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COMSOL Multiphysics User's Conference 2009, January 12-13, Dhahran, Saudi Arabia

COMSOL Multiphysics Modeling of Chloride Binding in Diffusive Transport of


Chlorides in Concrete
M.A. Shazali1, W.A. Al-Kutti2, M.K. Rahman3, A.H. Al-Gadhib2, M.H. Baluch2
1

INCO Precast Engineering, Industrial Contractors Co. Ltd., Al-Khobar, Saudi Arabia
Department of Civil Engineering, King Fahd Univ. of Petroleum & Minerals, Saudi Arabia
3
Research Institute, King Fahd Univ. of Petroleum & Minerals, Saudi Arabia

Abstract
chlorides ingress in concrete under field service conditions
is often ignored for formulation and analytical difficulty
reasons. Underlying effort of this paper is therefore to
demonstrate the use of COMSOL Multiphysics Software
[2], an interactive 3D-partial differential equation
development and simulation environment previously
known as FEMLAB, in effectively solving the diffusive
transport of chloride in concrete. In this regard, treatment
of the time-to-corrosion initiation problem is decisively
done in a manner averse to unrealistic assumptions of
constant diffusivity associated with null binding often
enforced for solution expediency.

One of the most revealing causes of deterioration leading to


durability loss in concrete structures is premature time-tocorrosion ignition due to chloride induced corrosion
associated with diffusive transport of chloride in concrete.
To permit a more realistic modeling of the diffusive
transport of chloride in concrete, chloride binding capacity
model based on experimental isotherm describing the
relation between total, bound, and free chlorides have to be
considered. The aim of this work is to demonstrate the
capability of using COMSOL Multiphysics modeling to
provide insight regarding a more realistic consideration of
chloride penetration behavior in concrete in view of
chloride binding. Simulations of the problem in COMSOL
allow main process of the chloride binding to be closely
captured in the light of its nonlinear concentration
dependence and influence on evolution of chloride
diffusivity governing the transport problem. Good
agreement of the model results with experimental data was
established to provide a basis for reasonable service life
prediction in view of the time-to-corrosion initiation
paradigm.
Keywords: COMSOL, multiphysics, modeling, concrete,
durability, chloride, diffusion, binding, corrosion.
Mohammed A. Shazali, PhD
Senior Structural Engineer, INCO Precast Division
P.O. Box 437 Al-Khobar 31952, Kingdom of Saudi Arabia
E-mail: mashazali@yahoo.com

Figure 1: Conceptual corrosion sequence in concrete [1].

Introduction

Chloride Diffusion Equations

The impact of environmental exposures in shortening the


service life or durability of concrete infrastructures in the
field has continued to be substantial worldwide. For
chloride exposures, the forecast to the service life loss
problem is closely related to ascertaining the corrosion
initiation time of the steel reinforcement in concrete. In
accordance with conceptual steel corrosion sequence model
advocated by Tuutti [1], the durability capacity of the
concrete structure is significantly limited to the corrosion
initiation time that is very much dependent on diffusive
transport of chloride in concrete.

The methodology proposed in this paper accounts for


external chloride penetration into concrete considering
influence of physical diffusion and chemical binding of
chloride transported in to concrete. Considering onedimensional space problem, the transport problem of
chlorides can be modeled according to the following form
of Ficks second law equation.

( .S .C f )
C a

= Dce
t
x
x

(1)

where Ca is the total chloride concentration in kg/m3


concrete, Cf if the free chloride concentration in kg/m3 pore
solution, Dce is the effective diffusivity in m2/s, is the
volumetric void fraction or the capillary porosity in m3

Although most corrosion initiation time studies in the


literature are observed to focus on pure physical diffusion
process of the problem, the role of binding mechanisms for
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COMSOL Multiphysics User's Conference 2009, January 12-13, Dhahran, Saudi Arabia

pore-voids /m3 concrete, and S is the degree of moisture


saturation in the foregoing voids in the concrete. From here
onwards the quantity S is dropped for taking a unit value in
the case of chloride diffusing through saturated voids
considered in this study.

aluminoferrite (C4AF) present as part of the cement or


binder component of the concrete substrate. According to
the anion exchange hypothesis, the formation of the Friedel
salt (Fr) in which unreacted aluminates react with the
intruding free chloride ions (Cl-) in the presence of
portlandite (calcium hydroxide, CH) can be represented as
follows.

