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C3S
C2S
C3A
C4AF
SG
FA
( ) H s H Q
E
R T T
i i i i T i
i
_
,
'
,
exp
0
1 1
0
Ca
2+
Ca
2+
Ca
2+
Ca
2+
+
( )
i
i
i
i
p
S
P
P
t
div K P S
t
W
t
+ = 0
Particle growth
MOISTURE
CONDUCTIVITY
Liquid + vapor
Computed from pore
structure directly
Random pore model
gel
Vapor
transport
Liquid transport
Knudsen
factor
History dependent liquid
viscosity
PORE STRUCTURE
DEVELOPMENT
Based on cement
particle expansion
Growth dependent on
the average degree
of hydration
s
a
t
u
r
a
t
i
o
n
RH
slope
MOISTURECAPACITY
Obtained from the
pore structures
(B.E.T theory)
Hysteresis isotherm
model considering
inkbottle effect
MOISTURE LOSS
DUE TO HYDRATION
Obtained directly from hydration
model. Based on reaction pattern
of each clinker component
Cement composition dependent
interaction among minerals and additive pozzolans are considered by sharing common variables
associated with pore solution, water and temperature.
During the hydration process, mass and heat energy conservations have to be satisfied with
respect to moisture and temperature. At the same time, moisture migration in terms of vapor and
liquid water and heat flux are incorporated in the conservation conditions of the second law of
thermo-dynamics. The equilibrium conditions are simultaneously to be solved together, and the mass
and energy transport resistance denoted by permeability and conductivity has to be formulated.
The permeability of vapor and liquid water is mathematically formulated based on the
micro-pore size distribution as demonstrated in Fig.3 [8][9]. The path of moisture in cement paste
is thought to be assembly of small sized fictitious pipes and its integration results in the
macroscopic permeability. Tortuosity on percolation and the thermo-dynamic activation of surface
energy onto the micro-scale viscosity of pore water are taken into account. It is to be noted that the
simple micro-mechanical modeling is applied without any variable fitting.
As a natural way, the pore structure formation model, as illustrated in Fig.4, is added in the
system dynamics of transient concrete performance modeling [1]. The statistical approach to the
Fig.5 Framework of DuCOM thermo-hygro physics
C
o
n
s
e
r
v
a
t
i
o
n
l
a
w
s
s
a
t
i
s
f
i
e
d
?
Hydration
computation
Microstructure
computation
Pore pressure
computation
N
e
x
t
I
t
e
r
a
t
i
o
n
START
yes
no
Chloride
transport and
equilibrium
I
n
c
r
e
m
e
n
t
t
i
m
e
,
c
o
n
t
i
n
u
e
Carbon dioxide
transport and
equilibrium
Corrosion model
Ion equilibrium
model
( )
( ) ( ) 0 , +
i i i i i
i
Q div
t
S
J
Governing
equations
Size, shape, mix proportions,
initial and boundary conditions
Temperature,
hydration level of
each component
Bi-modal porosity
distribution,
interlayer porosity
Pore pressures,
RH and moisture
distribution
Dissolved and
bound chloride
concentration
Carbon dioxide
transport and
equilibrium
Gas and dissolved
CO
2
concentration
pH in pore water
Gas and dissolved
O
2
concentration
Corrosion rate,
amount of O
2
consumption
Fig.4 Outline of the pore structure development computation
Matrix micro
pore structure
H
y
d
r
a
t
i
o
n
D
e
g
r
e
e
o
f
M
a
t
r
i
x
Total surface area (/m
3
)
Capillaries, gel, and interlayer
dr
r
ro
( )
r r r
Representative
CSH grain
Outer products
density at r
particle
radius
Mean
separation
max
m
The particle growth
Volume and weight of
inter and outer products
Bulk porosity of
Capillaries,
gel and interlayer
por osi
t y
0.0
1.0
outer
product
inner product
unhydrated
core
micro pore structural geometry of hardened cement paste having interlayer, C-S-H gel and
capillary pores is used. The porosity distribution of hydrated and non-hydrated compounds around
referential cement particles is calculated and the surface area of micro-pores is estimated
mathematically. By assuming statistical distribution function with regard to the pore sizes, the
authors extend the geometrical description of micro pores. The connective mode of each pore
volume is also defined with simple probability on the basis of which the path-dependency of
isotherm of moisture is successfully described [10].
