Cement and Concrete Research 57 (2014) 7078

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Cement and Concrete Research

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Analysis of an accelerated carbonation test with severe preconditioning

Ph. Turcry a,, L. Oksri-Nela a, A. Younsi b, A. At-Mokhtar a
a
b

University of La Rochelle, CNRS, LaSIE FRE 3474, Av. M. Crpeau, 17042 La Rochelle Cedex 1, France
University of Cergy-Pontoise, L2MGC, 5 Mail Gay-Lussac, 95031 Cergy-Pontoise Cedex, France

a r t i c l e

i n f o

Article history:
Received 6 September 2013
Accepted 6 January 2014
Keywords:
Carbonation (C)
Hydration (A)
Drying (A)
Thermal Analysis (B)

a b s t r a c t
In this paper, an analysis of the accelerated carbonation test according to the French Standard XP P18-458 is presented. It aims at a better understanding of the carbonation kinetics in the early days of this test. The inuence of
preconditioning by oven-drying was studied by means of carbonation depths monitoring (phenolphthalein
spraying and thermogravimetric analysis) and measurements of relative humidity (RH) inside concrete samples.
The main results question the relevance of the preconditioning because it does not establish a hydric balance between the tested samples and the carbonation chamber. Moreover, an absence of carbonation close to the sample
surface was revealed during the early days of testing. This is explained by the very low water content resulted
from oven-drying. This gives nally an explanation of the whole carbonation kinetics recorded during this test.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Performance-based approach is a promising method to design
concrete mixtures considering durability as a major parameter as
basic properties such as compressive strength [13]. It consists in
assessing the concrete performances with respect to external attacks
leading to the degradation of reinforced concrete structures. Such an
approach requires effective tools to assess durability indicators.
The diffusion of carbon dioxide (CO2) within concrete porosity is one
of the most common aggressive ingresses [4,5]. The consecutive carbonation of the cementitious matrix results in a drop of pH which may lead
to corrosion of the steel reinforcement. In order to assess the carbonation resistance, accelerated tests are classically used because carbonation in natural conditions is a slow phenomenon from an engineer
point of view. During accelerated tests, concrete samples are submitted
to a concentration of CO2 much higher than the concentration in the
ambient air (~ 0.03%). Prior to testing, samples are often oven-dried
during a short period in order to reduce the water saturation degree
and thus to enhance the CO2 diffusivity. Tests are performed under a
controlled relative humidity (RH), chosen in the range of RH known to
favor carbonation.
A literature review reveals that there is neither consensus on accelerated carbonation tests nor universal protocols. In their review article,
Pacheco Torgal et al. [6] report more than 20 test conditions and show
that the used concentration of CO2 ranges from 1 to 50%, while the RH
in the carbonation chamber ranges from 50 to 70%. Conditions before
testing vary also greatly. Not only varies the curing time (from 2 weeks
to 3 months of water-curing), but also the preconditioning (with or
without thermal treatment prior to accelerated carbonation test).
Corresponding author.
E-mail address: philippe.turcry@univ-lr.fr (P. Turcry).
0008-8846/$ see front matter 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.cemconres.2014.01.003

Our paper focuses on the analysis of the standardized accelerated

carbonation test according to the French Standard XP P18-458 [7].
This protocol can be classied within tests with the most severe conditions. Its test conditions are close to some other tests, e.g. [810]. The
test conditions can be discussed as follows:
Firstly, the CO2 concentration in the carbonation chamber is 50%,
which is signicantly higher than natural concentrations or concentrations used in other accelerated tests that are usually 5 to
20% [11]. A lot of studies reveal that the carbonation mechanism
for high concentration differs from that observed in natural conditions. The carbonation rate of CSH was found to be dependent
on the CO2 concentration [12,13]. The higher the concentration,
the higher the carbonation of CSH. Bernal et al. [14] studied the
role of the pore solution chemistry on the carbonation of alkaliactivated binders. The authors show through experiments and
calculations that the pore solution pH is more decreased in an accelerated test (with 4% CO2 concentration) than in natural CO2
concentration. Moreover, several authors show that the mineralogy of the CaCO3 which precipitates during carbonation (i.e. calcite, aragonite or vaterite) varies with the CO2 concentration
during the test and cement composition [15,16]. All these results
question the representativeness of accelerated tests using high
CO2 concentration.
Secondly, the RH in the carbonation chamber is xed to 65 5%.
This RH was chosen because carbonation kinetics is known to be
maximal between 50 and 70%. However, this RH range was
found to be optimal mainly for classical mixtures with Portland
cement, i.e. ordinary concretes and mortars [17,18]. Drouet [19]
shows that the optimal RH for mixtures with BFS is lower (due
to their ner pore structure, BFS mixtures usually remain more
water-saturated for RH N 50% than Portland cement mixtures).

