Cement and Concrete Composites 125 (2022) 104315

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Cement and Concrete Composites

journal homepage: www.elsevier.com/locate/cemconcomp

A review on the modelling of carbonation of hardened and fresh

cement-based materials
Xujia You a, b, Xiang Hu a, b, **, Pingping He a, b, Jianhui Liu a, b, Caijun Shi a, b, c, *
a
Key Laboratory for Green & Advanced Civil Engineering Materials and Application Technology of Hunan Province, International Science Innovation Collaboration Base
for Green & Advanced Civil Engineering Materials of Hunan Province, College of Civil Engineering, Hunan University, Changsha, 410082, PR China
b
Key Laboratory of Building Safety and Energy Efficiency of the Ministry of Education, Hunan University, Changsha, 410082, China
c
Department of Civil Engineering, The University of British Columbia, 6250 Applied Science Lane, Vancouver, BC, V6T 1Z4, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: Different models have been proposed to investigate and predict the carbonation process of cement-based ma­
Carbonation terials. This paper firstly introduces the carbonation process occurred in cement-based materials and those
Early CO2 curing influential factors. Then the proposed empirical, thermodynamic, kinetic and numerical models to characterize
Cement-based materials
the carbonation process of cement-based materials are reviewed. The theoretical basis, input parameters and
Modelling
major applications of different models are summarized and discussed. The advantages and disadvantages of those
models are comparatively reviewed. Finally, modelling of early CO2 curing of fresh cement-based materials is
also reviewed and compared with the carbonation of hardened cement-based materials.

1. Introduction
Carbonation of cement-based materials refers to the process that CO2
diffuses into the material through the pores, and then reacts with hy­
dration products and unhydrated cement clinker minerals. During the
carbonation process of hardened cement-based materials, calcium hy­
droxide (CH) is continuously consumed. Besides, other hydration
products such as calcium silicate hydrate (CSH) also take part in the
carbonation process, resulting in the shrinkage and cracking of cement-
based materials [1–3]. The carbonation of cement-based materials may
decrease the pH value of pore solution, which is the main reason to cause
the damage of protective layer on steel surface and the subsequent steel
corrosion [4,5]. It is very slow for natural carbonation of cement-based
materials, which may be proceeded for decades of years. Therefore, the
accelerated carbonation, during which a high CO2 concentration is
applied to evaluate the carbonation resistance of cement-based mate­
rials within a short period of time, has been proposed. The influential
factors on accelerated carbonation of different cementitious materials
have been studied [6,7]. Although some empirical equations for the
conversion between accelerated and natural carbonation have been
established [8–10], these equations are still not accurate enough and
there are still some uncertainties.
Considering all of the above factors, more and more researchers tend
to use mathematical models to predict the carbonation process and the
service life of hardened cement concrete structures. The earliest pro­
posed carbonation model is based on the law that the carbonation depth
√̅̅
is proportional to the square root of carbonation time, that is, x = k t
[11]. However, in this model, the influence of sophisticated factors is
reflected by a single parameter “k”, which limits the accuracy of this
model under different conditions. Therefore, researchers have estab­
lished more specific empirical models, in which the temperature [12],
relative humidity [13], CO2 concentration [14], aggregate [15], curing
time [16] and external loading [17] were taken into consideration to
determine the coefficient “k”. In addition, with the development of the
empirical carbonation models, the independent variable is no longer
limited to the carbonation time and the effects of environmental factors
on carbonation are also considered [18,19]. Although the empirical
models are simple in form and easy for calculation, they are usually
based on some over-idealized assumptions, such as considering the
diffusion coefficient of CO2 as a constant or inversely proportional to
time [20,21]. Therefore, more and more thermodynamic [22,23] and
kinetic models [11,24] have been proposed to simulate the carbonation
process. Besides, with the development of computer algorithms, nu­
merical models such as finite element analysis [25,26], machine

* Corresponding author. Key Laboratory of Building Safety and Energy Efficiency of the Ministry of Education, Hunan University, Changsha, 410082, China.
** Corresponding author. Key Laboratory of Building Safety and Energy Efficiency of the Ministry of Education, Hunan University, Changsha, 410082, China.
E-mail address: cshi@hnu.edu.cn (C. Shi).

