: Model geometry. Each metal surface is 12 mm wide.

The thickness of the electrolyte film depends on both the salt load density and the
relative humidity, see Figure 2. The film grows significantly towards 100% relative
humidity.
1 |
ATMOSPHERIC CORROSION
Figure 2: Thickness of the electrolyte for different relative humidities and salt load
densities. The conductivity varies linearly with the salt load density. (Ref. 1)
The oxygen solubility, oxygen diffusivity, and the electrolyte conductivity also depend
on the relative humidity, see Figure 3, Figure 4, and Figure 5.
2 |
Figure 3: Oxygen solubility vs relative humidity.(Ref. 1)
3 |
Figure 4: Oxygen diffusivity vs relative humidity.(Ref. 2)
4 |
Figure 5: Electrolyte conductivity vs relative humidity. (Ref. 1)

ELECTROCHEMICAL REACTIONS
The less nobler aluminum alloy is oxidized in the cell, with the electrode reaction
kinetics described by a Butler-Volmer expression. On the steel surface, oxygen
reduction occurs.
The oxygen reduction reaction is limited by oxygen transport through the film. The
limiting current density, ilim, O2 (SI unit: A/m2), depends on the film thickness, the
oxygen solubility and the oxygen diffusivity according to:
4FDc sol
i lim, O 2 = --------------------d film
where F (96485 C/mol) is Faradays constant, D (SI unit: m2/s) is the diffusivity of
oxygen in the film, csol (SI unit: mol/m3) is the solubility of oxygen, and dfilm
(SI unit: m) is the film thickness.
5 |
By assuming a first order dependency of the oxygen reduction kinetics on the local
current density of the oxygen concentration, the following expression for the current
density, ilim, O2 (SI unit: A/m2), can be derived:
i lim, O 2 i expr
i loc, O 2 = ----------------------------------i lim, O 2 + i expr
where iexpr is the local current density of the electrode reaction in absence of mass
transport limitations. In this model a cathode Tafel expression is used for iexpr.

Figure 6 shows the local current density of the electrode reactions for a salt load of
0.5 g/m2 and various relative humidities. The cathodic currents reach a plateau close
to x=0 at a magnitude that is significantly affected by the relative humidity. This is due
to a changing limiting current density for oxygen reduction. As the film thickness
grows, the electrolyte transport length for oxygen increases, in combination with an
increased oxygen solubility and diffusivity for higher relative humidities.
Figure 6: Local current densities along the metal surface at a salt loading of 0.5 g/m2 and
relative humidities (RH) spanning from 80 to 98 %.
6 |
Figure 7 shows the maximum anodic currents for various salt load densities and relative
humidities. For all salt loads, a maximum current density is seen around a relative
humidity of 90 %.
Figure 7: Maximum metal oxidation anodic current density on the aluminum alloy
metal surface for varied relative humidities and salt load densities (LD).
Looking at the maximum cathodic currents in Figure 8, it is seen that the maximum
oxygen currents are about one order of magnitude smaller than the anodic currents,
but that they follow the same trend with a maximum around a relative humidity of
7 |
90 %. These currents are very close to the limiting current densities for oxygen
reduction.
Figure 8: Maximum oxygen reduction cathodic current densities on the steel metal surface
for varied relative humidities and salt load densities (LD).
Finally, Figure 9 shows the average anode current density, which gives us a measure of
the total corrosion rate of the sample, for various relative humidities and salt load
densities. The maximum is found for a salt load density of 3.5 g/m2 and a relative
humidity of 95 %.
8 |
Figure 9: Average current densities on the aluminum alloy metal surface for varied
relative humidities and salt load densities (LD).

The model is implemented using the Secondary Current Distribution interface with
two Parametric Sweeps to study the impact of a range of different relative humidities
and salt load densities.
References
1. Z.Y. Chen, F. Cui, and R.G. Kelly, Calculations of the Cathodic Current Delivery
Capacity and Stability of Crevice Corrosion under Atmospheric Environments, J.
Electrochemical Society, vol. 155, no. 7, pp. C360368, 2008.
2. D. Mizuno and R.G. Kelly Galvanically Induced Interganular Corrosion of
AA5083-H131 Under Atmospheric Exposure Conditions - Part II - Modeling of the
Damage Distribution, Corrosion, vol. 69, no. 6, pp. 580592, 2013.
9 |
3. D. Mizuno, Y. Shi, and R.G. Kelly, Modeling of Galvanic Interactions between

AA5083 and Steel under Atmospheric Conditions, Excerpt from the Proceedings of
the 2011 COMSOL Conference in Boston.
Application Library path: Corrosion_Module/Galvanic_Corrosion/

atmospheric_corrosion
NEW

MODEL WIZARD

2 In the Select physics tree, select Electrochemistry>Secondary Current Distribution
(siec).
3 Click Add.
4 Click Study.
5 In the Select study tree, select Preset Studies>Stationary.
6 Click Done.
GLOBAL DEFINITIONS
Parameters
Load the model parameters from a text file.

atmospheric_corrosion_parameters.txt.
10 |
GEOMETRY 1
Draw the geometry as two adjacent rectangles, each 12 mm wide. The height of the
rectangles represents the film thickness. It depends both on the salt load density and
the relative humidity, which both will be varied by the parametric sweeps in the Study.
Rectangle 1 (r1)
1 On the Geometry toolbar, click Primitives and choose Rectangle.
2 In the Settings window for Rectangle, locate the Size section.
3 In the Width text field, type 12[mm].
4 In the Height text field, type d_film.
5 Locate the Position section. In the x text field, type -12[mm].
Rectangle 2 (r2)
1 Right-click Component 1 (comp1)>Geometry 1>Rectangle 1 (r1) and choose Duplicate.
2 In the Settings window for Rectangle, locate the Position section.
3 In the x text field, type 0.
4 Click the Build All Objects button.
The electrolyte film is much thinner than the geometry width, making it hard to make
selections in the actual 2D geometry. Create a user-defined View to view the geometry
using an aspect ratio that corresponds to the graphics window rather than the true
geometrical aspect ratio.
DEFINITIONS
1 In the Model Builder window, expand the Component 1 (comp1)>Definitions node.

2 Right-click Definitions and choose View.
Axis
1 In the Model Builder window, expand the View 2 node, then click Axis.
2 In the Settings window for Axis, locate the Axis section.
3 From the View scale list, choose Automatic.
Now create some average and maximum operators. These will be used later on when
post-processing the simulation results.
Average 1 (aveop1)
1 On the Definitions toolbar, click Component Couplings and choose Average.
2 In the Settings window for Average, locate the Source Selection section.
11 |

4 Select Boundary 2 only.
Maximum 1 (maxop1)
1 On the Definitions toolbar, click Component Couplings and choose Maximum.
2 In the Settings window for Maximum, locate the Source Selection section.
Maximum 2 (maxop2)
1 Right-click Component 1 (comp1)>Definitions>Maximum 1 (maxop1) and choose
Duplicate.
2 In the Settings window for Maximum, locate the Source Selection section.
3 Click Clear Selection.
SECONDARY CURRENT DISTRIBUTION (SIEC)
Electrolyte 1
Now start defining the physics. Start with the electrolyte conductivity.
1 In the Model Builder window, under Component 1 (comp1)>Secondary Current
Distribution (siec) click Electrolyte 1.
3 From the l list, choose User defined. In the associated text field, type sigma.
Use Electrolyte-Electrode Boundary Interface nodes to set up the electrode reactions

for the two metallic surfaces.

Interface.

2 In the Settings window for Electrode Reaction, locate the Equilibrium Potential
section.
12 |
3 In the Eeq text field, type Eeq_Al.

Butler-Volmer.
5 In the i0 text field, type i0_Al.
6 In the a text field, type alphaa_Al.
7 In the c text field, type alphac_Al.

Interface.

section.
3 In the Eeq text field, type Eeq_Fe.
6 In the Ac text field, type Ac_Fe.
8 In the ilim text field, type ilim.
Add an Initial Values node in order to define different initial values in the two domains.
This will shorten the number of iterative steps taken by the solver.
Initial Values 2
1 On the Physics toolbar, click Domains and choose Initial Values.
2 Select Domain 2 only.
4 In the phil text field, type -Eeq_Fe.
Initial Values 1
Distribution (siec) click Initial Values 1.
13 |
3 In the phil text field, type -Eeq_Al.
MESH 1
Use a mapped mesh for this problem. Since the electrolyte film is very thin we do not
expect significant potential drops in the y-direction. Use a mesh with a single element
in the y-direction.
Mapped 1
In the Model Builder window, under Component 1 (comp1) right-click Mesh 1 and choose
Mapped.
Distribution 1
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 right-click Mapped
1 and choose Distribution.
2 Select Boundaries 1, 4, and 7 only.
3 In the Settings window for Distribution, locate the Distribution section.
4 In the Number of elements text field, type 1.
Distribution 2
1 Right-click Mapped 1 and choose Distribution.
2 Select Boundaries 2 and 3 only.
3 In the Settings window for Distribution, locate the Distribution section.
4 From the Distribution properties list, choose Predefined distribution type.
5 In the Number of elements text field, type 50.
6 In the Element ratio text field, type 10.
Distribution 3
1 Right-click Component 1 (comp1)>Mesh 1>Mapped 1>Distribution 2 and choose
Duplicate.
2 In the Settings window for Distribution, locate the Boundary Selection section.
3 Click Clear Selection.
5 Locate the Distribution section. Select the Reverse direction check box.
14 |
Your finished mesh should now look like this:
STUDY 1
The problem is now ready for solving. Use a Parametric Sweep to study the corrosion
currents for a range of different relative humidities and salt load densities.
Parametric Sweep
1 On the Study toolbar, click Parametric Sweep.
2 In the Settings window for Parametric Sweep, locate the Study Settings section.
3 From the Sweep type list, choose All combinations.
4 Click Add.
Parameter name
Parameter value list
LD
0.0005 0.001 0.002 0.0035

0.007[kg/m^2]
Parameter unit
6 Click Add.
15 |

Parameter name
RH
range(0.8,0.03,0.98)
Parameter unit
Decrease the solver tolerance to improve the accuracy of the solutions.
Solution 1
1 On the Study toolbar, click Show Default Solver.
2 In the Model Builder window, expand the Solution 1 node, then click Stationary Solver
1.
3 In the Settings window for Stationary Solver, locate the General section.
4 In the Relative tolerance text field, type 0.00001.
5 On the Study toolbar, click Compute.
RESULTS
Electrolyte Potential (siec)

Reproduce the plots from the Results and Discussion section in the following way:
1D Plot Group 2
2 On the 1D Plot Group 2 toolbar, click Line Graph.
3 In the Settings window for Line Graph, locate the Data section.
4 From the Data set list, choose Study 1/Parametric Solutions 1.
5 From the Parameter selection (LD) list, choose First.
7 Click Replace Expression in the upper-right corner of the y-axis data section. From
the menu, choose Model>Component 1>Secondary Current Distribution>Electrode

kinetics>siec.iloc_er1 - Local current density.
8 Locate the x-Axis Data section. From the Parameter list, choose Expression.
9 In the Expression text field, type x.
11 On the 1D Plot Group 2 toolbar, click Plot.
1D Plot Group 3
16 |
4 On the 1D Plot Group 3 toolbar, click Global.
5 In the Settings window for Global, locate the y-Axis Data section.
Expression
Unit
maxop1(siec.iloc_er1)
A/m^2
Description
7 In the Model Builder window, click 1D Plot Group 3.

8 In the Settings window for 1D Plot Group, click to expand the Title section.
9 From the Title type list, choose Manual.
10 In the Title text area, type Maximum Anode Current Density.
11 Locate the Plot Settings section. Select the x-axis label check box.
12 In the associated text field, type Relative Humidity (1).
13 Select the y-axis label check box.
14 In the associated text field, type Current Density (A/m2).
15 Click to expand the Legend section. From the Position list, choose Upper left.
1D Plot Group 4
1 Right-click 1D Plot Group 3 and choose Duplicate.
2 In the Model Builder window, expand the 1D Plot Group 4 node, then click Global 1.
Expression
Unit
maxop2(-siec.iloc_er1)
A/m^2
Description

6 In the Settings window for 1D Plot Group, locate the Title section.
7 In the Title text area, type Maximum Cathode Current Density.
17 |
1D Plot Group 5
1 In the Model Builder window, under Results right-click 1D Plot Group 3 and choose
Duplicate.
2 In the Model Builder window, expand the 1D Plot Group 5 node, then click Global 1.
Expression
Unit
aveop1(siec.iloc_er1)
A/m^2
Description

7 In the Title text area, type Average Anode Current Density.
18 |
Cathodic Protection of Steel in

R e i nf o r c e d C o ncret e
Introduction
Cathodic protection (CP) is a common strategy for retarding the corrosion of
reinforcing steel in concrete structures, such as bridges and parking garages. By the use
of CP the potential of the corroding surface is lowered, thereby decreasing the rate of
undesired anodic corrosion reaction.
This example models the cathodic protection of a steel reinforcing bar (rebar) in
concrete. The corrosion cell consists of a zinc anode, the concrete, acting as
electrolyte, and the steel surface. Iron oxidation, water reduction (hydrogen
evolution) and oxygen reduction are considered on the steel surface, whereas oxygen
and charge transport are accounted for in the concrete electrolyte.
The anode and the steel surface are connected electrically via a potentiostat that
controls the cell voltage.
Concrete is a porous material, and an effect of this is that its transport properties for
ions and gases vary with the moisture content. Therefore the electrolyte conductivity
and oxygen diffusion coefficient are modeled to vary with the concrete pore saturation
level using empirical data.
The corrosion rate for various moisture contents is investigated.
The model example is based on a paper by Muehlenkamp et al. (Ref. 1).
For a more detailed description for how to build this model, including screen shots,
see the Introduction to the Corrosion Module.
Model Definition
GEOMETRY
Figure 1 shows the model geometry. The geometry modeled represents a two
dimensional cross section of a repeating unit cell in a larger structure where three
symmetry planes (top, bottom and right) have been used in order to reduce the model
geometry. The zinc anode has been coated onto the concrete by thermal spraying and
is assumed to be permeable to air.
1 |
CATHODIC PROTECTION OF STEEL IN REINFORCED CONCRETE
Rebar cathode
(steel)
Anode
(zinc)
Electrolyte
(concrete)
Figure 1: Model geometry. One electrolyte domain and two electrode surfaces.
CONCRETE DOMAIN EQUATIONS
Use a Secondary Current Distribution interface to model the electrochemical currents.

The electrolyte conductivity depends on the pore saturation level according to
Figure 2.
Figure 2: Electrolyte conductivity (S/m) as function of the concrete pore saturation level.
Oxygen transport in the concrete domain is modeled using the Transport of Diluted
Species interface. The oxygen diffusivity depends on the pore saturation level
2 |
according to Figure 3.
Figure 3: Oxygen diffusivity (m2/s) in the concrete as function of pore saturation.

BOUNDARY CONDITIONS
Choose the electrical potential of the Zn anode as ground for the system. By assuming
the kinetics of the Zn anode to be very fast the polarization is neglected in the model,
setting the electrolyte potential to
l, Zn = E eq, Zn + s, Zn = E eq, Zn
Set the concentration of oxygen at the Zn anode to atmospheric conditions according
to
c O 2, Zn = c O 2, ref
Consider three different electrode reactions on the steel rebar boundary: iron
oxidation, oxygen reduction, and hydrogen evolution:
Fe Fe
2+
+ 2e
O 2 + 2H 2 O + 4e 4OH
-
2H 2 O + 2e H 2 + 2OH
3 |
Model the reaction kinetics for these reactions with an Electrolyte-Electrode Boundary
Interface node in the Secondary Current Distribution interface, on which the external
electric potential of the steel bar, s, steel , is set to the applied cell potential of -1 V.
The electrode kinetics of the steel bar reactions are described by Tafel expressions
according to
i Fe = i 0, Fe 10
Fe
------A Fe
O
--------2-
i O2
cO2
AO
-i
= -------------- 10 2
c O 2, ref 0, O 2
i H 2 = i 0, H 2 10
H
--------2A H2
using the parameters shown in Table 1, where the overpotential for each reaction is
calculated as
= s, steel l E eq
TABLE 1: ELECTRODE REACTION PARAMETERS

PARAMETER
UNIT
Zn
Fe
O2
H2
Equilibrium potential, Eeq
-0.68
-0.76
0.189
-1.03
Exchange current density, i0
A/m2
7.110-5
7.710-7
1.110-2
Tafel slope, A
V/decade
0.41
-0.18
-0.15
The oxygen reduction reaction causes a flux of oxygen at the steel surface according to
Faradays law. Model this using an Electrolyte-Electrode Interface Coupling node in
the Transport of Diluted Species interface.
Apply Symmetry conditions on all other boundaries.
INITIAL VALUES
Set the electrolyte potential initial value to the same value as in the boundary condition
at the Zn anode.
Use atmospheric concentration as initial value for the oxygen concentration variable.
4 |
STUDY
Solve the model using a parametric sweep over a stationary study step, solving for a
range of pore saturation values from 0.2 to 0.8.

Figure 4 shows the electrolyte potential for a pore saturation level of 0.8. The
electrolyte potentials is lower towards the back (the right side) of the rebar.
Figure 4: Electrolyte potential for a pore saturation (moisture) level of 0.8.

Figure 5 shows the oxygen concentration in the electrolyte for a pore saturation level
of 0.8. The concentration is very low close to the rebar, indicating that the oxygen
reduction kinetics should be mass transport limited for this pore saturation level. The
concentration is lower towards the back of the rebar.
5 |
Figure 5: Oxygen concentration for a pore saturation (moisture) level of 0.8.

An important factor for the corrosion rate of the rebar is the operating electrode
potential, which is the difference between the electric potential (here the potential
applied by the potentiostat) and the electrolyte potential. Figure 6 shows the operating
electrode potential for various pore saturation levels for three different points (front,
6 |
middle and back) of the rebar surface. The potential drops considerably at a pore
saturation level of 0.65.
Figure 6: Operating electrode potential for three points at the rebar-concrete interface.
Figure 7 shows the local oxygen concentration at the rebar for various pore saturation
levels. The concentration drops significantly towards higher saturation levels. This is
7 |
an effect of the decreasing diffusivity of oxygen in the concrete for higher saturation
levels.
Figure 7: Local oxygen concentration at the rebar-concrete interface.

The local oxygen reduction current densities at the rebar are shown in Figure 8. The
magnitude of the oxygen reduction current density is highest around a pore saturation
level of 0.6 0.65. Up to this point the current densities are increasing due to
8 |
increased electrolyte conductivity, but for higher pore saturation levels the current
densities decrease due to decreased oxygen diffusivity.
Figure 8: Local oxygen reduction current densities at the rebar-concrete interface.

The hydrogen evolution current densities are shown in Figure 9. Hydrogen evolution
is very limited below a PS level of 0.65, which is the saturation level at which the
electrode potential gets below the equilibrium potential (1.03 V) for the hydrogen
evolution reaction, see Figure 6.
9 |
Figure 9: Local hydrogen evolution current densities at the rebar-concrete interface.

Finally, the iron oxidation current densities are shown in Figure 10. Corrosion current
densities are higher for low PS levels, which is in line with the higher electrode
potential for low PS levels (Figure 6). It should be noted that the magnitude of iron
oxidation current density is considerably smaller than oxygen reduction and hydrogen
evolution current densities at the steel rebar indicating the effectiveness of zinc coating
onto the concrete in protecting the steel rebar from corrosion.
10 |
Figure 10: Iron corrosion current densities at the rebar-concrete interface.
Reference
1. E.B. Muehlenkamp, M.D. Koretsky, and J.C. Westall, Effect of Moisture on the
Spatial Uniformity of Cathodic Protection of Steel in Reinforced Concrete,
Corrosion, vol. 61, no. 6, pp. 519533, 2012.
Application Library path: Corrosion_Module/Cathodic_Protection/

cathodic_protection_in_concrete
NEW
11 |
MODEL WIZARD

(siec).
3 Click Add.
4 In the Select physics tree, select Chemical Species Transport>Transport of Diluted
Species (tds).
5 Click Add.
6 Click Study.
7 In the Select study tree, select Preset Studies for Selected Physics Interfaces>Stationary.
8 Click Done.
GLOBAL DEFINITIONS
Parameters
cathodic_protection_in_concrete_parameters.txt.
DEFINITIONS
Create interpolation functions for the electrolyte conductivity and oxygen diffusivity
as functions of the pore saturation level. Load the data from text files.
Interpolation 1 (int1)
1 On the Home toolbar, click Functions and choose Local>Interpolation.
2 In the Settings window for Interpolation, locate the Definition section.
3 From the Data source list, choose File.
4 Click Browse.
cathodic_protection_in_concrete_sigma.txt.
6 Click Import.
7 In the Function name text field, type sigma.
12 |
8 Locate the Units section. In the Function text field, type S/m.
9 Click the Plot button.
The plot should look like Figure 2.
4 Click Browse.
cathodic_protection_in_concrete_D_O2.txt.
6 Click Import.
7 In the Function name text field, type D_O2.
8 Locate the Units section. In the Function text field, type m^2/s.
The plot should look like Figure 3.

