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Tetsuya ISHlDA and Koichi MAEKAWA
The objective of this study is to establish a computational system that can evaluate structural
petformances exposed to various environmentaVweather actions. In this study, equilibriurn,
adsorption/desorption, and transport phenomena of gas and ion, and corrosion of reinforcing
bars in concrete are formulated based on thermodynamics and electrochemistry. The core of
these formulations is based on thermodynamic couplings of moisture transport, powder
material hydration and the microstructure formation phenomenon's with very few assumed
funciional relationships. Preliminary simulation studies related to chloride transport,
carbonation and corrosion show the versatility and extensibility of the proposed schemes.
For the sustainable developrnent in the corning century, it is required that infrastructures retain the
required performances over the long terrn. In order to construct a durable and reliable structure, it is
necessary to evaluate a life cycle cost and its benefit as well as an initial const of construction. On the
other hand, for an already deteriorated structure, a rational maintenance and repair should be
conducted in accordance with the condition of the structure. Considering these rnatters, it is
indispensable to grasp the structural performances under the expected environmental and load
conditions during the service life.
In this study, equilibriurn, adsorption/desorption, and transport phenornena of gas and ion, and
corrosion of reinforcing bars in concrete are forrnulated based on therrnodynarnics and
electrochernistry. These rnaterial rnodels are installed into a therrno-hygro systern narned DuCOM,
which originally covered the developrnent of cernentitious rnaterials at early age [Maekawagg]. By the
proposed rnodels and their coupling systern, the authors airn to evaluate deterioration phenornena of
rnaterials and structures for under long-term environrnental actions.
Fig.1 shows an outline of the overall cornputational scherne of therrno-hygro systern DuCOM, which can
give the solutions of the material properties frorn birth to death. Developrnent of cernentitious rnaterials at
early age is traced by considering the rnutual linkage of hydration, rnoisture transport and pore structure
formation. The detailed discussions of these rnaterial rnodeling and their coupling systern are ornitted
here, since the details were already presented in other literatures [Maekawagg]. In this study, the authors
have extended the siope of this systern in order to cover the deterioration and degradation of
cernentitious rnaterials and steel corrosion under long-terrn environrnental actions. For that purpose,
concentrations of chloride ion, oxide, and carbon dioxide were added to the therrno-hygro systern as
additional degrees of freedorn to be solved. The inputs required in this scherne are rnix proportion,
powder rnaterial characteristic, casting ternperature, the geornetry of the target structure, and the
boundary conditions to which the structure will be exposed during its life cycle. In analysis, each degree
of freedom i (pore pressure, ternperature, concentration of chloride ions, carbon dioxide and oxygen)
should satisfy rnass and energy conservation law with sirnultaneous therrno-dynarnic equilibriurn
conditions. Potential terrn S(0), flux terrn J(0), and sink terrn Q(0) constituting the governing equations,
are forrnulated as a nonlinear function of variables 0; based on thermodynarnic theory. The obtained
rnaterial properties are shared through cornrnon variables beyond each sub-systern, therefore interactive
problern, such as corrosion due to sirnultaneous attack of chloride ions and carbon dioxide, can be
sirnulated in a natural way. Coupling these rnaterials rnodeling, an early age developrnent process and
deterioration phenornenon during the service period can be evaluated for arbitrary rnaterials, curing and
environrnental conditions in a unified rnanner. In the following sections, the authors will briefly introduce
the general ideas of each rnaterial rnodeling and its coupling systern
iWandbomcWy -+diwJ,(,,~,)-Q(~,)=o
Twics in this DaDer
Fig.1 Framework of DuCOM thermo-hygro physics
Chloride transport in cementitious materials under usual condition is an advective-diffusive
phenomenon. In the modeling, the advective transport due to the bulk movement of pore solution
phase is considered, as well as the ionic diffusion due to the difference of concentration. The mass
balance condition for free (movable) ion can be expressed as,
where, $; porosity of the porous media, S; degree of saturation of the porous medium, Co:
concentration of ions in the pore solution phase [molll], Jc,; flux vector of the ions [mol/m2.s], ~ = ( d 2 ) ~
accounts for the tortuosity for a 3-D pore network which is uniformly and randomly connected, uT = [u,
u,, u,] is the advective velocity of ions due to the bulk movement of pore solution phase [mls]. Material
parameters shown in Eq. (l), 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 andlor intentional fittings, once mix proportions, powder materials, curing and environmental
conditions are given to the analytical system. Here, it is a well-known fact that chlorides in
ce.mentitious materials have free and bound components. The bound components exist in the form of
chloro aluminates and adsorbed phase on the pore walls, In this study, the relationship between free
and bound components of chlorides under equilibrium conditions are expressed by the empirical
formulation proposed by Maruya [Maruya98]. Qo, which accounts for the rate of binding or the change
of free chloride to bound chloride per unit volume of concrete, can be obtained by Maruya's model.