https://doi.org/10.1016/j.cemconcomp.2021.104315
Received 26 June 2021; Received in revised form 30 August 2021; Accepted 15 October 2021
Available online 19 October 2021
0958-9465/© 2021 Elsevier Ltd. All rights reserved.
X. You et al.
learning methods (including artificial neural network [27,28], decision
tree [29,30] and deep learning [9,31,32]) and real aggregate and
porosity simulation [33,34] have also been developed to simulate the
carbonation of cement-based materials.
Although extensive carbonation models have been established, the
comparison of different models is still lacking, which brings lots of dif­
ficulties for researchers to understand the properties of different models
and choose the appropriate one according to their own needs. Besides,
there is still no systematic method to guide the selection of carbonation
model according to the properties of cement-based materials and
research targets. The application of different models in the same
carbonation process and their outputs still fail to be well discussed,
which is unfavorable for the improvement of the existing models.
In this paper, the chemical reactions occurred during the carbonation
process of hardened cement-based materials and their influential factors
are firstly introduced, which is the basis of the subsequent analyses on
model parameters. The existing empirical, thermodynamic, kinetic and
numerical models for carbonation are reviewed afterwards. Through the
discussion of different models, the theoretical basis, characteristics and
major applications of these four types of models are summarized. Be­
sides, the determination of model parameters for various materials and
environmental conditions are also summarized, which enables these
different models to be applied more efficiently. In addition to the
modelling of carbonation for hardened cement-based materials, the
modelling of early CO2 curing for fresh cement-based materials are also
reviewed in this paper. The main differences between carbonation
simulation of hardened cement-based materials and the modelling of
early CO2 curing for fresh cement-based materials are also present,
which may help to provide new directions for the modelling of early CO2
curing of fresh cement-based materials.
2. Modelling of carbonation of hardened cement-based
materials
2.1. Carbonation of hardened cement-based materials
For cement-based materials, the hydration products including CH,
CSH and ettringite (AFt) are the main carbonatable phases [35], their
reactions with CO2 can be expressed by equations (1)–(3). Besides, some
unreacted cement clinkers can also be carbonated as shown in equations
(4) and (5). Among these reactions, the reaction between CH and CO2 is
dominant. The consumption of CH during carbonation generally leads to
the decrease of pH in the pore solution [36–38], which potentially
causes the damage of the protective layer on steel surface and the
corrosion of steel bars [4,39]. Moreover, the change of moisture content
caused by the carbonation and decalcification of CH and CSH may result
in the carbonation shrinkage [1,40].
Ca(OH)2 + CO2 →CaCO3 + H2 O (1)
3CaO ⋅ 2SiO2 ⋅3H2 O + 3CO2 →3CaCO3 ⋅2SiO2 ⋅3H2 O (2)
3CaO ⋅ Al2 O3 ⋅3CaSO4 ⋅32H2 O + 3CO2 →3CaCO3 + 3CaSO4 ⋅2H2 O + 2Al(OH)3 + 9H2 O
3CaO ⋅ SiO2 + 3CO2 + nH2 O→SiO2 ⋅nH2 O + 3CaCO3 (4)
2CaO ⋅ SiO2 + 2CO2 + nH2 O→SiO2 ⋅nH2 O + 2CaCO3 (5)
The carbonation of hardened cement-based materials is mainly
influenced by the exposure condition, porosity and supplementary
2
Cement and Concrete Composites 125 (2022) 104315
cementitious materials (SCMs). The variations of exposure conditions
such as CO2 concentration, CO2 pressure, relative humidity and exter­
nally applied loading have different effects on the carbonation process.
The carbonation reactions can be accelerated by increasing the con­
centration of CO2 [41]. Castellote et al. [42] found that CSH partially
decomposed to Ca modified silica gel under natural carbonation (about
0.03% CO2), but was completely polymerised during carbonation with
10% CO2 and completely converted to silica gel for 100% CO2. Besides,
CH and AFt can also be completely carbonated under the conditions of
10% and 100% CO2 respectively.
As a way of accelerating carbonation by increasing the CO2 pressure
and temperature, supercritical carbonation has attracted more and more
attentions [43,44]. Supercritical carbonation refers to the carbonation
that occurs under the critical conditions (304.12 K, 7.38 Mpa). In this
case, CO2 can penetrate into very small pores, which can effectively
improve the degree of carbonation [45]. However, such a high CO2
pressure condition will also change the carbonation kinetics, which will
be explained in detail in Section 2.4.
Relative humidity affects the diffusion and dissolution processes of
CO2. Generally, appropriate moisture content within cement-based
materials is required for carbonation reactions [46,47]. A too much
high value of relative humidity may cut down the diffusion paths of CO2
and slow down the CO2 diffusion. Experimental results have shown that
the carbonation rate reached the maximum at 50–70% relative humidity
[48–50]. Under the effect of rainwater infiltration, the pore water
saturation of unsheltered structures such as the external walls of
buildings is often high, which hinders the diffusion of CO2 into the
cement matrix. Therefore, the carbonation process of unsheltered
structure is intermittent and the carbonation degree is relatively low
compared to that of the sheltered structure [51].
Hardened cement-based materials are usually subjected to external
loading, which can impact effects on the carbonation. Generally, limited
compressive stress can inhibit the growth of microcracks, thereby
reducing the penetration of CO2 and the degree of carbonation [52]. On
the contrary, tensile stress usually leads to the increase of carbonation
degree [53]. Fatigue loading may cause the generation of macro-cracks,
which can provide new paths for the diffusion of CO2, and sometimes
even lead to the structural damage of cement-based materials [46].
Under the influence of external loading, the carbonation depth of
hardened cement-based materials will be increased.
Porosity directly affects the transport of CO2 in cement-based ma­
terials. The initial water-binder ratio and aggregate-binder ratio are the
key influential factors on porosity. Water-binder ratio affects not only
the porosity, but also the pore water saturation, which is essential for the
diffusion of CO2 [54]. With the increase of aggregate-binder ratio, the
total amount of carbonatable phases decreases and the proportion of
interface transition zone increases, which provides more paths for the
diffusion of CO2 and leads to a higher degree of carbonation [55,56]. In
addition, the types of aggregates (e.g. normal aggregate and recycled
aggregate) [57,58] and their shapes (e.g. pebbles and crushed stones)
[34] also affect the carbonation depth.
The carbonation of hardened cement-based materials is a long-
(3)
lasting reaction process, during which the SCMs may lead to the
decrease of CH content [59]. Moreover, the surface of SCMs is generally
the thermodynamic favorable region for the formation of new phases
such as calcium carbonate [60]. The application of some filling materials
such as silica fume can make it more difficult for CO2 to penetrate into
the concrete matrix [61,62]. Although the addition of SCMs may reduce
the total porosity of cement-based materials, the increase of macropores
X. You et al.
content is also observed. The experimental results show that the pro­
portion of macropores in the concrete blended with blast furnace slag is
larger than that of the control group without blast furnace slag [63]. The
carbonation rate of slag-blended concrete is found to be significantly
higher than that of OPC, and with the increase of slag content, the
carbonation rate increases [64]. Except for blast furnace slag, limestone
stone powder [65], fly ash [66,67], palm oil fuel ash [68] and meta­
kaolin [69] have also been investigated to reduce the carbonation
resistance of concrete. Based on the above reasons, the addition of SCMs
always increase the carbonation depth of cement-based materials.
2.2. Empirical models
The empirical models are mainly established based on the observa­
tion and analysis of experimental data. This kind of models usually
consider only one independent variable, while other factors are
considered in a carbonation coefficient “K”. At present, the most widely
used empirical carbonation model is the “square root” model, that is, the
carbonation depth is proportional to the square root of carbonation
time:
√̅
xc = K⋅ t (6)
Where xc is carbonation depth，t is carbonation time and K is carbon­
ation coefficient.
The square root model has been verified by many experimental
studies. As shown in Fig. 1, with the variations of water-cement ratio,
aggregate-cement ratio, relative humidity and the dosage of fly ash, the
overall carbonation depth shows a linear relationship with the square
root of time and the correlation coefficients are all above 97%.
Besides, the square root law also achieves good agreement with data
obtained in the field test. Köliö et al. [71] measured the carbonation
depth of 18 groups of external walls and balconies with average service
life of 27 and 35 years respectively. The data obtained was in good
agreement with the square root law.
However, with the increasing amount of SCMs such as fly ash in
cement-based materials, the empirical square root model may no longer
be applicable. In this case, the empirical model can be rewritten in the
following form:
xc = K⋅tn (7)
Fig. 2 shows the change of the value of n with different contents of fly
ash. It can be found that in the concrete without fly ash and with low fly
Fig. 1. The relationship between carbonation depth and square root of time
(Date from references [11,24,70]).
3
Cement and Concrete Composites 125 (2022) 104315
ash content (10%–35%), the values of n are 0.4852 and 0.5189
respectively. These two values are close to 0.5, which shows that the
square root law is still applicable. However, with the increase of the fly
ash content to 40%–50%, the value of n increases to 0.7691 and the
carbonation depth is no longer proportional to the square root of
carbonation time. Besides, Ekolu et al. [72] observed that the carbon­
ation depth of the sheltered structure is lower than that of natural
exposed structure under the same condition. For the sheltered structure,
the value of n in the model is between 0.2 and 0.5.
In some empirical models, carbonation time is not taken as inde­
pendent variable and the relationship between environmental factors
and carbonation depth is directly established. Multiple linear function,
polynomial function and exponential function have been applied to
characterize the relationship between carbonation depth and environ­
mental factors including temperature, relative humidity and CO2 con­
centration [75,76]. Based on all of the above discussions, the
classification and framework of empirical models can be summarized, as
shown in Fig. 3.
The empirical models can be conveniently applied to characterize
the relationship between carbonation depth and carbonation time.
However, these models also have some shortcomings. Almost all the
influential factors are included in the coefficient “K”, which means that a
single factor cannot be separately considered in these models. Besides, it
is difficult to characterize the carbonation reactions and their effects on
the properties of cement-based materials by empirical models. There­
fore, theoretical carbonation models such as thermodynamic and kinetic
models based on the specific carbonation mechanism are required to
simulate the carbonation of cement-based materials.
2.3. Thermodynamic models
On the basis of thermodynamic database and initial element
composition, thermodynamic models can be used to calculate the
equilibrium state of carbonation reactions. There are two main methods
to solve the thermodynamic equilibrium problem: minimizing the Gibbs
free energy of the system and solving the law of mass action equations.
The former is mainly solved by GEM-Selektor [77,78] and the latter can
be solved by PHREEQC [79,80], CHESS [81] and EQ(3)/6 [82,83].
The thermodynamic databases are necessary for thermodynamic
modelling. At present, thermodynamic databases mainly include
Cement 18, PSI-Nagra, MILES and Thermodem, among which Cement
18 is most widely used. For alkali-activated binders, the solid solution
models of alkali substituted calcium aluminate silicate hydrate gels
(CNASH_ss) can be used [84]. Phases with uncertain composition such
as CSH and hydrotalcite can also be described by solid solution models
[85–87] or surface complexation models [88]. Data for Na-containing
and Ca-containing zeolites can be taken form Lothenbach et al. [89]
and magnesium silicate hydrates (M-S-H) from Nied et al. [90].
Before thermodynamic equilibrium calculation, the hydration de­
gree of cement and the reaction degree of SCMs are required. Portland
cement is generally assumed to be fully hydrated before carbonation
[22], while the reaction degree of fly ash or slag is determined by some
empirical data [91–93] or modified from previous studies [94,95]. Shah
et al. [23] studied the carbonation of cement paste by thermodynamic
modelling. The Rietveld analysis was applied to calculate the hydration
degree of cementitious materials, which was confirmed to be more ac­
curate than the direct assumption. During the carbonation simulation,
the stepwise CO2 addition method is generally used. The simulation
results of CO2 increments of 0.1, 0.3 and 1 g per step were compared and
the 0.3 g CO2 per step was proved to be sufficiently accurate to reflect
the overall phase assemblages [96,97]. The total amount of added CO2 is
generally set to 0–50 g [23,98] (or 0–40 g [22]) per 100 g of binder.
For thermodynamic simulation of carbonation, gaseous CO2 and
solid minerals involved in the carbonation all need to dissolve in the
pore solution before carbonation reactions. Therefore, the activity of ion
species is one of the key parameters. In order to calculate the activity of
X. You et al. Cement and Concrete Composites 125 (2022) 104315