GEOMETRY 1
Now create the geometry by using a rectangle and a circle.
Rectangle 1 (r1)
3 In the Width text field, type W.
4 In the Height text field, type L.
5 Right-click Component 1 (comp1)>Geometry 1>Rectangle 1 (r1) and choose Build
Selected.
Circle 1 (c1)
1 On the Geometry toolbar, click Primitives and choose Circle.
2 In the Settings window for Circle, locate the Size and Shape section.
3 In the Radius text field, type R_rebar.
4 Locate the Position section. In the x text field, type S+R_rebar.
5 In the y text field, type L.
13 |
6 Right-click Component 1 (comp1)>Geometry 1>Circle 1 (c1) and choose Build

Selected.
Difference 1 (dif1)
2 Select the object r1 only.
5 Select the object c1 only.
6 On the Geometry toolbar, click Build All.
Electrolyte 1
Now set up the physics for the current distribution. Start with the electrolyte settings.
1 In the Model Builder window, expand the Component 1 (comp1)>Secondary Current
Distribution (siec) node, then click Electrolyte 1.
3 From the l list, choose User defined. In the associated text field, type sigma(PS).
Electrolyte Potential 1
1 On the Physics toolbar, click Boundaries and choose Electrolyte Potential.
3 In the Settings window for Electrolyte Potential, locate the Electrolyte Potential
section.
4 In the l,bnd text field, type -Eeq_Zn.

Interface.
Boundary Condition section.
4 In the s,ext text field, type E_app.
Three different reactions occur at this electrode surface: oxygen reduction, iron
oxidation and hydrogen evolution.
14 |
node.
2 Right-click Electrode Reaction 1 and choose Rename.
3 In the Rename Electrode Reaction dialog box, type Oxygen reduction in the New
label text field.
4 Click OK.
section.
6 In the Eeq text field, type Eeq_O2.
8 In the i0 text field, type c/C_O2_ref*i0_O2.
The exchange current density depends on the oxygen concentration, which is solved
for in the Transport of Diluted Species interface.
9 In the Ac text field, type A_O2.
Distribution (siec)>Electrolyte-Electrode Boundary Interface 1 right-click Electrode
Reaction 2 and choose Rename.
3 In the Rename Electrode Reaction dialog box, type Iron oxidation in the New label
text field.
4 Click OK.
section.
15 |

Distribution (siec)>Electrolyte-Electrode Boundary Interface 1 right-click Electrode
Reaction 3 and choose Rename.
3 In the Rename Electrode Reaction dialog box, type Hydrogen evolution in the New
label text field.
4 Click OK.
section.
6 In the Eeq text field, type Eeq_H2.
8 In the i0 text field, type i0_H2.
9 In the Ac text field, type A_H2.
Initial Values 1
Complete the current distribution model by specifying the initial value for the
electrolyte potential.
TR A N S P O R T O F D I L U T E D S P E C I E S ( T D S )
Continue by setting up the model for the oxygen transport in the concrete. Start with
the domain transport properties.
1 In the Settings window for Transport of Diluted Species, locate the Transport
Mechanisms section.
2 Clear the Convection check box.
Transport Properties 1
1 In the Model Builder window, expand the Transport of Diluted Species (tds) node, then
click Transport Properties 1.

2 In the Settings window for Transport Properties, locate the Diffusion section.
3 In the Dc text field, type D_O2(PS).
The concrete is in contact with air at the left, and the concentration is therefore
constant at this boundary.
16 |
Concentration 1
1 On the Physics toolbar, click Boundaries and choose Concentration.
3 In the Settings window for Concentration, locate the Concentration section.
4 Select the Species c check box.
5 In the c0,c text field, type C_O2_ref.
Couple the flux of oxygen to the oxygen reduction current at the electrode surface.
Electrode-Electrolyte Interface Coupling 1

1 On the Physics toolbar, click Boundaries and choose Electrode-Electrolyte Interface
Coupling.
Reaction Coefficients 1
1 In the Model Builder window, expand the Electrode-Electrolyte Interface Coupling 1
node, then click Reaction Coefficients 1.

2 In the Settings window for Reaction Coefficients, locate the Model Inputs section.
3 From the iloc list, choose Local current density (siec/eebii1/er1).
5 In the c text field, type -1.
Initial Values 1
1 In the Model Builder window, under Component 1 (comp1)>Transport of Diluted
Species (tds) click Initial Values 1.
3 In the c text field, type C_O2_ref.
MESH 1
Use the physics-controlled mesh settings, with an extra fine mesh size.
1 In the Model Builder window, under Component 1 (comp1) click Mesh 1.
2 In the Settings window for Mesh, locate the Mesh Settings section.
3 From the Element size list, choose Extra fine.
STUDY 1
Step 1: Stationary
Set up an auxiliary continuation sweep for the 'PS' parameter.
17 |
1 In the Model Builder window, under Study 1 click Step 1: Stationary.

2 In the Settings window for Stationary, click to expand the Study extensions section.
3 Locate the Study Extensions section. Select the Auxiliary sweep check box.
4 Click Add.
Parameter name
PS
range(0.2, 0.05, 0.8)
Parameter unit

RESULTS

The model is now solved. Follow the remaining steps below to reproduce the plots
from the Results and Discussion section.
1D Plot Group 3
2 On the 1D Plot Group 3 toolbar, click Point Graph.
3 Select Points 35 only.
4 In the Settings window for Point Graph, locate the y-Axis Data section.
5 In the Expression text field, type E_app-phil.
Legends
Front
Middle
Back
9 In the Model Builder window, right-click 1D Plot Group 3 and choose Rename.
10 In the Rename 1D Plot Group dialog box, type Rebar electrode-electrolyte
potential in the New label text field.
11 Click OK.
18 |
Rebar electrode-electrolyte potential 1

1 Right-click Rebar electrode-electrolyte potential and choose Duplicate.
2 In the Model Builder window, under Results right-click Rebar electrode-electrolyte
potential 1 and choose Rename.
3 In the Rename 1D Plot Group dialog box, type Oxygen concentration in the New
label text field.
4 Click OK.
Oxygen concentration
1 In the Model Builder window, expand the Results>Oxygen concentration node, then
click Point Graph 1.

1>Transport of Diluted Species>c - Concentration.
Oxygen concentration 1
1 In the Model Builder window, right-click Oxygen concentration and choose Duplicate.
2 Right-click Oxygen concentration 1 and choose Rename.
3 In the Rename 1D Plot Group dialog box, type Oxygen reduction currents in the
New label text field.
4 Click OK.
Oxygen reduction currents

1 In the Model Builder window, expand the Results>Oxygen reduction currents node,
then click Point Graph 1.

1>Secondary Current Distribution>Electrode kinetics>siec.iloc_er1 - Local current
density.
Oxygen reduction currents 1

1 In the Model Builder window, right-click Oxygen reduction currents and choose
Duplicate.
2 Right-click Oxygen reduction currents 1 and choose Rename.
3 In the Rename 1D Plot Group dialog box, type Iron oxidation currents in the
4 Click OK.
19 |
Iron oxidation currents

1 In the Model Builder window, expand the Results>Iron oxidation currents node, then
click Point Graph 1.

density.
3 On the Iron oxidation currents toolbar, click Plot.
Iron oxidation currents 1

1 In the Model Builder window, right-click Iron oxidation currents and choose Duplicate.
2 Right-click Iron oxidation currents 1 and choose Rename.
3 In the Rename 1D Plot Group dialog box, type Hydrogen evolution currents in
the New label text field.

4 Click OK.
Hydrogen evolution currents

1 In the Model Builder window, expand the Results>Hydrogen evolution currents node,
then click Point Graph 1.

density.
3 On the Hydrogen evolution currents toolbar, click Plot.
20 |
Carbon Dioxide Corrosion in Steel

Pipes
Introduction
A flow mixture of water and carbon dioxide passing through a steel pipe can cause
significant steel corrosion. Properties such as pH and temperature affect the rate of the
corrosion.
This model simulates the corrosion taking place on the steel surface of a pipe for
turbulent flow of carbon dioxide and water. The model reproduces results by
Nordsveen et al. (Ref. 1) and Nesic et al. (Ref. 2).
Model Definition
The corrosion is investigated at an arbitrary position within a steel pipe through which
a turbulent flow of dissolved carbon dioxide in water passes. A 1D model is used. No
variations along the length of the pipe are considered and the interaction of the
mixture with the steel is confined to the boundary layer near the steel surface. The
boundary layer thickness is set to 0.001 mm. The model geometry and physical
considerations are shown in Figure 1. The diffusion and turbulent sublayers vary and
are accounted for with the mass transport parameters.
Boundary layer
Steel
Diffusion
sublayer
Turbulent
sublayer
Bulk
Figure 1: Description of the boundary layer adjacent to the steel surface.

All species are assumed to be diluted in water and the mass transport is modeled by
diffusion. The Electroanalysis interface is used in the model. Carbon dioxide
hydration, water dissociation, three reduction reactions, and iron dissolution are
accounted for; resulting in seven species in the model. The species and diffusion
1 |
CARBON DIOXIDE CORROSION IN STEEL PIPES
coefficients are tabulated in Table 1

TABLE 1: MODELED SPECIES WITH THEIR RESPECTIVE DIFFUSION COEFFICIENTS.
SPECIES
D (m2/s)109
CO2
1.96
H2CO3
2.00
1.11
HCO3
2-
CO3
0.92
9.31
OH-
5.26
Fe
0.72
The turbulent sublayer is modeled by adding a turbulent diffusivity term to the

diffusion coefficient. The term depends on the flow rate, viscosity, density of the liquid,
and distance from the steel surface (Ref. 1).
The Electrode Surface boundary feature is used to calculate the corrosion potential at
the steel surface using the mixed potential theory. The net total current of all
electrochemical reactions is set to zero, the equation that is solved is described by
ij =
(1)
where i (SI unit: A/m2) is the current density of j number of electrochemical reactions.
The initial value is set to -0.5 V around the free corrosion potential (Ref. 2).
For the Electroanalysis interface the outer point of the boundary layer is set to the bulk
concentrations of the species. Fluxes of species converted in the electrochemical
reactions, ij/F (Faradays constant = 96485 C/mol), are applied on the steel surface.
EQUILIBRIUM REACTIONS
The following equilibrium reactions are present in the electrolyte:

+
K 1 = 6.418 10
CO 2 ( aq ) + H 2 O ( aq ) H 2 CO 3 (aq)
K 2 = 2.580 10
K 3 = 1.251 10
2-
K 4 = 1.382 10
H 2 CO 3 (aq) H (aq) + HCO 3 (aq)

-
HCO 3 (aq) H (aq) + CO 3 (aq)
where K1 through K4 are the equilibrium constants (Ref. 1).
2 |
-15
H 2 O(l) H (aq) + OH (aq)
-10
These reactions are modeled using the Equilibrium Reaction domain node; one for
each reaction. The Equilibrium Reaction nodes solve for one additional degree of
freedom each, where the additional degree of freedom represents the local reaction
rate required in order to fulfill the equilibrium expression. The equilibrium expressions
are based on the reaction stoichiometry and equilibrium constant Kk according to
Kk =
a ( ci )
v ik
where ci (SI unit: mol/m3) is the concentration of species i, vik the stoichiometric
coefficient of species i in reaction k. The activity of a species, a(ci) is given by dividing
the concentration with 1 M.
The following electrochemical reactions are present at the steel surface (Equation 1):
Iron dissolution
Fe(s) Fe
2+
+ 2e
Proton reduction
+
H +e H
Water reduction
-
H 2 O + e H + OH
Carbonic acid reduction

-
H 2 CO 3 + e H + HCO 3
The current densities depend on mass transport limitations and charge transfer
resistances as given in Ref. 2.
STUDY SETTINGS
The problem is solved with an auxiliary sweep on a stationary solver in order to

investigate the impact of important parameters such as pH and temperature on
corrosion.
3 |

Figure 2 displays the concentration deviation from the bulk of the seven species along
the boundary layer at pH 6 and 20 C. The concentration of iron ions is significantly
higher at the steel surface due to the dissolution of iron. The deviation of carbon
dioxide and sodium carbonate ions show considerable hydration of the carbon dioxide.
All species show little variation in concentration compared to the bulk within a large
part of the boundary layer adjacent to the bulk and demonstrating the presence of a
turbulent sublayer.
Figure 2: Deviation in concentration of the species compared to the bulk along the liquid
boundary layer.
Figure 3 shows the corrosion rate of the steel surface at three different pH for
operating temperatures ranging from 20 C to 80 C. The corrosion rate is directly
proportional to the corrosion current, that is, the iron dissolution current since no
other anodic reaction is considered. Lowered pH and increased temperature increases
the rate of corrosion.
4 |
Figure 3: Corrosion rate in mm/year for pH 4, 5, and 6 and operating temperatures

range of 20 C-80 C.
References
1. M. Nordsveen, S. Nesic, R. Nyborg, and A. Stangeland, A Mechanistic Model for
Carbon Dioxide Corrosion of Mild Steel in the Presence of Protective Iron Carbonate
Films-Part 1: theory and Verification, Corrosion, vol. 59, no. 5, pp. 443455, 2003.
2. S. Nesic, J. Postlethwaite, and S. Olsen, An Electrochemical Model for Prediction
of Corrosion of Mild Steel in Aqueous Carbon Dioxide Solutions, Corrosion, vol. 52,
no. 4, pp. 280294, 1996.

co2_corrosion
5 |
NEW

MODEL WIZARD

2 In the Select physics tree, select Electrochemistry>Electroanalysis (elan).
3 Click Add.
4 In the Number of species text field, type 7.
5 In the Concentrations table, enter the following settings:
cCO2
cH2CO3
cHCO3
cCO3
cH
cOH
cFe
6 Click Study.
8 Click Done.
GEOMETRY 1
The geometry consists of a single interval.
Interval 1 (i1)
1 On the Geometry toolbar, click Interval.
2 In the Settings window for Interval, locate the Interval section.
3 In the Right endpoint text field, type 100e-6.
4 Right-click Component 1 (comp1)>Geometry 1>Interval 1 (i1) and choose Build
Selected.
GLOBAL DEFINITIONS
Parameters
6 |

co2_corrosion_parameters.txt.
DEFINITIONS
Variables 1
1 In the Model Builder window, under Component 1 (comp1) right-click Definitions and
choose Variables.
Load the variables from a text file.
2 In the Settings window for Variables, locate the Variables section.
co2_corrosion_variables.txt.
ELECTROANALYSIS (ELAN)
Start defining the physics. The turbulent contribution is accounted for with a turbulent
diffusivity, Dt.
1 In the Model Builder window, under Component 1 (comp1)>Electroanalysis (elan) click
Transport Properties 1.
3 In the DcCO2 text field, type DCO2+Dt.
4 In the DcH2CO3 text field, type DH2CO3+Dt.
5 In the DcHCO3 text field, type DHCO3+Dt.
6 In the DcCO3 text field, type DCO3+Dt.
7 In the DcH text field, type DH+Dt.
8 In the DcOH text field, type DOH+Dt.
9 In the DcFe text field, type DFe+Dt.
Initial Values 1
Set the initial values to the concentration of the species in the bulk.
1 In the Model Builder window, under Component 1 (comp1)>Electroanalysis (elan) click
Initial Values 1.
7 |
3 In the cCO2 text field, type cCO20.
4 In the cH2CO3 text field, type cH2CO30.
5 In the cHCO3 text field, type cHCO30.
6 In the cCO3 text field, type cCO30.
7 In the cH text field, type cH0.
8 In the cOH text field, type cOH0.
9 In the cFe text field, type cFe0.
Set the net total current of all the electrochemical reactions to zero. Also, set fluxes
according to the electrochemical reactions at the steel surface.
Electrode Surface 1
1 On the Physics toolbar, click Boundaries and choose Electrode Surface.
3 In the Settings window for Electrode Surface, locate the Boundary Condition section.
4 From the Boundary condition list, choose Total current.
5 In the Il,total text field, type 0.
6 In the s,ext text field, type -0.5.
1 In the Model Builder window, expand the Electrode Surface 1 node, then click
Electrode Reaction 1.
section.
3 In the Eeq text field, type Erev_Fe.
6 In the Aa text field, type b_Fe.
8 In the cFe text field, type -1.
8 |
section.
3 In the Eeq text field, type Erev_H2CO3.
5 In the i0 text field, type i0_H2CO3.
6 In the Ac text field, type -b_H2CO3.
8 In the ilim text field, type ilimH2CO3.
9 Locate the Stoichiometric Coefficients section. In the cH2CO3 text field, type -1.
10 In the cHCO3 text field, type 1.
section.
3 In the Eeq text field, type Erev_H2.
5 In the i0 text field, type i0_H2.
6 In the Ac text field, type -b_H2.
8 In the ilim text field, type ilimH2.
9 Locate the Stoichiometric Coefficients section. In the cH text field, type -1.
section.
3 In the Eeq text field, type Erev_H2O.
5 In the i0 text field, type i0_H2O.
6 In the Ac text field, type -b_H2O.
9 |
7 Locate the Stoichiometric Coefficients section. In the cOH text field, type 1.
Set four equilibrium reactions.
Equilibrium Reaction 1
1 On the Physics toolbar, click Domains and choose Equilibrium Reaction.
2 In the Settings window for Equilibrium Reaction, locate the Domain Selection
section.
3 From the Selection list, choose All domains.
4 Locate the Equilibrium Condition section. In the Keq text field, type KH2O.
5 Locate the Stoichiometric Coefficients section. In the cH text field, type 1.
6 In the cOH text field, type 1.
section.
4 Locate the Equilibrium Condition section. In the Keq text field, type KCO2H.
5 Locate the Stoichiometric Coefficients section. In the cCO2 text field, type -1.
6 In the cH2CO3 text field, type 1.
section.
4 Locate the Equilibrium Condition section. In the Keq text field, type KH2CO3.
5 Locate the Stoichiometric Coefficients section. In the cH2CO3 text field, type -1.
6 In the cHCO3 text field, type 1.
7 In the cH text field, type 1.
section.
10 |
4 Locate the Equilibrium Condition section. In the Keq text field, type KHCO3.
5 Locate the Stoichiometric Coefficients section. In the cHCO3 text field, type -1.
6 In the cCO3 text field, type 1.
Set bulk concentrations at the right most boundary.
Concentration 1
4 Select the Species cCO2 check box.
5 Select the Species cH check box.
6 Select the Species cFe check box.
7 In the c0,cCO2 text field, type cCO20.
8 In the c0,cH text field, type cH0.
9 In the c0,cFe text field, type cFe0.
MESH 1
Build a user-defined mesh with a maximum element size in the domain of 1e-6 and at
the left most boundary 1e-7.
3 From the Sequence type list, choose User-controlled mesh.
Size
type 1e-6.
Size 1
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 right-click Edge 1
and choose Size.

2 In the Settings window for Size, locate the Geometric Entity Selection section.
11 |

5 Locate the Element Size section. Click the Custom button.
6 Locate the Element Size Parameters section. Select the Maximum element size check
box.
7 In the associated text field, type 1e-7.
8 Click the Build Selected button.
STUDY 1
1 In the Model Builder window, click Study 1.

2 In the Settings window for Study, locate the Study Settings section.
3 Clear the Generate default plots check box.
Step 1: Stationary
For the stationary solver, use an auxiliary sweep to investigate the impact of pH and
temperature.
4 From the Sweep type list, choose All combinations.
5 Click Add.
Parameter name
pH
4 5 6
Parameter unit
7 Click Add.
Parameter name
293.15 323.15 353.15
9 From the Reuse solution for previous step list, choose Yes.
Solution 1
2 In the Model Builder window, expand the Solution 1 node.
12 |
Parameter unit
3 In the Model Builder window, under Study 1>Solver Configurations>Solution 1 click

Stationary Solver 1.
4 In the Settings window for Stationary Solver, locate the General section.
5 In the Relative tolerance text field, type 1e-4.
RESULTS
The following steps reproduce the plots from the Results and Discussion section.
1D Plot Group 1
Rename.
3 In the Rename 1D Plot Group dialog box, type Concentrations in the New label text
field.
4 Click OK.
6 From the Parameter selection (pH) list, choose Last.
7 From the Parameter selection (T) list, choose First.
9 In the Title text area, type pH=6, T=20circC.
11 In the associated text field, type Distance from steel surface (m).
13 In the associated text field, type Concentration (mol/m3).
Concentrations
1 On the Concentrations toolbar, click Line Graph.
2 In the Settings window for Line Graph, locate the Selection section.
4 Locate the y-Axis Data section. In the Expression text field, type cCO2-cCO20.
13 |
Legends
CO2
11 Right-click Results>Concentrations>Line Graph 1 and choose Duplicate.

12 In the Settings window for Line Graph, locate the y-Axis Data section.
13 In the Expression text field, type cH2CO3-cH2CO30.
Legends
H2CO3

17 In the Expression text field, type cHCO3-cHCO30.
Legends
HCO3-

21 In the Expression text field, type cCO3-cCO30.
Legends
CO32-

25 In the Expression text field, type cH-cH0.
Legends
H+
14 |

28 In the Settings window for Line Graph, locate the Legends section.
Legends
OH-

32 In the Expression text field, type cFe-cFe0.
Legends
Fe2+
34 On the Concentrations toolbar, click Plot.
1D Plot Group 2
Rename.
3 In the Rename 1D Plot Group dialog box, type Corrosion rate in the New label text
field.
4 Click OK.
6 From the Title type list, choose None.
8 In the associated text field, type Operating temperature (circC).
10 In the associated text field, type Corrosion rate (mm/year).
Corrosion rate
1 On the Corrosion rate toolbar, click Point Graph.
3 In the Settings window for Point Graph, locate the y-Axis Data section.
4 In the Expression text field, type CR.
15 |
5 From the Unit list, choose mm/yr.