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71

Table 2
Mix proportions (in kg/m3) and properties of the studied concrete.
Gravel 10/14
Gravel 6/10
Sand 0/4
Cement CEM I 52.5 N
Effective water
W/C ()
Slump (cm)
28-day compressive strength (MPa)
Porosity at 28 days air-curing (%)
Porosity at 28 days water-curing (%)

875
211
855
301
182
0.6
16
36
16.0
13.8

2. Experimental program
2.1. Materials and mixtures

Fig. 1. Example of results obtained according to the French Standard protocol: carbonation
depths determined by phenolphthalein spraying versus test duration [24].

The study was carried out on a concrete mixture which was already
tested in former works [2,24]. The mixture was made with a Portland
cement (CEM I 52.5) complying with the European Standard
EN 1971 (Table 1), a siliceous marine sand (0/4 mm) and two crushed
diorite gravels (6/10 and 10/14 mm). The mix proportions and the main
properties are given in Table 2.
2.2. Specimens and curing

Thirdly, French standard suggests oven-drying of samples for 14 days

at 40 5 C before carbonation tests. This severe preconditioning
aims at reducing the water saturation degree to enhance the diffusion of CO2. It was chosen to promote the carbonation of dense
concretes such as high performance concrete (HPC). For shorter
duration of preconditioning (for instance, in a previous protocol,
2 days at 40 C [20]), carbonation of HPC is very slow or even null
[21,22]. One can question the so-obtained proles of water content,
which are a priori non-homogeneous proles, with much lower
water-saturation in the sample skin than in the core [23].
In the present paper, we address the issue of the severe preconditioning of the French Standard protocol. Our rst aim is to assess the
inuence of this preconditioning on the accelerated carbonation kinetics.
Fig. 1 gives an example of carbonation kinetics usually obtained with the
studied protocol (carbonation depths determined with phenolphthalein
spraying). It has a linear form with the square root of time of carbonation
and seems to indicate a non-null initial carbonation depth, while
concrete samples should not be carbonated before testing, since they
are water-cured prior to preconditioning. Our aim was to better interpret
the carbonation rate, especially during the rst days of the test. Experiments were carried out on concrete made with Portland cement. Accelerated carbonation was monitored by mean of both phenolphthalein
spraying and thermogravimetric analysis coupled to chemical analysis.
Effects of drying and carbonation were also investigated by monitoring
over time relative humidity inside the tested specimens. Results are
discussed and comments are provided regarding carbonation kinetics
in order to improve the French standardized protocol.

11 22 cm cylinders (11 cm in diameter and 22 cm in height)

were manufactured. Two curing-modes denoted air-curing and
water-curing were studied to highlight the inuence of curing mode
on carbonation. All cylinders were demoulded 24 h after casting. A
rst set of cylinders was then stored in a room at 20 C and RH between
30 and 70% (air-curing) and a second set was cured under water for
27 days (water-curing). Specimens were regularly weighed.
Two experimental campaigns were carried out. The rst one was
done to compare various concrete mixtures (results are available in
[2]) and the second one to better understand accelerated test. In the
following, results from the rst campaign are denoted 1 while those
of the second one are denoted 2. Table 3 summarizes tests done during
experimental Campaign 1 and Campaign 2.
2.3. Protocols
2.3.1. Accelerated carbonation test
Accelerated carbonation tests were carried out in accordance with
the French Standard procedure XP P18-458 [7]. Concrete samples
were prepared as follows: at the age of 28 days, after air- or watercuring, 11 22 cm cylinders were sawn into 10 cm thick disks. The
sawn sections were sealed by adhesive aluminum in order to ensure radial CO2 diffusion during carbonation tests. Then, the disks were dried in
a ventilated oven at 45 3 C for 14 days. After this thermal treatment,
the disks were placed in a chamber containing 50 5% CO2 at
20 2 C and 65 5% RH. The relative humidity was imposed by a
salt solution of ammonium nitrate. At various dates, two disks per
curing-mode were taken from the carbonation chamber and split.