Fig. 2. The value of n under different fly ash content (Date from references [18,19,41,73,74]).

Fig. 3. Classification and framework of existing empirical models.

ion species, activity coefficient γ is introduced. The activity is equal to Extended Debye–Hückel equation, valid for I < 1 molal:
the activity coefficient multiplied by the concentration, i.e. {i} = γi [i]. √̅̅
Based on the range of ionic strength (I), different calculation methods to − Aγ Zi 2 I
log γi = √̅̅ + bγ I (9)
determine the activity coefficient including Davies equation [99], 1 + Bγ ai I
extended Debye–Hückel equation [100] and the specific ion interaction Specific ion interaction theory, valid for I < 3 molal:
theory [101] have been proposed. Their expressions and scopes of √̅̅
application are shown as follows: − Aγ Zi 2 I ∑
log γi = √̅̅ + ε(i, k)mk (10)
Davies equation, valid for 0.3 < I < 0.5 molal: 1 + By ai I k
√̅̅
− Aγ Zi 2 I Where Ay is the pressure dependent coefficient, By is the temperature
log γ i = √̅̅ − 0.3I (8)
1+ I dependent coefficient, Zi is the charge of species i, ai is the ion-size
parameter, by is the semi-empirical parameter, I is the effective ionic

4
X. You et al.
strength, ε(i, k) is the interaction coefficient which describes the short-
range interaction between the species i and k, mk denotes the mo­
lalities of species k.
Except for the main carbonatable phases such as CH and CSH,
thermodynamic models can also take other thermodynamically possible
phases into consideration. Besides, different forms of the same carbo­
natable phase can be separately described. For example, the CSHQ
model proposed by Kulik [102] can be used to characterize the CSH gel,
in which the CSH is divided into four types based on their calcium to
silicon ratio: TobH (C2/3SH1.5), TobD (C5/6S2/3H1.83), JenH (C1.33SH2.17)
and JenD (C1.5S0.67H2.5). Due to the advantage in calculating phase as­
semblages, thermodynamic models have been applied to simulate the
carbonation process of various cement-based materials. Weerdt et al.
[22] used Gibbs free energy minimization software GEMS 3.5 and
thermodynamic database Cement 18 to simulate the carbonation of
Portland cement. The predicted phase assemblages are shown in Fig. 4.
It can be found that CSH begins to be carbonated and progressively
decalcified after portlandite is completely exhausted. Calcite is pro­
duced continuously in almost the whole carbonation process. In addi­
tion, M-S-H, zeolite and gypsum are also formed in the later carbonation
stage. Except for ordinary Portland cement, the thermodynamic
modelling on the carbonation of blended Portland cement (blended with
fly ash, metakaolin or limestone [98], pozzolanic materials or limestone
calcined clay [23]), calcium sulfoaluminate cement (blended with blast
furnace slag or fly ash [103,104]) and alkali-activated slag cement [105,
106] are also studied.
With the help of thermodynamic modelling, the initial carbonatable
phases, reaction sequence, change of solid volume, CO2 consumption
and carbonated products during carbonation of different cement-based
materials can be clearly obtained. However, It is worth noting that
thermodynamic models cannot predict the formation of metastable or
transitional phases [107,108].
In the experimental studies, the pH change of pore solution during
carbonation process is always indirectly characterized by the discolor­
ation of phenolphthalein solution, and the underlying structural reason
behind this change is not clear. By applying the method of thermody­
namic simulation, the change of phase content and the corresponding
variation of pH value can be investigated. Ke et al. simulated the
carbonation of alkali activated slag cement [96], the obtained phase
Fig. 4. Modelled changes in the phase assemblage (cm3/kg mortar) for the
carbonation of CEM I 0.55 mortar (w/c = 0.55) exposed to 1% CO2 and 60%
relative humidity [22].
5
Cement and Concrete Composites 125 (2022) 104315
assemblages and change of pH are shown in Fig. 5. The mutation of pH
value mainly corresponds to the disappearance of CNASH_ss, while the
carbonation of other carbonatable phase such as ettringite impacts slight
effects on the variation of pH value.
The determination of porosity for specimens during carbonation
process is always a tough work due to the sophisticated influential fac­
tors. Although some empirical porosity calculation equations have been
proposed [24,109], the cumulative errors of multiple calculations
cannot be ignored due to some unreasonable assumptions. In thermo­
dynamic models, since the phase assemblages can be calculated, the
porosity can be directly obtained by subtracting the cumulative volume
of all phases from the initial volume. As shown in Fig. 6, the dash arrows
indicate the change in porosity after carbonation. The corresponding
phase assemblages can also be observed.
Except for minimizing the Gibbs free energy of the system, the
thermodynamic equilibrium state can also be calculated by the law of
mass action. The latter method is faster, but requires more assumptions
such as the fugacity of gases. According to the law of mass action, the
aqueous reactions that may occur in the system need to be determined
firstly and the mass and charge balance equations can be solved by
Newton-Raphson iterations [99,110]. The phase equilibrium is calcu­
lated based on the thermodynamic equilibrium constant K, which can be
expressed by the activity of specific species. The stability of CH and
CaCO3 is characterized by the threshold of ion activity. Moreover, the
variation of calcium to silicate ratio of CSH can be considered and the
detailed simulation method is found in Ref. [111]. Except for the
modelling of chemical reactions in carbonation, thermodynamic models
are also able to simulate the surface complexation reaction with the
generalised two-layer surface complexation module built in PHREEQC
[112]. As the structure of CSH has not been clearly understood, the
surface of CSH is usually assumed to consist of silanol sites (≡ SiOH)
based on a widely recognized fact that the structure of CSH is similar to
Tobermorite [113,114]. Through MCD, another module in PHREEQC,
the multi-component diffusion caused by the dissolved CO2 and other
ions can be simulated [115]. The application of this module in the
modelling of carbonation is significant because carbonation is consid­
ered as a diffusion-controlled process in most cases.
2.4. Kinetic models
During the carbonation of cement-based materials, a series of phys­
ical and chemical processes occur, which are shown in Fig. 7. However,
in many existing models, certain stage (such as the dissolution of CO2) is
often ignored, resulting in an inappropriate evaluation of the carbon­
ation process [116–118]. Various kinetic models have been applied to
characterize the different processes of carbonation within cement-based
materials. According to the physical and chemical reactions for
carbonation, the kinetic carbonation models can be divided into three
parts: the kinetic models of diffusion process, dissolution process and
carbonation reactions.
2.4.1. Kinetic models for diffusion process
The diffusion process in carbonation mainly refers to the process that
CO2 enters the pores of cement-based materials from external environ­
ment and reaches the reaction zone. In some empirical models, the
diffusion coefficient is often regarded as a linear function of the diffusion
distance or just obtained through experimental results [20,119]. Due to
the existence of these idealized assumptions, it’s usually hard to expand
the application scope of these models under the premise of ensuring the
accuracy. The diffusion process in actual carbonation situation is rela­
tively complicated and affected by multiple factors, which requires more
specific diffusion models.
At present, most of the kinetic models for carbonation are established
based on the Fick’s law. According to Fick’s law, diffusion is driven by
the concentration gradient, and the CO2 diffuses along the negative
gradient direction determined by its concentration field. Except for the