7 In the Expression text field, type T.
8 From the Unit list, choose degC.
Legends
pH=4
pH=5
pH=6
12 On the Corrosion rate toolbar, click Plot.
16 |
C r e v i c e C o r r o si on of Iron i n an
Acetic Acid/Sodium Acetate Solution
Introduction
Mass transport limitations within thin crevices can often result in the local
electrochemistry to differ significantly between the crevice opening (mouth) and end
(tip), and as a result of the differences in local chemistry, corrosion may occur.
This example models crevice corrosion of iron in an acetic acid/sodium acetate
solution. The model reproduces the results of Walton (Ref. 1).
Model Definition
The crevice investigated is 10 mm deep and 0.5 mm wide. Due to the high aspect ratio
of the crevice a 1D model geometry is used, in which concentration variations along
the width of the crevice are neglected.
Due to the absence of a supporting electrolyte the transport of all charged species need
to be accounted for. All species are considered to be diluted in water, and
Nernst-Planck equations are used to describe the transport of the species in the
electrolyte, together with an electroneutrality condition. A Tertiary Current
Distribution interface is used to model the electrolyte potential and the transport of
eight species.The modeled species, together with their respective diffusion coefficients
in water, are listed in Table 1.
TABLE 1: MODELED SPECIES WITH THEIR RESPECTIVE DIFFUSION COEFFICIENTS.
SPECIES
D (dm2/s)107
Fe2+
0.7
9.3
OH
5.3
FeOH+
1.3
Na
CH3COOH
CH3COO
CH3COOFe+
1 |
1.1
1.1
1.1
CREVICE CORROSION OF IRON IN AN ACETIC ACID/SODIUM ACETATE SOLUTION
The diffusion coefficients listed in Table 1 are divided by a factor of four to account
for the higher viscosity of the electrolyte used (compared to water). The mobilities
were calculated using the Nernst-Einstein relation:
Di
u m, i = -------RT
The mouth of the crevice is set to a measured value for the electrolyte potential and
the bulk concentrations. No flux / Insulation conditions are applied to the crevice tip.
EQUILIBRIUM REACTIONS
The following equilibrium reactions are present in the electrolyte:

2+
K 1 = 1,63 10
K 2 = 1,014 10
K 3 = 1,75 10
H 2 O OH (aq) + H (aq)
+
CH 3 COOH(aq) H (aq) + CH 3 COO (aq)

-
H 2 O + Fe (aq) FeOH (aq) + H (aq)
2+
CH 3 COO (aq) + Fe (aq) CH 3 COOFe (aq)
14
K 4 = 25,1
where K1 through K4 are the equilibrium constants.

These reactions are modeled using the Equilibrium Reaction domain node; one for
each reaction. The Equilibrium Reaction nodes solve for one additional degree of
freedom each, where the additional degree of freedom represents the local reaction
rate required in order to fulfill the equilibrium expression. The equilibrium expressions
are based on the reaction stoichiometry and equilibrium constant Kk according to
Kk =
a ( ci )
ik
where ci (SI unit: mol/m3) is the concentration of species i, vik the stoichiometric
coefficient of species i in reaction k.
The activity of a species, a(ci), is calculated as
ci
a ( ci ) = max ---------,
1M
where is an arbitrarily small number. By the use of the max() function negative
concentrations does not fulfill the equilibrium expression. (Numerical effects may
2 |
result in concentrations that are close to zero to take negative values at certain stages
during the solver process.)
Iron dissolution occurs in the crevice according to

2+
Fe(s) Fe (aq) + 2e
Experimental polarization data is used for this reaction according to Figure 1, where
the local current density (SI unit: A/m2) of the reaction is evaluated as:
i Fe = f ( s l )
The whole crevice is modeled as a porous electrode (with a single pore), with the
specific surface area 2/w (SI unit: 1/m).
Figure 1: Polarization curve (anodic) for uncreviced iron.

STUDY SETTINGS
Since the conductivity of the metal phase is very high, and the electric potential is
assumed to be constant over the crevice, solving for s is disabled in the solver.
The problem is solved using a parametric sweep on a stationary solver, sweeping the
potential in the electrode phase, V pol = s , from -0.6 V to 0.844 V (SHE). The
parametric sweep is needed to ensure that the intended active-to-passive polarization
3 |
behavior is captured in the simulation, since due to the non-monotonic shape of the
polarization curve the problem may have more than one solution.

Figure 2 shows the concentration distribution of the different species in the crevice.
The sodium concentration is significantly lower in the crevice, compared to the bulk,
whereas the iron, which is dissolved in the crevice, and the iron complexes have higher
concentrations towards the tip.
Figure 2: Concentration distribution in the crevice at 0.844 V(SHE).

Figure 3 shows the electrode potential of the metal, as compared to a reference placed
along the crevice surface in the electrolyte:
E vs ref = s s, ref = V pol ( l + E eq, ref ) = V pol l
4 |
Figure 3: Electrode potential vs. reference placed in electrolyte.

Figure 4 shows the corrosion current density along the crevice. The highest corrosion
rate occurs at a crevice depth of about 0.25 mm.
5 |
Figure 4: Corrosion current density in crevice.
Reference
1. J.C Walton, Mathematical Modeling of Mass Transport and Chemical Reaction in
Crevice and Pitting Corrosion, Corrosion Science, vol. 30, no. 8/9, pp. 915928,
1990.
Application Library path: Corrosion_Module/Crevice_Corrosion/

crevice_corrosion_fe
NEW
6 |
MODEL WIZARD

2 In the Select physics tree, select Electrochemistry>Tertiary Current Distribution,
Nernst-Planck (tcdee).
3 Click Add.
4 In the Number of species text field, type 8.
cFe
cH
cOH
cFeOH
cNa
cCH3COOH
cCH3COO
cCH3COOFe
6 Click Study.
8 Click Done.
GLOBAL DEFINITIONS
Parameters
crevice_corrosion_fe_parameters.txt.
GEOMETRY 1
The geometry consists of a single interval.
Interval 1 (i1)
7 |
3 In the Right endpoint text field, type L.

DEFINITIONS
Create an interpolation function for the iron oxidation current density using
polarization data in a text file.
4 Click Browse.
crevice_corrosion_fe_i_loc.txt.
6 Click Import.
7 In the Function name text field, type i_Fe.
8 Locate the Interpolation and Extrapolation section. From the Interpolation list,
choose Piecewise cubic.

9 Locate the Units section. In the Arguments text field, type V.
10 In the Function text field, type A/m^2.
12 Click the y-Axis Log Scale button on the Graphics toolbar.
This is the Figure 1.

TE R T I A R Y C U R RE N T D I S T R I B U T I O N , N E R N S T - P L A N C K ( T C D E E )
Start defining the physics. The crevice is modeled as a porous electrode.
Porous Electrode 1
1 On the Physics toolbar, click Domains and choose Porous Electrode.
3 In the Settings window for Porous Electrode, locate the Model Inputs section.
4 In the T text field, type T.
8 |
5 Locate the Electrode Current Conduction section. From the s list, choose User
defined.
Actually, the electrode conductivity is not needed for this model since you will later
modify the solver tree in order to not solve for the electric potential in the electrode.
6 In the associated text field, type 1000.
7 Locate the Diffusion section. In the DcFe text field, type DFe.
8 In the DcH text field, type DH.
9 In the DcOH text field, type DOH.
10 In the DcFeOH text field, type DFeOH.
11 In the DcNa text field, type DNa.
12 In the DcCH3COOH text field, type DCH3COOH.
13 In the DcCH3COO text field, type DCH3COO.
14 In the DcCH3COOFe text field, type DCH3COOFe.
15 Locate the Migration in Electric Field section. In the zcFe text field, type 2.
16 In the zcH text field, type 1.
17 In the zcOH text field, type -1.
18 In the zcFeOH text field, type 1.
19 In the zcNa text field, type 1.
In the zcCH3COOH text field, keep the default setting 0.

20 In the zcCH3COO text field, type -1.
21 In the zcCH3COOFe text field, type 1.
Set the porosity to unity. This implies that all the volume of the modeled domain
belongs to the electrolyte phase.
22 Locate the Volume Fractions section. In the l text field, type 1.
Porous Electrode Reaction 1

Set up the iron oxidation electrode reaction using the predefined interpolation
polynomial.
1 In the Model Builder window, expand the Porous Electrode 1 node, then click Porous
Electrode Reaction 1.
2 In the Settings window for Porous Electrode Reaction, locate the Electrode Kinetics
section.
9 |
3 From the Kinetics expression type list, choose User defined. In the iloc text field, type
i_Fe(V_pol-phil).
4 Locate the Active Specific Surface Area section. In the av text field, type 2/w.
6 In the cFe text field, type -1.
Add the heterogeneous equilibrium reaction sources.

7 In the Settings window for Tertiary Current Distribution, Nernst-Planck, locate the
Species section.
8 From the From electroneutrality list, choose cNa.
9 In the Model Builder windows toolbar, click the Show button and select Advanced
Physics Options in the menu.
section.
4 Locate the Equilibrium Condition section. In the Keq text field, type K1.
5 Locate the Stoichiometric Coefficients section. In the cFe text field, type -1.
7 In the cFeOH text field, type 1.
section.
6 In the cOH text field, type 1.
section.
10 |

6 In the cCH3COOH text field, type -1.
7 In the cCH3COO text field, type 1.
section.
5 Locate the Stoichiometric Coefficients section. In the cFe text field, type -1.
6 In the cCH3COO text field, type -1.
7 In the cCH3COOFe text field, type 1.
Set the concentrations at the crevice mouth to the bulk concentration values.
Concentration 1
4 Select the Species cFe check box.
5 In the c0,cFe text field, type cFe0.
6 Select the Species cH check box.
7 In the c0,cH text field, type cH0.
8 Select the Species cCH3COOH check box.
9 In the c0,cCH3COOH text field, type cCH3COOH0.
Specify the electrolyte potential at the crevice mouth.
3 In the Settings window for Electrolyte Potential, locate the Electrolyte Potential
section.
11 |
4 In the l,bnd text field, type phil_mouth.
Set the initial values to the values at the crevice mouth.
Initial Values 1
1 In the Model Builder window, under Component 1 (comp1)>Tertiary Current
Distribution, Nernst-Planck (tcdee) click Initial Values 1.
3 In the cFe text field, type cFe0.
4 In the cH text field, type cH0.
5 In the cOH text field, type cOH0.
6 In the cFeOH text field, type cFeOH0.
7 In the cCH3COOH text field, type cCH3COOH0.
8 In the cCH3COO text field, type cCH3COO0.
9 In the cCH3COOFe text field, type cCH3COOFe0.
10 In the phil text field, type phil_mouth.
MESH 1
Build a mesh with a finer resolution at the mouth.
Size
choose Edit Physics-Induced Sequence.

type 1e-5.
6 In the Maximum element growth rate text field, type 1.1.
Size 1
and choose Size.

12 |

box.
7 In the associated text field, type 1e-7.
STUDY 1
The model is highly non-linear. Use an auxiliary sweep with continuation to gradually
increase the polarization potential, lower the solver tolerance to improve the solution
accuracy for each polarization level.
Step 1: Stationary
4 Click Add.
Parameter name
V_pol
range(-0.6, 0.2, 0.8) 0.844
Parameter unit
Solution 1
The potential in the metal phase will be considered constant in this model. Modify
the default solver not to solve for phis.
2 In the Model Builder window, expand the Solution 1 node, then click Dependent
Variables 1.
3 In the Settings window for Dependent Variables, locate the General section.
4 From the Defined by study step list, choose User defined.
5 In the Model Builder window, expand the Study 1>Solver Configurations>Solution
1>Dependent Variables 1 node, then click Electric potential (comp1.phis).
6 In the Settings window for Field, locate the General section.
7 Clear the Solve for this field check box.
13 |
RESULTS
Electrolyte Salt Concentration (tcdee)

The following reproduces the plots from the Results and Discussion section. First
modify the default concentration plot to plot all concentrations.
2 From the Parameter selection (V_pol) list, choose Last.
4 In the Title text area, type Solution Composition at 0.844 V(SHE).
6 In the associated text field, type Position Inside Crevice (m).
7 In the Model Builder window, expand the Electrolyte Salt Concentration (tcdee) node,
then click Line Graph 1.1.

8 In the Settings window for Line Graph, click to expand the Title section.
9 From the Title type list, choose None.
Legends
Fe2+
13 Right-click Results>Electrolyte Salt Concentration (tcdee)>Line Graph 1.1 and choose

Duplicate.
15 In the Expression text field, type cH.
Legends
H+
17 Right-click Results>Electrolyte Salt Concentration (tcdee)>Line Graph 1.1.2 and
choose Duplicate.
19 In the Expression text field, type cOH.
14 |
Legends
OH-
21 Right-click Results>Electrolyte Salt Concentration (tcdee)>Line Graph 1.1.2.2 and
choose Duplicate.
23 In the Expression text field, type cFeOH.
Legends
FeOH+
25 Right-click Results>Electrolyte Salt Concentration (tcdee)>Line Graph 1.1.2.2.2 and
choose Duplicate.
27 In the Expression text field, type cNa.
Legends
Na+
29 Right-click Results>Electrolyte Salt Concentration (tcdee)>Line Graph 1.1.2.2.2.2 and
choose Duplicate.
31 In the Expression text field, type cCH3COOH.
Legends
CH3COOH
33 Right-click Results>Electrolyte Salt Concentration (tcdee)>Line Graph 1.1.2.2.2.2.2
and choose Duplicate.

35 In the Expression text field, type cCH3COO.
15 |
Legends
CH3COO-
37 Right-click Results>Electrolyte Salt Concentration (tcdee)>Line Graph 1.1.2.2.2.2.2.2
and choose Duplicate.

39 In the Expression text field, type cCH3COOFe.
Legends
CH3COOFe+
41 Click to expand the Coloring and style section. Locate the Coloring and Style section.
Find the Line style subsection. From the Line list, choose Dashed.
42 In the Model Builder window, click Electrolyte Salt Concentration (tcdee).
43 In the Settings window for 1D Plot Group, locate the Axis section.
44 Select the Manual axis limits check box.
45 In the x minimum text field, type 0.99e-6.
46 In the x maximum text field, type 0.0101.
47 In the y minimum text field, type 1e-3.
48 In the y maximum text field, type 1e4.
49 Select the x-axis log scale check box.
50 Select the y-axis log scale check box.
51 Click to expand the Legend section. From the Position list, choose Lower right.
52 On the Electrolyte Salt Concentration (tcdee) toolbar, click Plot.
The following plots the electrode potential versus a reference electrode in electrolyte
at varying positions in the crevice.
1D Plot Group 3
5 In the associated text field, type Position Inside Crevice (m).
16 |

7 In the associated text field, type Potential (V).
8 Locate the Title section. From the Title type list, choose Manual.
9 In the Title text area, type Electrode Potential vs. Reference Electrode in
Electrolyte.

13 In the Expression text field, type V_pol-phil.
The following plots the corrosion current density in the crevice.
1D Plot Group 4
4 Locate the Title section. From the Title type list, choose Manual.
5 In the Title text area, type Iron Oxidation Current Density.
6 Locate the Axis section. Select the x-axis log scale check box.
7 Select the y-axis log scale check box.
10 In the Settings window for Line Graph, click Replace Expression in the upper-right
1>Tertiary Current Distribution, Nernst-Planck>Electrode kinetics>tcdee.iloc_per1 Local current density.
13 Select the Description check box.
14 In the associated text field, type Position Inside Crevice.
17 |
Electrolyte Salt Concentration (tcdee)

1 In the Model Builder window, under Results right-click Electrolyte Salt Concentration
(tcdee) and choose Rename.
2 In the Rename 1D Plot Group dialog box, type Concentrations in the New label text
field.
3 Click OK.
1D Plot Group 3
Rename.
2 In the Rename 1D Plot Group dialog box, type Electrode potential in the New
label text field.
3 Click OK.
1D Plot Group 4
Rename.
2 In the Rename 1D Plot Group dialog box, type Corrosion current density in the
3 Click OK.
18 |
C r e v i c e C o r r o si on of N i ckel wi t h
Electrode Deformation
Introduction
This model exemplifies the basic principles of crevice corrosion and how a
time-dependent study can be used to simulate the electrode deformation.
The model is in 2D and the polarization data for the corrosion reaction is taken from
a paper by Absulsalam and others (Ref. 1). The model and the results are similar to a
1D model by Brackman and others (Ref. 2).
This model does not account for mass transport effects. For a more detailed treatment
of mass transport in a crevice, see the Crevice Corrosion of Iron in an Acetic Acid/
Sodium Acetate Solution model example.
Model Definition
The modeled cell is a laboratory cell (Figure 1), where an open-ended 10 mm crevice,
0.3 mm wide, has been created between a piece of nickel and a sheet of Plexiglas.
Plexiglas (insulator)
Electrolyte
Insulator
Ni electrode
Figure 1: Electrochemical cell for corrosion experiments. The gray area is the modeled
geometry.
Polarization data for a planar nickel electrode has been measured separately, with the
results shown in Figure 2. The polarization curve consists of two parts: the active
region, where the current density increases with the increased anodic polarization, and
1 |
CREVICE CORROSION OF NICKEL WITH ELECTRODE DEFORMATION
the passive region, where the current density decreases or remains constant with the
increased polarization. The electrolyte used is 1 N H2SO4.
Active
region
Passive
region
Figure 2: Polarization data for the nickel electrode reaction for a potential scan in the
active-to-passive direction.
An electrolyte of high conductivity is used, and the corrosion current densities are
expected to be fairly small so that a secondary current distribution can be assumed for
this cell (mass transport effects of dissolved nickel and other ions are neglected). Use
a Corrosion, Secondary physics to model the problem.
Model the cell geometry by including the crevice and a 2 mm square outside the
mouth of the crevice. Use one Electrolyte domain to model the electrolyte charge
transport, with a constant conductivity of 0.184 S/m.
Add an External Corroding Electrode boundary condition to model the nickel surface
deformation. Use the experimental polarization data for the electrode reaction kinetics
as an interpolation polynomial. Set the potential of the electrode to 0.3 V.
Use an Electrolyte Potential boundary condition to apply a 0 V electrolyte potential
along the leftmost boundary.
Use the default Insulation condition for all other boundaries.
For the deformed geometry, on the non-moving boundaries, the model is solved with
the default Noncorroding Boundary. These boundaries are all straight lines, so to
2 |
improve the shape of the deformation in the corners of the geometry, and also to
reduce the problem size, change the boundary condition setting of the feature to Zero
Normal Displacement.
Solve the problem using a Time Dependent with Initialization study. The study
contains two solver steps, a Current Initialization step first solves for the potentials
only, using a stationary solver. The second Time Dependent step solves for the full
problem for the prescribed 50 hours duration.
Due to the non-monotonic shape of the polarization data there are two possible
solutions to the modeled problem: One high current solution with low activation/
high ohmic losses, and one low current solution with high activation/low ohmic
losses. This case considers the former solution, which can be found by sweeping the
voltage from low polarization in the active-to-passive direction. Use a Parametric
solver in the Current Initialization step to gradually increase the polarization voltage
of the electrode.

Figure 3 shows the electrolyte potential and the electrode deformation after 50 hours.
The parts of the electrode outside the crevice are hardly deformed. The main
3 |
deformation occurs somewhere in the range 25 mm into the crevice. Outside the
crevice, in the bulk of the electrolyte, the potential drops are small.
Figure 3: Electrolyte potential and deformed geometry after 50 h.

Figure 4 shows the corrosion current density along the electrode surface for various
times. The maximum is found around x = 3.5 mm. As time increases, the current peak
broadens. Two effects account for the change of the corroding current density profile:
4 |
the lowered ohmic drop due to the widening of the crevice, and the increased available
surface area due to the changed curvature of the electrode.
Figure 4: Corrosion current density along the nickel surface.

Figure 5 shows the potential difference between the electric potential in the electrode
and the electrolyte potential along the nickel surface. The shape of the potential plot,
in combination with the polarization data in Figure 2, explains the corrosion current
density peak seen in Figure 4. As current enters the crevice, the potential is shifted due
to ohmic losses, and the nickel corrosion reaction is thereby shifted from the passive
region in the polarization curve towards higher activity, resulting in higher corrosion
currents.
5 |
Figure 5: Electrode-electrolyte potential along the nickel surface.