Recently, in addition to the above modeling related to early age development phenomenon,
the authors have been extending the scope of DuCOM in order to cover the deterioration and
resolution of cementitious materials and steel corrosion. Here, concentrations of chloride ion,
oxide, and carbon dioxide were added to the thermo-hygro system, as additional degrees of
freedom to be solved (Fig.5). Each physical variable should satisfy the law of mass conservation
shown in Fig.5, same as the story in terms of the temperature and moisture profile computation in
the previous discussions. Potential term S(), flux term J(), and sink term Q() constituting the
governing equations, are formulated as a nonlinear function of variables
i
based on
thermodynamic theory. The obtained material properties are shared through common variables
beyond each sub-system, therefore interactive problem, such as corrosion due to simultaneous
attack of chloride ions and carbon dioxide, can be simulated in a natural way. Coupling these
materials modeling, an early age development process and deterioration phenomenon during the
service period can be evaluated for arbitrary materials, curing and environmental conditions in a
unified manner. In the following sections, the authors will introduce the general ideas of each
material modeling and its coupling system.
Formulation of Chloride Ion Transport
It is a well-known fact that chlorides in cementitious materials have free and bound
components. The bound components exist in the form of chloro aluminates and adsorbed phase on
the pore walls, making them unavailable for free transport. It has been reported that the amount of
bounded chlorides would be dependent on the binders, electric potential of pore wall, and pH in
pore solutions. However, their exact mechanisms are still not clear. In this paper, the free and
bound components of chlorides under equilibrium conditions are tentatively expressed by the
following empirical equations proposed by Maruya et al. as [11],
( )
tot
tot
tot
tot fixed
C
C
C
C
0 . 3
0 . 3 1 . 0
1 . 0
543 . 0
1 . 0 35 . 0 1
1
25 . 0
(1)
where, C
tot
; total amount of chloride [wt% of cement] (=C
free
+ C
bound
, amount of free chloride and
bound chloride, respectively),
fixed
= C
free
+ C
bound
; equilibrium ratio of fixed chloride component
to the total chloride ion component.
Considering the advective transport due to the bulk movement of pore solution phase as well
as the ionic diffusion due to concentration difference, the flux of free chlorides in pore water can
be expressed as,
S
P K
C S C D
S
Cl Cl Cl Cl
u u J (2)
where, J
Cl
T
= [J
x
J
y
J
z
] ; flux vector of the ions [mol/m
2
.s], ; porosity of the porous media, S; degree
of saturation of the porous medium, D
Cl
; diffusion coefficient of the chloride ions in pore solution
phase [m
2
/s], =(/2)
2
accounts for the average tortuosity of a single pore as a fictitious pipe for
mass transfer, and this parameter considers the tortuosity of hardened cement paste matrix, which is
uniformly and randomly connected in 3-D system [1][9],
T
= [/x /y /z] : the gradient operator,
C
Cl
: concentration of ions in the pore solution phase [mol/l], : density of water, and u
T
= [u
x
u
y
u
z
]
is the advective velocity of ions due to the bulk movement of pore solution phase [m/s]. The
advective velocity u is directly obtained from the pore pressure gradient P and moisture
conductivity K, which depends on water content, micro pore structures, and moisture history as
shown in Fig. 3. In the case of chloride ion transport in concrete, S represents the degree of saturation
in terms of the free water only, as adsorbed and interlayer components of water are also present. Here,
it has to be noted that diffusion coefficient D
Cl
would be a function of ion concentration, since ionic
interaction effects will be significant in the fine micro structures at increased concentrations, thereby
reducing the apparent diffusive movement driven by the gradient of ion concentration [12]. This
mechanism, however, is not clearly understood, therefore we neglect the dependency of the ionic
concentration on the diffusion process in the modeling. From the several numerical sensitivity
analysis, a constant value of 3.010
-11
[m
2
/s] is given for D
Cl
.
The first term on the right-hand side of Eq. (2) expresses the diffusion of ions, whereas the
second term describes the advective transport due to the bulk movement of condensed pore water.