X. You et al.
Fig. 5. The phase assemblages and pH change of NaOH-activated slag paste under step-wise accelerated carbonation (1% CO2) [96].
Fig. 6. Changes in phase assemblages and total porosities predicted by ther­
modynamic modelling for Portland cement samples under 1% CO2 [98].
concentration gradient, all the other influential factors are included in
the diffusion coefficient. Thus, the calculation models of diffusion co­
efficient are one of the most important parts in the carbonation
modelling.
So far, various calculation models of CO2 diffusion coefficient have
been proposed, as shown in Table 1. The existing calculation models on
diffusion coefficient mainly include the models based on kinetic theory
of gases and the parameters fitting methods. According to the relation­
ship between pore diameter and the mean free path of CO2 (45 nm), the
models based on kinetic theory of gases can be divided into three
6
Cement and Concrete Composites 125 (2022) 104315
categories. If the pore diameter is smaller than the mean free path of
CO2, the collision between gas molecules and pore walls will be domi­
nant, while the collision between molecules can be ignored. In the pores
larger than the 10 times of mean free path of CO2, the motion of gas
molecules is mainly driven by the collision against one another. In the
pores with diameter between one and ten times of the CO2 mean free
path, these two kinds of diffusion will occur at the same time. According
to the different fitting equations, the fitting models can be divided into
power function models, exponential function models and piecewise
function models. The features of these models are also summarized in
Table 1.
When CO2 diffuses into the cement-based materials, the internal CO2
concentration will change constantly due to the reactions of CO2 with
the hydration products and clinkers. Under this condition, the Fick’s law
proposed for steady-state diffusion condition will no longer be appro­
priate. Although models based on Fick’s second law, which is applicable
to unsteady diffusion have been proposed, each of them only takes a
limited number of factors into account. Therefore, it is still a challenging
work to simulate the CO2 diffusion behavior in complicated environ­
ment and establish multi factors coupling models to better evaluate the
diffusion coefficient of CO2 in cement-based materials.
In addition to the carbonation at atmospheric temperature and
pressure, supercritical carbonation (when the temperature and pressure
of CO2 exceed their critical values, i.e. 304.12 K and 7.38 MPa [133])
and its simulation have also attracted extensive attention. Under the
condition of supercritical carbonation, the main driving force of diffu­
sion is pressure gradient rather than concentration gradient. Therefore,
in this case, the Fick’s law is not applicable and Darcy’s law should be
used. The specific application of Darcy’s law in the modelling of su­
percritical carbonation can be found in the research of Zha et al. [134].
The supercritical carbonation model has also been coupled with the
leaching model of hazardous waste such as Sr and Cs, which helps to
explore the solidification effect of supercritical carbonated
cement-based materials on reducing the leaching of hazardous waste
[135]. The coupled model considers the temperature field and the
concentration field at the same time. It introduces the thermal diffusion
X. You et al.
Fig. 7. The physical and chemical processes of carbonation.
coefficient on the basis of common effective diffusion coefficient, which
is of great significance for evaluating the diffusion process under
different temperature conditions. In addition, the introduction of the ion
coefficient [136] enables the model to consider the influence of chem­
ical fixation on the diffusion coefficient of hazardous waste, which
makes the model closer to the real leaching situation.
2.4.2. Kinetic models for dissolution process
The dissolution process discussed in this section mainly refers to the
dissolution of CO2 and carbonatable phases in pore solution. In the past,
many studies focused on the diffusion of CO2 and the carbonation re­
actions without fully discussing the intermediate dissolution process
[116–118]. In fact, the dissolution of CO2 is an indispensable process for
the carbonation of cement-based materials. Although CO2 can directly
diffuse to the reaction area under appropriate relative humidity condi­
tions [137,138], it still needs to be dissolved in the pore solution before
it reacts with the carbonatable phases.
When CO2 enters into the cement-based materials, the materials can
be usually divided into three parts: carbonation zone, carbonation front
and non-carbonation zone [11,118]. However, studies of Rimmelé et al.
[139] have shown that there is a dissolution front between the
non-carbonation zone and the carbonation front, as shown in Fig. 8. The
dissolution front affects both the diffusion process and carbonation re­
actions. Thus, the dissolution process must be considered in the
carbonation models.
In most existing models, the dissolution process of CO2 is expressed
by Henry’s law. The concentration of CO2 dissolved into liquid phase Cl
can be calculated by the following equation [24,130]:
Ci = HRTCg (11)
Where H is Henry’s constant, R is the ideal gas constant and Cg is the CO2
concentration in gas phase. Henry’s constant varies with temperature
according to the following equation [140]:
⃒( )⃒
⃒ ⃒
⃒Δ T 1 T1 ⃒
⃒ ref ⃒
H(T)= Href e (12)
Where the Href is the reference Henry’s constant and Δ is the enthalpy
constant. The rate of dissolution can be expressed by the following
equation [17,21]:
rD,CO2 = kt (H ⋅ [CO2 (g) − CO2 (l)]) (13)
7
Cement and Concrete Composites 125 (2022) 104315
Where kt is the interfacial gas-liquid mass transfer coefficient.
Although Henry’s law has been used to approximately calculate the
dissolution rate of CO2 at normal pressure, it was proved to be unsuit­
able for high pressure systems, as shown in Fig. 9(a). The solubility
values calculated by Henry’s law deviate greatly from the experimental
results when the pressure is greater than 7 MPa. Therefore, during the
carbonation process with high pressure such as supercritical carbon­
ation, the existing model should be modified. Zha et al. [134] used the
solubility of CO2 instead of the concentration in the pore solution to
establish the governing equations of their supercritical carbonation
model. This is based on the fact that, for supercritical carbonation, there
is always enough CO2 in the pores to keep the pore solution in a satu­
rated state.
Minoo et al. [140] have proposed a new solubility calculation
method that is suitable for a wide pressure range, as shown in the
following equations:
/
ρd = (αT + β)⋅PCO2 ρd ≤ 50kg m3 (14)
/
ρd = 5.3 × 10− 7 (PCO2 − 50 / αT + β)⋅PCO2 ρd > 50kg m3 (15)
Where α = − 1.231 × 10− 7, β = 4.993 × 10− 5, ρd is the solubility of CO2
and PCO2 is the pressure of CO2.
As shown in Fig. 9 (b), the modified model is in good agreement with
the experimental results whether under low or high pressure conditions,
which is a significant supplement to the existing carbonation models.
2.4.3. Kinetic models for carbonation reactions
Carbonation reactions refers to the chemical reactions that occur
between CO2 and carbonatable phases, as represented by equations (1)–
(5) in Section 2.1. The most critical factor for carbonation reactions is
the reaction rate. According to Papadakis [11] and Jeong et al. [25], the
carbonation rate can be calculated by the following equation:
−
ri = ki αs [j]Vi [CO2 ] (16)
Where ki is the rate constant for the reaction of constituent j with CO2, αs
is the specific surface area, [j] is the molar concentration of constituent j,
V i is the molar volume.
In addition to the reactant concentration, the carbonation rate is also
affected by pore water saturation and temperature, as shown by the
model proposed by Mi [122] and Pan et al. [33].
X. You et al. Cement and Concrete Composites 125 (2022) 104315