Finally, Figure 6 shows the deformation of the electrode at various times.
6 |
Figure 6: Electrode deformation at various times.
References
1. M. Abdulsalam and H.W. Pickering, The Effect of Crevice-Opening Dimension on
the Stability of Crevice Corrosion for Nickel in Sulfuric Acid, J. Electrochemical
Society, vol. 145, no. 7, pp. 22762284, 1998.
2. M. Brackman, C.B. Clemons, D. Golovaty, K.L. Kreider, G.W. Young, R.S. Lillard,
and J. Payer, Modeling and Computational Simulation of Crevice Corrosion Damage
Evolution, NACE Corrosion Conference, 2012.
Application Library path: Corrosion_Module/Crevice_Corrosion/

crevice_corrosion_with_deformation
7 |
NEW

MODEL WIZARD

3 Click Add.
4 Click Study.
5 In the Select study tree, select Preset Studies>Time Dependent with Initialization.
6 Click Done.
GLOBAL DEFINITIONS
Start by adding values for the parameters that will be used in several places in the
model.
Parameters
Name
Expression
Value
Description
V_pol
0.3[V]
0.3 V
Polarization voltage
0.35[mm]
3.5E-4 m
Crevice width
GEOMETRY 1
Now build the geometry as a union of a rectangle (the crevice) and a square (part of
the electrolyte outside the crevice).
Rectangle 1 (r1)
3 In the Width text field, type 10[mm].
4 In the Height text field, type w.
5 Right-click Component 1 (comp1)>Geometry 1>Rectangle 1 (r1) and choose Build
Selected.
8 |
Square 1 (sq1)
1 On the Geometry toolbar, click Primitives and choose Square.
2 In the Settings window for Square, locate the Size section.
3 In the Side length text field, type 2[mm].
4 Locate the Position section. In the x text field, type -2[mm].
5 In the y text field, type -1[mm]+w/2.
6 Right-click Component 1 (comp1)>Geometry 1>Square 1 (sq1) and choose Build
Selected.
Union 1 (uni1)
1 On the Geometry toolbar, click Booleans and Partitions and choose Union.
2 Select both objects r1 and sq1.
3 In the Settings window for Union, locate the Union section.
4 Clear the Keep interior boundaries check box.
5 Right-click Component 1 (comp1)>Geometry 1>Union 1 (uni1) and choose Build
Selected.
DEFINITIONS
Now add the polarization data for the nickel dissolution reaction. Add the data as an
interpolation polynomial.
4 Click Browse.
crevice_corrosion_with_deformation_i_Ni.txt.
6 Click Import.
7 In the Function name text field, type i_Ni.

9 From the Extrapolation list, choose Linear.
9 |
11 In the Function text field, type mA/cm^2.

13 Click the y-Axis Log Scale button on the Graphics toolbar.
This is the Figure 2.

Now set up the electrochemistry. Start with the electrolyte conductivity.
Electrolyte 1
(corrsec) click Electrolyte 1.
3 From the l list, choose User defined. In the associated text field, type 0.184[S/cm].
Now set up the corroding electrode.

3 In the Settings window for External Corroding Electrode, locate the Boundary
Condition section.
4 In the s,ext text field, type V_pol.
1 In the Model Builder window, expand the External Corroding Electrode 1 node, then
click Surface Properties 1.

3 In the Mccorr text field, type 0.05869[kg/mol].
4 In the ccorr text field, type 8900[kg/m^3].
(corrsec)>External Corroding Electrode 1 click Electrode Reaction 1.
2 In the Settings window for Electrode Reaction, locate the Electrode Kinetics section.
3 From the Kinetics expression type list, choose User defined.
Set the local current density of the electrode reaction to a user-defined expression
using the polarization data of the interpolation polynomial. The corrsec.phisext
variable is the potential in the metal phase of the electrode surface.
10 |
4 In the iloc text field, type i_Ni(corrsec.phisext-phil).

5 Locate the Stoichiometric Coefficients section. In the ccorr text field, type 1.
6 In the nm text field, type 2.
Set the electrolyte potential to zero on the left most boundary.
Noncorroding Boundary 1
The following applies a stronger constraint (than the default condition) for the planar
non-depositing walls in order to enforce a zero boundary movement in the normal
direction.
(corrsec) click Noncorroding Boundary 1.
2 In the Settings window for Noncorroding Boundary, locate the Noncorroding
Boundary section.
3 From the Boundary condition list, choose Zero normal displacement.
MESH 1
The model is now ready for solving. Use a mesh with an Extremely fine mesh
resolution along the crevice electrode surface.
Free Triangular 1
Edit Physics-Induced Sequence.
Size 1
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 right-click Free
Triangular 1 and choose Size.
5 Locate the Element Size section. From the Predefined list, choose Extremely fine.
11 |
STUDY 1
Due to the non-monotonic shape of the polarization data there are two solutions to
the problem: One with high activation/low ohmic losses (low currents), and one with
low activation/high ohmic losses (high currents). Edit the default solver by adding an
auxiliary sweep with continuation to the initialization step. This will ensure that the
high current solution will be solved for.

Initialization.
2 In the Settings window for Current Distribution Initialization, click to expand the
Study extensions section.
4 Click Add.
Parameter name
V_pol
range(-0.2,0.1,V_pol)
Parameter unit
Step 2: Time Dependent

1 In the Model Builder window, under Study 1 click Step 2: Time Dependent.
2 In the Settings window for Time Dependent, locate the Study Settings section.
3 In the Times text field, type range(0,10*3600,50*3600).
RESULTS
A 2D plot of the electrolyte potential and the deformation is created by default

(Figure 3). Change the frame of the data set edges to Geometry in order to show the
outline of the original (non-deformed) geometry in the figure.
Electrolyte Potential (corrsec)

1 In the Model Builder window, expand the Results node, then click Electrolyte Potential
(corrsec).
2 In the Settings window for 2D Plot Group, locate the Plot Settings section.
3 From the Frame list, choose Geometry (Xg, Yg, Zg).
5 On the Electrolyte Potential (corrsec) toolbar, click Plot.
12 |
Create a plot of the corrosion current density in the following way:
1D Plot Group 2
4 In the Settings window for Line Graph, click Replace Expression in the upper-right
1>Corrosion, Secondary>Electrode kinetics>corrsec.iloc_er1 - Local current density.
Legends
0 h
10 h
20 h
30 h
40 h
50 h
Duplicate the plot and change the expression in the new plot. This will create a plot of
the electrode-electrolyte potential difference:
1D Plot Group 3
1 In the Model Builder window, right-click 1D Plot Group 2 and choose Duplicate.
2 In the Model Builder window, expand the 1D Plot Group 3 node, then click Line Graph
1.
4 In the Expression text field, type V_pol-phil.
Finally, duplicate the plot and change the expression again to create a plot of the
deformation for various times.
13 |
1D Plot Group 4
1 In the Model Builder window, right-click 1D Plot Group 3 and choose Duplicate.
2 In the Model Builder window, expand the 1D Plot Group 4 node, then click Line Graph
1.
4 In the Expression text field, type y.
5 From the Unit list, choose mm.
7 In the Settings window for 1D Plot Group, click to expand the Legend section.
8 From the Position list, choose Lower right.
Optionally, give the plot group nodes more descriptive names:
1D Plot Group 2
Rename.
2 In the Rename 1D Plot Group dialog box, type Corrosion current density in the
3 Click OK.
1D Plot Group 3
Rename.
2 In the Rename 1D Plot Group dialog box, type Electrode-Electrolyte
Potential in the New label text field.
3 Click OK.
1D Plot Group 4
Rename.
2 In the Rename 1D Plot Group dialog box, type Electrode shape in the New label
text field.
3 Click OK.
14 |
Diffuse Double Layer

Introduction
sIn the very vicinity of an electrode surface (in the range of up to a few nanometers),
in the diffuse double layer, the assumption of electroneutrality is not valid due to
charge separation. Typically the diffuse double layer may be of interest when modeling
very thin layers of electrolyte, for instance in electrochemical capacitors and in
atmospheric corrosion problems.
To model the behavior of the diffuse double layer, one needs to solve for the
Nernst-Planck equations for all of the ions, in combination with the Poissons equation
for the potential. The combination of these equations is frequently referred to as the
Poisson-Nernst-Planck (PNP) equations.
This example shows how to couple the Nernst-Planck equations, solved using the
Transport of Diluted Species interface, to the Poissons equation, solved using the
Electrostatics interface.
A problem that arises when modeling the PNP equations is that of how to handle the
boundary condition for the potential equation. In this example an assumption of a
Stern layer with a constant capacity is used to derive surface charge boundary
conditions for Poissons equation.
The model reproduces the results of Bazant and Chu (see Ref. ? and Ref. ?).
Model Definition
The model geometry is in 1D (a single interval between 0 and L) and consists of one
single domain, representing the electrolyte phase, including the diffuse double layer.
DOMAIN EQUATIONS
The concentrations, ci (SI unit: mol/m3, i=+,-), of two ions of opposite charge (+1/
-1) are solved for in the electrolyte phase. The fluxes (Ni, SI unit: mol/(m2s)) of these
are described by the Nernst-Planck equation
N i = D i c i u m, i z i Fc i
with Di (SI unit: m2/s) being the diffusion coefficient, um,i (SI unit: smol/kg) the
mobility, F (SI unit: C/mol) Faradays constant, and (SI unit: V) the potential.
1 |
DIFFUSE DOUBLE LAYER
Assuming no heterogenous reactions in the electrolyte, the governing equations for

the two species become:
Ni = 0
For the potential, Poissons equation states
( ) =
where is the permittivity (SI unit: F/m) and the charge density (SI unit: C/m3),
depending on the ion concentrations according to:
= F ( c+ c- )
BOUNDARY CONDITIONS
The boundaries reside in the reaction plane of the electrodes on each side. The same
electrode reaction, in which the positive ion, S+,participates, takes place on both
electrodes.
+
S + e S(s)
The reaction rate r (SI unit: mol/(m2s)) is
a F
c F
r = K a c M exp ----------------- K c + exp --------------------
RT
RT
c
where Ka and Kc (SI unit: m/s) are the anodic and cathodic rate constants, cM the
metal species activity (SI unit: mol/m3, constant) and a and c the anodic and
cathodic transfer coefficients. (SI unit: V) is the difference in potential between the
metal phase, M (SI unit: V), and the reaction plane:
= M
The electrode reaction renders an inward flux for the positive ion according to
n N+ = r
on both boundaries. For the negative ion, a zero flux condition is used.
n N- = 0
Assuming the reaction plane to be placed at the boundary between the inner
(compact) and diffuse double layer, and with the assumption of a Stern compact layer
2 |
of a constant thickness, S (SI unit: m), one can derive the following Robin type of
boundary condition for the potential:
+ S ( n ) = M
This condition reduces to a Dirichlet voltage condition for S = 0, that is, in the
absence of a Stern layer. For the case of a non-zero stern layer thickness, the condition
can be reformulated as a surface charge condition

n ( ) = --------S
CELL POTENTIAL EQUATION
The problem formulated above can now be solved for given voltages of M in the
metal electrode phase for each side. Typically one grounds one electrode and specifies
the cell voltage as V so that
M
M
x=0
x=L
= 0
= V
However, to solve for a given cell current density, icell (SI unit: A/m2), with V not
known a priori, an additional global equation, solving for V, is used, fulfilling the
condition:
i cell = Fr
x=L
GLOBAL CONCENTRATION CONSTRAINT FOR THE NEGATIVE ION
When solving this system for a stationary solution, the negative ion concentration
needs an additional boot-strap to render a stable, unique, solution. This is done by
adding the following global constraint to the equation system:
L
c0 L =
0 c- dx
where c0 is the initial ion concentration (SI unit: mol/m3), equal for both ions.
The constraint assures that the total number of negative ions is preserved during the
iterative solver process. (For time-dependent simulations the constraint can be
omitted.)
3 |
DIMENSIONLESS NUMBERS AND PARAMETER VALUES
A number of dimensionless numbers can be derived that govern the behavior of the
cell. The problem is solved using a parametric study for a dimensionless parameter
D = (0.001, 0.01, 0.1), defined as
D = D L
D =
RT --------------2
2F c 0
where D is the Debye length.

The current of the cell is defined via the dimensionless number j=0.9,
j = i cell i D
i D = 4FD + c 0 L
where iD is the Nernstian limiting current density.
The cathodic reaction rate constant is defined using the dimensionless number
kc = 10,
Kc L
k c = ----------4D +
The rate of the anodic reaction term is governed by the dimensionless number kr = 10,
K r Lc M
k r = -----------------4D + c 0
and the Stern layer thickness is set using the dimensionless number =0.1,
S
= ------D

The following dimensionless variables are used when presenting the results:
4 |
x
x = ---L
( c+ + c- )
c = --------------------2c 0
( c+ c- )
= -------------------2c 0
F
= -------RT
Figure ??? shows the dimensionless concentration, c . The concentration gradients are
steepest close to the electrodes.
Figure 1: Dimensionless concentration profile.

Figure ??? shows the dimensionless charge density profile. Charge separation occurs
close to the electrodes. For higher values of D, the region of charge separation, the
diffuse double layer, stretches further into the domain. This is expected since higher
D values effectively mean a shorter domain length.
5 |
Figure 2: Dimensionless charge density profile.

Figure ??? shows the potential profile. For higher values of D the voltage over the cell
decreases. This is an expected result since a shorter domain length shortens the
potential losses due to ion transport.
6 |
Figure 3: Dimensionless potential profile.

The element order is set to 2 for the Transport of Diluted Species to match the default
element order 2 of the Electrostatics physics.
References
1. M. Bazant, K. Chu, and B. Bayly. Current-Voltage Relations for Electrochemical
Thin Films, SIAM Journal of Applied Math, vol. 65, no. 5, pp. 14631484, 2005.
2. K. Chu and M. Bazant, Electrochemical Thin Films at and Above the Classical
Limiting Current, SIAM Journal of Applied Math, vol. 65, no. 5, pp. 14851505,
2005.
Application Library path: Corrosion_Module/General_Electrochemistry/

diffuse_double_layer
7 |
NEW

MODEL WIZARD

2 In the Select physics tree, select AC/DC>Electrostatics (es).
3 Click Add.
4 In the Electric potential text field, type phi.
5 In the Select physics tree, select Chemical Species Transport>Transport of Diluted
Species (tds).
6 Click Add.
7 Click Add Concentration.
cp
cm
9 In the Select physics tree, select Mathematics>ODE and DAE Interfaces>Global ODEs and
DAEs (ge).
10 Click Add.
11 Click Study.
12 In the Select study tree, select Preset Studies for Selected Physics Interfaces>Stationary.
13 Click Done.
GLOBAL DEFINITIONS
Start by loading some parameters from a text file.
Parameters
diffuse_double_layer_parameters.txt.
8 |
GEOMETRY 1
Build the geometry as a single interval.
Interval 1 (i1)
3 In the Right endpoint text field, type L.
DEFINITIONS
Proceed by adding some variable expressions. (Some of the expressions use variables
that have not yet been defined and are hence marked in orange color, this is expected.)
Variables 1
1 On the Home toolbar, click Variables and choose Local Variables.
2 In the Settings window for Variables, locate the Geometric Entity Selection section.
5 Locate the Variables section. Click Load from File.
diffuse_double_layer_variables.txt.
Variables 2
5 Locate the Variables section. In the table, enter the following settings:
Name
Expression
Unit
Description
phiM
0[V]
Metal phase potential

(ground)
Variables 3
9 |

5 Locate the Variables section. In the table, enter the following settings:
Name
Expression
phiM
Unit
Description
Metal phase potential
(cell voltage)
Integration 1 (intop1)
Add integration coupling operators to be used when setting up the global voltage
equation and the global constraint.
1 On the Definitions toolbar, click Component Couplings and choose Integration.
2 In the Settings window for Integration, locate the Source Selection section.
ELECTROSTATICS (ES)
Charge Conservation 1
Now start setting up the physics, begin with the Electrostatics physics (Poisson's
equation).
1 In the Model Builder window, under Component 1 (comp1)>Electrostatics (es) click
Charge Conservation 1.
2 In the Settings window for Charge Conservation, locate the Electric Field section.
3 From the r list, choose User defined.
Space Charge Density 1

1 On the Physics toolbar, click Domains and choose Space Charge Density.
3 In the Settings window for Space Charge Density, locate the Space Charge Density
section.
4 In the v text field, type F_const*Z*(cp-cm).
10 |
Surface Charge Density 1

1 On the Physics toolbar, click Boundaries and choose Surface Charge Density.
3 In the Settings window for Surface Charge Density, locate the Surface Charge Density
section.
4 In the s text field, type rho_s.
Now set up the model for the transport of the ions. Enable migration and change the
element order to 2 to match the default element order of the Electrostatics physics.
1 In the Model Builder window, under Component 1 (comp1) click Transport of Diluted
Species (tds).
Mechanisms section.
4 Select the Migration in electric field check box.
5 In the Model Builder windows toolbar, click the Show button and select Discretization
in the menu.
6 Click to expand the Discretization section. From the Concentration list, choose
Quadratic.
Species (tds) click Transport Properties 1.
2 In the Settings window for Transport Properties, locate the Model Inputs section.
3 In the V text field, type phi.
5 Locate the Diffusion section. In the Dcp text field, type Dp.
6 In the Dcm text field, type Dm.
7 Locate the Migration in Electric Field section. In the zcp text field, type Z.
8 In the zcm text field, type -Z.
Flux 1
1 On the Physics toolbar, click Boundaries and choose Flux.
11 |
3 In the Settings window for Flux, locate the Inward Flux section.
4 Select the Species cp check box.
5 In the N0,cp text field, type r.
Initial Values 1
3 In the cp text field, type cref.
4 In the cm text field, type cref.
5 In the Model Builder windows toolbar, click the Show button and select Advanced
Physics Options in the menu.
Global Constraint 1
Add a global constraint to boot-strap the average concentration of negative ions to the
initial value.
1 On the Physics toolbar, click Global and choose Global Constraint.
2 In the Settings window for Global Constraint, locate the Global Constraint section.
3 In the Constraint expression text field, type intop2(cm)-(cref*L).
GLOBAL ODES AND DAES (GE)
Global Equations 1
Finally, add the equation for the cell potential.
1 In the Model Builder window, under Component 1 (comp1)>Global ODEs and DAEs (ge)
click Global Equations 1.

2 In the Settings window for Global Equations, locate the Global Equations section.
12 |
Name
f(u,ut,utt,t) (1)
Initial value
(u_0) (1)
Initial value
(u_t0) (1/s)
Description
intop1(iloc)-ic
ell
Cell voltage
MESH 1
Edit the default meshing sequence, make the mesh parameter dependent to make sure
the mesh is always a well resolved at the boundaries. (The parametric sweep will change
the size of the geometry during the solver process.)
Edge 1
Size 1
and choose Size.

box.
5 In the associated text field, type L/20.
Size 2
1 Right-click Edge 1 and choose Size.
box.
7 In the associated text field, type lambdaD/10.
Edge 1
Right-click Edge 1 and choose Build Selected.
STUDY 1
Solve the problem using a parametric sweep.
Parametric Sweep
1 On the Study toolbar, click Parametric Sweep.
2 In the Settings window for Parametric Sweep, locate the Study Settings section.
3 Click Add.
13 |

Parameter name
epsilon
0.001 0.01 0.1
Parameter unit

RESULTS
Reproduce the figures from the Results and Discussion section in the following way:
1D Plot Group 1
5 In the Expression text field, type (cp+cm)/(2*cref).
7 In the Expression text field, type x/L.
13 In the Title text area, type Dimensionless concentration.
14 Click to expand the Legend section. From the Position list, choose Lower right.
16 Right-click 1D Plot Group 1 and choose Rename.
17 In the Rename 1D Plot Group dialog box, type Dimensionless concentration in

18 Click OK.
14 |
Dimensionless concentration 1
1 Right-click Dimensionless concentration and choose Duplicate.
3 In the Title text area, type Dimensionless charge density.
4 Locate the Legend section. From the Position list, choose Upper right.
5 In the Model Builder window, expand the Dimensionless concentration 1 node, then
click Line Graph 1.

7 In the Expression text field, type (cp-cm)/(2*cref).
8 On the Dimensionless concentration 1 toolbar, click Plot.
9 In the Model Builder window, right-click Dimensionless concentration 1 and choose
Rename.
10 In the Rename 1D Plot Group dialog box, type Dimensionless charge density in

11 Click OK.
Dimensionless charge density 1

1 Right-click Dimensionless charge density and choose Duplicate.
3 In the Title text area, type Dimensionless potential.
4 Locate the Legend section. From the Position list, choose Lower right.
5 In the Model Builder window, expand the Dimensionless charge density 1 node, then
click Line Graph 1.

7 In the Expression text field, type phi*Z*F_const/(R_const*T).
8 On the Dimensionless charge density 1 toolbar, click Plot.
9 In the Model Builder window, right-click Dimensionless charge density 1 and choose
Rename.
10 In the Rename 1D Plot Group dialog box, type Dimensionless potential in the
11 Click OK.
15 |
16 |
Galvanic Corrosion with Electrode

Deformation
Introduction
This example models the galvanic corrosion and deformation of a magnesium alloy
(AE44) in contact with mild steel in brine solution. While similar to the Galvanic
Corrosion of a Magnesium Alloy in Contact with Steel example, the present model also
investigates the deformation of the corroding electrode over time.
The example is based on a paper by Deshpande (Ref. 1).
Model Definition
The model geometry is shown in Figure 1. Use one single electrolyte domain. The left
part of the bottom boundary is the surface of the mild steel material, the right part is
the corroding magnesium alloy. Because the alloy corrodes in the model, the right
boundary is displaced downwards in the geometry. Introduce a small height step of
0.1 mm in the negative y direction at the origin in the geometry to ensure that the
topology of the geometry is preserved during the simulation. Let the vertical boundary
of the step belong to the steel surface.
1 |
GALVANIC CORROSION WITH ELECTRODE DEFORMATION
Electrolyte (salt water)
Cathode
(mild steel)
Anode
(magnesium alloy)
x=0
Figure 1: Model geometry.

