Journal of Applied Science and Engineering, Vol. 18, No. 2, pp. 195-211 (2015) DOI: 10.6180/jase.2015.18.2.

13

A Nonlinear Theoretical Study of Modelling Chloride

Diffusion in Concrete Containing Fly Ash and Slag
Wen-Hu Tsao1,2*, Ming-Te Liang1, Jiang-Jhy Chang3 and Ming-Yi Fang3
1
Department of Civil Engineering, China University of Science and Technology,
Taipei, Taiwan 115, R.O.C.
2
Department of Banking and Finance, Tamkang University,
Tamsui, Taiwan 215, R.O.C.
3
Department of Harbor and River Engineering, National Taiwan Ocean University,
Keelung, Taiwan 202, R.O.C.

Abstract
The principal objective of this paper is to investigate the modelling of chloride diffusion in fly
ash and slag concretes laden in chloride environments. The capacity of the concrete cementitious
system to bind chloride ions has an important effect on the rate of chloride ionic transport in concrete.
Four mathematical models concerning chloride binding in concrete are stated and used. The analytical
solution of Fick’s second law of nonlinear (diffusivity ¹ constant) diffusion in conjunction with initial
and boundary conditions is used as a predictive model. The experimental data obtained by Thomas and
Bamforth [Modelling chloride diffusion in concrete: Effect of fly ash and slag. Cement and Concrete
Research 1999;31:487-495] was cited as input parameters. The results at the present study show that
after 30 years the predicted chloride profiles obtained by the nonlinear model may be one order of
magnitude lower than that of linear (diffusivity = constant) model. The nonlinear model associated
with four mathematical models related to chloride binding in concrete is not suitable to predict the
transport mechanism of chloride diffusion in concrete containing fly ash and slag. However, the
analytical solution of a nonlinear partial differential equation (PDE) in association with initial and
boundary conditions for the concentration of Cl - in the aqueous phase [Cl(-aq) ] (in kg/m3 pore solution)
is proper to estimate the transport behavior of chloride diffusion in both fly ash and slag concretes. The
Cl - bound in the solid phase [Cl(-s) ] (kg/m3 concrete) can thus be computed algebraically. Further
research in-depth is obviously needed and suggested.

