CONCRETE CARBONATION MODELING

1. INTRODUCTION

In order to estimate the service life of reinforced concrete structures that are severely impacted by
carbonation, numerous models have been presented, but this is not a simple concept to analyze.
Starting from the aggressive diffusion of gasses in the environment to the initiation of decaying and
corrosion, there are number of uncertainties and variables that must be analyzed. (Bakker, 1988)

2. MODELS FOR PREDICTING CARBONATION

Owing to the sophistication of the processes that this method entails, modelling the
progression of carbonation is often a challenging task. The process of carbonation is regulated by the
diffusion of CO2. This diffusion takes place through the pores present in the concrete structure.
Various factors like CO2 concentration, temperature, moisture and nature of cement controls the
diffusion rate. By evaluating all these variables collectively, properties like capacity of penetration of
alkali content can be measured.

Few of the most popular computational models being used to estimate the service life of
carbonation susceptible concrete structures are discussed below.

2.1 ANALYTICAL MODEL

This particular model is based on the supposition that in pores of concrete, all three phases of
CO2 (Solid, liquid and gaseous) occurs in an equilibrium state. The analytical model can be
expressed in 2 steps on the basis of the process of carbonation.

The first step is a physical process based on the assumption that CO 2, from the atmosphere,
diffuses in to the concrete via inter-connected spaces presented in the concrete structure and
this CO2 immediately dissolves into water present in these spaces (Ueki et al., 2002).
Calculations for this diffusion can be done by using the following equation;

δC δ2 C
=D CO −∆ C s
δt δx 2
2

Where,
C = CO2 Concentration (mol/L)
DCO2 = Diffusion co-efficient of CO2 in concrete (cm²/sec)
t = Time (second)
x = Distance from concrete surface (cm)
ΔCs = Diffused CO2 Quantity, dissolved per Δt (mol /L /sec)

Following assumptions holds the basis of this physical model:

 CO2 which is present in Gaseous state, diffuses through one dimension i.e. in the
direction of depth through the concrete.
 No liquid phase movement is factored into the equation.
  The coefficient of diffusion of carbon dioxide and water content in concrete remains
constant.
 There is a constant accumulation of carbon dioxide on the concrete surface.

After the first step the second step involves the process of attaining the chemical equilibrium
and this step is based on the assumption that reaction of carbonation immediately moves to
the equilibrium state. As a result, the rate of carbonation reaction is a function of the rate of
diffusion (Ueki et al., 2002)
Following assumptions hold the basis of this model:
 Alkalis and the Calcium oxide are the elements reacting with CO 2
 The material that does not undergo any reaction and the products from the hydration
reaction yield all the components mentioned above.
 The equilibrium between the solid and liquid state is always present.
 The equilibrium between the liquid and gaseous state is always present.
The modelling of these gaseous, liquid and solid phase equilibriums in the concrete is shown
in Figure 1 below.

Figure 1: Model for Chemical Equilibrium

The reversible reactions take place between all the chemical equilibrium reactions. The depth
below the surface up to which calcium hydroxide is present in solid state is the depth up to
which the reaction of carbonation take place. The depth of carbonation reaction may be
influenced by the coefficient of diffusion and the amount of calcium reacting.

2.2 RECYCLED AGGREGATE CONCRETE MODEL

Another most popular approaches used for the assessment of the carbonation process is
Recycled Aggregate Concrete (RAC). Carbonation of recycled aggregate concrete can be
estimated as per this model with the help of following equation.(Zhang and Xiao, 2018)
k ac
x= √t
ke
C d . ke
k ac=
γ s t sl
Where,
x = Depth of Carbonation (mm)
 kac = Co-efficient of accelerated carbonation (mm. year 0.5)
Cd = Design value for the Reinforcement cover (mm)
k e = Environmental exposure factor of RAC (9.9 for medium humid environment and
15.0 for dry and wet cyclic environment)
ϒ s = Safety Factor (1.0 for medium humid environment and 1.25 for dry and wet
cyclic environment)
tsl = Service life Stated (years)
RAC carbonation depends, as per this model, on many aspects relevant to the use of recycled
aggregates, which are discussed below.
2.2.1 RECYCLED AGGREGATE REPLACEMENT RATIO