The advective velocity of free chloride ions might be also dependent on the ion concentration,
similarly to the diffusion coefficient. In this paper, however, we assumed that the velocity vector
of ions would be equal to that of pore liquid water, since there is not enough experimental data to
establish a model for this aspect.
Material parameters shown in the Eq.(2), such as porosity, saturation and advective velocity,
are obtained directly by the thermo-hygro physics. Therefore, the flux of chloride ions can be
obtained without any empirical equations and/or intentional fittings, once mix proportions, powder
materials, curing and environmental conditions are given to the analytical system. Same story can
be applied for other modeling, say, formulation of CO
2
and O
2
transport, steel corrosion and ion
equilibrium.
The mass balance condition for free chloride can be expressed as,
( ) 0 +
Cl Cl cl
Q divJ SC
t
(3)
where, Q
Cl
; the rate of binding or the change of free chloride to bound chloride per unit volume of
concrete [mol/m
3
.s], which can be computed by assuming local equilibrium conditions shown in
the eq.(1) . From the above discussions and formulations, distribution of bounded and free
chloride ions can be obtained at arbitrary stage.
Modeling of Carbonation
For simulating carbonation phenomena in concrete, equilibrium of gas and dissolved carbon
dioxide, their transport, ionic equilibriums, and carbonation reaction process are formulated based
on thermodynamics and chemical equilibrium theory. Mass balance condition for dissolved and
gaseous carbon dioxide in porous medium can be expressed as,
( ) 0 ]} 1 [ {
2 2 2 2
+ +
CO CO dCO gCO
Q divJ S S
t
(4)
where,
gCO2
; density of CO
2
gas [kg/m
3
],
dCO2
; density of dissolved CO
2
in pore water [kg/m
3
],
J
CO2
; total flux of dissolved and gaseous CO
2
[kg/m
2
.s], Q
CO2
; sink term that represents the rate of
CO
2
consumption due to carbonation [kg/m
3
.s]. For representing local equilibrium between
gaseous and dissolved CO
2
, we use Henrys law, which states the relationship between the
solubility of gas in pore water and the partial pressure of the gas [13].
The transfer of the carbon dioxide is considered in both phases of dissolved and gaseous
carbon dioxide. The flux of carbon dioxide can be formulated based on Ficks first law of
diffusion. However, factors such as complicated pore network, Knudsen diffusion etc, reduce the
apparent diffusivity of carbon dioxide. Considering the effect of Knudsen diffusion, tortuosity, and
connectivity of pores on diffusivity, the flux of CO
2
J
CO2
can be expressed as,
( )
+
c
c
r
k
g
gCO
r
d
dCO gCO gCO dCO dCO CO
N
dV D
D dV
D
D D D J
1
0
0
0
2 2 2 2 2 2 2
(5)
where, D
gCO2
; diffusion coefficient of gaseous CO
2
in porous medium[m
2
/s], D
dCO2
; diffusion
coefficient of dissolved CO
2
in porous medium[m
2
/s], D
0
g
; diffusivity of CO
2
gas in a free
atmosphere[m
2
/s], D
0
d
; diffusivity of dissolved CO
2
in pore water [m
2
/s], V; pore volume, r
c
; pore
radius in which the equilibrated interface of liquid and vapor is created, which is determined by
thermodynamic conditions, N
k
; Knudsen number, which is the ratio of the mean free path length
of a molecule of CO
2
gas to the pore diameter. Knudsen effect on the gaseous CO
2
transport is not
negligible in low RH condition, since porous medium for gas transport becomes finer as relative
humidity decreases. As shown in eq.(5), diffusion coefficient D
dCO2
is obtained by integrating the
diffusivity of saturated pores over the entire porosity distribution, whereas D
dCO2
is obtained by
summing up the diffusivity of gaseous CO
2
through unsaturated pores.
The carbonation reaction in cementitious materials is simply described by the following
chemical reaction.