Key Words: Chloride, Diffusion, Mathematical Model, Fly Ash, Slag, Pozzolan

1. Introduction such chloride content in concrete. The analysis does not

The chloride ion content of hardened concrete is
usually decided by chemical analysis of the concrete ma-
trix powder. The acid-soluble (or total) chloride concen-
tration in the concrete can be yielded by the chemical
analysis based on a Mohr titration through nitric acid for
the dissolution of the chloride ion. Everett and Treadway
[1] described a detailed test technique for measuring
*Corresponding author. E-mail: tsaowh@cc.cust.edu.tw
distinguish between free chloride that exists in solution
in the pore fluid and bound chloride that is chemically
bound or physically absorbed to the hydration products
of cement. Since only the free chlorides are thought to be
capable of initiating steel reinforcement corrosion in
concrete [2], it is of interest to decide the quantity of
chloride ions that are bound by different cementations
matrices.
Bound chlorides are physically absorbed or chemi-
cally bound to the products of hydration of cement with
196 Wen-Hu Tsao et al.
chloride ions. Friedel’s salt, i.e., 3CaO × Al2O3 × CaCl2 ×
10H2O, is a well-known reaction product containing
chloride [3-9]. It can be learn from the composition of
Friedel’s salt that the quantity of chloride that can be
chemically bound trusts upon the tricalcium aluminate
(C3A) content of cement. Nevertheless, not all the C3A
content is useful for chloride binding, as approximately
5% of C3A reacts preferentially with the gypsum con-
tent of cement [10]. Friedmann et al. [11] used a physi-
cal medelling of the electrical double layers (EDL) effect
on multispecies ions transport in cement-based mate-
rials. They found that the EDL results in the non-respect
of the local electroneutrality. For the cement-based mate-
rials, the overlapping of the diffusion layers happens in
the gel pores rather than in capillary pores. Bourbatache
et al. [12] adopted periodic homogenization technique to
model the chloride transport in cementitious materials.
The results shows that the chemical and electrocapillary
adsorption phenomena (or electrical double layer effect)
cannot be neglected for ionic diffusion in cementitious
materials. It presents to slow down the ionic transfer even
more than a complex turtuosity and constrictivity of the
porous network.
Nilsson et al. [13] pointed out that the concentration
of free chloride in the pore fluid is a function not only of
the diffusion characteristics of the cement matrix but
also of its chloride-binding capacity. The excellences of
cement replacement materials of pozzolanic materials
such as pulverized fly ash [14-20], ground granulated
blastfurnace slag (ggbs) [10,14,15,17,21-37] and silica
fume [10,14,24] in enhancing chloride binding capacity
have been interested by many researchers in recent years.
According to the concept of rapid chloride perme-
ability test and using the Nernst-Plank equation, Andrade
[38] used migration test based on electrochemical tech-
nique to calculate the chloride diffusion coefficient and
the transference number of concrete from ionic migra-
tion measurements. For the part concerning for the cal-
culation done by Andrade [38], some points are worthy
to be discussed by Xu and Chandra [39]. They pointed
out that: (1) When active C3A is saturated with chloride,
i.e., when it is consumed by passing Cl - ions to form
3CaO × Al2O3 × CaCl2 × 10H2O (Friedel’s salt), it will pro-
duce expansion. (2) Chloride flow plus reaction is gener-
ally not a method to be used for the measurement of po-
rosity and permeability. (3) The effective diffusion coef-
ficient depends on both concrete electric resistivity and
concentration of test solution. The mathematical model
of chloride diffusion expressed by Xu and Chandra [39]
is really relevant. Nonetheless, both the analytical solu-
tion proposed in transitory state and the one that drives
in steady (when time t ® ¥) are not correct. They are
pointed out and rectified by Amiri et al. [40].
Few studies have been done on the effect of chloride
diffusion in concrete containing fly ash and slag by theo-
retical methodology. Thomas and Bamforth [28] used
Frank’s solution of Fick’s second law of linear diffusion
equation in conjunction with initial and boundary con-
ditions to predict the chloride profiles for PC, fly ash
and slag concretes. To date, however, no studies have at-
tempted to predict the chloride profiles for PC, fly ash,
and slag concretes without employing Fick’s second law
of nonlinear diffusion equation. This is a notable short-
coming, because the use of Fick’s second law of non-
linear diffusion equation may have difficulty in numeri-
cal calculation.
The objective of the present study was to predict the
chloride profiles for PC, fly ash, and slag concretes by
the analytical solution obtained from Fick’s second law
of nonlinear diffusion equation associated with initial
and boundary conditions. We also considered the chlo-
ride profiles of four mathematical models related with
binding effect changed by temperature. Moreover, the
analytical solution of a nonlinear partial differential equ-
ation (PDE) for the concentration of Cl - in the aqueous
phase [Cl(-aq) ] (kg/m3 pore solution, i.e., free chloride con-
centration) described the physico chemical processes of
Cl - diffusion in concrete is discussed and suggested. The
Cl - bound in the solid phase [Cl(-s) ] (kg/m3 concrete, i.e.,
bound chloride concentration) can thus be computed al-
gebraically. The studied results may be provided for the
service life prediction of concrete or reinforced concrete
structures containing fly ash or slag.
2. Theoretical Model
2.1 Nonlinear Diffusion Equation
Suppose that concrete is in a saturated state. When
chloride ions penetrate the concrete by ionic diffusion oc-
curring the existing concentration gradient between the
 A Nonlinear Theoretical Study of Modelling Chloride Diffusion in Concrete Containing Fly Ash and Slag
exposed surface and the pore solution of the cement ma-
trix. This process due to diffusion driving force is usually
expressed by Fick’s first law of diffusion [41]
(1)
where Jc is the flux of chloride ions due to diffusion, Da
is the effective diffusion coefficient when the concen-
tration is represented in kilograms per cubic meter of
concrete, Da is the effective diffusion coefficient when
the concentration is expressed in kilograms per cubic
meter of pore solution, we is the evaporable water con-
tent, and Cf is the free chloride concentration at depth x.
Based on the concrete in a saturated situation, the
mass conservation of chloride ions in concrete leads to
(2)
where Ct is the total chloride concentration and t is the
time.
The relationship among the total, bound, and free
chloride concentrations in concrete can be expressed as
(3)
where Cb is the concentration of bound chlorides.
If the coefficient of diffusion, Da, is not constant,
then the substitution of Eq. (1) into Eq. (2) yields
(4)
Inserting Eq. (3) into Eq. (4), we have
(5a)
were
(5b)
in which Da* is the apparent diffusion coefficient (m2/s)
197
and ¶Cb/¶Cf is the binding capacity of the concrete bin-
der (m3 of pore solution/m3 of concrete) as defined by
Nilsson et al. [13]. Let Eq. (5a) be associated with ini-
tial and boundary conditions
(5c)
(5d)
(5e)
where Cs is the chloride concentration on the concrete
surface. Using the Kirchhoff transformation [42-44] in
conjunction with the Laplace transformation [45], the
analytical solution of Eq. (5) can be obtained [46]
(6)
where CR is the any reference value of chloride concen-
tration. For convenience, we may take CR = 0. Thus, Eq.
(6) can be rewriter as
(7)
Equation (7) provides the relationship among ap-
parent diffusion coefficient Da* , free chloride concentra-
tion Cf, penetration depth x, and time t. The left side of
Eq. (7) purely represents the area ratio between areas un-
der the Da* - Cf curve from CR = 0 to Cf and CR = 0 to Cs,
respectively. The geometrical meaning of the left side of
Eq. (7) is plotted as shown in Figure 1.
2.2 Boltzmann-Matano Methodology
In order to theoretically calculate the apparent diffu-
sion coefficients varied with free chlorides Cf, i.e., varied
with both distance x and time t mentioned above Eq. (7).
Tumidajski et al. [47] substituted the Boltzmann variable
1
-
2
u = xt [48] into Eq. (5a) to obtain a solvable homoge-
neous differential equation. After integrating the equa-
198 Wen-Hu Tsao et al.
Figure 1. The area ratio under the D*a - Cf curve.
tion between Cf = 0 and Cf = C *f , (0 < C *f < Cs), they ob-
tained
(8)
Tumidajski et al. [47] named the method “Boltzmann-
Matano methodology” to determine apparent diffusion
coefficients as a function of time and distance/concentra-
tion for concrete exposed to chloride solutions.
2.3 Chloride Binding Isotherm
The chloride binding isotherm is defined as the de-
scribed relationship between the bound and free chlo-
ride concentrations in concrete under a given tempera-
ture condition. Now a brief description is introduced in
the following [41]:
· No binding
(9)
· Linear binding
(10)
where a is the binding constant.
· Langmuir isotherm
(11)
where a and b are the binding constants.
· Freundlich isotherm
(12)
where a and b are the binding constants.
Substituting the values of Cs and Da* represented by
Eqs. (9)-(12) into Eq. (7), we can obtain the free chloride
concentrations at depth x and time t of the analytical so-
lutions of nonlinear diffusion equations.
2.4 Diffusion
Boddy et al. [49] supposed that the diffusion coef-
ficient varied with temperature and time. Therefore, the
rate of ion diffusion through concrete may be represented
by the following relationship
(13)
where D(t, T) is the diffusion coefficient at time t and
temperature T in m2/s, Tref is the reference temperature
(in this paper, we take room temperature Tref = 23 °C =
296 K), U is the activation energy of the diffusion pro-
cess (In this paper, U = 3500 J/mol was to be used [50]),
and R = 8.31 J/mole × K is the gas constant.
3. Results and Analysis
For the sake of applying the theoretical model men-
tioned before to investigate the chloride diffusion in con-
crete containing fly ash and slag, the data listed in Table
1 are cited from Thomas and Bamforth [28]. Some data
obtained by Thomas and Bamforth [28] and proposed
evaporable water content are listed in Table 2. With re-
spect to the values of binding constants a and b of the
 A Nonlinear Theoretical Study of Modelling Chloride Diffusion in Concrete Containing Fly Ash and Slag 199