Table 1
Properties of the used cement (CEM I 52.5 N type complying
with EN 1971).
Density ()
Blaine surface (cm2/g)
Passing 32 m (%)
Clinker (%)

3.11
3400
82
95

Chemical composition (%)

CaO
SiO2
Al2O3
Fe2O3
SO3

64.8
20.5
4.5
2.7
3.4

Table 3
Tests carried out during the two experimental campaigns.
Tests

Campaign 1

Campaign 2

Monitoring of mass variation

during preconditioning
Accelerated carbonation test
Carbonation depths measured at:

X
7, 14, 21,
28, 42 days

X
0, 0.5, 1, 3, 5,
7, 14, 28 days
X
X

Determination of Ca(OH)2 proles

Determination of RH proles

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P. Turcry et al. / Cement and Concrete Research 57 (2014) 7078

Fig. 2. Views of 11 22 cm cylinder with drilled holes (left), with RH sensors (right) and top view (middle) with location of the holes (distances between lateral surface and center of hole).

Carbonation depths were measured by a pH indicator solution (phenolphthalein) sprayed on the sections of the split disks. It is assumed that
the non-colored zone (pH b 9) is totally carbonated while the pinkcolored one (pH N 9) is not carbonated.
During the rst experimental campaign, carbonation depths were
measured after 7, 14, 21, 28 and 42 days of accelerated carbonation, as
recommended by the French standard protocol. During the second campaign, our objective was to determine the carbonation kinetics at early
beginning of accelerated test. Thus, carbonation depths were measured
earlier than during the rst campaign, i.e. after 0, 0.5, 1, 3, 5, 7, 14 and
28 days of accelerated carbonation.
2.3.2. Determination of carbonation proles
The result of pH indicator spraying suggests a sharp carbonation
front, between a carbonated zone and a non-carbonated one. In fact,
the carbonation of cementitious materials is progressive [4,23]. Especially, carbonation starts usually beyond the carbonation front. In
order to obtain more precise data on the real carbonation state on the
samples, one can measure the content of calcium carbonate (CaCO3)
produced by carbonation. However, different sources of CaCO3 are generally present in the concrete sample, for instance from cement or sand.
Thus, it could be difcult to distinguish CaCO3 from carbonation and that
from concrete compounds. One can also quantify the Portlandite content (Ca(OH)2), one of cement hydrates consumed by carbonation reactions. This second method was adopted in our study since Portlandite is
easily quantied by TGA in the case of Portland cement concretes.
Portlandite proles were measured only during the second experimental campaign.
The Ca(OH)2 content was assessed by thermogravimetric analysis
(TGA) carried out on concrete samples taken from the 10 cm high
disks tested in the carbonation chamber (TGA equipment: Setaram

Fig. 3. Mass variations of concrete samples due to 27-day air- and water-curing and
14-day oven-drying. 1 and 2 denotes the rst and the second campaign, respectively.

Setsys Evolution). First, samples were saw-cut from carbonated disks.

The so-obtained samples were then crushed in a grinder during
3 min. Finally, the obtained powder was sieved at 315 m.
During TGA measurements, powder samples of around 100 mg
were heated at 10 C/min from 20 to 1000 C in Argon atmosphere.
The Portlandite content was determined using the tangent method
described in [25]. It was obtained from the weight loss between the
tangents of the TG curve at two temperatures T1 and T2. The latter
was determined with the derivative thermogravimetry (DTG). T1 and
T2 are close to 380 and 550 C, respectively.
From TGA, the Portlandite content is expressed in g per g of sample.
However, the tested powder samples are not enough representative of
concrete. In order to express the Ca(OH)2 content as a function of a
quantity representative of concrete, the cement content in the powder
was determined by chemical analysis, as proposed in [26].
After grinding and sieving, powder samples of 100 mg were
immersed in 2 mg of nitric acid (HNO3) for 24 h. Then, a solution of
HNO3 (with 1/50 dilution in pure water) was added. A week later, the
obtained suspensions were analyzed by Inductively Coupled Plasma
Atomic Optical Emission Spectroscopy (ICPAES) in order to determine
their contents of oxides, such as CaO, Al2O3, Fe2O3 and MgO, of the initial
powder sample (ICPAES equipment: Varian Vista Pro). Finally, Al2O3
was chosen as a marker of cement. A discussion on this choice can be
found in [26]. Knowing the Al2O3 contents of both the powder sample
and the cement, the Ca(OH)2 contents determined from TGA can be
expressed in g per g of anhydrous cement.