Usually, substitution ratio of the recycled aggregate varies in accordance with the depth of
carbonation reaction. The water absorption ability of Recycled Aggregate Concrete (RAC) is
way more than that of Natural Aggregate Concrete (NAC). This results in the increased
porosity in the Recycled Aggregate Concrete (RAC) for a constant value of water to cement
ratio thus resulting in the reduced resistance against the carbonation reactions. (Carević,
Ignjatović and Dragaš, 2019)
2.2.2 RECYCLED AGGREGATE SUBJECTED TO DIFFERENT CRUSHING
PROCEDURES

The technique adopted for the crushing has an important effect on the properties of RAC. For
RAC, two types of crushing techniques are present, that are Primary crushing procedure and
Primary plus secondary crushing procedure.
The depth of carbonation depends on the technique used for crushing. The depth is lesser
when both primary and secondary technique is being applied as compared to the depth
obtained when only primary crushing technique is used. The main reason for the reduction in
the carbonation reaction depth is the spherical shape of aggregate resulting from the
secondary crushing technique. Better packing of concrete elements is achieved in this way
and the porosity is decreased. (Carević, Ignjatović and Dragaš, 2019)
2.2.3 EXPOSURE TO DIFFERENT CURING CONDITIONS

In general, the sensitivity of RACs to varying environments has a major effect on the depth of
carbonation compared to that of the equivalent NAC blends. The depth of carbonation
reaction for all samples generally increased when curing was done in a drier environment and
vice versa.
2.2.4 INFLUENCE OF THE WATER REDUCING ADMIXTURES

More water is required to maintain the workability of RCA due to higher water absorptions
and rougher surface as compared to the NAC. Plasticizers can be used along with RCA to
ensure the same workability while keeping all other variable same as in an equivalent sample
for NAC. Hydration time of cement is decreased by using super plasticizers resulting in the
extended curing time thus improving the depth of carbonation reaction.
On the basis of all of these factors, it is clear that RAC mixes possess sufficient reliability of
carbonation resistance to meet the target of service life and thus RAC is a good solution for
reinforced concrete structures subject to corrosion caused by carbonation. Moreover, their
design is relatively easier.
 2.3 SILICA FUME MODEL
Silica fume model stems from the similarities between the pozzolonic action and the cement
hydration. The water and cement reacts in the first step and the glass phase of pozzolonic
material and calcium hydroxide undergo a reaction. Boundary reaction time, an initial
dormant time and diffusion period are included in this step. Diffusion is the primary factor
that controls the reaction in the later stages of hydration. In the second step, the unreacted
particle’s surface gets covered with the products formed as the result of hydration reaction. In
the third step only the bigger particles undergo dormant period. However, silica fume particles
are very small thus showing no initial dormant period (Wang and Lee, 2009). In addition to
this, some variations between cement hydration and pozzolonic activity are also present. The
pozzolonic action is the result of consumption of calcium hydroxide which produced by
hydration of cement. Therefore, to estimate the carbonation reaction of Silica Fume-Concrete,
the following mathematical model can be used;
x=√ ¿
a
εc RH b
De = A
(
C P W
+ +
ρC ρ P ρW ) (1−
100
)

Where,
x = Depth of Carbonation (m)
De = Effective diffusivity of CO2
[CO2] = Molar concentration of CO2
t = time (sec)
CH = calcium hydroxide quantity to be used in hydration period
CSH = calcium silicate hydrate quantity used in hydration period
ϵc = carbonated concrete porosity
RH = Relative Humidity of environment
ρC , ρ p , ρw are the density of cement , silica fume∧water .
A, a, b are parameters regressed from measured carbonation depth

2.4 HIGH VOLUME FLY ASH MODEL

High volume fly ash model says that microstructure of the fly ash is responsible for the
resisting the carbonation reaction. Fly ash undergo pozzolonic reaction and thus the amount of
calcium hydroxide is significantly reduced in the concrete. Since the depth of carbonation is
higher, a greater proportion of concrete will be carbonated by the same volume of carbon
dioxide. Thus the carbonation rate and carbonated region is improved by the addition of CO 2
(Zhang, Cheng and Zhu, 2020).
In order to determine the depth of carbonation reaction involving large volume of fly ash in
concrete, a series of research surveys have been conducted resulting in a mathematical model
depending upon the fly ash quality. This analysis implies that the microstructure will not
change over time in the concrete in which diffusion takes place. HVFA carbonation depends
on many variables as per this model, including time required for curing, water cement ratio,
 exposure time, way of adding flay ash in concrete mix. The adjustment coefficient whose
value depends on the fitting function is implemented to take these variables into account when
predicting carbonation. The Following mathematical relation can be used for this model,
(Woyciechowski, Woliński and Adamczewski, 2019)
x=ab √ t
0.76
a=1.753− ( P−14.59)/ 3.748
1+e
Where,
x = Depth of Carbonation (mm)
a = adjustment coefficient for Fly ash
b = Adjustment coefficient for all other factors (taken equal to 2.78)
t = time for Carbonization (day)
P = Fly Ash content (%)