Assuming constant diffusivity and null binding capacity,


(Ca = Cf) the solution to Equation (1) for semi infinite
concrete with initial and boundary condition set to
Cf(x,0)=0 and Cf(0,t)=Cs respectively is given by

x
C f ( x, t ) = C s 1 Erf

4
D
t

ce

2Cl

CH +10 H 2O
+ C 3 A
C 3 A.CaCl 2 .10 H 2 O + 2OH

(4)

Classical empirical isotherms of the Linear, Langmuir,


Freundlich, and Langmuir-Freundlich types are commonly
employed to characterize binding behavior of this nature,
independent of the chloride transport. It is further assumed
in this paper that both the C3A and C4AF aluminates
content of the cement paste portion of the concrete
substrate contribute equally in reacting with the free
chloride ions (Cl-), and thus both equally serve as reactants
for the reaction product formation.

(2)

Although Equation (2) is widely used, the solution to the


chloride transport problem is more complex because
whereas the chloride diffusivity is not constant, the role of
chloride binding is significant owing to adsorption affinity
of cementitious material to chlorides. Based on model
proposed by Bazant [3], Saetta et al. [4, 5], and adopted
elsewhere [6], a chloride diffusivity parameter Dc can be
defined using a multivariate law characterized by use of
empirical functions predicating the influence of parameters
embraced in the following form:
Dc = Dco .F Tc , H c , Bc , d c = Dco .Fct .Fch .Fcb .Fcd

Following the Langmuir isotherm, the chloride binding in


which the chloride concentration in the pore phases (Cf) is
in steady state equilibrium with the chloride concentration
on the concrete adsorbent (Cb) can be expressed with the
following algebraic expression:

(3)

Cb =

in which Fct, Fch, Fcb, and Fcd are chloride diffusivity


influence functions arising from effects of temperature (T),
humidity (h), binding (b) and chemical damage (d)
respectively on diffusivity of free chloride in concrete. For
isothermal and saturated moisture conditions, only the
effect of binding on chloride diffusivity (Fcb) needs to be
considered together with the Fcd influence which however
remains to be the focus of ongoing further studies. The
diffusivity parameter Dco, represents the effective
diffusivity quantity obtained at reference or unit influence
function conditions. The Fcb influence function calls for an
additional formulation to account for the rate of formation
of bound chlorides in a form of algebraic equation
governing conservation of the binding equilibrium process.
This requires experimental identification of chloride
binding isotherm relevant to the cementitious constituent of
the concrete.

C f
1 + C f

(5)

in which Cb is the concentration of the bound chlorides in


kg/ m3 of concrete and the parameters and are
empirical binding constants that vary according to the
concrete binder composition. The relationship between the
total (Ca), bound (Cb), and free (Cf) chloride contents in
concrete can be expressed as:

C a = C f + Cb

(6)

By virtue of Equations (3) and (6), Equation (1) needs to be


modified to express Ca in Cf terms to become:

C f
t

( .S .C f )

Dc
x
x

(7)

For the Langmuir isotherm, the binding capacity influence


function Fcb drawn on Equations (3), (6) and (7), can then
be expressed as:

Chloride Binding Equations


Many investigators have reported about the chloride
binding affinity of cementitious materials and its
dependence on various concrete mix-proportioning
parameters [7-9]. The studies have adequately highlighted
the importance of proper binding representation and hence
its direct impact on the reliability of conclusions drawn
from results of simulation involving chloride transport
problems in concrete. In terms of reaction mechanism, the
main form of chloride binding is generally reported as a
reaction with the aluminate and iron phases to produce
calcium chloro-aluminate of the Friedel Salt type. The
aluminate and iron phases are essentially those of
tricalcium
aluminate
(C3A)
and
tetra-calcium