four mathematical models for PC, fly ash, and slag con- chloride profiles of experimental data as shown in Fig-
cretes at different times are referenced from Martín-Pérez ures 1-3 in the Ref. of Thomas and Bamforth [28] and
et al. [41] and proposed by this paper using the method of using Eq. (8), the apparent diffusion coefficients are ob-
interpolation as listed in Table 3. In the process of calcu-
lation, the commercial software programme “Mathema- Table 2. Best-fit surface concentration [28] and proposed
evaporable water content for the Folkestone
tica” [51] is used as an algorithmic tool. According to the
blocks
Proposed
Table 1. Chloride concentration profiles for Folkestone
Best-fit values evaporable
blocks (average from three curing conditions)
water content
[28]
Concrete Cs (percent We (percent
Chloride content Age
mix concrete) concrete)
(percent mass of concrete)
PC Control 6 months 0.35 8
Depth 6 1 2 3 6 8 1 year 0.69 8
Mix
(mm) months year years years years years 2 years 0.38 7.8
PC 00-10 0.267 0.493 0.313 0.370 0.257 0.288 3 years 0.42 7.6
10-20 0.140 0.193 0.273 0.273 0.237 0.264 6 years 0.28 7.2
20-30 0.050 0.043 0.143 0.190 0.197 0.203 8 years 0.31 6.9
30-40 0.010 0.017 0.093 0.117 0.153 0.183 P/PFA 6 months 0.42 8
40-50 0 0 0.053 0.073 0.133 0.159 1 year 0.53 8
P/PFA 00-10 0.280 0.427 0.333 0.383 0.367 0.419 2 years 0.45 7.8
10-20 0.087 0.097 0.160 0.173 0.193 0.308 3 years 0.54 7.6
20-30 0.007 0.010 0.037 0.013 0.010 0.057 6 years 0.48 7.2
30-40 0 0.023 0.010 0.010 0.010 0.012 8 years 0.56 6.9
40-50 0 0 0.010 0.010 0.010 0.012 P/GBS 6 months 0.58 8
P/GBS 00-10 0.437 0.493 0.340 0.387 0.363 0.381 1 year 0.68 8
10-20 0.173 0.140 0.173 0.153 0.227 0.216 2 years 0.46 7.8
20-30 0.077 0.090 0.023 0.027 0.067 0.068 3 years 0.54 7.6
30-40 0.027 0.073 0.010 0.013 0.040 0.035 6 years 0.46 7.2
40-50 0 0 0.013 0.010 0.030 0.035 8 years 0.48 6.9

Table 3. Values of a and b of four mathematical models for PC, fly ash, and slag concretes at different times
PC concrete Fly ash concrete Slag concrete
Time Value Linear Langmuir Freundlic Linear Langmuir Freundlic Linear Langmuir Freundlich
binding isotherm h isotherm binding isotherm h isotherm binding isotherm isotherm
6 months a 0.205726 1.057320 1.02738 0.202996 1.04390 1.02783 0.196755 1.013210 01.02887
b 0.318831 0.36000 00.313826 0.36000 0.302385 0.3600
1 year a 0.192465 0.992118 1.02959 0.198705 1.02280 1.02855 0.192855 0.994036 01.02952
b 0.294519 0.36000 0.30596 0.36000 0.295234 0.3600
2 years a 0.204556 1.051570 1.02757 0.201826 1.03814 1.02803 0.201436 1.036230 01.02809
b 0.316686 0.36000 0.31168 0.36000 0.310965 0.3600
3 years a 0.202996 1.043900 1.02783 0.198315 1.02088 1.02861 0.198315 1.020880 01.02861
b 0.313826 0.36000 00.305245 0.36000 0.305245 0.3600
6 years a 0.208456 1.070740 1.02692 0.200656 1.03239 1.02822 0.201436 1.036230 01.02809
b 0.323837 0.36000 00.309535 0.36000 0.310965 0.3600
8 years a 0.207286 1.064990 1.02712 0.197535 1.01705 1.01705 0.200656 1.032390 01.02822
b 0.321692 0.36000 00.303815 0.36000 0.309535 0.3600
200 Wen-Hu Tsao et al.

tained. Using Tables 1-3 and substituting both the cal- Eqs. (9)-(12) into Eq. (7), we may obtain the chloride
culated apparent diffusion coefficients stated above and profiles of the PC, fly ash, and slag concretes as shown in

Figure 2. Comparison chloride profiles predicted by four mathematical models for PC concrete.
 A Nonlinear Theoretical Study of Modelling Chloride Diffusion in Concrete Containing Fly Ash and Slag 201

Figures 2-4. According to the Figures 2-4, results show concretes may be two orders of magnitude lower than the
that the chloride concentrations of the fly ash and slag Portland concrete.

Figure 3. Comparison chloride profiles predicted by four mathematical models for fly ash concrete.
202 Wen-Hu Tsao et al.

According to the chloride profiles of experimental Ref of Thomas and Bamforth [28], we may calculated
data at time with 8 years as shown in Figures 1-3 in the the apparent diffusion coefficients for PC, fly ash, and