2.5 STATISTICAL MODEL

By applying the multiple linear regression technique, considering the coefficient of
carbonation as the dependent variable while concrete factors like molding conditions,
exposure to the environment and curing as independent variables, the statistical simulation of
carbonation phenomenon of concrete was carried out (Silva, Neves and De Brito, 2014).
Statistical Analysis introduces 2 mathematical equations to estimate the Concrete carbonation
as given below. These equations depend on the proportion of relative humidity (RH).

k d=0.556 c−3.62 X−0.148 f c + 18.734 for RH ≤70 %

k w =3.355 c−0.019 C−0.042 f c +10.83 for RH >70 %
Where,
kd = Carbonation coefficient (mm/year0.5) for RH ≤ 70%
kw = Carbonation coefficient (mm/year0.5) for RH > 70%
c = CO2 content (%)
X = Exposure factor (1 for dry, 2 for medium humid environment and 3 for dry
and wet cyclic environment)
C = Clinker content (kg/m 3)
fc = 28-day compressive strength (MPa)
It is possible to revise the depth of carbonation as a function of the RH in the surroundings
when the carbonation coefficient has been determined.
h=k d √ t for RH ≤ 70 %

h=k w √ t for RH >70 %

Where,
h = Carbonation depth (mm)
t = CO2 exposure time (years)
 It is easy to implement and acknowledge the statistical approach suggested above, but it
contains some uncertainties. This would not impair its implementation, because it can be seen
as a way of approximating facts and providing evidence for future research & innovation. In a
mix design, it could be helpful to limit the large number of variables including target
compressive strength or clinker material. It is assumed that it is indeed reasonable to estimate
the service life in existing buildings, if there is no experimental evaluation of depths of
carbonation and data on properties of concrete and fabrication techniques is available, given
that it is compatible with the concepts.

2.6 META MODEL

For the structures affected by the environmental and atmospheric conditions, the depth of
carbonation can be estimated by using this semi-empirical approach called Meta model. The
absorbed amount of CO2 and diffusion coefficient of CO2 is used in this model. Various
variables involved in this model include: sand to gravel ratio, mix design of concrete, type of
cement, cement’s chemical composition, maximum aggregate size, external relative humidity,
temperature of the surrounding environment and the Concentration of CO 2 present in the air.
(Ta et al., 2016)
The mathematical form for this model is as:

2 DCO [ CO2 ] ext

x CO =
2
√ 2

a
.√ t

M CO
a=0.75 x C x CaO x φclinker x 2

M CaO
Where,
XCO2 = Carbonation depth (m)
DCO2 = diffusion coefficient of CO2 (m2/sec)
[CO2]ext = CO2 Molar concentration
t = exposure time of CO 2 (sec)
a = Amount of CO 2 absorbed (kg/m3)
C = Amount of cement content (kg/m 3)
CaO = Amount of calcium oxide per weight of cement
MCO2 = Molar weight of CO2 (gm/mol)
MCaO = Molar weight of CaO (gm/mol)
Ɵclinker = Cement clinker content

The advantage of using the semi-empirical Meta Model is that a complete theoretical analysis
will explicitly take into account the existence of all parameters involved in the model.
Therefore, in order to evaluate more efficient options for durability of material in terms of
carbonation, additional research should be conducted on this model.
 REFERENCES

1. Bakker, R. F. . (1988) ‘Initiation Period, in Corrosion of Steel in Concrete’, pp. 22–55.

2. Carević, V., Ignjatović, I. and Dragaš, J. (2019) ‘Model for practical carbonation depth prediction
for high volume fly ash concrete and recycled aggregate concrete’, Construction and Building
Materials, 213, pp. 194–208. doi: 10.1016/j.conbuildmat.2019.03.267.
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concrete’, Cement and Concrete Composites, 50, pp. 73–81. doi:
10.1016/j.cemconcomp.2013.12.001.
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structures’, Construction and Building Materials, 129, pp. 172–181. doi:
10.1016/j.conbuildmat.2016.10.103.
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