2.3.3. Determination of RH proles

During the second experimental campaign, RH proles were determined using hygrometric probes (capacitive humidity sensors from

Fig. 4. Time-evolutions of external conditions (from concrete manufacturing) during

27-day air-curing and 14-day oven-drying.

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73

Fig. 5. Time-evolutions of RH measured at different distances (depths) inside concrete cylinders during 27-day curing and during 14-day oven-drying, for the two curing modes: air (left)
and water (right).

Ahlborn). In the case of air-curing, ve holes (0.5 cm in diameter and

5 cm in depth) were drilled in an 11 22 cm cylinder after demoulding
at the age of 24 h. The locations of the holes are indicated in Fig. 2. In the
case of water-curing, holes with the same locations were drilled, after
water immersion, at the age of 28 days. In each case, RH sensors were
placed in the holes after drilling. The top of the holes was sealed by
silicone and the top and the bottom of the specimen were covered by
aluminum adhesive in order to obtain radial drying. After that, the
time-evolution of RH inside the holes was recorded from the age of
24 days for the air-curing and 28 days for the water-curing, during
drying phase and accelerated carbonation test.
3. Results and discussion
3.1. Mass variations and RH proles before carbonation test
Fig. 3 gives the relative mass variations of the concrete samples during air- and water-curing followed by the 14-day long oven-drying
at 45 C. In the case of water-curing, a gain of mass can be noticed
due to absorption of water. The mass variations of the samples from
the two batches (Water 1 and Water 2) are almost identical. This
tends to prove that the reproducibility is pretty good. However, in the
case of air-curing, the mass variation measured during the second

campaign (Air 2) is higher than the one measured during the rst
campaign (Air 1). This can be partly explained by the fact that RH in
the storing room was, in average, not the same during the two
campaigns. During the rst one, RH was rather constant (equal to
66 3%). During the second one, RH was more variable, as shown in
Fig. 4, with lower average value (equal to 59 7%).
RH was also measured inside concrete cylinders during campaign 2.
Fig. 4 gives the external conditions (RH and temperature) and Fig. 5
gives RH evolutions at different distances (depths) from the drying surface. In the case of air-curing, RH at 10 or 20 mm decreases from the
rst days after demolding due to drying. When cylinders are put in
oven at 45 5 C, at 28 days, one can notice a sudden increase in RH
inside concrete, while RH in the oven (outside) decreases to about
15%. The change in RH inside concrete can be explained by the dependency of the water retention of concrete on temperature. For a given
RH, the higher the temperature, the lower the water content at equilibrium [27]. Heat transfer is much faster than water transfer. Thus, while
the temperature of concrete varies rapidly from 20 to 45 C, the water
content remains almost constant. Since the vapor water sorption isotherm is not the same at 20 than at 45 C, the RH inside concrete should
then increases.
After this short increase in RH, drying restarts faster than during
curing because the outside RH is lower and the water transfer properties
of concrete are higher at 45 than at 20 C. The RH proles obtained at
the end of oven-drying are shown in Fig. 6. In both curing-modes,
there is a strong RH gradient between the surface and the core of the
specimens. Just before the accelerated carbonation test, the concrete
disks are far from hydric balance with the ambiance in the carbonation
chamber where the RH is equal to 65 5%. Of course, this result
questions the method of preconditioning.
3.2. Carbonation front by phenolphthalein spray

Fig. 6. RH proles (drying surface corresponds to depth = 0 mm) at the end of the 14-day
long oven-drying at 45 C, i.e. just before accelerated carbonation test, for air- and
water-curing.