Figure 4. Comparison chloride profiles predicted by four mathematical models for slag concrete.
 A Nonlinear Theoretical Study of Modelling Chloride Diffusion in Concrete Containing Fly Ash and Slag
slag concretes at t = 8 years, respectively. Using these
apparent diffusion coefficients and Eqs. (9)-(12) and
taking Tref = 23 °C, we may calculate the corresponding
diffusion coefficients at T = 5 °C and 35 °C for the PC,
fly ash, and slag concretes of four mathematical models
from Eq. (13). Substituting these calculated diffusion co-
efficient at T = 5 °C and 35 °C into Eq. (7), we may ob-
tain the predicted chloride profiles with different tem-
perature values for the PC, fly ash, and slag concrete as
shown in Figures 5-7. From the Figures 5-7, we may
know that the PC, fly ash, and slag concretes have higher
penetration depths at the same chloride concentration
and T = 35 °C than those values at T = 5 °C. According
to the measured chloride profiles of PC and fly ash con-
cretes as shown in Figure 5 of the Ref of Thomas and
Bamforth [28] and using Eq. (8), we may have the pre-
dicted chloride concentration profiles for the Folkestone
blocks at 30 years using Eq. (7). The differences between
Figure 5. Predicted chloride profiles with different T values for PC concrete at t = 8 years.
203
the PC and fly ash concretes are substantial. The PC and
fly ash concretes have penetration depths 1.98 and 5.25
mm at chloride concentration with 0.05% (mass of con-
crete) while the PC and fly ash concretes have penetra-
tion depths 16.78 and 9.72 mm at chloride concentration
with 0.02% (mass of concrete), respectively. In the case of
the Folkstone blocks at 30 years, the intersection points,
(x, C), of the PC and fly ash concretes in the predicted
and measured chloride profiles obtained by the linear mo-
del are (10, 0.32) and (4.52, 0.47) (see Figure 5 of the Ref.
[28]), respectively, while the intersection point, (x, C), of
the PC and fly ash concrete in the predicted chloride
profile obtained by the nonlinear model is (6.2, 0.0492)
(see Figure 8). It is worthy to point out that the penetra-
tion depth 6.2 mm predicted by the nonlinear model is
on the interval values (4.52, 10.0) of measured and pre-
dicted penetration depths calculated by the linear model.
While the chloride concentration 0.0492% predicted by
204 Wen-Hu Tsao et al.

Figure 6. Predicted chloride profiles with different T values for fly ash concrete at t = 8 years.

the nonlinear model is near lower one order magnitude By using the method of Laplace transform [45] to Eq.
than those of the linear model. (14), the analytical solution of Eq. (14) [52] yields

4. Discussion
(15)

In order to compare the results predicted by linear

(diffusivity = constant) and nonlinear (diffusivity ¹ con- where erfc is the complementary error function, and erf
stant) diffusion models, the linear diffusion model should is the error function.
be introduced herein. According to the experimental data of Figures 1-3 in
the Ref. [28] and using Eq. (8), the value of Da can be ob-
tained. Based on the value of Da and Eqs. (9)-(12), the
(14a) chloride profiles of the PC, fly ash, and slag concretes
can be obtained by the Eq. (15). Table 4 listed the com-
pared penetration depths at chloride concentration with
(14b) 0.3% mass of concrete for the four mathematical models
under both constant and inconstant diffusivities. From
(14c)
the Table 4 we may see that the penetration depths of
(14d) chloride concentrations under inconstant diffusivity may
 A Nonlinear Theoretical Study of Modelling Chloride Diffusion in Concrete Containing Fly Ash and Slag 205

Figure 7. Predicted chloride profiles with different T values for slag concrete at t = 8 years.

be from one to five orders of magnitude lower than those

of chloride concentrations under constant diffusivity.
Furthermore, for the case of inconstant diffusivities the
penetration depths of both fly ash and slag concretes may
be two orders of magnitude lower than the PC concrete.
According to the measured chloride profile of Figure
5 as shown in the Ref. [28] and using Eq. (8), the values of
apparent diffusion coefficients can be evaluated. Using
the Tables 1-3 and inserting both the calculated apparent
diffusion coefficients stated before and Eqs. (9)-(12)
into Eq. (7) the chloride profile of PC and fly ash con-
cretes may be obtained as shown in Figure 8. If compared
the predicted chloride profiles obtained by the nonlinear
model (Eq. (7)) with inconstant diffusivity (see Figure 8)
and the linear model (Eq. (15)) with constant diffusivity Figure 8. Predicted chloride profiles at t = 30 years.
(see Figure 5 in the Ref of Thomas and Bamforth [28]),
the intersection points between the PC and fly ash con- C = 0.32%, respectively. It is obvious that after 30 years
cretes occur at x = 6.2 mm, C = 0.0492% and x = 10 mm, the predicted chloride profiles obtained by the nonlinear
206 Wen-Hu Tsao et al.

Table 4. Compared penetration depths at chloride concentration with 0.3% mass of concrete for the four mathematical
models under both constant and inconstant diffusivities
Penetration depth, x (mm)
Mathematical
Diffusivity 6 months 1 year 2 years
model
PC Fly ash Slag PC Fly ash Slag PC Fly ash Slag
Constant No binding 4 4 9 11 6.6 10.4 8 6.5 6.9
Linear binding 3 2 5.5 6.8 3.5 5.8 4.8 3.5 3.5
Langmuir 1 1 2.5 3.5 9.9 3.1 2.5 1.9 2.2
isotherm
Freundlich 1 1 2.3 3.4 1.8 3.0 2.4 1.8 2.1
isotherm
Non No binding 4.8 ´ 7´ 7´ 1.03 ´ 1.52 ´ 1.14 ´ 4.07 ´ 2.28 ´ 3.2 ´
constant 10-1 10-4 10-5 10-2 10-4 10-4 10-2 10-4 10-4
Linear binding 1.7 ´ 4´ 3´ 3.69 ´ 1.32 ´ 4.7 ´ 1.74 ´ 8.4 ´ 1.3 ´
10-1 10-4 10-4 10-3 10-4 10-5 10-2 10-4 10-4
Langmuir 7.0 ´ 2.1 ´ 1.7 ´ 1.69 ´ 4.3 ´ 2.4 ´ 8.5 ´ 4´ 5.5 ´
isotherm 10-2 10-5 10-4 10-3 10-5 10-5 10-3 10-4 10-5
Freundlich 5.5 ´ 1.9 ´ 1.5 ´ 1.67 ´ 3.7 ´ 2.4 ´ 6.9 ´ 3.2 ´ 4.8 ´
isotherm 10-2 10-5 10-4 10-3 10-5 10-5 10-3 10-4 10-5

Penetration depth, x (mm)