Table 1
Summary of the different diffusion coefficient calculation models.
Classification Models Key parameters Features Refs
√̅̅̅̅̅̅̅̅̅̅̅̅
Models based on Knudsen 1 8⋅R⋅T ● DK: Knudsen diffusion ● Suitable for pores less than 45 nm. [120]
kinetic theory of diffusion DK = ⋅ ⋅d coefficient. ● Based on the assumption of straight
3 π⋅M k
gases. ● M: molecular weight of cylindrical pores.
CO2.
Transition DF ● DT: transition area ● Suitable for pores between 45 nm [120–122]
DT =
area diffu- 1 + λ/(dT − 2W) diffusion coefficient. and 450 nm.
sion ● λ : mean free path of CO2.
√̅̅̅̅̅̅̅̅̅̅̅̅
Fick diffusion 1 8⋅R⋅T ● DF: Fick diffusion ● Suitable for pores larger than 450 [120]
DF = ⋅ ⋅λ coefficient. nm.
3 π⋅M
● M: 0.044 kg/mol. ● The absolute pressure at both ends
● λ : 45 nm. of the pore must be assumed the
same.
⎛ ⎞a
Models based on Power ● εc : the porosity ratio of ● The effect of SCMs is evaluated. [109,
( )b
parameter function ⎜ εc ⎟ RH concrete. ● The value of b in different 123–126]
D e = A⎜
⎝C
⎟ 1−
fitting. P W⎠ 100 ● ρc, ρp, ρw : the densities of literatures fluctuates in a large
+ +
ρc ρp ρw cement, fly ash, and water. range (0.6–2.8).
DITZ = D0 ⋅(0.001 + 0.07⋅φ(x)2 + ● D0 : the diffusion ● The diffusion coefficient of CO2 in [122,127]
1.8⋅H1 ⋅[φ(x) − 0.18]3 ) coefficient of CO2 in the ITZ can be estimated.
natural atmosphere. ● The model needs to assume that the
● φ(x) : the capillary porosity diffusion of CO2 in ITZ is similar to
at a distance x from the that of chloride.
nearest aggregate surface.
1 εr ● εr : the residual strain ● The influence of fatigue damage [53,128]
Dd = Dnd + Dsl
1 + εr 1 + εr ● Dnd : the diffusion and cracks is considered.
coefficient in non-damaged ● The diffusion coefficients of CO2 in
part. water and aggregate are usually
● Dsl : the diffusion ignored, which may cause errors.
coefficient in cracks.
Dg (εp , S) = Dg0 εp n (1 − S)m ● Dg0 : the diffusion ● The interaction of porosity and pore [24,117,
coefficient of CO2 in the solution saturation is considered. 129–131]
air. ● Lack of the consideration of
● εp : porosity. external environmental factors.
● S: the pore solution
saturation.
Exponen-tial De,CO2 = 10− 7 ⋅10− 0.025fck ● fck : the compressive ● Suitable for the concrete sheltered [132]
function strength of the concrete in from rain.
Mpa.
De,CO2 = 0.5⋅10− 7 ⋅10− 0.025fck ● fck : the compressive ● Suitable for the concrete exposed to [132]
strength of the concrete in rain.
Mpa.
⃒ ( )⃒
⃒Q 1 1 ⃒
⃒ ⃒ ● Q: the diffusion activation ● The effect of temperature on [124]
D(T) = Dref e
⃒R T T ⃒
ref energy. diffusion is described theoretically.

Piecewise D = K1 × f(RH) ● K1: influence coefficient of ● The model is fitted by experimental [116]
{
function 6.1 × 10− 7 (0 ≤ RH ≤ 55%) bulk density. data of autoclaved aerated
f(RH) ​ =
− 0.12 × 10− 5 × (RH − 55%) + ​ ● f (RH): relative humidity concrete, which limits the model
6.1 × 10− 7 (55% ≤ RH ≤ 80%) influence factor of application.
diffusion.

rc = Kc0 Smatrix
3.7
[i]HCg
rc,i = Ki HRTCi CCO2 (g)
Where Smatrix is the water saturation, H is the Henry’s constant, Cg is the
molar concentration of CO2, Ci is the molar concentration of constituent
i, k0c and ki are the carbonation reaction rate constants.
As can be seen, “carbonation rate constant (k)” is used in all above
models. However, there is still no accurate method to calculate the value
of “k”. At present, the most widely used estimation method to calculate
the carbonation rate constant is still based on the Arrhenius equation
[75,124], in which the reaction rate constant is regarded as a function of
temperature and activation energy. In addition to temperature, the
specific surface area of the reactants is another factor affecting the
carbonation reaction rate. It can be approximately calculated through
the total pore surface area and the volume ratio of reactants [109].
Besides, the calcium carbonate coating formed on the surface of re­
actants makes it difficult for CO2 to penetrate into the reaction area and
reduces the final degree of carbonation. However, many existing models
fail to consider the hindering effect of calcium carbonate layer, or only
(17) express it indirectly by the decrease of reactant concentration and
empirical factors [122,141–143]. Although the formation rate of the
(18) calcium carbonate layer is slow under natural carbonation conditions,
its effective characterization can effectively improve the long-term ac­
curacy of the model.
The calculation of carbonation rate under supercritical carbonation
is different from that of natural carbonation. Zha et al. [134] proposed a
calculation method of carbonation rate based on humidity, CO2 con­
centration, carbonation degree and temperature, and improved it in
Ref. [136]. The improved model mainly considers the uptake of CO2
instead of the formation of calcium carbonate as the evaluation of
carbonation degree, because in the case of high CO2 concentration,
calcium carbonate will react with water, CO2 and SiO2 to form
by-products such as calcium bicarbonate.
Based on the above discussions on the modelling of diffusion,
dissolution and carbonation reaction rate, the mass transfer equations of
the carbonation process can be solved. Although different forms of mass
transfer equations have been proposed [11,24,25], the basic framework
consists of the above three parts is generally considered. These equations
can be solved in many ways, including but not limited to finite difference