During the rst experimental campaign, the carbonation depth, denoted Xc, was measured from 7 days in the carbonation chamber.
Classically, the spraying of phenolphthalein created a clear contrast
between a carbonated zone (pH b 9) and a non-carbonated zone
(pH N 9) as shown in Fig. 7(a). On the other hand, between 0.5 and
7 days of carbonation during the second campaign, three zones appeared after spraying of phenolphthalein, as schematized in Fig. 7(b)
and shown in Fig. 7(c). The pH indicator reveals non-carbonated zone
(i.e. pH N 9) within the rst mm from the surface in contact with CO2
(depth denoted Xc2).

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P. Turcry et al. / Cement and Concrete Research 57 (2014) 7078

Fig. 7. Schematic representation of a carbonated section: (a): classical carbonation front; (b) and (c): results obtained from the second campaign tests, schematic view and sample's image,
respectively.

Fig. 8 gives time-evolutions of the depths Xc1 (carbonation fronts

the most in depth), for both curing-modes and both experimental
campaigns. As previously observed on the mass variations, the reproducibility is better for water-curing than for air-curing. For the latter
curing, the higher carbonation depths measured during the second
campaign may be the consequence of the more important drying (see
Section 3.1).
Until 0.5 day, the depth Xc1 is quasi null. Only the skin of the aircured disks appeared to be carbonated (Xc1 ~ 1 mm). This result can
be attributed to a natural carbonation during air-curing. Xc1 increases
abruptly between 0.5 and 1 day and then evolves much more slowly.
After 1 day, the Xc1 increase is approximately linear with the square
root of time.
For both air- and water-curing, the depth Xc2, dened in
Fig. 7(b), appears at 1 day and then decreases until nullify at about
7 days (Fig. 9). Thus, the non-carbonated zone, according to the pH
indicator, seems to carbonate gradually during the rst week. This
explains why this non-carbonated zone was not observed during the
rst experimental campaign, which did not focus on this period.
3.3. Carbonation proles by TGA and chemical analysis
Measurements of Portlandite contents by TGA and chemical analysis
(Fig. 10) conrm the results obtained with phenolphthalein (Fig. 8). Indeed, after 1 and 3 days of carbonation, lower contents of Ca(OH)2 were
measured near the carbonation front Xc1 (indicated by arrows in
Fig. 10) than upstream or downstream to this front. For instance, the
Portlandite content of air-cured samples after 1 day is lower at 14 mm
than at 7 mm. From the pH indicator spraying, the carbonated zone
after 1 day was situated approximately between Xc2 = 13 mm

Fig. 8. Carbonation depths versus duration of accelerated carbonation test, for the two
curing modes Air and Water.

(Fig. 9) and Xc1 = 16 mm (Fig. 8). This highlights that the zone of
thickness Xc2 is clearly less carbonated than the zone between Xc2
and Xc1. The same behavior can be seen for both curing modes. Using
gammadensimetry, Thiery et al. [9] observed also this kind of phenomenon: a concrete sample which was submitted to extreme preconditioning (oven-drying at 45 C and 60 C before carbonation) was less
carbonated near the drying surface than deeper after 3 days of accelerated carbonation.
In the case of air-curing, we note also that the Portlandite content
(after 1 day) in the concrete skin (depth b 2 mm) is lower than found
deeper in the sample. This is due to the natural carbonation during curing, as assumed previously following results obtained by pH indicator
(Section 3.2). This low Portlandite content can also be due to a stop of
cement hydration caused by drying during curing [24,28].
3.4. RH evolution during carbonation test
Evolutions of temperature and RH inside and outside the concrete
disks were recorded during the accelerated carbonation test as shown
in Fig. 11 (temperature) and 12 (RH). We notice that, at the beginning
of the carbonation test (time = 2 h in Fig. 11), the temperature of the
tested disks (~ 32 C) is not yet equal to the ambient temperature
(~ 25 C). Two hours between the oven-drying and the carbonation
test are not enough to cool the samples. In Fig. 12, it can be seen that
the outside RH is lower than that expected by the use of ammonium
nitrate solution (65%). Of course, this difference could be due to the

Fig. 9. Depths Xc2 dened in Fig. 7(b) versus duration of accelerated carbonation test, for
the two curing modes Air and Water.