Mathematical
Diffusivity 3 years 6 years 8 years
model
PC Fly ash Slag PC Fly ash Slag PC Fly ash Slag
Constant No binding 12 8 7 0 8 8.5 3 10.5 8.8
Linear binding 6 4.5 4.7 0 3.8 4.2 2 5.5 5
Langmuir 3 2.5 2.0 0 2.3 2.3 1 3 2.5
isotherm
Freundlich 2 2 1.9 0 2.1 2.2 1 2.8 2.4
isotherm
Non No binding 2.8 ´ 2.9 ´ 3.2 ´ 4.5 ´ 7.3 ´ 8´ 2.8 ´ 1.7 ´ 1.0 ´
constant 10-2 10-4 10-4 10-3 10-4 10-4 10-1 10-3 10-3
Linear binding 9.5 ´ 1.1 ´ 1.1 ´ 2.2 ´ 6.0 ´ 3.2 ´ 1.2 ´ 6.5 ´ 3.9 ´
10-2 10-4 10-4 10-3 10-4 10-4 10-1 10-4 10-4
Langmuir 4.5 ´ 4.9 ´ 4.8 ´ 8.8 ´ 2.7 ´ 1.6 ´ 5.0 ´ 2.7 ´ 1.9 ´
isotherm 10-2 10-5 10-4 10-3 10-4 10-4 10-2 10-4 10-4
Freundlich 3.8 ´ 3.0 ´ 4.0 ´ 6.9 ´ 2.2 ´ 1.3 ´ 4.5 ´ 2.6 ´ 1.8 ´
isotherm 10-2 10-5 10-4 10-4 10-4 10-4 10-2 10-4 10-4