The electrolyte is well mixed so that a secondary current distribution can be assumed,
solving for the electrolyte potential, l (V), in the domain. Set the electrolyte
conductivity to 5 S/m.
ELECTRODE REACTIONS
Set the equilibrium (corrosion) potentials to the experimental values of -0.58 V(SCE)
and -1.55 V(SCE) for the mild steel and the magnesium alloy surfaces, respectively.
This implies that the mild steel acts as a cathode for this galvanic couple. Use a cathodic
Tafel expression to describe the kinetics of the reaction:
--------
i cat = i 0, cat 10 Acat
where i0,cat = 103 A/m2 is the exchange current density, and Acat = -160 mV (the
Tafel slope).
The overpotential, (SI unit: V), of an electrode reaction is generally defined as
= s l E eq
2 |
where s and l are the potentials in the electrode (metal) and electrolyte,
respectively, and Eeq the equilibrium potential. For the cathode, use an equilibrium
potential, Eeq,cat, of -0.58 V.
The magnesium alloy here is an anode of the galvanic couple, oxidizing magnesium
according to
Mg(s) Mg 2+ (aq) + 2e The alloy consists mainly of magnesium, the oxidation reactions of the other alloying
elements are neglected in this model.
To describe the measured polarization data for this reaction, use a diffusion limited
anodic Tafel expression for the anodic electrode reaction current density, ian (SI unit:
A/m2):
-------
i tafel = i 0, an 10 A an
i lim
i an = -------------------i lim
1 + ---------i tafel
where i0,an = 101 A/m2, Aan = 50 mV, and ilim = 102 A/m2 is a limiting current
density.
This type of expression can be derived from the assumption of a Nernstian diffusion
layer in combination with a first-order dependence of concentration on the kinetics.
The equilibrium potential for this reaction is set to -1.55 V.
The dissolution of magnesium metal causes the electrode boundary to move, with a
velocity in the normal direction, v (SI unit: m/s), according to
i an M
v = ------- ----2F
where M is the mean molar mass (25 g/mol) and the density (1820 kg/m3) of the
magnesium alloy.
Solve the model in a time-dependent study, simulating the corrosion for three days of
immersion in salt water.
3 |

Figure 2 shows the electrode current densities at the beginning and the end of the
simulation. As expected, the highest electrode current densities are found at the
contact point between the two metals.
Figure 2: Electrode current densities at t = 0 and t = 72 h.
4 |
Figure 3 shows the current density and potential distribution in the electrolyte, and the
model geometry, at the beginning of the simulation.
Figure 3: Model geometry, electrolyte potential, and current densities at t = 0.

Figure 4 shows the current density and potential distribution in the electrolyte and the
changed geometry at the end of the simulation. Because the electrode current densities
are highest at the contact point of the metals, the metal dissolution is also maximum
at this point. When compared to Figure 3, the electrolyte potential is quite similar,
which matches the results of Figure 2 with quite similar electrode current densities at
the beginning and the end of the simulation.
5 |
Figure 4: Model geometry, electrolyte potential, and current densities after 72 h.

Use the Corrosion, Secondary interface to set up this model. For the mild steel surface,
which is not deforming, use an Electrolyte-Electrode Boundary Interface node to
model the reduction reaction. For the magnesium alloy surface, use an External
Corroding Electrode node, which sets up both the deformation of the geometry and
the magnesium electrode reaction. Set the two electrode surfaces to the same electric
potential in the metal phase.
Change the boundary condition setting of the default Noncorroding Boundary node
to Zero normal displacement. This imposes pointwise (instead of weak) constraints on
the geometry displacement, and thereby fix the corners of the geometry.
Solve the model using a time-dependent study with automatic remeshing enabled.
6 |
Reference
1. K.B. Deshpande, Validated numerical modelling of galvanic corrosion for couples:
Magnesium alloy (AE44)-mild steel and AE44-aluminium alloy (AA6063) in brine
solution, Corrosion Science, vol. 52, pp 35143522, 2010.

galvanic_corrosion_with_deformation
NEW

MODEL WIZARD

3 Click Add.
4 Click Study.
6 Click Done.
GEOMETRY 1
Create the model geometry as a union of two rectangles.
Rectangle 1 (r1)
3 In the Width text field, type 0.01.
4 In the Height text field, type 0.01.
5 Locate the Position section. In the x text field, type -0.01.
7 |
Rectangle 2 (r2)
3 In the Width text field, type 0.01.
4 In the Height text field, type 0.01+1e-4.
5 Locate the Position section. In the y text field, type -1e-4.
Union 1 (uni1)
1 On the Geometry toolbar, click Booleans and Partitions and choose Union.
2 Select the objects r1 and r2 only.
3 In the Settings window for Union, locate the Union section.
4 Clear the Keep interior boundaries check box.
GLOBAL DEFINITIONS
Parameters
galvanic_corrosion_with_deformation_parameters.txt.
Electrolyte 1
Now start setting up the physics. Start with the electrolyte domain.
3 From the l list, choose User defined. In the associated text field, type 5.
The following steps set up the cathodic reduction reaction.
8 |

Interface.

section.
3 In the Eeq text field, type Eeq_cat.
5 In the i0 text field, type i0_cat.
6 In the Ac text field, type A_cat.
The following steps set up the anodic corrosion reaction and the resulting boundary
movement.

3 In the Settings window for External Corroding Electrode, locate the Active Species
section.
4 Find the Corroding species concentrations subsection. In the Corroding species
concentrations table, enter the following settings:
Mg

3 In the MMg text field, type 0.025[kg/mol].
4 In the Mg text field, type 1820[kg/m^3].
9 |
section.
3 In the Eeq text field, type Eeq_an.
5 In the i0 text field, type i0_an.
6 In the Aa text field, type A_an.
8 In the ilim text field, type ilim_an.
10 In the Mg text field, type 1.
The following applies a stronger constraint (than the default condition) for the planar
non-depositing walls in order to enforce a zero boundary movement in the normal
direction.
Boundary section.
The problem is now ready for solving. Enable automatic remeshing.

STUDY 1

The simulation time is 72 h.
3 In the Times text field, type range(0, 12*3600, 3*24*3600).
4 Select the Relative tolerance check box.
5 In the associated text field, type 0.001.
10 |
6 Click to expand the Study extensions section. Locate the Study Extensions section.
Select the Automatic remeshing check box.

RESULTS

The following reproduces the figures in the Results and Discussion section.
3 Clear the Plot data set edges check box.
4 Right-click Results>Electrolyte Potential (corrsec) and choose Arrow Surface.
5 In the Settings window for Arrow Surface, locate the Coloring and Style section.
6 From the Color list, choose Black.
7 Click Replace Expression in the upper-right corner of the Expression section. From
the menu, choose Model>Component 1>Corrosion, Secondary>corrsec.Ilx,corrsec.Ily Electrolyte current density vector (Material).
8 In the Model Builder window, right-click Electrolyte Potential (corrsec) and choose
Streamline.
9 In the Settings window for Streamline, click Replace Expression in the upper-right
corner of the Expression section. From the menu, choose corrsec.Ilx,corrsec.Ily Electrolyte current density vector (Material).
11 Right-click Electrolyte Potential (corrsec) and choose Line.
12 In the Settings window for Line, locate the Expression section.
13 In the Expression text field, type 1.
14 Locate the Coloring and Style section. From the Coloring list, choose Uniform.
15 From the Color list, choose Black.
17 In the Model Builder window, click Electrolyte Potential (corrsec).
19 From the Time (s) list, choose 0.
11 |
1D Plot Group 2
4 From the Data set list, choose Study 1/Remeshed Solution 1.
5 From the Time selection list, choose First.
6 Select Boundaries 2, 4, and 5 only.
the menu, choose Model>Component 1>Corrosion, Secondary>Electrode

kinetics>corrsec.iloc_er1 - Local current density.
Legends
t=0 h
13 Right-click Results>1D Plot Group 2>Line Graph 1 and choose Duplicate.

15 From the Time selection list, choose Last.
Legends
t=72 h
12 |
Galvanized Nail
Introduction
This tutorial example serves as an introduction to the Corrosion Module and models
the metal oxidation and oxygen reduction current densities on the surface of a
galvanized nail, surrounded by a piece of wet wood, which acts as electrolyte.
The protecting zinc layer on the nail is not fully covering, so that at the tip of the nail
the underlaying iron surface is exposed. First the electrolyte conductivity and the
electrode reaction kinetics are modeled to obtain a secondary current distribution
(concentration variations in the cell are not accounted for), in a second part the oxygen
transport is included to model a tertiary current distribution.
Nail
Atmosphere
Covering Zn surface
Exposed Fe surface
Figure 1: Modeled geometry (2D axisymmetric). The nail surface has two parts: the main
part is protected by zinc, on the tip the underlaying iron is exposed. The top boundary is in
contact with the atmosphere.
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Model Definition
Figure 1 shows the model geometry. Due to the symmetry of the problem the
geometry is made 2D axisymmetric, and consists of one single domain, the electrolyte.
The actual nail is not included in the model geometry as a domain since the metal
electric potential can be considered constant due to the high conductivity of the metal,
in combination with the low expected current densities.
The surface of the nail consists two parts, the zinc covered part, and the tip, where the
zinc has been scratched off to expose the underlaying iron. The top electrolyte
boundary is in contact with the atmosphere, all other boundaries are insulating.
ELECTROLYTE CHARGE TRANSPORT
The currents expected are small in relation to the total amount of charge carrying ions
in the electrolyte. This implies that a constant conductivity can be assumed, use the
Secondary Current Distribution interface to solve for the electrolyte potential, l
(SI unit: V), according to:
i l = l l
il = 0
where il (SI unit: A/m2) is the electrolyte current density vector and l (SI unit: S/
m) is the electrolyte conductivity. Use the default insulating conditions for all
boundaries except the nail surface:
n il = 0
Where n is the normal vector, pointing out of the domain.
METAL OXIDATION REACTIONS
The nail is not included as a domain in the model, therefore use the Electrolyte Electrode Boundary Interface boundary node to model the nail surface, and set the
potential of the metal phase s (SI unit: V) to 0 on this boundary.
The Electrolyte-Electrode Boundary Interface sets the boundary condition for the
electrolyte potential to
n il =
iloc, m
m
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where iloc,m (SI unit: A/m2) are the local individual electrode reaction current
densities.
Add Electrode Reaction nodes to the Electrolyte-Electrode Boundary Interface to
define the individual electrode reactions.
On the zinc surface, oxidation occurs according to
Zn ( s ) Zn
2+
+ 2e
E eq, Zn = 0.76 3 V
whereas on the exposed iron surface, iron is oxidized according to

Fe ( s ) Fe
2+
+ 2e
E eq, Fe = 0.409 V
where Eeq,m (SI unit: V) is the equilibrium potential of the electrode reaction.
Use an anodic Tafel expression to model these reactions, this sets the local current
density to
i loc, m = i 0, m 10
------mAm
for each reaction, where i0,m is the exchange current density, Am (SI unit: V) is the
Tafel slope and the overpotential (SI unit: V) is calculated from
= s l E eq,m
(1)
OXYGEN REDUCTION AND OXYGEN TRANSPORT
Oxygen is reduced on both the zinc and iron electrode surfaces according to
+
O 2 + 4H + 4e 2H 2 O
E eq, O2 = 1.229 V
Use a cathodic Tafel expression to model this reaction, which sets the local current
density to
i loc, O2 = i 0, O2 10
O2
-------A O2
Since zinc and iron have different catalytic properties for oxygen reduction, use
different parameter values for AO2 and i0,O2 on the different surfaces.
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It is often good modeling practice to solve for a secondary current distribution first,
before adding mass transfer. Once one has obtained a satisfactory solution for the
secondary problem, one can proceed to increase the complexity of the model.
For this model, solve for the Secondary Current Distribution interface first then add a
Transport of Diluted Species interface to model oxygen transport by Fickian diffusion:
N = Dc
N = 0
where c (SI unit: mol/m3) is the oxygen concentration, N (SI unit: mol/(m2s)) the
flux vector, and D (SI unit: m2/s) the diffusion coefficient.
Use the default No Flux conditions for the right and bottom boundary:
nN = 0
The top boundary is in contact with the surrounding air, set the concentration to a
fixed value on this boundary.
c = c ref
On the nail surface, couple the oxygen flux over the boundary to the oxygen reduction
current density by using an Electrode-Electrolyte Interface Coupling boundary
condition. This sets the flux to be proportional to the electrode current density
according to Faradays law:
i loc, O2
n N = -------------------nF
where F is Faradays constant (96,485 C/mol), the stoichiometric coefficient for
oxygen in the reduction reaction and n the number of electrons in the reaction.
The sign convention for is that it should be negative for reactants and positive for
products in a reduction reaction (A reaction with the electrons participating as
reactants). n is always positive. Set to -1 and n to 4 for this model.
When including oxygen transport in the model, also change the electrode kinetics for
the oxygen reduction reaction to the following expression:
O2
--------
A
c
i loc, O2 = -------- i
10 O2
c ref
0, O2
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Figure 2 shows the electrode reaction current densities for the secondary current
distribution model. Zinc oxidation dominates on the zinc surface, with a maximum at
the point between the iron and zinc surfaces. Oxygen reduction dominates on the iron
surface.
Figure 2: Individual electrode reaction current densities.
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Figure 3 shows the concentration of oxygen for the second study step when oxygen
transport has been included in the model, for the tertiary current distribution. The
concentration of oxygen decreases towards the tip of the nail.
Figure 3: Oxygen concentration in the electrolyte.
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Figure 4 shows a comparison of the iron oxidation current densities between the
secondary and tertiary current distribution models. The current density decreases
slightly when including oxygen transport in the model.
Figure 4: Iron oxidation current densities. Effect of including oxygen transport in the
model.

The initial value for the electrolyte potential is set to Eeq,Zn to reduce the
computational time. It is generally good practice to set initial values for the potentials,
if they can be derived.
In this case it was assumed that the zinc reaction would be governing due to the larger
area of the zinc surface, and the faster reaction kinetics of the zinc reaction in relation
to the oxygen reduction reaction. Assuming zero overpotential for the zinc reaction,
and using Equation 1, the initial value for the electrolyte potential can be calculated
according to:
l, 0 = s E eq, Zn = E eq, Zn
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galvanized_nail
NEW

MODEL WIZARD
1 In the Model Wizard window, make use of symmetry to model the nail using a 2D
axisymmetric geometry.
2 click 2D Axisymmetric.
Create the model in two steps: First, model a Secondary Current Distribution and
solve for it in a Stationary study. Then, add more physics in a later step to include
oxygen transport, and solve that model in a second study step.
(siec).
4 Click Add.
5 Click Study.
7 Click Done.
GLOBAL DEFINITIONS
Parameters
galvanized_nail_parameters.txt.
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GEOMETRY 1
Draw the geometry as the difference between a square (the electrolyte) and a polygon
(the nail). Set the length unit so that the default unit is millimeters when specifying the
polygon.
1 In the Model Builder window, under Component 1 (comp1) click Geometry 1.
2 In the Settings window for Geometry, locate the Units section.
3 From the Length unit list, choose mm.
Square 1 (sq1)
1 On the Geometry toolbar, click Primitives and choose Square.
2 In the Settings window for Square, locate the Size section.
3 In the Side length text field, type 1.5*L_nail.
4 Locate the Position section. In the z text field, type -1.5*L_nail.
Polygon 1 (pol1)
1 On the Geometry toolbar, click Primitives and choose Polygon.
2 In the Settings window for Polygon, locate the Coordinates section.
3 From the Data source list, choose Table.
r (mm)
z (mm)
-1
-1
5-L_nail
-L_nail
5 Right-click Component 1 (comp1)>Geometry 1>Polygon 1 (pol1) and choose Build

Selected.
Difference 1 (dif1)
2 Select the object sq1 only.
5 Select the object pol1 only.
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The finished geometry should now look like this:
DEFINITIONS
Create explicit selections of the zinc and iron parts of the nail surface. Then create a
selection for the whole nail surface by using a union. You will use the selections later
on when specifying the physics, setting up the mesh, and plotting the results.
Explicit 1
1 On the Definitions toolbar, click Explicit.
2 In the Settings window for Explicit, locate the Input Entities section.
4 Select Boundaries 46 only.
5 Right-click Component 1 (comp1)>Definitions>Explicit 1 and choose Rename.
6 In the Rename Explicit dialog box, type Zinc surface in the New label text field.
7 Click OK.
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Explicit 2
6 In the Rename Explicit dialog box, type Iron surface in the New label text field.
7 Click OK.
Union 1
2 In the Settings window for Union, locate the Geometric Entity Level section.
3 From the Level list, choose Boundary.
5 In the Add dialog box, In the Selections to add list, choose Zinc surface and Iron
surface.
6 Click OK.
7 Right-click Component 1 (comp1)>Definitions>Union 1 and choose Rename.
8 In the Rename Union dialog box, type Nail surface in the New label text field.
9 Click OK.
Electrolyte 1
Now specify the physics for the secondary current distribution problem. Start with the
electrolyte conductivity.
Model the two parts of the nail surface using Electrolyte-Electrode Boundary
Interfaces, onto which Electrode Reactions can be added. Keep the electric potential
default value of zero (ground) on both parts of the surface. This is the potential of the
metal in the nail.

Interface.
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3 From the Selection list, choose Zinc surface.
Set up the parameters for the two electrode reactions on the zinc surface.

section.
3 In the Eeq text field, type Eeq_Zn.
5 In the i0 text field, type i0_Zn.
6 In the Aa text field, type A_Zn.
7 Right-click Component 1 (comp1)>Secondary Current Distribution
(siec)>Electrolyte-Electrode Boundary Interface 1>Electrode Reaction 1 and choose
Rename.
8 In the Rename Electrode Reaction dialog box, type Zinc reaction in the New label
text field.
9 Click OK.
section.
3 In the Eeq text field, type Eeq_O2.
5 In the i0 text field, type i0_O2_on_Zn.
6 In the Ac text field, type A_O2_on_Zn.
(siec)>Electrolyte-Electrode Boundary Interface 1>Electrode Reaction 2 and choose
Rename.
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8 In the Rename Electrode Reaction dialog box, type Oxygen reaction in the New
label text field.
9 Click OK.
Use the duplicate functionality to make a copy of the zinc Electrolyte-Electrode

Boundary Interface and apply it to the iron part of the nail surface. Modify the kinetics
parameters for this surface.

Distribution (siec) right-click Electrolyte-Electrode Boundary Interface 1 and choose
Duplicate.
3 From the Selection list, choose Iron surface.
Zinc reaction
node, then click Zinc reaction.

section.
4 Locate the Electrode Kinetics section. In the i0 text field, type i0_Fe.
(siec)>Electrolyte-Electrode Boundary Interface 2>Zinc reaction and choose Rename.
7 In the Rename Electrode Reaction dialog box, type Iron Reaction in the New label
text field.
8 Click OK.
Oxygen reaction
2 In the i0 text field, type i0_O2_on_Fe.
3 In the Ac text field, type A_O2_on_Fe.
Initial Values 1
Provide an initial guess for the electrolyte potential to reduce computational time.
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MESH 1
Create a mesh with higher resolution at the electrode boundaries. Refine the mesh at
the intersection point between the zinc and iron surfaces further.
Free Triangular 1
Size 1
4 From the Selection list, choose Nail surface.
Size 2
1 Right-click Free Triangular 1 and choose Size.
3 From the Geometric entity level list, choose Point.
box.
7 In the associated text field, type 0.01.
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Your finished mesh should now look like this:
STUDY 1
Now solve the secondary current distribution model.

On the Home toolbar, click Compute.
RESULTS
Plot the electrode reaction currents in the following way:
1D Plot Group 3

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7 In the Expression text field, type z.
Legends
Zinc oxidation


18 Locate the Legends section. Select the Show legends check box.
Legends
Iron oxidation

23 From the Selection list, choose Nail surface.

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Legends
Oxygen reduction

32 In the Settings window for 1D Plot Group, click to expand the Legend section.
The figure should now look like Figure 2.

COMPONENT 1 (COMP1)
Now expand the model by adding oxygen transport through the electrolyte, also
modify the oxygen reduction kinetics expressions to be concentration dependent.
Solve the model using two study steps.
ADD PHYSICS
1 On the Home toolbar, click Add Physics to open the Add Physics window.
2 Go to the Add Physics window.
Add the Transport of Diluted Species physics to model oxygen transport by Fickian
diffusion.
3 In the Add physics tree, select Chemical Species Transport>Transport of Diluted Species
(tds).
4 Click Add to Component in the window toolbar.
The electrolyte is quiescent so there is no need to model convection. Migration is not

used either in this model. (Note that if migration and convection is enabled, Transport
of Diluted Species models the full Nernst-Planck equations.)
Species (tds).
Mechanisms section.
Set the diffusion coefficient in the electrolyte.
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Species (tds) click Transport Properties 1.
3 In the Dc text field, type D_O2.
Concentration 1
Use a Concentration boundary condition on the top boundary to fix the

concentration along this boundary, set the initial value for the concentration to the
same value.
4 Select the Species c check box.
5 In the c0,c text field, type c_O2_ref.
Initial Values 1
3 In the c text field, type c_O2_ref.
Now couple oxygen flux at the electrode boundary to the electrode reaction currents
in the Secondary Current Distribution physics by using Electrode-Electrolyte
Interface coupling features. This will specify an oxygen flux according to Faraday's law.

Coupling.
2 In the Settings window for Electrode-Electrolyte Interface Coupling, locate the

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The oxygen molecules are reactants when the oxygen reaction is written as a
reduction reaction, if one writes the reaction using four electrons the stoichiometric
number for oxygen is -1.