Fcb =

+ (C b / C f )

(8)

where Cb/ Cf is the slope of the chosen isotherm function,


which from Equation (5) is given by

C b

=
C f (1 + C f

(9)

and thus the binding capacity influence function Fcb


becomes:
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COMSOL Multiphysics User's Conference 2009, January 12-13, Dhahran, Saudi Arabia

Fcb =

+ / (1 + C f )2

(10)

It follows that Ca can be obtained from Equation (6), once


Equation (7), augmented by Equations (3) and (10), is
solved for Cf. The problem is non-linear for which
analytical solution is complicated to evaluate because of the
high nonlinearity involved. Analytical treatment of the
augmented formulation requires solution that depends upon
integrals of Bessel functions or inverse Laplace transforms.
Appropriate COMSOL Multiphysics procedures were
accordingly drawn and implemented to seamlessly achieve
the required solution for Cf and hence that of Cb as well as
Ca accordingly.

2.

Declare consistent units by selecting "None" at [Model


Navigator] > [Settings] tab > [Unit system:] section.

3.

At the [Model Navigator] > [New] tab, select 1D from


[Space dimension] drop down list.

4.

In the list under [Application Modes], select


[COMSOL Mutiphysics] > [Convection and Diffusion]
> [Diffusion] > [Transient analysis]. And click [OK] to
display the COMSOL Multiphysics top window.

5.

Under [Draw] > [Specify Object] > [Line], enter "0


(space) 50" in the [Coordinates] > [x:] edit field. Click
[OK].

6.

Under the [Mesh] > [Free Mesh Parameters] >


[Global] tab, specify 0.5 in the [Maximum element
size] edit field. Click [Remesh] > [OK] to have the
mesh have 100 elements.

7.

Click on [Zoom Extents] button on the [Main Toolbar]


to adjust the coordinate system to the size of the line.

8.

Under the [Options] > [Constants], in the [Constant]


dialog box enter the following Name-Expression pairs:

COMSOL Multiphysics Procedures


Study Problem
To assess the predictive capability of deploying COMSOL
Multiphysics to model diffusive transport of chlorides in
view of the chloride binding, chloride concentration profile
with measured chloride binding data reported by Sergi et al.
[10] was simulated as a case study problem. Available
information and known parameter values for the measured
chloride profiles include the use of OPC cement based
paste samples made at water to cement ratio (w/c) equal to
0.5 by weight. The paste samples were submitted to
external chlorides concentration of 1M NaCl for and an
exposure period of a total of 100 days. The samples were
tested for their chlorides concentration profiles, over a
penetration or cover depth of 50mm, and chloride binding
analysis to accord with Langmuir relation at =1.67 mL/g
and = 4.08L/mol. Base on best fit of the COMSOL model
with the experimental data, a chloride diffusivity (Dco)
associated with the given Langmuir binding constant is
found here to equal 1.85 mm2/day. The saturated porosity
value was not reported but is commensurately taken here to
equal 0.31 considering the w/c information given for the
test sample.

Name
eta
alpha
beta
Cs
Ci
Dco
9.

Expression
0.31
1.67
4.08
1
0
1.85

Under the [Options] > [Expressions] > [Subdomain


Expressions], in the [Subdomain Expressions] dialog
box, with [Subdomains] tab > [Subdomain selection] at
1, enter the following Name-Expression pairs:
Name
dbdf
Fcb

Expression
alpha/(1+beta*c)^2
1/(1 + dbdf/eta)

10. Under the [Physics] > [Subdomain Settings], the


following equation is displayed:

Problem in COMSOL
Based on the governing differential-algebraic equations,
Equations (7) and (9), modeling the chloride transport and
chloride binding problem involves three unknown
variables, namely Cf, Cb, and Ca, but with only Cf seen to
be independent prime mover to the problem formulation.
When Equation (3) defining the dependency of the
diffusivity coefficient on the binding parameters (, ) and
the free chlorides (Cf) are included in Equation (7), the
resulting governing equation involved becomes strongly
nonlinear and difficult to solve. In this regard, recourse to
numerical solution technique offered by COMSOL
Multiphysics has been sought and adopted to completely
cope with complexity and nonlinearity of the onedimensional problem in a pragmatic manner.

ts

c
+ .( Dc) = R
t

(11)

where ts is the time scale coefficient, c is the


concentration, D is the diffusion coefficient, and R is a
reaction rate. Make this equation to match up with
Equation (7).
11. Under the [c] tab from the [Subdomain Settings], with
[Subdomains] tab > [Subdomain selection] at 1, enter
the corresponding parameters:
Parameter
ts
D
R

The 1D model of the physical problem is developed in


COMSOL according to the following key modeling steps:
1. Start COMSOL Multiphysics to display the [Model
Navigator] startup window.

Value/Expression
1
Dco*Fcb
0

12. Under the [init] tab from the [Subdomain Settings],


with [Subdomains] tab > [Subdomain selection] at 1,
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COMSOL Multiphysics User's Conference 2009, January 12-13, Dhahran, Saudi Arabia

enter the corresponding parameters for the initial


condition c(x, t=to=0) = Ci as follows:
Parameter
C(to)

The complete set of associated chloride profiles comprising


free, bound and total components is shown in Figure (4),
normalized to same unit of measurement for comparison
purposes.

Value
Ci

13. Under the [Physics] > [Boundary Settings], in the


[Boundary Settings] dialog box , with [Boundaries] tab
> [Boundary selection] at 1, enter the corresponding
parameters for the boundary condition c(x=0, t) = Cs
as follows:
Parameter
C0

Value/Expression
Cs

14. Condition at right boundary c(x=50, t) defaults to the


insulated flux condition; Assert this by selecting
"Insulation/Symmetry" with [Boundaries] tab >
[Boundary selection] at 2. [Apply] > [OK].
15. Under the [Solve] > [Solver Parameters] > [General]
tab, enter "0:0.1:100" in the [Times:] edit field. [OK].
16. Under the [Postprocessing] > [Plot Parameters] >
[general] tab, select "100" in the [solution at time:]
drop down list.

Figure 2. COMSOL predicted Cf chloride profiles.

17. In the [Line] tab, select "Concentration c" and click


[OK] to obtain the plot of the concentration displayed
in the drawing area of the COMSOL screen.

1.0
Time = 100 days :
Sergi et al. [10]
0.8

content, [mol/L]

18. Under the [Postprocessing] > [Domain Plot


Parameters] > select "stored output times" from the
[select via:] drop down list.
19. In the [Solution to use] section, choose "100" and click
[Apply] to obtain plot of the concentration displayed in
a separate window for the chosen time, t=100 days.

COMSOL model
Analytical Eq.(2)

0.6

0.4

0.2

Results and Discussions

0.0
0

10

15

20

25

30

35

40

45

depth [mm]

The last stage of the COMSOL modeling steps enumerated


above provides the plot of the concentration, c, displayed in
a separate [Figure] window. Thereafter the plot was
formatted further to obtain the style of the one shown as
Figure (2). This figure thus represents COMSOL solution
of the free chlorides concentration, Cf, to the problem.
Comparison of the COMSOL solution with the
experimental data to the modeled problem as reported by
Sergi et al. [10] is shown in Figure (3). The good
agreement observed between the measured and predicted
results in the figure suggests the ability of the COMSOL
thus far to predict experimentally observed behavior.

Figure 3. Comparison of Cf profiles with measured data.