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75

Fig. 10. Depth-proles of Ca(OH)2 contents after 1, 3 and 14 days of accelerated carbonation for air-curing (left) and water-curing (right). Arrows indicate the carbonation front (Xc1)
obtained by phenolphthalein spraying.

accuracy of the RH probe (RH +/ 5%). It is more interesting to note

that this outside RH is very stable.
Inside the concrete specimens, huge variations in RH were measured, especially at depths affected by the oven-drying, i.e. at 10 and
20 mm for air-curing and at 10 mm for water-curing (Fig. 12).
Similar variations are observed for both curing modes: rst a sharp increase of RH during the rst day of carbonation, then a slow decrease.
In order to better understand the observed phenomena, the evolution of RH at 10 mm in an air-cured specimen was plotted in Fig. 13
(log scale). Let us analyze the three phases which can be distinguished:
Phase 1: From the beginning of the carbonation test, RH increases
suddenly during 1 h. This RH variation could not be explained by
the change in concrete temperature, since temperature varies slowly
within this short period (Fig. 11). During this hour, the carbonation
chamber is lled with CO2 to reach a concentration of 50%. Although
the excess of gas in the chamber is evacuated, the injection of CO2
creates a little increase in pressure (equal to less than 5 mbars).
This increase in pressure gives a possible explanation of the increase
in RH (i.e. increase in vapor pressure). After which, RH decreases.

Fig. 11. Time-evolutions of temperatures at various depths inside concrete from the end of
oven-drying (t = 0 h) and during the rst 12 h of accelerated carbonation test (aircuring). Carbonation test begins at t = 2 h.

Phase 2: After the rst increase in RH, a second one, more progressive, is observed during about 24 h. Results from TGA (Fig. 10) and
phenolphthalein spraying (Fig. 8) highlight that carbonation begins
during this period. Carbonation reactions are known to release
water, especially due to the dissolution of Portlandite. Generally
speaking, the carbonation of 1 mol of Ca(OH)2 produces 1 mol of
H2O. In our case, the carbonation of all Portlandite content, equal
to about 25% of the 301 kg of cement per m3 of concrete according
to TGA, should produce w = 18 kg of water per m3 of concrete.
In order to assess the resulting increase in RH due to w, we use
the water vapor sorption isotherm of our concrete (from [29]). As
shown in Fig. 14, RH should increase from 45 to 65%. The theoretical
RH is a quite rough estimation because the used isotherm was
determined from a desorption experiment on a non-carbonated
material. The measured RH is higher: RH reached a maximum of
85% at the end of the phase 2 (Fig. 13). Basically, carbonation generates not only a release of free water but also a change in microstructure such as a reduction of porosity, since CaCO3 has higher molar
volume than Portlandite and CSH [30]. Hyvert [31] measured vapor
sorption/desorption isotherms of carbonated and non-carbonated
mortars made with Portland cement (Fig. 15). It can be seen on the
reproduced curves from Hyvert that carbonation changes the
shape of the isotherm curves. Especially, a small increase in water
saturation will lead to a larger increase in RH after carbonation
than before. Finally, we can attribute the increase in RH observed
in phase 2 to carbonation.
Phase 3: Finally, RH tends to decrease. This is the consequence
of water transfers due to gradient of water content between the
sample and its ambience.
The evolution of RH in three phases is similar for both curing modes
and for each depth inside specimens. However, as revealed in Fig. 16,
the kinetics of RH increase during the rst hours of carbonation
(phase 2) depends on depth and curing mode. In the case of watercuring, the increase in RH attributed to carbonation at 10 mm begins
at 4 h and is very fast. In the case of air-curing, the RH increases
from 6 h and is more rapid at 20 than at 10 mm. This could be surprising
since CO2 diffuses from the surface and passes rst at 10 and then at
20 mm. In fact, carbonation kinetics is affected by the water saturation
degree. As result, carbonation reactions occur earlier and faster where
the saturation degree (or the RH) is optimal. Before carbonation, the
initial RH is higher at 20 mm (~55%) than at 10 mm (~40%) in the aircured specimen and is higher in the water-cured specimen (~ 60%)
than the air-cured one (Figs. 5 and 12).

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P. Turcry et al. / Cement and Concrete Research 57 (2014) 7078

Fig. 12. Time-evolutions of RH measured during oven-drying and accelerated carbonation test, for the two curing modes: Air (left) and Water (right).