Species (tds) right-click Electrode-Electrolyte Interface Coupling 1 and choose
Duplicate.

ROOT
Also couple the oxygen electrode reaction currents to the oxygen concentration by
including the concentration variable in the exchange current density expressions.
On the Physics toolbar, click Transport of Diluted Species (tds) and choose Secondary
Current Distribution (siec).
Oxygen reaction
Distribution (siec)>Electrolyte-Electrode Boundary Interface 1 click Oxygen reaction.
3 In the i0 text field, type i0_O2_on_Zn*c/c_O2_ref.
4 In the Model Builder window, click Oxygen reaction.
6 In the i0 text field, type i0_O2_on_Fe*c/c_O2_ref.
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STUDY 1
Step 1: Stationary
2 In the Settings window for Stationary, locate the Physics and Variables Selection
section.
Physics interface
Solve for
Transport of Diluted Species
Discretization
physics
It is general good practice to solve this type of problems by solving for the potentials
first, and then the fully coupled problem. Disable Transport of Diluted Species from
the first step, and add a second step to solve for the full problem.
4 On the Study toolbar, click Study Steps and choose Stationary>Stationary.
RESULTS
Plot the concentration profile on the revolved geometry, created from the 2D
axisymmetric geometry, in the following way:
3D Plot Group 4
Surface.
of the Expression section. From the menu, choose Model>Component 1>Transport of

Diluted Species>c - Concentration.

Finally, analyze the impact of introducing the oxygen concentration to the model by
comparing the iron oxidation current densities from the two different study steps
(Solution 1 and Solution 2). Since the first study step (Solution 2) does not solve for
the oxygen concentration it is kept constant to its initial value.
1D Plot Group 5
20 |
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the menu, choose siec.iloc_er1 - Local current density.

8 Locate the Data section. From the Data set list, choose Study 1/Solution 1.
Legends
Tertiary current distribution (with oxygen transport limitation)

14 From the Data set list, choose Study 1/Solution Store 1.
Legends
Secondary current distribution (no oxygen transport limitation)

17 In the Settings window for 1D Plot Group, locate the Legend section.
20 In the Title text area, type Iron Oxidation Current Density.
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Localized Corrosion
Introduction
A metallic alloy with two constituent phases of different equilibrium potentials is
susceptible to corrosion when it is exposed to an electrolyte solution. The constituent
phase with a lower potential acts as an anode and preferentially corrodes whereas the
other phase with a positive potential acts as a cathode. In order to capture the
preferential dissolution of the anode phase, an explicit tracking of the dissolving
interface is required which makes it a moving boundary problem.
In this model formulation, the electrode kinetics at both the anode and cathode phases
are implemented in a unique way in terms of the level set function. Similarly,
movement of the anode surface is implemented using the level set function and the
in-built moving mesh formulation.
This model example simulates the cross-sectional microstructure evolution during a
corrosion event and is based on a paper by Deshpande (Ref. 1).
Model Definition
The model geometry considered in this example is shown in Figure 1 along with a
representative cross-sectional microstructure comprising of the alpha and beta phases
exposed to the electrolyte solution. The cross-sectional microstructure shown in
Figure 1 is represented in terms of the level set function using an interpolation
function called micro. It has width of 200 m and depth of 25 m and the
maximum depth of the alpha phase is 10 m. The alpha and beta phases at the
electrode boundary are identified when the interpolated level set function, micro, has
value of 0 and 1, respectively.
Use the Corrosion, Secondary interface to solve for the electrolyte potential, fl(V),
over the electrolyte domain according to:
i l = l l
il = 0
m) is the electrolyte conductivity which is assumed to be a constant of 2.5 S/m.
1 |
LOCALIZED CORROSION
Use the default Insulation condition for all boundaries except the electrode surface:
n il = 0
where n is the normal vector, pointing out of the domain.
Electrolyte (salt water)
alpha phase
beta phase
Figure 1: Model geometry along with cross-sectional microstructure comprising of the

alpha and beta phases and exposed to the electrolyte solution.
Use the External Corroding Electrode boundary condition at the electrode surface
which sets the boundary condition for the electrolyte potential to
n il =
iloc, m + idl
m
where iloc,m (SI unit: A/m2) is the local individual electrode reaction current density.
The dissolution at the electrode surface with a velocity in the normal direction is
evaluated according to
n
2 |
LOCALIZED CORROSION
x
=
t
R dep, i, m M i
----------------------------i
i
where Mi is the molar mass (23.98 g/mol) and i is the density (1770 kg/m3) of the
corroding species i.
Rdep,i,m is evaluated using the following equation:
dep, i, m i loc,m
R dep, i, m = ----------------------------------nm F
where udep,i,m is the stoichiometric coefficient and nmis the number of electrons
participating in the electrode reaction.
Use a User Defined electrode kinetics expression type to model the electrode reaction
at the alpha phase on the electrode surface.
Set the local current density for the alpha phase at the electrode surface to
i alpha = f ( s, ext l ) ( 1 micro ( x, y ) )
(1)
A relationship between the local current density and the electrolyte potential for the
alpha phase at the electrode surface is incorporated in the model using a piecewise
cubic interpolation function for the experimental polarization data as shown in
Figure 2.
Figure 2: Anodic polarization data for the alpha phase.
3 |
LOCALIZED CORROSION
It should be noted that the expression, 1 - micro(x,y), ensures that the local current
density is applied only at the alpha phase on the electrode surface.
Similarly, set the electrode kinetics to model the electrode reaction at the beta phase
on the electrode surface using the following expression for the local current density:
i beta = f ( s, ext l ) micro ( x, y )
A relationship between the local current density and the electrolyte potential for the
beta phase at the electrode surface is incorporated in the model using a piecewise cubic
interpolation function for the experimental polarization data as shown in Figure 3. The
level set function micro(x,y) ensures that the local current density is applied only at
the beta phase on the electrode surface.
Figure 3: Cathodic polarization data for the alpha phase.

In this model formulation, it is assumed that the anodic dissolution reaction takes place
at the alpha phase surface and the cathodic hydrogen evolution reaction, where there
is no material loss, takes place at the beta phase surface. Hence, the alpha phase surface
is considered to be moving (dissolving) whereas the beta phase surface is considered
to remain intact. This is achieved in the model by setting the value of stoichiometric
coefficient to 1 and 0 for the alpha phase and beta phase electrode reactions,
respectively.
4 |
LOCALIZED CORROSION
The mesh used in the model is shown in Figure 4.
Figure 4: The mesh used in the model.

Figure 5 shows a surface plot of the electrolyte potential at time t = 2.11105 s. It can
be seen that the alpha phase, being electrochemically more active, is dissolving from
the electrode surface whereas the beta phase, being relatively nobler, remains intact.
With the preferential dissolution of the alpha phase, the underneath beta phase gets
exposed to the electrolyte solution resulting in an increase in the surface beta phase
fraction at the electrode surface. The computations are stopped when the surface beta
phase fraction reaches a value of 0.95 which happens at time t = 2.11105 s in this
case. It can be seen in Figure 5 that most of the alpha phase shown in Figure 1 is
dissolved in the electrolyte solution at time t = 2.11105 s.
5 |
LOCALIZED CORROSION
alpha phase
beta phase
Figure 5: A surface plot of the electrolyte potential at time t = 2.11105 s where the
dissolved alpha phase and intact beta phase are highlighted.
The surface beta phase fraction at the electrode surface is evaluated using the following
equation:
micro ( x, y ) d
Surface beta phase fraction =
---------------------------------------------------------------------------------------------------------
micro ( x, y ) d + ( 1 m icro ( x, y ) ) d
It can be seen in Figure 6 that the surface beta phase fraction is around 0.2 at an initial
stage and it increases with time due to preferential dissolution of the alpha phase from
the electrode surface exposing the underneath beta phase. The change in surface beta
phase fraction with time is considerably gradual until time t = 1.4105 s, however, it
becomes more rapid for a higher value of surface beta phase fraction.
6 |
LOCALIZED CORROSION
Figure 6: The change in the surface beta phase fraction with time.
The average anode current density at the electrode surface is evaluated using the
following equation:
ialpha d
Average anode current density =
-------------------------------------------------------
( 1 m icro ( x, y ) ) d
where ialpha defined in Equation 1 is used.

Figure 7 shows the change in the average anode current density with time where it is
found to be gradual for the lower surface beta phase fraction, similar to the change in
surface beta phase fraction. The average anode current density increases very rapidly
for the higher surface beta phase fraction which is attributed to a higher cathode to
anode area ratio at the electrode surface.
7 |
LOCALIZED CORROSION
Figure 7: The change in the average anode current density with time.

The Corrosion, Secondary interface, which has in-built moving mesh formulation, is
used in this model.
A cross-sectional microstructure comprising of the alpha and beta phases is prescribed
in the model using a level set type of function through interpolation.
The electrode kinetics is incorporated in the model using a piecewise cubic
interpolation function for the experimental polarization data obtained separately for
the two phases.
A time dependent study with current distribution initialization is used to solve the
model. The use of stop condition to stop the solver is demonstrated here.
A free triangular mesh is used for meshing, with a finer resolution at the electrode
surface.
The model also demonstrates utility of an integration operator during computations as
well as post processing of results.
8 |
LOCALIZED CORROSION
Reference
1. K.B. Deshpande, Numerical modeling of micro-galvanic corrosion,
Electrochimica Acta, vol. 56, pp 17371745, 2011.

localized_corrosion
NEW

MODEL WIZARD

3 Click Add.
4 Click Study.
6 Click Done.
GEOMETRY 1
Now, create the model geometry as a rectangle.
Rectangle 1 (r1)
3 In the Width text field, type 200e-6.
4 In the Height text field, type 100e-6.
5 Locate the Position section. In the x text field, type -100e-6.
9 |
LOCALIZED CORROSION
Now, create a predefined cross-sectional microstructure, which gets exposed to the

electrolyte solution at the bottom boundary of the domain, using an interpolation
function. Please note that the interpolation function creates the same microstructure
as reported in Ref. 1.
GLOBAL DEFINITIONS
1 On the Home toolbar, click Functions and choose Global>Interpolation.
4 Click Browse.
localized_corrosion_microstructure.txt.
6 Click Import.
7 Find the Functions subsection. In the table, enter the following settings:
Function name
Position in file
micro
8 Locate the Units section. In the Arguments text field, type m.

9 In the Function text field, type 1.
10 Right-click Global Definitions>Interpolation 1 (int1) and choose Create Plot.
RESULTS
2D Plot Group 1
1 In the Model Builder window, under Results click 2D Plot Group 1.
3 From the View list, choose View 1.
4 In the Model Builder window, expand the 2D Plot Group 1 node.
5 In the Model Builder window, expand the Results>2D Plot Group 1>Surface 1 node.
6 Right-click Height Expression 1 and choose Disable.
7 Right-click 2D Plot Group 1 and choose Rename.
8 In the Rename 2D Plot Group dialog box, type 2D Plot Group : Cross-sectional
microstructure in the New label text field.
10 |
LOCALIZED CORROSION
9 Click OK.
The cross-sectional microstructure should now look like Figure 1.

GLOBAL DEFINITIONS
Load the model parameters.
Parameters
localized_corrosion_parameters.txt.
Now, create interpolation functions for the alpha phase and beta phase to prescribe a
piecewise cubic relationship between the local current density and the electrolyte
potential obtained from the experimental polarization data (Ref. 1).
DEFINITIONS
3 In the Function name text field, type i_alpha.
localized_corrosion_i_alpha.txt.

The interpolation plot for the alpha phase should look like Figure 2.
11 |
LOCALIZED CORROSION

3 In the Function name text field, type i_beta.
localized_corrosion_i_beta.txt.

The interpolation plot for the beta phase should look like Figure 3.
Define an integration operator which would enable integration of several model
variables to be used later in representing the model results.
2 In the Settings window for Integration, locate the Source Selection section.
Now, load the model variables which are used to evaluate the average surface beta
phase fraction and the average anode current density.
Variables 1
1 On the Definitions toolbar, click Local Variables.
localized_corrosion_variables.txt.
Now set up the physics for the current distribution.
Electrolyte 1
12 |
LOCALIZED CORROSION

Now, prescribe the electrode kinetics for both the alpha phase and beta phase at the
electrode boundary surface making use of the level set type interpolated function.

3 In the Settings window for External Corroding Electrode, locate the Active Species
section.
4 Find the Corroding species concentrations subsection. Clear the Solve for corroding
species concentrations check box.

3 In the Mccorr text field, type M.
4 In the ccorr text field, type rho.
(i_alpha(-phil))*(1-micro(x,y)).
4 Locate the Stoichiometric Coefficients section. In the nm text field, type z_charge.
5 In the ccorr text field, type 1.
(i_beta(-phil))*micro(x,y).
13 |
LOCALIZED CORROSION
Boundary section.
MESH 1
Now, mesh a computational domain with a finer resolution at the electrode surface.
Free Triangular 1
Free Triangular.
Size 1
3 From the Geometric entity level list, choose Domain.
5 Locate the Element Size section. From the Predefined list, choose Coarse.
Size 2
1 Right-click Free Triangular 1 and choose Size.
The mesh should look like Figure 4.

STUDY 1
Finally, set the time steps and a stop condition for time dependent solver.

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LOCALIZED CORROSION
3 In the Times text field, type range(0,60,3600*24*3).
Solution 1
2 In the Model Builder window, expand the Solution 1 node, then click Time-Dependent
Solver 1.
3 In the Settings window for Time-Dependent Solver, click to expand the Output
section.
4 From the Times to store list, choose Steps taken by solver.
5 Right-click Study 1>Solver Configurations>Solution 1>Time-Dependent Solver 1 and
choose Stop Condition.

6 In the Settings window for Stop Condition, locate the Stop Expressions section.
7 Click Add.
Stop expression
Stop if
Active
Description
comp1.beta_phase_fra
ction>0.95
true
Stop
expressio
n 1
9 Locate the Output at Stop section. From the Add solution list, choose Steps before
and after stop.
The model is now ready to be solved.

RESULTS

A 2D plot of the electrolyte potential and the deformation is created by default.
Change the frame of the data set edges to Geometry in order to show the outline of
the original (non-deformed) geometry in the figure.
2 From the Frame list, choose Geometry (Xg, Yg, Zg).
Now, plot the change in the average surface beta phase fraction with time.
15 |
LOCALIZED CORROSION
1D Plot Group 3
2 In the Settings window for 1D Plot Group, click to expand the Title section.
3 From the Title type list, choose Manual.
4 In the Title text area, type Change in surface beta phase fraction with
time.
6 In the associated text field, type Time, s.
8 In the associated text field, type Surface beta phase fraction.
9 On the 1D Plot Group 3 toolbar, click Global.
Expression
Unit
beta_phase_fraction
Description
12 Click to expand the Legends section. Clear the Show legends check box.
14 In the Rename 1D Plot Group dialog box, type 1D Plot Group : Surface beta
phase fraction evolution in the New label text field.
15 Click OK.
Finally, plot the change in the average anode current density with time.
1D Plot Group : Surface beta phase fraction evolution 1

1 Right-click 1D Plot Group : Surface beta phase fraction evolution and choose Duplicate.
3 In the Title text area, type Change in average anode current density with
time.
4 Locate the Plot Settings section. In the y-axis label text field, type Average anode
current density, A/m2.
5 In the Model Builder window, expand the 1D Plot Group : Surface beta phase fraction
evolution 1 node, then click Global 1.
16 |
LOCALIZED CORROSION

Expression
Unit
i_alpha_phase/
alpha_phase
Description
8 In the Model Builder window, right-click 1D Plot Group : Surface beta phase fraction
evolution 1 and choose Rename.
9 In the Rename 1D Plot Group dialog box, type 1D Plot Group : Average anode
current density evolution in the New label text field.
10 Click OK.
17 |
LOCALIZED CORROSION
18 |
LOCALIZED CORROSION
Corrosion Protection of an Oil

Platform Using Sacrificial Anodes
Introduction
Steel structures immersed in seawater can be protected from corrosion through
cathodic protection. This protection can be achieved by an impressed external current
or by using sacrificial anodes. The use of sacrificial anodes is often preferred due to its
simplicity.
The principle for cathodic protection using sacrificial anodes is quite simple: the steel
structure is electronically connected to a less noble metal, for example aluminum,
which causes the sacrificial anode to be anodically polarized and the steel structure to
be cathodically polarized when the electrodes are immersed in seawater. The anodes
are dissolved through anodic dissolution of the metal while oxygen reduction takes
place at the surface of the steel structure. The supply of oxygen is what often limits the
current density for oxygen reduction, which means that a limiting current of an almost
constant value over a few hundreds of millivolts in potential is obtained at the surface
of the steel structure.
Potential, V
Iron
dissolution
Current, I
Metal
dissolution
Iron
dissolution
Oxygen
reduction
Icorr
Oxygen
Hydrogen reduction
evolution
Potential, V
Metal
dissolution
Hydrogen
evolution
log(lcorr)
log(l)
Figure 1: Polarization behavior of the sacrificial anodes (blue) and steel surface (red).
Figure 1 above shows the schematic polarization of the sacrificial anodes and of the
oxygen reduction reaction at the surface of the steel structure. The red curve
1 |
CORROSION PROTECTION OF AN OIL PLATFORM USING SACRIFICIAL ANODES
represents the polarization of the steel surface while the blue curve is the polarization
of the sacrificial anode. On the left, the currents at the steel structure (red) and at the
sacrificial anodes (blue) are plotted as functions of the electric potential measured
relative to a common reference. The plot to the right shows the electric potential as a
function of the logarithm of the absolute value of the current. As shown in the left
graphs, oxygen reduction is achieved at the steel surface along the range of the
cathodic limiting current represented by the flat horizontal part of the red curve. In
the right plot, the vertical part of the red curve represents oxygen reduction. The
system operates at the point where the cathodic current (red) is equal in size (but
opposite in sign) as the anodic current.
The shape of the blue curve changes depending on the number and design of the
anodes in the system, and the designer of the system needs to ensure that the different
parts of the steel structure are well within the corrosion protected range of potentials
(the flat part of the red cathodic curve); otherwise the structure is not fully
protected and may start to corrode. The width of the oxygen reduction part of the
curve is a few hundred millivolts. In addition, the anodes have to be able to deliver the
required potential to keep the given current.
The first step in the design of a cathodic protection system is therefore to investigate
the potential of the steel structure assuming a constant cathodic current (oxygen
reduction). The potential has to be well within the required range where oxygen
reduction protects the structure and also avoiding hydrogen evolution, which may
eventually cause hydrogen embrittlement.
Model Definition
Figure 2 and Figure 3 show the model geometry. The sacrificial anodes are placed
relatively close to the oil platform. The radius of the inner cylinder is chosen so that
the main part of the charge transport occurs within this cylinder. The outer cylinder is
2 |
modeled as an infinite Element Domain, which rescales the equations to represent an

approximately thousand times larger cylinder.
Infinite Element
Domain
Oil platform structure

polarized cathodically
Cylindrical sacrificial
anodes
Cylinder fates representing
outer boundaries
Figure 2: Model geometry.
Cylindrical sacrificial
anodes
Oil platform structure
polarized cathodically
Figure 3: Close-up view of the cylindrical sacrificial anodes and the oil platform structure.
3 |
At the sacrificial anode surfaces, a constant potential is set assuming a relatively fast
kinetics. This assumption implies that a very small change in surface overpotential leads
to a very large change in current density and it is therefore reasonable to set a constant
potential. At the cathode surface, it is assumed that oxygen reduction takes place at a
limiting current density, limited to the rate of transport of dissolved oxygen to the
surface. This yields a constant normal current density boundary condition at the steel
surfaces of the structure. All other boundaries are insulated boundaries.
In seawater, the composition is assumed to vary to a very small extent and diffusion of
the ions that carry the current is negligible compared to the contribution from
migration of these ions in the electric field. This assumption, together with the
boundary conditions, allows using a primary current density distribution analysis on
the system where only the influence of ohmic effects in the given geometry are taken
into account. The model can be easily extended to secondary current density
distribution analysis in order to add the kinetics of the electrode reactions in a second
stage. (A tertiary current density distribution analysis that also accounts for the
transport of charged species is also possible in the Corrosion Module, although this
would require the use of a different physics interface.)

Figure 4 shows the potential in the electrolyte at the surfaces on the steel structure and
on the anodes. The potential on the steel structure surface varies several hundreds of
millivolts, depending on position. The further the distance from an anode the lower
the potential, an expected result since the current in the electrolyte flows from the
anodes to the cathode.
One can relate the electrolyte potential, l , to the electrode potential shown in
Figure 1 by considering a reference electrode placed in the electrolyte in close vicinity
to the steel surface. The electric potential of a reference electrode, s,ref , is
s, ref = E eq, ref + l
The electric potential of the steel surface, s , is constant due to the high conductivity
of the metal, and the potential of the steel surface versus the reference electrode
becomes
E vs ref = s s, ref = s E eq, ref l
(1)
Combining Equation 1 with Figure 1 shows that the parts of the steel surface with the
lowest values for l are the parts least protected.
4 |
Figure 5 shows a close-up of one of the structure legs. The inside bottom part of the
leg has the lowest potential, indicating that this part of the structure is the part most
susceptible to corrosion.
Figure 4: Electrolyte potential on the sacrificial anodes and on the platform.
5 |
Figure 5: Electrolyte potential on one of the legs of the platform structure.