8
X. You et al.
Fig. 8. The SEM micrograph of different carbonation zones in Portland cement paste [139].
Fig. 9. The solubility relationship in Henry’s low (a) and the model of Minoo et al. (b) [140].
method, Matlab pdetool, COMOSL Multiphysics, ReactMiCP and Keller’s
difference scheme.
2.5. Numerical models
Numerical models can deal with huge amounts of data to better
simulate the real carbonation situation and improve the accuracy of
prediction. For example, numerical models can be used in the recon­
struction of aggregate and the simulation of porosity distribution [33,
34]. In addition, based on the finite element method, the
three-dimensional carbonation models can be established and the steric
diffusion path of CO2 can be simulated [25,26]. Due to the complexity of
the parameters in carbonation process, machine learning methods such
as artificial neural network [27,28], decision tree [30] and deep learning
[9] have also been applied in carbonation modelling.
The shape of aggregate affects the porosity of concrete, which is an
important factor influencing the diffusion process of CO2 and carbo­
natable phases. The image-based method has been applied for the 3D
reconstruction of aggregates in the carbonation model of Pan et al. [33].
This method enables the model to simulate the carbonation in corner
and edge areas, which effectively avoids the problem of ignoring the
partial carbonation zone near the interface. The partial carbonation
zone can explain why calcium carbonate is formed in the areas deeper
than the phenolphthalein indication depth [114–116]. Therefore, this
9
Cement and Concrete Composites 125 (2022) 104315
method can make the simulation closer to the real carbonation process.
However, this kind of method requires many representative pictures,
which brings difficulties to the preliminary preparation of the model.
Another aggregate simulation method proposed by Bao et al. [34]
does not require images, and the data can be generated by computer. In
this model, each step can be accurately controlled and the calculation is
convenient. Through the model, it was found that the carbonation depth
of concrete with crush stones was larger than the concrete with pebbles,
which might be closely related to the irregular boundaries of crush
stones. The irregular boundaries can lead to greater porosity and makes
it easier for CO2 to diffuse into concrete. However, this model is limited
to two-dimensional plane and can only simulate a limited variety of
aggregates.
In addition to the simulation of aggregates, numerical models of
porosity have also been proposed. Yu et al. [144] established the models
of random porosity field based on the probability density function and
the ellipsoid autocorrelation function, and then introduced them into
the supercritical carbonation model. This kind of method can avoid the
isotropic and uniform assumptions of cement-based materials and was
applied to simulate the irregular boundaries of carbonation zone in the
modelling work of Bao et al. [145]. Besides, it can also help to obtain the
maximum and minimum carbonation depths instead of just the average
value. It is worth noting that the maximum carbonation depth is decisive
for assessing the corrosion risk of steel bars.
X. You et al.
Fig. 10. The CO2 distribution and diffusion streamline from sample outer surfaces toward sample core. (a) carbonation in 10% CO2, (b) carbonation in 75%
CO2 [25].
The finite element models are applied for simulating the trans­
portation of heat, moisture and CO2 during carbonation process
[146–148]. In these models, the equilibrium equations of CO2 can be
coupled with temperature and humidity, so as to make the models closer
to the field conditions. In addition, some finite element models consider
carbonation, chloride ion penetration and steel corrosion at the same
time, which enables them to keep good adaptability in marine envi­
ronment [149,150]. The finite element method can help to build the
Fig. 11. Artificial neural network for carbonation process [27].
10
Cement and Concrete Composites 125 (2022) 104315
three-dimensional carbonation models and avoid the theoretical errors
caused by the two-dimensional flat assumption [25,26]. Jeong et al.
[25] developed the model of Papadakis to three-dimensional scale using
finite element model and obtained the CO2 distribution and diffusion
streamline from sample outer surface toward sample core, as shown in
Fig. 10. Through this model, the diffusion paths of CO2 can be displayed
intuitively, and the influence of aggregates and CO2 concentration on
the diffusion process is reflected. Compared with the case of 10% CO2
concentration, the diffusion streamline under 75% CO2 concentration is
continuous and smoother, which indicates that the increase of CO2
concentration is beneficial to the diffusion of CO2 from the surface to the
core area of concrete.
Due to the advantage in describing the interaction between multiple
factors, artificial neural network (ANN), as shown in Fig. 11, has also
been applied to simulate the carbonation process. The output parameter
of the existing neural network models is usually the carbonation depth
and the input parameters include carbonation time, CO2 concentration,
cement content, relative humidity, SCMs, water-binder ratio and
aggregate-binder ratio [27,28,151]. In addition to ANN, other machine
learning methods such as decision tree and deep learning are also
applied to the carbonation modelling. The decision tree can divide the
instance space into different subspaces and adopt different model stra­
tegies in each subspace [29]. Moreover, the data processing of decision
tree has higher interpretability than that of ANN. Taffese et al. [30]
integrated neural network and decision trees (including bagged and
boosted decision trees) and built a composite carbonation prediction
X. You et al.
model. The training and testing results showed that the model can
guarantee low errors while considering almost all the parameters that
affect carbonation process. Deep learning is often regarded as the
development and advanced form of ANN. It is a machine learning al­
gorithm that uses deep neural networks (DNN) to combine a variety of
nonlinear analysis techniques [31,32]. DNN has stronger learning ability
than ANN and can achieve the self-identification of variables and
adjustment of weights. Lee et al. [9] calculated the carbonation rate
coefficient by deep learning model. The results showed that the errors
between the experimental data and the model predictions of carbon­
ation rate were minor, ranging from 0.01 mm/year1/2 to 0.1
mm/year1/2, which are much smaller than that of finite element analysis
and the empirical model from Architectural Institute of Japan.
Although machine learning methods are remarkably accurate in
predicting carbonation, there are also some shortcomings. First, these
methods can only obtain the value of output parameter such as
carbonation depth through data processing, the specific carbonation
process and mechanism cannot be reflected. Besides, the accuracy of
machine learning method depends too much on the accuracy of the data
sets provided for training, so its application is usually limited by the data
source. Expanding the number of data sets as much as possible,
improving the accuracy of data sets and giving the model self-learning
ability are effective to improve the applicability of this kind of models.
2.6. Comparison of different models for carbonation of hardened cement-
based materials
The existing carbonation models for hardened cement-based mate­
rials consist mainly of empirical, thermodynamic, kinetic and numerical
models. Their features, advantages, disadvantages and solving software
are shown in Table 2.
Most empirical models are based on the square root model, which is
simple and can be conveniently used to predict carbonation depth and
service life of reinforced concrete structures. However, the prediction
accuracy of empirical models is relatively low and the influence of a
single factor cannot be effectively evaluated. With the high content of
SCMs or long-term load effect, the square root model may no longer be
applicable. For these models, the carbonation coefficient is often
determined indirectly by experimental data.
Compared with empirical models, theoretical models such as ther­
modynamic and kinetic models can evaluate the carbonation in more
detail, rather than just calculate the carbonation depth. Based on the
thermodynamic database, thermodynamic models can effectively eval­
uate all possible phases instead of only discussing the main carbonatable
phases such as calcium hydroxide and tricalcium silicate. Based on the
calculation of phase assemblages, the porosity of the carbonated speci­
mens and the pH value of pore solutions can also be obtained. However,
it is worth noting that the thermodynamic models can only calculate the
final state of the carbonation reactions, while the kinetic models can
Table 2
Comparison of different models for carbonation of cement-based materials.
Classifications Features Advantages
Empirical models Fitted based on the experimental results. ● Simple in form
● Quickly obtain the results.
Thermodyna-mic Solved by minimizing the Gibbs free energy ● Obtain the phase assemblages of
models or the law of mass action. carbonated products.
● Consider a variety of products.
Kinetic models Based on Fick’s law, Henry’s law and ● Theoretically analyze the whole
carbonation reaction rate constant. carbonation process.
Numerical models Simulation based on big data. ● Closest to the real carbonation
process.
● High prediction accuracy.
11
Cement and Concrete Composites 125 (2022) 104315
evaluate the whole carbonation process, such as diffusion, dissolution
and carbonation reactions. Generally speaking, the kinetic models can
consider the carbonation process in more detail, but they require a lot of
assumptions and the model solution is relatively complicated. The
existing calculation methods of thermodynamic equilibrium can be
divided into two types: minimizing the Gibbs free energy and solving the