model (Eq. (7)) may be 0.32%/0.0492% = 6.5 times lower
than that of linear model (Eq. (15)).
The nonlinear model of Eq. (5) with four mathe-
matical models related to chloride binding in concrete is
not suitable to predict the transport mechanism of chloride
diffusion in concretes containing fly ash and slag due
to neglecting a chloride-solid phase interaction term. By
introducing a chloride-solid phase interaction term, the
calculation of an intrinsic effect diffusivity is possible.
A nonlinear PDE for the concentration of Cl - in the
aquous phase [Cl(-aq) ] (kg/m3 pore solution), from which
that of Cl - bound in the solid phase [Cl(-s) ] (kg/m3 con-
crete) can be compute algebraically [53,54], in conjunc-
tion with initial and boundary conditions is described as
follows
(16a)
 A Nonlinear Theoretical Study of Modelling Chloride Diffusion in Concrete Containing Fly Ash and Slag
(16b)
(16c)
(16d)
where
(17)
The intrinsic effective diffusivity of Cl - in concrete
(m2/s) can be estimated by the following semiempirical
equation for NaCl
(18)
where n is a parameter equal with 3.5, k is the effi-
ciency factor of the supplementary cementing materials
(SCM) for chloride penetration (k = 6 for silica fume, k
= 2.5 for low-calcium fly ash, k = 2 for high-calcium fly
ash, k = 1 for natural pozzolans), C is the content of ce-
ment in concrete (kg cement/m3), P is the content of
SCM in concrete (kg SCM/m3), W is the content of wa-
ter in concrete (kg water/m3), rc and rw are the densities
of cement and water, respectively (kg/m3) and eeff is an
effective, for diffusion, porosity, calculated as follows:
(19)
The total porosity of concrete, e, can be simply cal-
culated using the mathematical expression as follows:
(20)
where eair is the entrained or entrapped air content (In
this work, eair = 1% is to be used).
The parameters [Cl(-s) ]sat and Keq (ratio of adsorption
to desorption rate constants) in Eq. (17) can be estimated
by the following empirical expressions
(21)
(22)
Assume Eq. (16a) to be a qusi-linear PDE. Using the
method of Laplace transformation [45], the analytical
solution of Eq. (16) can be obtained [50]
207
(23)
It is worthy to point out that the concentrations of
[Cl(-aq) ( x, t )] and [Cl(-aq) ]0 are equivalent to the concentra-
tions of Cf (x, t) and Cs, respectively. Based on experi-
ment, Lu et al. [55] pointed out that the total chloride
concentration is 2.2~3.2 times the free chloride con-
centration in concrete while the total chloride diffusivity
is 2.2~3.4 times the free chloride diffusivity. Based on this
experimental data, we take that the total chloride con-
centration is 2.5 times the free chloride concentration
whereas the total chloride diffusivity is 2.8 times the free
chloride diffusivity. According to the related parameters
in the Tables 1-4 of the Ref. [28] and using the require-
ment Eqs. (18)-(22), we may obtain the comparison re-
sults between model (refer to Eq. (23)) and experimental
data [28] for PC, fly ash, and slag concretes as shown in
Figure 9. If compared the results of (a), (b), and (c) of
Figure 9 with the results of Figures 1, 2, and 3 for the PC,
fly ash, and slag concretes at t = 8 years, then the pre-
dicted results obtained by Eq. (23) is smaller than those
of experimental data obtained by Thomas and Bamforth
[28]. However, Fang [56] pointed out that the results of
Figures 1, 2, and 3 for the PC, fly ash, and slag concretes
are in good agreement with the no binding, i.e., total
chloride concentrations in concrete. The predicted re-
sults of (a), (b), and (c) of Figure 9 are obtained from the
free chloride concentration as shown in Eq. (23). Accor-
dingly, in the case of the concretes containing fly ash and
slag, we may use Eq. (23) to predict the effect of fly ash
and slag on concretes while we may not use Eq. (7) to
estimate the influence of fly ash and slag on concretes. It
is herein worthy to point out that the Cl - bound in the
solid phase [Cl(-s) ] (kg/m3concrete, i.e., Cb) can thus be
computed algebraically by the following equation
(24)
5. Conclusions
The approach to obtaining the analytical solution of
one-dimensional non-steady-state diffusion equation in
208 Wen-Hu Tsao et al.
conjunction with initial and boundary conditions (i.e.,
nonlinear model) by the Kirchhoff transformation tech-
nique in association with the Laplace transformation has
Figure 9. Comparison between model and experimental data
for PC, fly ash, and slag concretes.
been described and the predicted results were compared
with those results calculated by the linear model. The
physicochemical processes of diffusion in Cl - in the
aqueous phase of pores described by a nonlinear PDE in
conjunction with initial and boundary conditions are also
discussed as a nonlinear model. Some important results
may be made in the following:
1. Based on the same chloride concentration, the pre-
dicted penetration depths obtained by the nonlinear
model (Eq. (7)) for the PC and fly ash or slag con-
cretes may be one~two orders of magnitude and three~
five orders of magnitude lower than those of linear
model (Eq. (15)), respectively.
2. Under the condition of same chloride concentration,
the penetration depths due to chloride ions in the PC,
fly ash and slag concretes at T = 35 °C are higher than
those values at T = 5 °C.
3. After 30 years the chloride profiles predicted by the
non-linear model (Eq. (7)) may be 6.5 times lower
than that of linear model (Eq. (15)).
4. The nonlinear model (Eq. (7)) in combination with
the four mathematical modes pertain chloride binding
in concrete is not accommodated to predict the trans-
port behavior of chloride diffusion in fly ash and slag
concretes. However, the nonlinear model (Eq. (23)) is
suitable to estimate the transport properties of free
chloride diffusion in fly ash and slag concretes. The
Cl - bound in the solid phase can thus be computed al-
gebraically.
Based on the results described above, the non-linear
model (Eq. (23)) due to diffusivity with inconstant can be
used to predict the transport behavior of chloride in the
PC, fly ash, and slag concretes as if it were resonable and
accurate theory of diffusion transport. Nevertheless, it
might be accurate and convenient enough to evaluate or