Finally, Figure 6 shows the current densities on the anodes, which are of interest
because their magnitudes are directly proportional to the consumption rate of the
anode metal. The highest current density for the anodes is about four times the lowest
current density.
6 |
Figure 6: Current densities on the anodes.

oil_platform
NEW

MODEL WIZARD

2 In the Select physics tree, select Electrochemistry>Primary Current Distribution (siec).
3 Click Add.
4 Click Study.
7 |

6 Click Done.
GLOBAL DEFINITIONS
Add some parameters for use in the model.
Parameters
Name
Expression
Value
Description
sigma_sea
5[S/m]
5 S/m
Seawater conductivity
i_oxygen
-0.1[A/m^2]
-0.1 A/m
Limiting current for

oxygen reduction at
cathode
GEOMETRY 1
Import the geometry of the oil platform from a geometry file.
Import 1 (imp1)
3 Click Browse.
oil_platform.mphbin.
5 Click Import.
box.
This generates selections of the imported geometry, which you will use later on
when setting up the physics on the boundaries (the anodes and cathodes).
7 Right-click Component 1 (comp1)>Geometry 1>Import 1 (imp1) and choose Build
Selected.
Add a surrounding cylinder around the platform.
Cylinder 1 (cyl1)
1 On the Geometry toolbar, click Cylinder.
2 In the Settings window for Cylinder, locate the Size and Shape section.
8 |

4 In the Height text field, type 92.
Add a second cylinder with a larger radius, this cylinder will be used to define an
Infinite Element Domain.
Cylinder 2 (cyl2)
1 Right-click Component 1 (comp1)>Geometry 1>Cylinder 1 (cyl1) and choose
Duplicate.
2 In the Settings window for Cylinder, locate the Size and Shape section.
4 Click the Wireframe Rendering button on the Graphics toolbar.
Create the final geometry as the difference between the cylinders and the imported oil
platform structure.
Difference 1 (dif1)
2 Select the objects cyl1 and cyl2 only.
9 |
5 Use the Select Box toolbar button to select the imported platform geometry.
10 |
6 Right-click Component 1 (comp1)>Geometry 1>Difference 1 (dif1) and choose Build

Selected.
The finalized geometry should now look like that in the figure below.
DEFINITIONS
Now set the outer cylinder to be an Infinite Element Domain, this will scale the
equations of the outer cylinder to have an approximately 1000 times larger radius.
Infinite Element Domain 1 (ie1)

1 On the Definitions toolbar, click Infinite Element Domain.
3 In the Settings window for Infinite Element Domain, locate the Geometry section.
4 From the Type list, choose Cylindrical.
Create a selection for the anodes by using a difference between selections that were
created (by enabling Create selections) by the geometry node.
Difference 1
1 On the Definitions toolbar, click Difference.
2 In the Settings window for Difference, locate the Geometric Entity Level section.
11 |
5 In the Add dialog box, select Import 1 in the Selections to add list.
6 In the Selections to add list, select Import 1.
7 Click OK.
8 In the Settings window for Difference, locate the Input Entities section.
9 Under Selections to subtract, click Add.
10 In the Add dialog box, select Import 1(41) in the Selections to subtract list.
11 In the Selections to subtract list, select Import 1(41).
12 Click OK.
13 Right-click Component 1 (comp1)>Definitions>Difference 1 and choose Rename.
14 In the Rename Difference dialog box, type Anodes in the New label text field.
15 Click OK.
MATERIALS
Set the sea water conductivity in the Materials node.
Material 1 (mat1)
1 In the Model Builder window, under Component 1 (comp1) right-click Materials and
choose Blank Material.

2 In the Settings window for Material, click to expand the Material properties section.
3 Click to collapse the Material properties section. Locate the Material Contents section.
In the table, enter the following settings:

Property
Electrolyte conductivity
Name
Value
Unit
Property group
sigmal
sigma_
sea
S/m
Electrolyte conductivity
PRIMARY CURRENT DISTRIBUTION (SIEC)
Now add boundary conditions for the anodes and the cathode.
Electrolyte Current Density 1

1 On the Physics toolbar, click Boundaries and choose Electrolyte Current Density.
2 In the Settings window for Electrolyte Current Density, locate the Boundary
Selection section.
3 From the Selection list, choose Import 1.
4 Locate the Electrolyte Current Density section. In the in,l text field, type i_oxygen.
12 |
2 In the Settings window for Electrolyte Potential, locate the Boundary Selection
section.
MESH 1
The physics is now complete. Add mesh settings and solve the model.
3 From the Sequence type list, choose User-controlled mesh.
Size
type 5.
5 In the Minimum element size text field, type 0.5.
6 In the Curvature factor text field, type 0.9.
7 In the Resolution of narrow regions text field, type 0.5.
STUDY 1

RESULTS
Plot the electrolyte potential along the electrode boundaries by first adding a data set
with a selection for these boundaries, then plot the potential using this data set.
Data Sets
13 |
5 From the Selection list, choose Import 1.
3D Plot Group 1
3 From the Data set list, choose Study 1/Solution 1 (2).
5 Right-click Results>3D Plot Group 1 and choose Surface.
The plot should look like that in Figure 4.

Proceed in a similar way to plot the electrolyte potential along one of the platform legs.
Data Sets
14 |
5 Select Boundaries 212214, 218220, 223, and 224 only.
3D Plot Group 2
1 Right-click 3D Plot Group 1 and choose Duplicate.
Compare the resulting plot with that in Figure 5.

Finally, proceed in the following way to plot the electrolyte current magnitude on the
anodes.
Data Sets
15 |
3D Plot Group 3
Duplicate.
4 In the Model Builder window, expand the 3D Plot Group 3 node, then click Surface 1.
of the Expression section. From the menu, choose Model>Component 1>Primary

Current Distribution>siec.nIl - Normal electrolyte current density.
6 Locate the Expression section. In the Expression text field, type abs(siec.nIl).
Compare with Figure 6.
16 |
Orange Battery
Introduction
This tutorial example serves as an introduction to electrochemistry modeling in
COMSOL. The example simulates the currents and the concentration of dissolved
metal ions in a battery (corrosion cell) made from an orange and two metal nails.
Metal nails
Orange
Figure 1: Modeled geometry. Orange and two metal nails. (Due to the high conductivity
of the metal nails, only the orange pulp is included in the computational domain.)
This type of battery is commonly used in chemistry class demonstrations. Instead of an
orange, also lemons or potatoes can be used.
Model Definition
The citric acid and various other ions in the orange serves as electrolyte, and using nails
of different metals as electrodes creates a galvanic potential over the cell.
In this example a zinc nail is used as one of the electrodes, giving rise to the following
electrode reaction:
Zn ( s ) Zn
2+
+ 2e
E eq, 0 = 0.76 V
1 |
ORANGE BATTERY
The other nail consists of copper, and here hydrogen evolution is assumed to take
place:
+
2H + 2e H 2 ( g )
E eq, 0 = 0 V
Eeq,0 above denotes the equilibrium potentials at standard conditions versus a standard
hydrogen electrode (SHE). In the model, the equilibrium potentials are corrected for
the pH and zinc concentration of the orange pulp using the Nernst equation.
The model for the currents in the orange and electrodes is set up using the Secondary
Current Distribution interface. The electrolyte current in the orange is thereby solved
for by Ohms law. The conductivity of the metal nails is so high that the electrode
domains are not included in the model, instead boundary conditions on the nail
surfaces are used to set the nail potentials. One nail is grounded and the other one is
set to a cell potential to comply with a total current condition. This would correspond
to a situation where the cell is controlled galvanostatically, for instance by the use of a
potentiostat.
Butler-Volmer type expressions, with concentration dependent exchange current
density for the zinc reaction, are used for the electrode kinetics on the surface of the
nails within the orange.
The initial values electrolyte potential is set to correspond to the potential of a cell at
open circuit (that is, no activation potential). Following the definition of the
overpotential:
= s l E eq
the initial value becomes:
l, init = s E eq = 0 E eq, Zn 0 = E eq, Zn
In an extension of the model, the diffusion and migration of the dissolved zinc ions in
the orange from the zinc electrode reaction is modeled by the Transport of Diluted
Species interface in a time-dependent simulation. This assumes that the zinc ion
transport can be described by the Nernst-Planck equations (without an
electroneutrality condition due to a supporting electrolyte). In addition, the zinc
electrode kinetics are modified to be dependent on the zinc concentration, which
increases in the orange as more and more zinc is dissolved.
The zinc concentration is set to 0.001 mol/m3 at the start of the simulation. All
boundaries except the zinc electrode are insulated.
2 |
ORANGE BATTERY

Figure 2 shows the potential field in the orange. The potential decreases as the current
flows from the zinc electrode (left) to the upper electrode (right). The main part of the
cell voltage loss is due to Ohmic losses in the electrolyte.
The performance of the battery could probably be increased by using an electrolyte of
higher conductivity (for example, a lemon instead of an orange) or by decreasing the
distance between the nails.
Figure 2: Potential field in the electrolyte at t=0.

Figure 3 shows a polarization plot as the total current of the battery increases from 0
to 1 mA. The large change in cell voltage seen at low currents is due to overpotential
3 |
ORANGE BATTERY
losses at the zinc electrode. Increasing the area of the zinc electrode would decrease
this effect.
Figure 3: Polarization plot for the initial concentrations.

Figure 4 shows an isosurface for the 0.2 mol/m3 concentration level of zinc ions after
running the battery for five minutes. Figure 5 shows the how far the 0.2 mol/m3
isosurface level has reached after one hour.
4 |
ORANGE BATTERY
Figure 4: 0.2 mol/m3 zinc concentration isosurface after five minutes.
5 |
ORANGE BATTERY
Figure 5: 0.2 mol/m3 zinc concentration isosurface after one hour.

Figure 6 shows how the cell current evolves with time. Due to the increase of zinc ions
at the zinc nail electrode, the battery current decreases for a constant cell current.
6 |
ORANGE BATTERY
Figure 6: Cell current vs. time.
Suggested Exercises and Extensions of the Model

Change the radius of the nails and the value of the electrolyte conductivity and
investigate how this affects the polarization plot.
The hydrogen concentration is not included in the model. Add an additional
concentration under Dependent Variables on the Transport of Diluted Species node
to monitor the change in pH of the cell then couple the flux of hydrogen ions on the
copper surface by using an additional Electrode-Electrolyte Interface Coupling node.
The dissolved zinc ions may form a layer of zinc hydroxide on the zinc surface, giving
rise to an additional potential drop. You may use the Film Resistance section on the
Electrolyte-Electrode Boundary node to include this potential drop. The value of the
film resistance could for instance be a function of the zinc ion concentration variable
in the pulp. Alternatively you may add a Surface Reactions interface to model the
buildup of the surface concentration of zinc hydroxide, and then couple the film
resistance to the hydroxide concentration.
7 |
ORANGE BATTERY
Application Library path: Corrosion_Module/General_Electrochemistry/

orange_battery
This example models the current distribution in an orange. From the File menu,
choose New.
NEW

MODEL WIZARD

(siec).
3 Click Add.
4 Click Study.
6 Click Done.
GEOMETRY 1
Start by drawing the geometry; one sphere (the orange) and two cylinders (the metal
nails).
Sphere 1 (sph1)
1 On the Geometry toolbar, click Sphere.
2 In the Settings window for Sphere, locate the Size section.
3 In the Radius text field, type 5e-2.
Cylinder 1 (cyl1)
1 On the Geometry toolbar, click Cylinder.
2 In the Settings window for Cylinder, type Zinc nail in the Label text field.
3 Locate the Size and Shape section. In the Radius text field, type 2e-3.
4 In the Height text field, type 5e-2.
5 Locate the Position section. In the x text field, type -2e-2.
8 |
ORANGE BATTERY
6 In the z text field, type 2e-2.
By enabling Create Selection you can easily select all boundaries of the nail later on
when setting up the physics.
box.
Duplicate the cylinder and change the x position to draw the second nail.
Zinc nail 1 (cyl2)

1 Right-click Component 1 (comp1)>Geometry 1>Zinc nail and choose Duplicate.
2 In the Settings window for Cylinder, type Copper nail in the Label text field.
3 Locate the Position section. In the x text field, type 2e-2.
DEFINITIONS
Add a manual explicit selection for the orange domain. This will facilitate if the
geometry needs to be changed in the future. Selections is generally a convenient way
to group different parts of the geometry together.
Explicit 1
2 In the Settings window for Explicit, type Orange in the Label text field.
GLOBAL DEFINITIONS
Load some global parameters from a file. These will be used in multiple places in the
model.
Parameters
orange_battery_parameters.txt.
Load also some variable definitions from a file.
9 |
ORANGE BATTERY
DEFINITIONS
Variables 1
1 In the Model Builder window, under Component 1 (comp1) right-click Definitions and
choose Variables.
orange_battery_variables.txt.
Now, start setting up the current distribution model.

Change the selection of the entire physics interface to the orange domain only.
1 In the Model Builder window, click Secondary Current Distribution (siec).
2 In the Settings window for Secondary Current Distribution, locate the Domain
Selection section.
3 From the Selection list, choose Orange.
Electrolyte 1
An Electrolyte node has already been added to the model by default. The selection is
locked to all selected domains of the physics interface, which in this case is the orange
only. Set the electrolyte conductivity.
Distribution (siec) click Electrolyte 1.

Use an Electrolyte-Electrode Boundary Interface nodes to define the electrode
surfaces. The Electrolyte-Electrode Boundary Interface node defines both a metal
electrode potential and an electrode-electrolyte interface. Use a Bulter-Volmer
expression for the zinc electrode. The hydrogen kinetics are assumed to be very fast so
that a linearized Butler-Volmer expression is applicable.
Interface.
10 |
ORANGE BATTERY

3 From the Selection list, choose Zinc nail.
Enable transparency and inspect the active boundaries in the graphics window.

2 In the Settings window for Electrode Reaction, locate the Model Inputs section.
4 Locate the Equilibrium Potential section. In the Eeq text field, type E_eq_Zn.
Butler-Volmer.
6 In the a text field, type alpha_a_Zn.
7 In the c text field, type alpha_c_Zn.
8 In the i0 text field, type 10[A/m^2]*(c_Zn20/c_ref)^0.5.

Now define the copper electrode in a similar way. First add a parameter for the total
current. This parameter will also be used in the study to perform a galvanic polarization
sweep over the cell.
Interface.
3 From the Selection list, choose Copper nail.
4 Locate the Boundary Condition section. From the Boundary condition list, choose
Total current.
5 In the Il,total text field, type -i_app.

2 In the Settings window for Electrode Reaction, locate the Model Inputs section.
11 |
ORANGE BATTERY
4 Locate the Equilibrium Potential section. In the Eeq text field, type E_eq_H2.
5 Locate the Electrode Kinetics section. In the i0 text field, type 10[A/m^2].
Initial Values 1
We are using non-linear kinetics in the model. Provide an initial value for the
electrolyte potential in order to reduce solver time and improve convergence. As a rule
of thumb one can often use the negative of the equilibrium potential of the grounded
electrode as initial value for the electrolyte potential.
3 In the phil text field, type -E_eq_Zn0.
STUDY 1
Since we are using the default mesh settings, the model is now ready for solving.
RESULTS

Plots of the electrolyte potentials are created by default.
3D Plot Group 3
Use an isosurface for visualizing the potential field in the electrolyte.
2 In the Settings window for 3D Plot Group, type Potential Isosurface in the
Label text field.
Potential Isosurface
1 Right-click Results>Potential Isosurface and choose Isosurface.
2 In the Settings window for Isosurface, locate the Levels section.
3 In the Total levels text field, type 25.
4 On the Potential Isosurface toolbar, click Plot.
Compare with Figure 2 in the Results and Discussion section.
12 |
ORANGE BATTERY
STUDY 1
Step 1: Stationary
Now use an Auxiliary Sweep to solve over a range of cell currents in order to create a
polarization plot.
4 Click Add.
Parameter name
Parameter unit
i_app
0 10^range(-5,0.2,-3)

RESULTS
Create a polarization plot as follows:
1D Plot Group 4
2 In the Settings window for 1D Plot Group, type Polarization Plot in the Label
text field.
Polarization Plot
1 On the Polarization Plot toolbar, click Global.
Expression
Unit
Description
siec.phis_eebii2
Electric potential
4 On the Polarization Plot toolbar, click Plot.

COMPONENT 1 (COMP1)
Now, extend the model to investigate the battery voltage over time at a certain load
current. Start by adding a physics interface to handle the mass transport of zinc ions.
13 |
ORANGE BATTERY
ADD PHYSICS
1 On the Home toolbar, click Add Physics to open the Add Physics window.
2 Go to the Add Physics window.
3 In the Add physics tree, select Chemical Species Transport>Transport of Diluted Species
(tds).
4 Click Add to Component in the window toolbar.
5 On the Home toolbar, click Add Physics to close the Add Physics window.
Species (tds).
2 In the Settings window for Transport of Diluted Species, locate the Domain Selection
section.
3 From the Selection list, choose Orange.
The orange pulp is quiescent so convection can be ignored in the model.

4 Locate the Transport Mechanisms section. Clear the Convection check box.
(Due to the presence of a lot of other ions in the pulp, acting as supporting
electrolyte, we assume the potential gradients to be small and hence also ignore the
effect of migrative transport of the zinc ions.)

For this example we will use the default diffusion coefficient value in the Tranpsort
Properties node so no settings are needed on the default domain node. The following
steps couple the electrochemical reaction currents to the ion flux at the electrode
surface:
Coupling.
4 From the Selection list, choose Zinc nail.

14 |
ORANGE BATTERY

The stochiometric number refers to the stochiometry number of the reacting species
when written as a reduction reaction.
Initial Values 1
Set the initial zinc ion concentration at the start of the time-dependent simulation.
3 In the c text field, type c_Zn20.
DEFINITIONS
The zinc ion concentration is no longer constant. Modify the equilibrium potential
and exchange current density variables for the zinc electrode to be dependent on the
local concentration of zinc ions. The name of this variable is 'c' by default in the
Transport of Diluted Species interface.
Variables 1
1 In the Model Builder window, under Component 1 (comp1)>Definitions click Variables
1.
Name
Expression
Unit
Description
c_Zn2
mol/m
Zinc ion concentration

(used in above
expressions)
ADD STUDY
Create a new time-dependent study for the concentration simulation.

1 On the Home toolbar, click Add Study to open the Add Study window.
2 Go to the Add Study window.
3 Find the Studies subsection. In the Select study tree, select Preset Studies>Time
Dependent with Initialization.
4 Click Add Study in the window toolbar.
15 |
ORANGE BATTERY
5 On the Home toolbar, click Add Study to close the Add Study window.
STUDY 2

Use a secondary current distribution during the initialization step.
Initialization.
2 In the Settings window for Current Distribution Initialization, locate the Study
Settings section.
3 From the Current distribution type list, choose Secondary.

3 In the Times text field, type range(0,60,3600).
RESULTS
Plot the zinc concentration in the orange as follows:
3D Plot Group 9
2 In the Settings window for 3D Plot Group, type Concentration Isosurface in
the Label text field.

4 From the Time (s) list, choose 300.
Concentration Isosurface
1 Right-click Results>Concentration Isosurface and choose Isosurface.
2 In the Settings window for Isosurface, click Replace Expression in the upper-right
corner of the Expression section. From the menu, choose Component 1>Transport of
Diluted Species>c - Concentration.
3 Locate the Levels section. From the Entry method list, choose Levels.
4 In the Levels text field, type 0.2.
5 On the Concentration Isosurface toolbar, click Plot.
16 |
ORANGE BATTERY
Export
The following steps create an animation of the zinc ion isosurface during the simulated
time:
1 On the Results toolbar, click Animation and choose Animation.
2 In the Settings window for Animation, locate the Target section.
3 From the Target list, choose Player.
4 Locate the Scene section. From the Subject list, choose Concentration Isosurface.
5 Locate the Animation Editing section. From the Time selection list, choose From list.
6 At t=0 there is no concentration gradient in the orange, de-select the first time-step.
In the Times (s) list, choose all steps except 0.