From the above discussions and formulations, distribution of bounded and free chloride ions can be
obtained at arbitrary stage.
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,
where, pgco2; density of CO2 gas [kgIrni, pdcy; density of dissolved CO2 in pore water [kglm3], Jmz;
total flux of dissolved and gaseous CO2 [kglm .SI. For representing local equilibrium between gaseous
and dissolved CO2, we use Henry's law, which states the relationship between the solubility of gas in
pore water and the partial pressure of the gas. 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 Fick's first law of diffusion, considering the effect of Knudsen diffusion, tortuosity, and connectivity
of pores on diffusivity. QCO2 in the above equation is a sink term that represents the rate of CO2
consumption due to carbonation [kglm3.s]. The rate of CO2 consumption can be expressed by the
following differential equation, assuming that the reaction is of the first order with respect to ca2' and
~ 0 3 ~ - concentrations as,
Ca2+ + CO:- + CaCO,
where, Ccac03;concentration of calcium carbonate, k is a reaction rate coefficient. In order to calculate
the rate of reaction with Eq. (3), 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;
dissociation of water.and carbonic acid, and dissolution and dissociation of calcium hydroxide and
calcium carbonate.
H20 H H' +OH- c~(oH), ++ ca2+ + 20H-
, ..
H2C03 H H+ + HC0; w 2H' +CO:- CaCO, w Ca2' +CO:-
As shown in Eq. (4), carbonation is an acid-base reaction, where cation and anion act as Bronsted
acid and base respectively. Furthermore, the solubility of precipitations is dependent on pH in pore
solutions. Therefore, in order to calculate the ionic concentration in the pore solutions, the authors
formulated an equation with respect to proton [H'], according to the basic principles on ion equilibrium;
laws of mass action, mass conservation, and proton balance in the system [lshida99]. Using this
equation, 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.
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 corrosion would occur uniformly over
Cornputation of
Evaluation of the condition _
the surface areas of the reinforcing bars in a finite
electric potential
-b of the passivity
volume, whereas the formation of pits due to localized
of corrosion
attack of chlorides and the corrosion with macro cell ,
remains for future study. Fig.2 shows the flow of the output
computation of corrosion rate. First of all, electric
in pore water
potential of corrosion cell is obtained from the ambient
~h-iount of steel
temperature, pH in pore solution and partial pressure of
oxide. which are calculated by other subroutine in the
Cornputation of the
corrosion rate
system. Next, based on the thermo-dynamical
conditions, the condition of passive layers is evaluated Fig.2 Overall scheme of corroion computation
by the Pourbaix diagram, depending upon the pH and
the potential of the steel. From the electric potential
and the formation of passive layers, electric current that involves chemical reaction can be calculated so
that conservation law of electric charge should be satisfied in a local area. When the amount of oxygen
supplied to the reaction is not enough, the rate of corrosion would be controlled by the diffusion process
of oxygen. In this research, coupling with oxygen transport model, this phenomenon can be simulated.
Finally, using the Faraday's law, electric current of corrosion is converted to the rate of steel corrosion.
The detailed discussions on the formulations of the oxygen and steel corrosion are omitted for lack of
space [lshida99].
Using the proposed method, transport of chloride ion under alternate drying wetting conditions were
simulated. For verification, the experimental data by Maruya et al. were used. The size of mortar
specimens were 5x5~10 [cm] and the water to powder ratio was 50%. After 28 days of sealed curing,
the specimens were exposed to cyclic alternate drying (7 days) and wetting (7 days) cycles. The
drying condition was 60%RH, whereas the wetting was exposed to a chloride solution of 0.51 [mol/l] at
20.. In the FEM analysis, mix proportions and the chemical composition of the cements (&A, C4AF,
C3S, CpS, and gypsum) were given. The curing conditions and exposure conditions were also given as
boundary conditions for the target structures. All of these input values corresponded to the
experimental conditions. Fig.3 shows the distribution of free and bound chlorides from the boundary
surface. For comparison, we analyzed two cases; one considering only diffusive movement, and the
other including the advective transport due to the bulk movement of pore water as well as the diffusion
process. As shown in the analytical results, the distribution of bound and free chlorides can be
reasonably simulated with advective transport due to the rapid suction of pore water under wetting
nictanre frnm the C I I ~ ~ C P Iml
Depth of carbonation[mm]
- - - - - - -.