3
- 2
3
2
CaCO CO Ca +
+
(6)
The calcium ion decomposed from the dissolution of calcium hydroxide is assumed to react with
carbonate ion, whereas the reaction of silicic acid calcium hydrate (C-S-H) is not considered, since
its solubility is quite low compared with calcium hydroxide. The rate of the reaction can be
expressed by the following differential equation, assuming that the reaction is of the first order
with respect to Ca
2+
and CO
3
2-
concentrations as,
( )
] CO ][ Ca [
2
3
2
CaCO
3
2
+
k
t
C
Q
CO
(7)
where, C
CaCO3
; concentration of calcium carbonate, k is a reaction rate coefficient, which shows
the temperature dependence. In the current stage, we focus on the carbonation phenomenon under
constant temperature, and coefficient k is assumed to be constant (k=2.08 [l/mol.sec]) determined
from several sensitivity analyses. The authors understand that the formulation based on the
Arrhenius law of chemical reaction should be considered for more generic treatment.
In order to calculate the rate of reaction with eq.(7), it is necessary to obtain the concentration
of calcium ion and carbonic acid in the pore water at arbitrary stage. In this study, we consider the
following ion equilibriums; the dissociation of water and carbonic acid, and the dissolution and
the dissociation of calcium hydroxide and calcium carbonate. Here, the presence of chlorides is
not considered, although we understand that chloride ions are likely to affect the equilibrium
conditions. The formulation including chlorides remains for future study.
+ +
+
+ +
+
2
3 3 3 2
2
CO 2H HCO H CO H
OH H O H
( )
- 2
3
2
3
2
2
CO Ca CaCO
2OH Ca OH Ca
+
+
+
+
(8)
Although the hydronium ion H
3
O
+
is present in water and confers acidic properties upon aqueous
solutions, it is customary to use the symbol H
+
in place of H
3
O
+
. As shown in eq.(8), carbonation
is an acid-base reaction, where cation and anion act as Brnsted acid and base respectively.
Furthermore, the solubility of precipitations is dependent on pH in pore solutions. Therefore,
according to the basic principles on ion equilibrium, the authors aim to formulate the carbonate
reaction in concrete [14].
First of all, let us consider the equilibrium reaction of carbonic acid. From the law of mass
action, the corresponding equilibrium expression is,
] OH ][ H [
+
w
K
] HCO [
] CO ][ H [
] CO H [
] HCO ][ H [
3
2
3
3 2
3
+ +
b a
K K (9)
where, K
i
is the equilibrium constant of concentration for each dissociation, we give these values
as, K
w
=1.0010
-14
, K
a
=1.0010
-14
, K
b
=4.7910
-14
at 25 respectively [13]. Next, the mass
conservation law is applied for the ions from dissolution of carbon dioxide and re-dissolution of
calcium carbonate.
[ ] [ ] [ ]
- 2
3
-
3 3 2 1 0
CO HCO CO H + + + S C (10)
where, C
0
is the concentration of dissolved carbon dioxide [mol/l], which can be obtained from
dCO2
in eq.(4). S
1
is the solubility of calcium carbonate, which can be calculated by the
solubility-product constant. Using eq.(9) and (10), concentrations of H
2
CO
3
, HCO
3
-
and CO
3
2-
can
be obtained as,
( )
( )
( )
b a a
b a
b a a
a
b a a
K K K
K K
S C
K K K
K
S C
K K K
S C
+ +
+
+ +
+
+ +
+
+ +
+ +
+
+ +
+
] H [ ] H [
] [CO
] H [ ] H [
] H [
] [HCO
] H [ ] H [
] H [
] CO [H
2
2 1 0 2
- 2
3
2
1 1 0 1
-
3
2
2
0 1 0 0 3 2
(11)
The solubility of calcium carbonate can be obtained by the following relationship as,
] CO ][ Ca [
2
3
2 1 +
sp
K (12)
where,
1
sp
K is the solubility-product constant of the calcium carbonate (=4.710
-9
, at 25).
Similarly, the solubility of calcium hydroxide can be calculated as,
2 - 2 2
] OH ][ Ca [
+
sp
K (13)
where,
2
sp
K is the solubility-product constant of the calcium hydroxide (=5.510
-6
, at 25) [13].