7 Right-click Results>Export>Animation 1 and choose Play.
Compare the last frame at time 3600 s with Figure 5 in the Results and Discussion
section.
1D Plot Group 10
Finally, create a plot for how the cell potential changes with time.
2 In the Settings window for 1D Plot Group, type Cell Potential vs Time in the
Label text field.
Cell Potential vs Time

1 On the Cell Potential vs Time toolbar, click Global.
2 In the Settings window for Global, click Replace Expression in the upper-right corner
of the y-axis data section. From the menu, choose Component 1>Secondary Current
Distribution>siec.phisext_eebii2 - External electric potential.
3 On the Cell Potential vs Time toolbar, click Plot.
17 |
ORANGE BATTERY
STUDY 1
Step 1: Stationary
Note that if you want to experiment with the model by changing parameter values and
simulate new polarization plots, you have to disable the Transport of Diluted Species
interface in the stationary study as follows:
2 In the Settings window for Stationary, locate the Physics and Variables Selection
section.
Physics interface
Solve for
Discretization
Secondary Current Distribution
physics
Transport of Diluted Species
18 |
ORANGE BATTERY
physics
Corrosion Protection of a Ship Hull

Introduction
Impressed current cathodic protection (ICCP) is a commonly employed strategy to
mitigate ship hull corrosion, by which an external current is applied to the hull surface,
polarizing it to a lower potential. Although there are various parameters such as
salinity, temperature, hull surface coating that contribute to the current demand, the
area of bare metal (mainly propeller) is the most influential parameter.
This model example simulates the effect of propeller coating on the current demand
and is based on a paper by Huber and Wang (Ref. 1). Two different cases are
investigated; a coated and an uncoated propeller.
Model Definition
The CAD built geometry of the ship hull considered in this example is shown in
Figure 1. The model geometry is created by adding rectangular block outside the hull
geometry to represent the ocean.
Hull
Anode
Propeller and shaft
Figure 1: The geometry of the ship hull surface, which is exposed to the sea water.
1 |
CORROSION PROTECTION OF A SHIP HULL
The zoomed-in model geometry highlighting the propeller features is shown Figure 2
where the anode, shaft and propeller surfaces and the electrolyte domain are
highlighted.
Anode
Shaft
Electrolyte (sea water)

Propeller
Figure 2: The zoomed-in model geometry of the ship hull surface highlighting anode, shaft,
propeller surfaces and electrolyte domain.
Use the Secondary Current Distribution interface to solve for the electrolyte potential,
l(SI unit: V), over the electrolyte domain according to:
i l = l l
il = 0
m) is the electrolyte conductivity which is assumed to be a constant at 4 S/m.
Use the Electrolyte Current boundary condition to prescribe the total current of
0.87 A in the case for a coated propeller, and 3.1 A in case of an uncoated propeller.
Use the Electrolyte-Electrode Boundary Interface boundary condition at the electrode
surfaces, which sets the boundary condition for the electrolyte potential to
2 |
n il =
iloc, m
m
where iloc,m (SI unit: A/m2) is the local individual electrode reaction current density.
Use a Butler-Volmer expression to model the electrode reaction at the hull surface and
the propeller surface in case of uncoated propeller. This sets the local current density to
a F
c F
i loc = i 0 exp -------------- exp --------------
RT
RT
where the overpotential is calculated as
= s, ext l E eq
The propeller and the shaft are considered to be made up of nickel aluminum bronze
(NAB) alloy and Alloy 625, respectively. The electrode kinetics parameters used in the
Butler-Volmer expression for the shaft and propeller are shown in Table 1 and are
taken from Ref. 2.
TABLE 1: ELECTRODE KINETICS PARAMETERS
PARAMETER
UNIT
NAB PROPELLER
ALLOY 625
SHAFT
Equilibrium potential, Eeq
V vs Ag/Agcl
-0.31
-0.18
Exchange current density, i0
mA/cm2
1.510-2
1.310-4
Anodic transfer coefficient, a
0.78
0.45
Cathodic transfer coefficient, c
0.44
0.57
Use the default Insulation condition for all boundaries of the ship hull surfaces:
n il = 0
where n is the normal vector, pointing out of the domain.
Use an Infinite Electrolyte condition on the external boundaries to the Electrolyte
domain to describe the infinite extension of the ocean. Specify the ocean surface and
mid ship plane as symmetry planes. This models the current conduction outside the
drawn geometry, using the boundary element method.
The mesh used in the model is shown in Figure 3, with a close-up of the propeller
shown in Figure 4.
3 |
Figure 3: The mesh used in model.
Figure 4: The mesh used in model, zoomed-in around propeller.
4 |

A surface plot of the electrolyte potential for the ship hull surface with coated propeller
is shown in Figure 5. It can be seen that the potential distribution across the ship hull
surface is quite uniform, except in the region close to the anode surface. The
electrolyte potential is higher near the anode surface when compared to the rest of the
ship hull surface. The overpotential at the shaft surface is found to be well below its
equilibrium potential indicating the cathodic activity at the surface.
Figure 5: A surface plot of the electrolyte potential for the case with a coated propeller.
Figure 6 shows a surface plot of the local current density for the shaft surface for the
coated propeller case. The negative sign of the local current density confirms the
cathodic reaction at the shaft surface, indicating that the applied current of 0.87 A
sufficient to protect the bare metal from corrosion.
5 |
Figure 6: A surface plot of the local current density for the shaft surface in the coated
propeller case.
Figure 7: A surface plot of the electrolyte potential for the ship hull surface in case of an
uncoated propeller.
6 |
Figure 7 shows the electrolyte potential for the case with an uncoated propeller. The
electrolyte potential is higher near the anode surface when compared to the rest of the
ship hull surface. The overpotentials at the shaft and uncoated propeller surfaces are
found to be below their respective equilibrium potentials indicating cathodic activity
at these surfaces. It can be seen that the potential distribution across the ship hull
surface is less uniform compared to the coated propeller case.
A surface plot of the local current density for the shaft and propeller surfaces in case of
uncoated propeller is shown in Figure 8. The negative sign of the local current density
confirms the cathodic reaction at both the shaft and propeller surfaces indicating that
the applied current of 3.1 A in case of uncoated propeller is good enough to protect
the shaft and propeller surfaces from corrosion.
Figure 8: A surface plot of the local current density for the shaft and uncoated propeller
surfaces.
7 |
Figure 9: The electrolyte potential variation at a representative line across the length of the
ship hull surface for both coated and uncoated propellers.
Figure 9 shows the electrolyte potential variation at a representative line across the
length of the ship hull surface for both coated and uncoated propellers. It can be seen
that the electrolyte potential in the regions closer to the anode and the propeller
surfaces deviates significantly from the potential at the rest of the ship hull surface in
case of uncoated propeller. This deviation is less significant in the case of a coated
propeller. Thus, the electrolyte potential distribution across the length of ship hull
surface is found to be considerably uniform in case of coated propeller and
non-uniform in case of uncoated propeller.
Finally, the surface averaged electrolyte potential at the reference electrode surface,
located a few meters towards the stern in relation to the anode, is evaluated for the two
cases, it is found to be the same (around 0.52 V) for both cases.
Reference
1. T. Huber and Y. Wang, Effect of propeller coating on cathodic protection current
demand: Sea trial and modeling studies, Corrosion, vol. 68, pp 441448, 2012.
8 |
2. H. P. Hack, Atlas of polarization diagrams for naval materials in seawater, Naval

Surface Warfare Centre Technical Report, CARDIVNSWC-TR-61-94/44, April
1995.

ship_hull
NEW

MODEL WIZARD

(siec).
3 Click Add.
4 Click Study.
6 Click Done.
GEOMETRY 1
Import the geometry of the ship hull from a geometry file.
Import 1 (imp1)
3 Click Browse.
ship_hull_geometry.mphbin.
5 Click Import.
9 |
The geometry is divided into two domains, use a mesh control domain to remove this
split when setting up the physics. This will reduce the number of geometry entities that
can be selected when setting up the physics.
Mesh Control Domains 1 (mcd1)

1 On the Geometry toolbar, click Virtual Operations and choose Mesh Control Domains.
2 On the object fin, select Domain 2 only.
The geometry should now look like Figure 1.

Select Zoom Box and a region closer to propeller. The zoomed in geometry should
now look like Figure 2.
GLOBAL DEFINITIONS
Load the model parameters.
Parameters
ship_hull_parameters.txt.
Create explicit selections for the propeller, shaft, anode, reference electrode and hull
surfaces. Then create a selection for the ship hull surface by using a union. The
selections will be used later on when specifying the physics, setting up the mesh and
when plotting and evaluating the results.
DEFINITIONS
Explicit 1
4 Click Paste Selection.
5 In the Paste Selection dialog box, type 19-23, 25-28, 42-45 in the Selection text
field.
6 Click OK.
10 |

8 In the Rename Explicit dialog box, type Propeller in the New label text field.
9 Click OK.
Explicit 2
5 In the Paste Selection dialog box, type 40,41 in the Selection text field.
6 Click OK.
8 In the Rename Explicit dialog box, type Shaft in the New label text field.
9 Click OK.
Explicit 3
5 In the Paste Selection dialog box, type 18 in the Selection text field.
6 Click OK.
8 In the Rename Explicit dialog box, type Anode in the New label text field.
9 Click OK.
Explicit 4
5 In the Paste Selection dialog box, type 17 in the Selection text field.
6 Click OK.
11 |
8 In the Rename Explicit dialog box, type Reference electrode in the New label text
field.
9 Click OK.
Explicit 5
5 In the Paste Selection dialog box, type 6-16, 24, 29-39, 46-51 in the Selection
text field.
6 Click OK.
8 In the Rename Explicit dialog box, type Hull surface in the New label text field.
9 Click OK.
Union 1
5 In the Add dialog box, In the Selections to add list, choose Propeller, Shaft, Anode,
Reference electrode, and Hull surface.
6 Click OK.
8 In the Rename Union dialog box, type Ship hull surface in the New label text
field.
9 Click OK.
Union 2
5 In the Add dialog box, In the Selections to add list, choose Propeller and Shaft.
12 |
6 Click OK.
8 In the Rename Union dialog box, type Propeller and Shaft in the New label text
field.
9 Click OK.
Now, set up the Secondary Current Distribution interface for the case of a coated
propeller. Start with the electrolyte conductivity.
Electrolyte 1
Specify the total current at the anode surface.
Electrolyte Current 1
1 On the Physics toolbar, click Boundaries and choose Electrolyte Current.
2 In the Settings window for Electrolyte Current, locate the Boundary Selection
section.
3 From the Selection list, choose Anode.
4 Locate the Electrolyte Current section. In the Il,total text field, type Itot_coated.
Specify the electrode kinetics for shaft surface.

Interface.
3 From the Selection list, choose Shaft.

section.
3 In the Eeq text field, type Eeq_alloy_625.
13 |
Butler-Volmer.
5 In the i0 text field, type i0_alloy_625.
6 In the a text field, type alphaa_alloy_625.
7 In the c text field, type alphac_alloy_625.
Add an Infinite Electrolyte to describe an infinite extension of the electrolyte. Use

symmetry planes to describe the ocean surface and the mid-ship symmetry planes.
Infinite Electrolyte 1
1 On the Physics toolbar, click Boundaries and choose Infinite Electrolyte.
3 In the Settings window for Infinite Electrolyte, locate the Electrolyte section.
4 In the l text field, type sigma.
5 Click to expand the Symmetry planes section. Locate the Symmetry Planes section.
Select the yz-plane check box.

6 Select the xy-plane check box.
No more boundary conditions are needed since Insulation condition is applied by

default, including the coated propeller surface.
Initial Values 1
Provide an initial value for the electrolyte potential to reduce the computational time.
3 In the phil text field, type 0.5.
MESH 1
Build a mesh with a finer resolution at the propeller, shaft and ship hull surface. Mesh
the domain around the propeller first.
Free Tetrahedral 1
choose Free Tetrahedral.

2 In the Settings window for Free Tetrahedral, locate the Domain Selection section.
3 From the Geometric entity level list, choose Domain.
14 |
Size 1
1 Right-click Component 1 (comp1)>Mesh 1>Free Tetrahedral 1 and choose Size.
3 From the Predefined list, choose Extra fine.
Size 2
1 Right-click Free Tetrahedral 1 and choose Size.
4 From the Selection list, choose Propeller and Shaft.
Free Tetrahedral 1
Right-click Free Tetrahedral 1 and choose Build Selected.
Free Tetrahedral 2
Right-click Mesh 1 and choose Free Tetrahedral.
Size 1
Tetrahedral 2 and choose Size.
4 From the Selection list, choose Hull surface.
5 Locate the Element Size section. From the Predefined list, choose Finer.
Free Tetrahedral 2
1 Right-click Free Tetrahedral 2 and choose Build Selected.
The mesh should look like Figure 3.

Now, solve the model for the coated propeller case.

STUDY 1

15 |
Copy the solution for the coated propeller case and rename it.
Solution 1
In the Model Builder window, expand the Study 1>Solver Configurations node.
Solution 1 - Copy 1
1 Right-click Solution 1 and choose Solution>Copy.
2 In the Model Builder window, under Study 1>Solver Configurations right-click Solution
1 - Copy 1 and choose Rename.
3 In the Rename Solution dialog box, type Coated propeller in the New label text
field.
4 Click OK.
RESULTS
Add some additional data sets with selections to use during post-processing.
1 In the Model Builder window, expand the Results node.
Data Sets
1 In the Model Builder window, expand the Results>Data Sets node.
2 Right-click Study 1/Coated propeller and choose Rename.
3 In the Rename Solution dialog box, type Coated propeller in the New label text
field.
4 Click OK.
5 Right-click Results>Data Sets>Coated propeller and choose Duplicate.
6 Right-click Results>Data Sets>Coated propeller 1 and choose Rename.
7 In the Rename Solution dialog box, type Coated propeller : Ship hull surface
in the New label text field.

8 Click OK.
12 From the Selection list, choose Ship hull surface.
Now, plot the electrolyte potential and local current density at the ship hull surface for
the coated propeller case.
16 |
3D Plot Group 1
3 From the Data set list, choose Coated propeller : Ship hull surface.
5 Click to expand the Color legend section. Locate the Color Legend section. From the
Position list, choose Left.
6 Right-click Results>3D Plot Group 1 and choose Surface.
The surface plot of the electrolyte potential for the whole ship surface with a coated
propeller should look like Figure 5.
10 In the Rename 3D Plot Group dialog box, type 3D Plot Group : Electrolyte
potential, coated propeller in the New label text field.
11 Click OK.
Data Sets
1 In the Model Builder window, under Results>Data Sets right-click Coated propeller :
Ship hull surface and choose Duplicate.
2 In the Model Builder window, expand the Results>Data Sets>Coated propeller : Ship
hull surface 1 node, then click Selection.
4 From the Selection list, choose Propeller and Shaft.
Ship hull surface 1 and choose Rename.
6 In the Rename Solution dialog box, type Coated propeller : Propeller and
shaft in the New label text field.
7 Click OK.
3D Plot Group : Electrolyte potential, coated propeller 1

1 In the Model Builder window, under Results right-click 3D Plot Group : Electrolyte
potential, coated propeller and choose Duplicate.
3 From the Data set list, choose Coated propeller : Propeller and shaft.
17 |
4 In the Model Builder window, expand the 3D Plot Group : Electrolyte potential, coated
propeller 1 node, then click Surface 1.
of the Expression section. From the menu, choose Model>Component 1>Secondary

Current Distribution>Electrode kinetics>siec.iloc_er1 - Local current density.
7 On the 3D Plot Group : Electrolyte potential, coated propeller 1 toolbar, click Plot.
8 In the Model Builder window, right-click 3D Plot Group : Electrolyte potential, coated
propeller 1 and choose Rename.
9 In the Rename 3D Plot Group dialog box, type 3D Plot Group : Local current
density, coated propeller in the New label text field.
10 Click OK.
The surface plot of the local current density on the shaft and the coated propeller
should look like Figure 6.
Now, set up the problem for an uncoated propeller case by describing the electrode
kinetics at the propeller surface and modifying the applied current at the anode surface.
Click the Transparency button on the Graphics toolbar.

Interface.
3 From the Selection list, choose Propeller.

section.
3 In the Eeq text field, type Eeq_NAB.
Butler-Volmer.
5 In the i0 text field, type i0_NAB.
18 |
6 In the a text field, type alphaa_NAB.

7 In the c text field, type alphac_NAB.
Electrolyte Current 1
Distribution (siec) click Electrolyte Current 1.
2 In the Settings window for Electrolyte Current, locate the Electrolyte Current
section.
3 In the Il,total text field, type Itot_uncoated.
STUDY 1
Now, solve the model for the case of an uncoated propeller.

On the Home toolbar, click Compute.
RESULTS
Data Sets
1 In the Model Builder window, under Results>Data Sets right-click Study 1/Solution 1
and choose Rename.

2 In the Rename Solution dialog box, type Uncoated propeller in the New label text
field.
3 Click OK.
Ship hull surface and choose Duplicate.
5 In the Settings window for Solution, locate the Solution section.
6 From the Solution list, choose Solution 1.
7 Right-click Results>Data Sets>Coated propeller : Ship hull surface 1 and choose
Rename.
8 In the Rename Solution dialog box, type Uncoated propeller : Ship hull
surface 1 in the New label text field.
9 Click OK.
Propeller and shaft and choose Duplicate.
11 In the Settings window for Solution, locate the Solution section.
12 From the Solution list, choose Solution 1.
19 |
13 Right-click Results>Data Sets>Coated propeller : Propeller and shaft 1 and choose

Rename.
14 In the Rename Solution dialog box, type Uncoated propeller : Propeller and
shaft 1 in the New label text field.
15 Click OK.
3D Plot Group : Electrolyte potential, coated propeller 1

1 In the Model Builder window, under Results right-click 3D Plot Group : Electrolyte
potential, coated propeller and choose Duplicate.
2 Right-click 3D Plot Group : Electrolyte potential, coated propeller 1 and choose
Rename.
3 In the Rename 3D Plot Group dialog box, type 3D Plot Group : Electrolyte
potential, uncoated propeller in the New label text field.
4 Click OK.
6 From the Data set list, choose Uncoated propeller : Ship hull surface 1.
8 On the 3D Plot Group : Electrolyte potential, uncoated propeller toolbar, click Plot.
The surface plot of the electrolyte potential for the whole ship surface with uncoated
propeller should look like Figure 7.
3D Plot Group : Local current density, coated propeller 1

1 In the Model Builder window, under Results right-click 3D Plot Group : Local current
density, coated propeller and choose Duplicate.
2 Right-click 3D Plot Group : Local current density, coated propeller 1 and choose
Rename.
3 In the Rename 3D Plot Group dialog box, type 3D Plot Group : Local current
density, uncoated propeller in the New label text field.
4 Click OK.
6 From the Data set list, choose Uncoated propeller : Propeller and shaft 1.
The surface plot of the local current density for the zoomed in region near the
uncoated propeller should look like Figure 8.
20 |
8 On the 3D Plot Group : Local current density, uncoated propeller toolbar, click Plot.
Now, create a Cut Line 3D selection to plot the electrolyte potential across a
representative line on the ship surface for both coated and uncoated propellers.
Data Sets
1 On the Results toolbar, click Cut Line 3D.
2 In the Settings window for Cut Line 3D, locate the Line Data section.
3 In row Point 1, set x to -1.6.
4 In row Point 1, set z to -1.5.
5 In row Point 2, set x to -1.6.
6 In row Point 2, set y to 25.
7 In row Point 2, set z to -1.5.
8 Right-click Results>Data Sets>Cut Line 3D 1 and choose Rename.
9 In the Rename Cut Line 3D dialog box, type Cut Line 3D : Uncoated propeller
in the New label text field.

10 Click OK.
11 Right-click Results>Data Sets>Cut Line 3D : Uncoated propeller and choose Duplicate.
12 In the Settings window for Cut Line 3D, locate the Data section.
13 From the Data set list, choose Coated propeller.
14 Right-click Results>Data Sets>Cut Line 3D : Uncoated propeller 1 and choose Rename.
15 In the Rename Cut Line 3D dialog box, type Cut Line 3D : Coated propeller in

16 Click OK.
1D Plot Group 5
3 From the Data set list, choose None.
6 From the Data set list, choose Cut Line 3D : Uncoated propeller.
21 |

Legends
Uncoated propeller

12 From the Data set list, choose Cut Line 3D : Coated propeller.
Legends
Coated propeller

16 In the Rename 1D Plot Group dialog box, type 1D Plot Group : Comparison in

17 Click OK.
The electrolyte potential comparison plot for the coated and uncoated propellers
should look like Figure 9.
Derived Values
Evaluate the average potential over the reference electrode surface for the respective
applied current values for both coated and uncoated propellers.
1 On the Results toolbar, click More Derived Values and choose Average>Surface
Average.
2 In the Settings window for Surface Average, locate the Selection section.
3 From the Selection list, choose Reference electrode.
4 Click the Evaluate button.
TABLE
1 Go to the Table window.

2 Right-click Results>Derived Values>Surface Average 1 and choose Duplicate.
RESULTS
Derived Values
1 In the Settings window for Surface Average, locate the Data section.
22 |
2 From the Data set list, choose Coated propeller.

3 Click the Evaluate button.
23 |
24 |

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Corrosion Module

Application Library Manual

CorrosionApplicationLibraryManual.book Page 1 Monday, April 13, 2015 5:05 PM

Corrosion Module Application Library Manual

CorrosionApplicationLibraryManual.book Page 1 Monday, April 13, 2015 5:05 PM

Solved with COMSOL Multiphysics 5.1

Ano de Fi lm R esi st an ce E ffec t on

ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION

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Results and Discussion

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Figure 2: Potential vs SHE at t=0.

ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION

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Figure 3: Potential vs SHE at t=365 days.

ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION

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Figure 4: Precipitated anode film thickness at t=360 days.

ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION

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Figure 5: Corrosion current density vs time.

Notes About the COMSOL Implementation

Model Library path: Corrosion_Module/Cathodic_Protection/

1 In the New window, click Model Wizard.

ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION

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1 In the Model Wizard window, click 3D.

ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION

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4 In the Sector angle text field, type 90.

ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION

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ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION

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External Corroding Electrode 1

ANODE FILM RESISTANCE EFFECT ON CATHODIC CORROSION PROTECTION

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Electrolyte-Electrode Boundary Interface 1

node, then click Electrode Reaction 1.

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CORROSION, SECONDARY (CORRSEC)

choose Edit Physics-Induced Sequence.

Step 1: Current Distribution Initialization

Step 2: Time Dependent, Fixed Geometry

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3 From the Time unit list, choose d.

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