predict the chloride profiles for the concretes containing
fly ash and slag by using the same method through the
further research.
References
[1] Everett, L. H. and Treadaway, K. W., “Deterioration
due to Corrosion in Reinforced Concrete,” Information
paper 12/80, Building Research Establishment, Gars-
tion, (1980).
 A Nonlinear Theoretical Study of Modelling Chloride Diffusion in Concrete Containing Fly Ash and Slag
[2] Schiessl, P., Corrosion of Steel in Concrete, RILEM
Report, Chapman and Hall, Loudon (1988).
[3] Arya, C., Buenfeld, N. R. and Newman, J. B., “Assess-
ment of Simple Methods of Determining the Free Chlo-
ride Ion Content of Cement Paste,” Cement and Con-
crete Research, Vol. 17, No. 6, pp. 907-918 (1987).
doi: 10.1016/0008-8846(88)90062-2
[4] Arya, C. and Newman, J. B., “An Assessment of Four
Methods of Determining the Free Chloride Content of
Concrete,” Materials and Structures, Vol. 23, pp. 319-
330 (1990). doi: 10.1007/BF02472710
[5] Birnin-Yauri, U. A. and Glasser, F. P., “Friedal’s Salt,
Ca2Al(OH)6(Cl, OH) × 2H2O: Its Solid Solutions and
their Pole in Chloride Binding,” Cement and Concrete
Research, Vol. 28, No. 12, pp.1713-1723 (1998). doi:
10.1016/S0008-8846(98)00162-8
[6] Lambart, P., Page, C. L. and Short, N. R., “Pore Solu-
tion Chemistry of the Hydrated System Tricalcium Sil-
icate/Sodium Chloride/Water,” Cement and Concrete
Research, Vol. 15 pp. 675-680 (1985). doi: 10.1016/
0008-8846(85)90068-7
[7] Rasheeduzzafar, Al-Saadoun, S. S., Al-Gahtani, A. S.
and Dahhil, F. H., “Effect of Tricalcium Aluminate
Content of Cement on Corrosion of Reinforcing Steel
in Concrete,” Cement and Concrete Research, Vol. 20,
pp. 723-738 (1990). doi: 10.1016/0008-8846(90)900
06-J
[8] Rasheeduzzafar, Ehtesham Hussain, S. and Al-Saadoun,
S. S., “Effect of Cement Composition on Chloride Bin-
ding and Corrosion of Reinforcing Seel in Concrete,”
Cement and Concrete Research, Vol. 21, pp. 777-794
(1991). doi: 10.1016/0008-8846(91)90173-F
[9] Rasheeduzzafer, Ehtesham Hussain, S. and Al-Saadoun,
S. S., “Effect of Tricalcium Aluminate Content of Ce-
ment on Chloride Binding and Corrosion of Reinforc-
ing Steel in Concrete,” ACI Materials Journal, Vol. 89,
No. 1, pp. 3-12 (1992). doi: 10.14359/1239
[10] Margat, P. S. and Molloy, B. T., “Chloride Binding in
Concrete Containing PFA, gbs or Silica Fume under Sea
Water Exposure,” Magazine of Concrete Research, Vol.
47, No. 171, pp. 129-141 (1995). doi: 10.1680/macr.
1995.47.171.129
[11] Friedmann, H., Amiri, O. and Aït-Mokhtar, A., “Phys-
ical Modeling of the Electrical Double Layer Effects
on Multispecies ions Transport in Cement-based Ma-
209
terials,” Cement and Concrete Research, Vol. 38, pp.
1394-1400 (2008). doi: 10.1016/j.cemconres.2008.
06.003
[12] Bourbatache, K., Millet, O., Aït-Mokhtar, A. and Amiri,
O., “Modeling the Chlorides Transport in Cementi-
tious Materials By Periodic Homogenization,” Tran-
sport in Porous Media, Vol. 94, pp. 437-459 (2012).
doi: 10.1007/s11242-012-0013-1
[13] Nilsson, L. O., Massat, M. and Tang, L., “The Effect
of Non-linear Chloride Binding on the Prediction of
Chloride Penetration into Concrete Structures,” in : V.
M. Malhotra (Ed.), Durability of Concrete, ACI, De-
troit, pp. 469-486 (1994).
[14] Anil Dogan, U., Bora Kunt, E., Görkem Saran, A. and
Hulusi Ozkul, M., “Benchmarking Concretes with
Pozzolanic Materials in Terms of Rapid Chloride Pen-
etration Test,” ACI Materials Journal, Vol. 106, No. 3,
pp. 251-257 (2009). doi: 10.14359/56549
[15] Bamforth, P. B., “In Situ Measurement of the Effect of
Partial Portland Cement Replacement using either Fly
Ash or Ground Granulated Blast-Furnace Slag on the
Performance of Mass Concrete,” Proceeding of Insti-
tution of Civil Engineers, Part 2, Vol. 69, pp. 777-800
(1980). doi: 10.1680/iicep.1981.1904
[16] Berry, E. E., Hemmings, R. T., Zhang, M. H., Cornelius,
B. J. and Golden, D. M., “Hydration in High-Volume
Fly Ash Concrete Binders,” ACI Materials Journal,
Vol. 91, No. 4, pp. 382-389 (1994). doi: 10.14359/4054
[17] Bifen, J., “Benefits of Slag and Fly Ash,” Construction
and Building Materials, Vol. 10, No. 5, pp. 309-314
(1996). doi: 10.1016/0950-0618(95)00014-3
[18] Bilodeau, A., Sivasundaram, V., Painter, K. E. and
Malhotra, V. M., “Durability of Concrete Incorporating
High Volumes of Fly Ash from Sources in the U.S.,”
ACI Materials Journal, Vol. 91, No. 1, pp. 3-12 (1994).
doi: 10.14359/4411
[19] Chowdhury, S. and Basu, P. C., “New Methodology to
Proportion Self-Consolidating Concrete with High-
Volume Fly Ash,” ACI Materials Journal, Vol. 107,
No. 3, pp. 222-230 (2010). doi: 10.14359/51663750
[20] Dhir, R. K., Ho, N. Y. and Munday, J. G. L., “Pulver-
ized Fuel Ash in Sturctural Precast Concrete,” Con-
crete, Vol. 19, No. 1, pp. 32-35 (1985).
[21] Dhir, R. K., Munday, J. G. L. and Ong, L. T., “Inves-
tigations of the Engineering Properties of OPC/Pul-
210 Wen-Hu Tsao et al.
verized-Fuel Ash Concrete: Deformation Propertied,”
The Structural Engineer, Vol. 64B, No. 2, pp. 36-42
(1988).
[22] Domone, P. L. and Soutsos, M. N., “Properties of High-
Strength Concrete Mixes Containing PFA and ggbs,”
Magazine of Concrete Research, Vol. 47, No. 173, pp.
355-367 (1995). doi: 10.1680/macr.1997.49.180.263
[23] Katyal, N. K., Sharma, J. M., Phawan, A. K., Ali, M.
M. and Mohan, K., “Development of Rapid Method
for the Estimation of Reactive Silica in Fly Ash,” Ce-
ment and Concrete Research, Vol. 38, pp. 104-106
(2008). doi: 10.1016/j.cemconres.2007.08.020
[24] Mehta, P. K. and Gjfrv, O. E., “Properties of Portland
Cement Concrete Containing Fly Ash and Condensed
Silica-Fume,” Cement and Concrete Research, Vol.
12, pp. 587-595 (1982). doi: 10.1016/0008-8846(83)
90114-X
[25] Thomas, M. D. A., Osborne, G. J., Matthews, J. D. and
Cripwell, J. B., “A Comparison of the Properties of
OPC, PFA and ggbs Concrete in Reinforced Concrete
Tank Walls of Slender Section,” Magazine of Concrete
Research, Vol. 42, No. 152, pp. 127-134 (1990). doi:
10.1680/macr.1990.42.152.127
[26] Thomas, M. D. A., “Marine Performance of PFA Con-
crete,” Magazine of Concrete Research, Vol. 4., No.
150, pp. 171-185 (1991). doi: 10.1680/macr.1992.44.
159.141
[27] Thomas, M. D. A. and Matthews, J. D., “Performance