Also shown in Figure (3) is the analytical solution provided


by use of Equation (2) under constant diffusivity
assumption. In this case the solution obtained with
stationary Dc = Dco value could not reflect the nonlinearity
evidently accruable from the associated binding behavior
and concentration dependence. The implication of the
mismatch between the experimental and the analytical
results in this regard is seen to be quite significant. It
inadvertently exposes the inherent inaccuracy associated
with the constant diffusivity assumption underlying validity
of such analytical equations.

Figure 4. COMSOL predicted Cf, Cb, and Ca profiles.

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COMSOL Multiphysics User's Conference 2009, January 12-13, Dhahran, Saudi Arabia

[2] COMSOL User guide (http://www.comsol.com)

Once the free chloride content (Cf) is known from the


COMSOL solution, the corresponding bound chloride (Cb)
can readily be post-processed by algebraic relation given in
Equation (5). Likewise, post processing on Equation (6)
provides for the total chlorides (Ca). Concurrent increase in
the level of the total chlorides (Ca) is observed throughout
the penetrated zone. This simultaneous change in Ca is
evidently attributable to the chloride binding capacity front
active within the zone.

[3] Z.P. Bazant, "Physical model for steel corrosion in


concrete sea structures-theory," ASCE Journal of
Structural Division, 105(6), 1979: 1137-1153.
[4] A.V. Saetta, R.V. Scotta, and R.V. Viataliani,
"Analysis of chloride diffusion into partially saturated
concrete," ACI Material Journal, 90(5), 1993: 441-451.
[5] A.V. Saetta, R.V. Scotta, and R.V. Viataliani,
"Reliability of reinforced concrete structures under
chemical-physical attack," The Arabian Journal of
Science and Engineering, 23(2C), 1998: 41-56.

Conclusions
A model of chloride transport in concrete considering
chloride diffusion and chloride binding has been presented.
Concordance of experimental data with results obtained
from the COMSOL Multiphysics solutions illustrates the
suitability and robustness of the COMSOL simulations
approach to completely cope with complexity and
nonlinearity of the problem. Modeling to account for
chloride binding in diffusive transport of chlorides in such
a pragmatic manner would have otherwise proved
cumbersome and far much difficult to accomplish. The
contrasting behavior observed between the free and bound
chlorides levels underscores the importance of including
chloride binding as a pre-requisite to realistic modeling of
chloride transport in concrete. Further efforts are under way
to promote exploration and evaluation of the software in
terms of higher space dimension, established material
properties, and synergetic coupling of other physics crucial
to holistic rather than isolated study of the problem within
the realm of concrete durability mechanics.

[6] M.A.
Shazali,
"Computational
Chemodamage
Transport Modeling of Durability Synergies in
Concrete", Ph.D. Dissertation, Civil Engineering
Dept., King Fahd Univ. of Petroleum & Minerals,
Saudi Arabia, 2004: 524pp.
[7] Rasheeduzzafar, S.E. Hussain, and S.S. Al-Saadoun,
"Effect of tricalcium aluminate content of cement on
chloride binding and corrosion of reinforcing steel in
concrete," ACI Material Journal, 1992:3-12.
[8] Rasheeduzzafar, S.S Al-Saadoun, A.S. Al-Gahtani, and
F.H. Dakhil, "Effect of tricalcium aluminate content of
cement on corrosion of reinforcing steel in concrete,"
Cement and Concrete Research, 20(5), 1990: 723-738.
[9] Rasheeduzzafar, S.E. Hussain, and S.S. Al-Saadoun,
"Effect of cement composition on chloride binding and
corrosion of reinforcing steel in concrete," Cement and
Concrete Research, 21(1), 1991: 777-794.

References

[10] G. Sergi, S. Yu, and C. Page, "Diffusion of chloride


and hydroxyl ions in cementitious materials exposed to
a saline environment," Magazine of Concrete
Research, 44(158), 1992: 6369.

[1] K. Tuutti, "Corrosion of Steel in Concrete", Swedish


Cement and Concrete Research Institute, Stochkolm,
1982.