Considering the common ion effect on the each solubility, eq. (12) and eq. (13) can be replaced
with the solubility of calcium carbonate S
1
and that of calcium hydroxide S
2
as,
( ) ( ) ( ) [ ]
2
-
2 1
2
1 0 2 2 1
1
OH + + + S S K S C S S K
sp sp
(14)
From the mass conservation conditions, concentration of ions should satisfy the following
relationships.
d d d
C ] CO [ ] HCO [ ] CO H [
- 2
3
-
3 3 2 0
+ + (15)
s s s s
S ] Ca [ ] CO [ ] HCO [ ] CO H [
2 - 2
3
-
3 3 2 1
+
+ +
c
S ] Ca [
2
2
+
(16)
where, [i]
d
, [i]
s
, and [i]
c
are the concentration of ion from the dissolution of CO
2
gas, calcium
carbonate and calcium hydroxide, respectively. For example, the total concentration of carbonic
acid [H
2
CO
3
] shown in eq. (9) becomes the summation of [H
2
CO
3
]
d
from CO
2
gas and [H
2
CO
3
]
s
from CaCO
3
.
In addition, the above ions should satisfy the law of proton balance, in which the amount of
donor is equal to that of accepter in terms of proton in the Brnsted-Lowry theory. The equation
deduced by the law of proton balance is obtained as,
c c s s c
] CO [ 2 ] HCO [ ] OH [ ] HCO [ ] CO H [ 2 ] Ca [ 2 ] H [
- 2
3
-
3 3 3 2
2
+ + + + +
+ +
(17)
From the above equations describing the conditions of ion equilibrium, finally we obtain as,
[ ]
0 2 0 1 1 1 0 1 2
2 H 2 2 ] H [ C C K S S S
w
+ + + + +
+ +
(18)
Using eq.(18), the concentration of proton in pore solutions can be calculated at arbitrary
stage, once the concentration of calcium hydroxide and that of carbonic acid before dissociation
are given.
It has been reported that micro-pore structure in cementitious materials would be changed
due to carbonation. In this paper, the authors use an empirical set of equations that are proposed by
Saeki et al. as [15],
( )
6 . 0 0.5
0 . 1 0.6
2
2 2
Ca(OH)
Ca(OH) Ca(OH)
< <
R
R R
(19)
where, ; porosity after carbonation, R
Ca(OH)2
; the ratio of the amount of consumed Ca(OH)
2
for
the total amount of Ca(OH)
2
.
Micro-Cell Based Corrosion Model
In this section, we introduce the general scheme of micro-cell corrosion model based on
thermodynamics and electro-chemistry. In our modeling, it has been assumed that the steel
corrosion would occur uniformly over the surface areas of the reinforcing bars in a finite volume,
whereas the formation of pits due to localized attack of chlorides and the corrosion with macro
cell remains for future study. For making it possible to treat the formation of macro cell, we
understand that it is necessary to consider magneto-electrical field governed by Maxwells
principle as well as the mass, momentum and energy conservations. Fig.6 shows the flow of the
computation of corrosion rate. When we consider the micro-cell based corrosion, it can be
assumed that the area of anode is equal to that of cathode and they are not separated from each
other. Therefore, we do not treat the electrical conductivity of concrete, which governs the
macroscopic transfer of ions in pore water.
First of all, electric potential of corrosion cell is obtained from the ambient temperature, pH
in pore solution and partial pressure of oxide, which are calculated by other subroutine in the
system. The potential of half-cell can be expressed with the Nernst equation as [16],
( ) ( ) ( )
( )
+
+
+
+
2
Fe Fe Fe
Fe
2
ln
Pt aq Fe s Fe
h F z RT E E
e
( ) ( ) ( ) ( )
( ) ( ) pH P P F z RT E E
e
06 . 0 ln
aq OH 4 Pt 4 l O H 2 g O
2
O 2
2
O
2
O
O
-
2 2
+
+ +
(20)
where, E
Fe
; standard cell potential of Fe, anode (V, SHE), E
O2
; standard cell potential of O
2
,
cathode (V, SHE), E
Fe
; standard cell potential of Fe at 25 (=-0.44V,SHE), E
O2
; standard cell
potential of O
2
at 25 (=0.40V,SHE), z
Fe
; the number of charge of Fe ions (=2), z
O2
; the number
of charge of O
2
(=2), P
'
+ + +
+