law of mass action equations. The calculation speed of the latter is faster,
but the phases involved in the reactions, the fugacity of gases and the
number of reaction steps need to be set in advance. The former method
can avoid these assumptions and calculate the thermodynamic equilib­
rium state from all the stoichiometrically possible phases’ combinations.
With enough data or image information, the numerical models can
better simulate the real carbonation process and obtain high precision
predictions. The finite element models can make the simulation of
carbonation no longer limited to two-dimensional plane, but fully
consider the aggregate, porosity distribution and the steric diffusion
path of CO2. This allows the numerical models to consider more details
of carbonation such as the partial carbonation zone. In addition, the
application of machine learning methods such as ANN, decision tree and
deep learning enables the carbonation models to analyze the explicit or
hidden relationships between different influential factors, which makes
up for the deficiency of empirical models to a certain extent. However,
the accuracy of machine learning methods depends too much on the
accuracy of data sets provided for training, and the specific carbonation
process and mechanism cannot be reflected.
Fig. 12. The reaction procedures of early CO2 curing [154].
Disadvantages Software
● Analysis of influential factors is not Any data processing and
available. fitting tools.
● Only predict the final state. GEMS-Selektor,
● Regardless of the actual formation PHREEQC,
conditions of the products. MINEQL+,
CHESS,
EQ(3)/6.
● Too many specific assumptions are Matlab PDE,
needed. ReactMiCP,
Parallel direct.
● Difficult to solve. ABAQUS,
● A huge amount of data is needed. COMSOL Multiphysics,
Pytorch,
Tensorflow.
X. You et al.
3. Modelling of early CO2 curing of fresh cement-based materials
Early CO2 curing is a kind of curing regime that makes CO2 reacts
with fresh cement-based materials after molding and utilizes the reac­
tion products such as calcium carbonate and silica gel to improve the
early strength of cement-based materials. As a promising CO2 capture
and storage technology, early CO2 curing receives more and more at­
tentions [152,153]. Although the reactions of CO2 with cement clinker
minerals, as shown in equations (4) and (5) in Section 2.1, are the main
reactions that occur in early CO2 curing process, there are still some
hydration products which can also be involved in the reactions, as
shown in (1)-(3). The reaction procedures of early CO2 curing are shown
in Fig. 12.
The factors affecting the CO2 curing degree of cement-based mate­
rials mainly include curing condition and curing regime. The main
curing condition factors consist of CO2 concentration, CO2 pressure,
curing temperature and relative humidity. The increase of CO2 con­
centration tends to cause the increase of reaction rate and degree [155].
However, with the increase of curing time, the dense calcium carbonate
layer formed on the surface of carbonated products hinders the pene­
tration of CO2 [156,157]. Then, the promoting effect of increased CO2
concentration will gradually decrease. Generally, the efficiency of CO2
curing of cement-based materials is increased with the increase of CO2
pressure. However, when CO2 pressure is higher than 0.2 MPa, the ef­
ficiency of CO2 curing will no longer increase even the pressure con­
tinues to rise. The effect of high pressure is gradually lost when CO2 is
transmitted in cement-based materials and the higher the initial pres­
sure, the greater the loss [158]. The influence of temperature on early
CO2 curing is complex. On the one hand, increasing the temperature will
reduce the solubility of CO2 and Ca2+ in the pore solution, which leads to
the decrease of reactant concentration [159]. On the other hand, the
increase of temperature can accelerate the CO2 diffusion in the pores of
cement-based materials and promote the CO2 curing process [35,160].
Relative humidity affects the diffusion of CO2 by changing the water
saturation degree in pores. When the humidity is increased, the pore
water content of cement-based materials is also increased, which slows
down the CO2 diffusion rate [155,161]. However, H2O is one of the
reactants and appropriate amount of aqueous phase is necessary for the
dissolution of CO2 and carbonatable phases.
Before the early CO2 curing, pre-curing of specimens can effectively
improve the extent of CO2 uptake and the compressive strength of
specimens. Experimental results have proved that the degree of CO2
curing of cement-based materials is relatively low if the specimens
expose to CO2 immediately after being molded [162,163]. This is mainly
caused by the high water saturation degree in the pores of early age
concrete, in which the penetration rate of CO2 is only 1/10000 of that in
unsaturated pores [138]. If the specimens can be pre-cured in the
flowing dry air before CO2 curing, the water saturation degree of pores
will be effectively reduced and the penetration of CO2 can be greatly
accelerated. Shi et al. [137] found that the compressive strength of
concrete blocks after 2 h of proper pre-curing and 4 h of CO2 curing was
almost comparable as that of the specimens with 20 h of steam curing.
Compared with the carbonation models of hardened cement-based
materials, the existing models of early CO2 curing for fresh cement-
based materials are less and mainly kinetic models. Although the ki­
netic modelling framework of early CO2 curing and passive carbonation
is similar, there are still some differences in the specific simulation
process such as the mass transfer kinetics of CO2 and the calculation of
carbonation reaction rate.
The calculation model of CO2 diffusion coefficient in early CO2
curing process is different from that of carbonation for hardened
cement-based materials. The diffusion of CO2 in hardened cement-based
materials is Knudsen diffusion and the effective diffusion coefficient is
inversely proportional to the square root of its molar weight [120,152].
Thus, the diffusion coefficient of CO2 can be obtained by multiplying the
diffusion coefficient of inert gas such as N2 by (MN2 /MCO2 )1/2 . However,
12
Cement and Concrete Composites 125 (2022) 104315
for early CO2-cured cement-based materials, Knudsen’s law is no longer
suitable due to the lower hydration degree and the presence of more
macroscopic pores whose diameters are much larger than the mean free
path of CO2 molecules. Baroghel-Bouny et al. [164] characterized the
effect of porosity on effective diffusion coefficient in the form of power
function and provided the range of power exponent. This method has
been proved to be effective for calculating the diffusion coefficient in
early CO2 curing process [155,165].
The specific calculation equations for the diffusion coefficient are
shown below.
Dg = Dg0 ⋅kDg (ε, τ)⋅kDg (S) (19)
kDg (ε, τ) = εθ (20)
kDg (S) = (1 − S)β (21)
Where Dg0 is the inhere diffusion coefficient of gas, KDg(ε,τ) is coefficient
relates to the contribution of porosity and tortuosity, KDg(S) describes
the impact of saturation degree on Dg, θ is the fitting shape factor that
ranges from 1.33 to 2.74, β is fitting parameter ranges from 3.33 to 6.0.
The diffusion coefficient of CO2 in the liquid phase can be calculated
by the similar method:
Dl = Dl0 ⋅kDl (ε, τ)⋅kDl (S) (22)
kDl (ε, τ) = 0.001 + 0.07ε2c + 1.8H(εc − 0.18)⋅(εc − 0.18)2 (23)
kDl (S) = Sβ (24)
Where H(εc-0.18) is the Heaviside function and εc is capillary porosity.
Porosity is one of the key parameters in the modelling of diffusion
process. According to the models proposed by Chen [155] and Papadakis
et al. [11], the variations of porosity is proportional to the differences in
molar volumes between solid reactants and solid products. The main
modelling difference between early CO2 curing for fresh cement-based
materials and carbonation for hardened cement-based materials is that
the change of porosity caused by early hydration reactions during CO2
curing process cannot be ignored. Based on the data provided by
Papadakis et al. [109], the porosity reduction caused by the carbonation
of CH is only 7.2% of that caused by the hydration of equivalent amount
of C3S. Considering all possible porosity changes in the carbonation and
hydration reactions, the rate of porosity reduction of hardened
cement-based materials is only 3.9% of that of early CO2-cured samples
in the case of the same reactant concentration. Thus, although carbon­
ation can theoretically lead to the porosity reduction of hardened
cement-based materials, the rate of reduction is very slow.
In addition to porosity, models of early CO2 curing and carbonation
for hardened cement-based materials also differ in the evaluation of
aqueous phase. Experimental results have shown that there is an optimal
range of relative humidity (50–70%) in the process of early CO2 curing
[48,155]. However, in the carbonation models of hardened cement
paste, the influence of relative humidity is always expressed in the form
of power function [109] or linear function [116]. According to this kind
of models, when the relative humidity increases from 45% to 80%, the
effective diffusion coefficient will keep decreasing until it reaches 9.7%
of the initial value. Obviously, these models are not suitable for early
CO2 curing. It has been proved that the introduction of water saturation
degree instead of relative humidity can more accurately characterize the
effect of aqueous phase on early CO2 curing process. By combining the
models proposed by Liu et al. [166] and Baroghel-Bouny et al. [164], it
can be concluded that the diffusion coefficients calculated by water
saturation degree are close to the experimental results. In addition, it is
worth noting that the early CO2 curing models are more sensitive to the
changes in water-cement ratio than the carbonation models of hardened
cement-based materials. Under the condition of 70% relative humidity,
when the water-cement ratio changes from 0.65 to 0.5, the diffusion
X. You et al. Cement and Concrete Composites 125 (2022) 104315