The previous results allow analyzing the carbonation kinetics during

the accelerated test. The preconditioning in oven at 45 C results in a
drying on several cm of the concrete disks (Fig. 6), which should facilitate the diffusion of CO2. During the rst hours of testing, we observed a
very slow carbonation (Fig. 10) and even no carbonation (Fig. 8). As

suggested previously, this comes from the well-known dependency of

carbonation with RH, which is highlighted by literature results in
Fig. 17 [19]. Carbonation reactions occur in the interstitial solution
after dissolution of the gaseous CO2. Thus, when the water saturation
degree (or RH) is too low, carbonation cannot occur. During the carbonation test, CO2 diffuses rst freely without reacting with the cementitious matrix because of too low RH close to the concrete surface. Then,
CO2 is consumed by carbonation at a depth where the saturation degree
is enough high. The change in kinetics of the carbonation front Xc1
reveals this phenomenon at macroscopic scale.
The extreme preconditioning recommended by the French Standard
dries the specimen excessively and it results paradoxically in an accelerated carbonation without carbonation during the rst days of testing.
Finally, it questions this kind of protocol and the exploitation of the results, since it makes uncertain any comparison of carbonation depths
deduced from pH indicator spraying. Indeed, the measured depth Xc1 is
the sum of two terms, as explained in Fig. 18: the depth 1 which corresponds to the zone where water content is initially too low for carbonation (free diffusion of CO2 without dissolution) and the depth 2 which
corresponds to the zone where carbonation can really occur.
Consequently, when different concretes have to be compared using
this accelerated test, it seems more relevant to compare carbonation
kinetics, i.e. the slope of the Xc1 curve, rather than carbonation depths.
For instance, the carbonation kinetics of the water-cured specimens
(Water 2) was found equal to 1.30 mm/day1/2 (Fig. 18).

Fig. 14. Water vapor desorption isotherm of the studied concrete (from [29]). w is the
theoretical increase in water content due to the carbonation of all Portlandite content
and RH the resulting variation of RH.

Fig. 15. Water vapor desorption isotherms of mortars made with Portland cement before
and after carbonation (from [31]).

Fig. 13. Time-evolution of RH at 10 mm from the surface inside an air-cured cylinder.

3.5. Discussion

P. Turcry et al. / Cement and Concrete Research 57 (2014) 7078

77

Fig. 18. Carbonation depths Xc1 and Xc2 measured on the water-cured specimens (Water 2).
Fig. 16. Time-evolution of RH at depths = 10 or 20 mm inside the concrete cylinders from
the end of oven-drying (t = 0) and during the rst 22 h of carbonation test (beginning at
t = 2 h), for the two curing modes Air and Water.

4. Conclusion
The accelerated carbonation test performed according to the French
Standard XP P18-458 was analyzed by studying the carbonation kinetics
during the rst days of the test and the inuence of preconditioning on
CO2 diffusion. The following conclusions can be drawn.
Measurements of relative humidity using hygrometric probes inside
concrete specimens submitted to oven-drying at 45 5 C
highlighted a strong relative humidity gradient between the surface
and the core of the specimens. These measurements show no hydric
equilibrium between the samples and the ambiance of the carbonation chamber.
The characterization of accelerated carbonation, with both phenolphthalein spraying and measurements of Portlandite contents by
TGA coupled to chemical analysis, shows that concrete samples are
less carbonated near the surface than more in depth during the
rst days of the test. This is due to the preconditioning, which highly
dries the rst mm and facilitates therefore the CO2 diffusion without
carbonation until the depth where the carbonation reaction can
occur, i.e. where water content is enough. This gives an explanation
of the observed carbonation kinetics.
The present results question the relevance of the preconditioning
recommended by French Standard. With this protocol, the use of single
values of carbonation depth may lead to erroneous interpretation in the

Fig. 17. Examples of literature results highlighting the link between carbonation and RH
(comparison done in [19]).

scope of comparison of concrete mixture performances. It would be

preferable to compare the carbonation kinetics determined from the
linear part of the carbonation depth evolution as a function of the square
root of time.
Nowadays, concrete mixtures are more and more designed with
blended cements, such as blast furnace slag cement. In a performancebased approach, accelerated tests should apply to any cementitious
systems. Thus, it would be judicious to extend the present study to
other cementitious materials containing mineral additions or with
high mechanical performances.
Acknowledgments
The authors would like to acknowledge Carine Churlaud (from
LIENSs UMR CNRS 7266, University of La Rochelle) for chemical analyses
by ICPAES.
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