of Fly Ash Concrete in U.K. Structures,” ACI Mate-
rials Journal, Vol. 90, No. 6, pp. 586-593 (1993). doi:
10.14359/4436
[28] Thomas, M. D. A. and Bamforth, P. B., “Modelling
Chloride Diffusion in Concrete: Effect of Fly Ash and
Slag,” Cement and Concrete Research, Vol. 29, pp.
487-495 (1999). doi: 10.1016/S0008-8846(98)00192-6
[29] Wang, X. Y., Lee, H. S. and Park, K. B., “Simulation of
Low-Calcium Fly Ash Blended Cement Hydration,”
ACI Materials Journal, Vol. 106, No. 2, pp. 167-175
(2009). doi: 10.14359/56464
[30] Zhang, Y., Sun, W., Li, Z. and Zhou, X., “Geopolymer
Extruded Composites with Incorporated Fly Ash and
Polyvinyl Alcohol Short Fiber,” ACI Materials Jour-
nal, Vol. 100, No. 1, pp. 3-10 (2009). doi: 10.14359/
56310
[31] De Ceukelaire, L. and Van Nieuwenburg, D., “Accel-
erated Carbonation of a Blast-Furnace Cement Con-
crete,” Cement and Concrete Research, Vol. 23, pp.
442-452 (1993). doi: 10.1016/0008-8846(93)90109-M
[32] Gouda, V. K., Shater, M. A. and Mikhail, R. Sh.,
“Hardened Portland Blast-Furnace Slag Cement Pastes
II. The Corrosion Behavior of Steel Reinforcement,”
Cement and Concrete Research, Vol. 5, pp. 1-13 (1975).
doi: 10.1016/0008-8846(75)90068-X
[33] Jiang, L., Lin, B. and Cai, Y., “A Model for Predicting
Carbonation of High-Volume Fly Ash Concrete,” Ce-
ment and Concrete Research, Vol. 30, pp. 699-702
(2000). doi: 10.1016/S0008-8846(00)00227-1
[34] Macphee, D. Z. and Cao, H. T., “Theoretical Descrip-
tion of Impact of Blast Furnace Slag (BFS) on Steel
Passivation in Concrete,” Magazine of Concrete Re-
search, Vol. 45, No. 162, pp. 63-69 (1993). doi: 10.
1680/macr.1994.46.167.151
[35] Sha, W. and Pereira, G. B., “Differential Scanning Cal-
orimetry Study of Hydrated Ground Granulated Blast-
Furnace Slag,” Cement and Concrete Research, Vol.
31, pp. 327-329 (2001). doi: 10.1016/S0008-8846(00)
00472-5
[36] Števule, L., Madej, J., Kozánková, J. and Madejová,
J., “Hydration Products at the Blastfurnace Slag Ag-
gregate-Cement Paste Interface,” Cement and Con-
crete Research, Vol. 24, No. 3, pp. 413-423 (1994).
doi: 10.1016/0008-8846(94)90128-7
[37] Thomas, M. D. A., Scott, A., Bremner, T., Bilodeau, A.
and Day, D., “Performance of Slag Concrete in Marine
Environment,” ACI Materials Journal, Vol. 105, No.
6, pp. 628-634 (2008). doi: 10.14359/20205
[38] Andrade, C., “Calculation of Chloride Diffusion Coef-
ficients in Concrete from Ionic Migration Measure-
ments,” Cement and Concrete Research, Vol. 3, pp.
724-742 (1993). doi: 10.1016/0008-8846(94)90067-1
[39] Xu, A. and Chandra, S., “A Discussion of the Paper
“Calculation of Chloride Diffusion Coefficients in
Concrete from Ionic Migration Measurements,” by C.
Andrada,” Cement and Concrete Research, Vol. 24, No.
2, pp. 375-379 (1994). doi: 10.1016/S0008-8846(97)
00083-5
[40] Amiri, O., Aït-Mokhtar, A. and Seigneurin, A., “A
Complement to the Discussion of A. Xu, and S. Chan-
dra about the Paper “Calculation of Chloride Coeffi-
cients Diffusion in Concrete from Ionic Migration Mea-
 A Nonlinear Theoretical Study of Modelling Chloride Diffusion in Concrete Containing Fly Ash and Slag
surements,” by C. Andrade,” Cement and Concrete
Research, Vol. 27, No. 6, pp. 951-957 (1997). doi: 10.
1016/S0008-8846(97)00082-3
[41] Martín-Pérez, B., Zibara, H., Hooton, R. D. and
Thomas, M. D. A., “A Study of the Effect of Chloride
Binding on Service Life Predictions,” Cement and
Concrete Research, Vol. 32, pp. 1215-1223 (2000).
doi: 10.1016/S0008-8846(00)00339-2
[42] Brebbia, C. A., Telles, J. C. and Wrobl, L. C., Boun-
dary Element Techniques: Theory and Application
Engineering, Springer-Verlag, New York (1984). doi:
10.1007/978-94-009-6192-0_2
[43] Gebhart, B., Heat Conduction and Mass Diffusion,
McGraw-Hill Inc., New York (1993). doi: 10.5860/
CHOICE.31-0358
[44] Kane, J. H., Boundary Element Analysis: In Engi-
neering Continuous Mechanism, Prentice Hall, Eng-
lewood (1994).
[45] O’Neil, P. V., Advanced Engineering Mathematics,
5th Edition, Brooks/Cole-Thomson Learning Inc., CA
(2003).
[46] Sun, Y. M., Chang, T. P. and Liang, M. T., “Kirchhoff
Transformation Analysis for Determining Time/Depth
Dependent Chloride Diffusion Coefficient in Con-
crete,” Journal of Material Science, Vol. 43, No. 4, pp.
1429-1437 (2008). doi: 10.1007/s10853-007-2304-4
[47] Tumidajski, P. J., Chan, G. W., Feldman, R. F. and
Strathdee, G., “A Boltzmann-Matano Analysis of Chlo-
ride Diffusion,” Cement and Concrete Research, Vol.
25, No. 7, pp. 1556-1566 (1995). doi: 10.1016/0008-
8846(95)00149-7
[48] Carslaw, H. S. and Jaeger, J. C., Conduct of Heat in
Solids, Second Edition, Oxford University Press, New
York (1959).
[49] Boddy, A., Benta, E., Thomas, M. D. A. and Hooton,
R. D., “An Overview and Sensitivity Study of a Mul-
211
timechenistic Chloride Transport Model,” Cement and
Concrete Research, Vol. 29, pp. 827-837 (1999). doi:
10.1016/S0008-8846(99)00045-9
[50] Page, C. L., Short, N. R. and El Tarras, A., “Diffusion
of Chloride Ions into Hardened Cement Paste,” Ce-
ment and Concrete Research, Vol. 11, No. 3, pp.
395-406 (1981). doi: 10.1016/0008-8846(81)90111-3
[51] Wolfam Research, Mathematica User Manual, Version
4.0, Trade Center Drive, Champaign, IL 61820-7237,
USA (1999).
[52] Crank, J., The Mathematics of Diffusion, Second Edi-
tion, Oxford University Press, London (1975).
[53] Papadakis, V. G., “Effect of Supplementary Cementing
Materials on Concrete Resistance Against Carbon-
ation and Chloride Ingress,” Cement and Concrete Re-
search, Vol. 30, pp. 291-299 (2000). doi: 10.1016/
S0008-8846(99)00249-5
[54] Papadakis, V. G. and Tsimas, S., “Supplementary Ce-
menting Materials in Concrete Part I: Efficiency and
Design,” Cement and Concrete Research, Vol. 32, pp.
1525-1532 (2002). doi: 10.1016/S0008-8846(02)00
827-X
[55] Lu, X., Li, C. and Zhang, H., “Relationship between
the Free and Total Chloride Diffusivity in Concrete,”
Cement and Concrete Research, Vol. 32, pp. 323-326
(2002). doi: 10.1016/S0008-8846(02)00970-5
[56] Fang, M. Y., Theoretical Modelling Chloride Diffusion
in Concretes Containing Fly Ash and Slag, Master
Thesis, Department of Harbor and River Engineering,
National Taiwan Ocean University, Keelung, Taiwan,
ROC (2011).
Manuscript Received: Sep. 12, 2012
Accepted: May 15, 2015