coefficient calculated by the early CO2 curing model [155,166] will be

decreased by 71.7%, while the value calculated by the carbonation
model [109] is only decreased by 47.6%. For the carbonation of hard­
ened cement-based materials, the water-cement ratio mainly affects the
porosity, but for the early CO2 curing, it also directly affects the content
of aqueous phase in the pores.
The initial saturation degree that directly affects the efficiency of
CO2 penetration into cement-based materials can be calculated by the
model of Liu et al. [166] or combining Kelvin Laplace equation [167]
and the model proposed by Zhou [168], as shown in the following
equations.
( )
RT 1 κ2 − 1 + S0− 1
− ln(RH) = ln gρH2 O (25)
V H2 O κ 1 κ2

Where R is the universal gas constant, V H2 O is the molar volume of water,

κ1 and κ2 are fitting shape factors.
The calculation of the reaction rate during early CO2 curing process
is more complex than that of the carbonation of hardened cement-based
materials, mainly because more reactants other than CH and the rapid
formation of calcium carbonate need to be considered in the modelling
of CO2 curing. As the early CO2 curing proceeds, the generated calcium
carbonate covers the surface of the reactants, thus reducing the specific
surface area of the active minerals. Although calcium carbonate is also
formed in the carbonation process of hardened cement-based materials,
the rate of formation is relatively slow and its impact on the subsequent
carbonation reactions is limited [122,130]. According to the carbon­
ation rate model of hardened cement-based materials [11], after 550
days of carbonation, there is still 44.5% of CH remained unreacted.
However, based on the model of early CO2 curing [155], it takes only 4 h
to consume the same amount of C3S. Therefore, for early CO2 curing, it is
important to consider the reduction of specific surface area of reactants
during such a rapid process. The method of introducing a reduction
factor can be used to characterize the changes of specific surface area.
The specific calculation equations and the impact of the reduction factor
on effective CO2 uptake are shown below.
The chemical reaction rate of early CO2 curing can be expressed by
the equation shown below [169]:
ri = ki as,i [CO2 (aq)] (26)
Where αs,i is the surface area of reactive solid compound i such as C3S
and C2S, it can be calculated by following equations [152]:
as,i = as [i](1 / (1 − ε))Vi (27)
as = aso − fc ⋅[CaCO3 ] (28)
as0 = Sρcon (29)
Where αs is the surface area of pores in compacted cement mortar per
unit volume, Vi is molar volume of compound i, αs0 is the initial specific
surface area of pores and fC is a reduction coefficient.
The effect of the parameter fC is shown in Fig. 13. When the reduction
of specific surface area of active minerals is not considered, that is, fC =
0, the error between the model and the experimental results is large.
While if the value of fC is set to 5.6 m2/mol, the model results will be in
good agreement with the experimental data. This proves the necessity of
taking the reduction of specific surface area into consideration for early
CO2 curing models.
4. Conclusions
In this paper, the existing models for the carbonation of hardened
cement-based materials and early CO2 curing of fresh cement-based
materials are reviewed. The following conclusions can be drawn:
Fig. 13. Predicted and experimental ratio of outlet CO2 concentration to inlet
CO2 concentration with carbonation time for flow-rate 1.17 Lpm, w/c =
0.26 [152].
(1) The empirical models are mainly used to calculate the carbon­
ation depth. They are simple to solve and can be conveniently
applied in engineering practice. However, the influence of
different factors on carbonation cannot be effectively reflected in
this kind of models. The prediction results of empirical models
can be considered as the preliminary evaluation of carbonation
depth, but it is unreasonable to regard them as the only basis for
determining the corrosion risk of reinforcement and the service
life of structures.
(2) The thermodynamic models can be used to calculate the phase
assemblages, pH value and porosity of cement-based materials
after carbonation. This kind of models consider all possible
phases, so it can be used for comprehensive evaluation of the
complex carbonation reactions. However, these models can only
predict the final state of carbonation, but cannot simulate the
specific carbonation processes. Besides, the formation of meta­
stable or transitional phases is also ignored.
(3) The kinetic models can simulate the whole carbonation process in
detail, including diffusion, dissolution and carbonation reactions.
They can reveal the mechanism of carbonation and achieve the
accurate parameters control of carbonation process. However,
compared with other models, kinetic models require more as­
sumptions and are generally more difficult to solve. It is still a
challenging work to combine different processes reasonably and
reduce the errors.
(4) The numerical models can make the carbonation simulation
closer to the real situation. They can obtain much higher pre­
diction accuracy than empirical models and extend the tradi­
tional two-dimensional carbonation models to three-dimensional
models. However, a huge amount of data is generally required.
Various factors can be considered in the models but the in­
teractions between these factors are still not clear.
(5) Due to the fast reaction rate, the reduction of specific surface area
of active minerals should be especially noted in the modelling
process of early CO2 curing. Extensive modelling works are still
needed to evaluate and understand the whole CO2 curing process,
especially to characterize the hindering effect of calcium

13
X. You et al. Cement and Concrete Composites 125 (2022) 104315

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