Secondly, computations were performed to predicchIoride
[*% Of
Chloride content [wt% of cernent]
Depth of carbonation[mm]
' ' ' 1 W/CSO% WlC6OX WIC7OI - - -
- - - -
Cornputation Experirnent
Advective transport
concentrations and water to cement ratio. The amount of Ca(OH)2 existing in cementitious materials
can be obtained by multi-component hydration. First, the accelerated carbonation tests were studied.
For verification, the experimental data done by Uomoto et al were used [Uomoto93]. Fig.4 shows the
comparison of analytical results and empirical formula that was regressed with the square root t
equation. Analytical results show the relationship between the depth of concrete in which pH in pore
water becomes less than 10.0 and exposed time. The simulations can roughly predict the progress of
carbonation for different CO2 concentration and water to powder ratio. Fig.5 shows the distribution of
pH in pore water, CO2, calcium hydroxide, and calcium carbonate inside concrete, exposed to the CO2
concentration of 3%. Two different water to powder ratio, W/C=25% and 50%, were analyzed. It can
be shown that higher resistance for the carbonic acid action is achieved in the case of low WIC.
Wetting 7days
CI ion:0.5l[rnol/l]
Diffusion only
0.01 0.02 0.03 0.04 0.05
Distance frorn the surface [rn]
0.01 0.02 0.03 0.04 O.O%te exposea to cyciic wetting ana arying
After 182days Markers : Test data (Mawya et al.)
Lines : Cornputation
Drying 7days
Corrosion of steel in concrete due to sirnultaneous attack of chloride ions and carbon dioxide were
Ca(OH)2 [kglm31 CaC03 [molll] PH CO2 [molll]
After 1800days
8 ', CO2 After 1800days
O 2 4 6 8 10 12
Distance from the surface [cm] Distance from the surface [cm]
Fig.5 Distribution of pH, calcium hydroxide and calcil lm carhnnate I inder the actinn nf carhnnir: acid
Structural age until cracking due to corrosion [year]
sirnulated. One-dirnensional concrete rnernbers c02:3%
that have three different water to powder ratio,
WlC=40, 50, 60%, with only one face exposed to
the environrnent were considered. In this
analysis, the stage where concrete cracking 20 99%RH I Oda~s
occurs was defined as a lirnit state with respect
to the steel corrosion. The progressive period
until the initiation of longitudinal cracking were IO
estirnated by the equation proposed by Yokozeki
et al. which is a function of cover depth
[Yokozeki97]. Fig.6 shows the relationships
between cover depth and structural age until
O 20 40 60 80 100 120
Cover depth [mm]
cracking due to corrosion obtained by the
proposed therrno-hygro systern. It cari be seen Fig.6 Tirne till first signs of cracking due to corrosion
that the concrete nearer to the exposure surface
for concrete exposed to CO2 gas and salty
would show early sign of corrosion induced
cracking, and low WIC concrete has a higher
resistance against corrosion.
Therrno-dynarnical based rnodels for chloride transport, pH fluctuation, ions equilibriurn, transport and
equilibriurn of oxide and carbon dioxide, and steel corrosion were presented in this paper. Material
pararneters needed in the formulations were obtained by therrno-hygro systern, sirnulating an early
age developrnent process. Coupling these rnaterials rnodeling, deterioration phenornenon during the
service period can be evaluated for arbitrary rnaterials, curing and environrnental conditions in a
unified rnanner. Nurnerical verifications show that this rnethod can roughly predict ingress of ion,
carbonation and corrosion phenornena for different rnaterials, curing and environrnental conditions.
Through further research and effort for generalization and upgrading of rnaterial rnodels, the authors
understand that this frarnework can be served as so-called lifespan simulation in future.
[Maekawa991 Maekawa, K., Chaube, R.P. and Kishi, T. Modeling of Concrete Performance, E&FN SPON,
[Maruya98] Maruya, T., Tangtemsirikul, S. and Matsuoka, Y. Modeling of chloride ion rnovernent in the
surface layer of hardened concrete, Concrete Library of JSCE, No.32, pp.69-84, 1998
[Freiser63] Freiser, H. and Fernando, Q. lonic equilibria in analytical chemistry, John Wiley and Sons, Inc., 1963
[Uornoto93] Uornoto, T. and Takada, Y. Factors affecting concrete carbonation and prediction of carbonation
process of concrete, Concrete Library of JSCE, No.21, pp.31-44, 1991
[Yoikozeki97] Yokozeki, K., Motohashi, K., Okada, K. and Tsutsurni, T. A rational rnodel to predict the service
life of RC structures in marine environment, Forth CANMETIACI International Conference on Durability of
Concrete, SP 170-40, pp.777-798, 1997
[Ishida99] Ishida, T. An integrated computational systern of masslenergy generation, transport and rnechanics
of rnaterials and structures, PhD thesis submitted to University of Tokyo, 1999