Cement and Concrete Composites 90 (2018) 257–265

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Cement and Concrete Composites

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Effect of curing time on granulated blast-furnace slag cement mortars T

carbonation
Miguel Ángel Sanjuána,∗, Esteban Estévezb, Cristina Argizc, Daniel del Barriob
a
Spanish Institute for Cement and its Applications (IECA), C/ José Abascal, 53, 28003, Madrid, Spain
b
Department of Cement Chemical Testing, LOEMCO, Polytechnic University of Madrid (UPM), Avda. Eric Kandel 0001, LOEMCO Building, South Tecnológical Area
“Acedinos”, 28906, Getafe, Madrid, Spain
c
Department of Science and Technology of Building Materials, Civil Engineering School, Polytechnic University of Madrid (UPM), 28040, Madrid, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: Currently, ground granulated blast-furnace slag cements use in cement-based materials is being increasing be-
Ground granulated blast-furnace slag cause perform well in marine and other aggressive environments. However, mortars and concretes made of this
Cement type of cement exhibit high carbonation rates, particularly in badly cured cement-based materials and when high
Durability blast-furnace slag contents are used. Concrete reinforcement remains passive but can be corroded if the pore
Carbonation testing
solution pH drops as a result of the carbonation process promoting the reinforced concrete structure failure
Carbon dioxide
during its service life. Results show the very sensitive response to wet-curing time of slag mortars with regard to
the natural carbonation resistance. Then, a minimum period of 3–7 days of wet curing is required in order to
guarantee the usual projected service life in reinforced concrete structures. In this work, estimation models of
carbonation depth and carbon dioxide diffusion coefficient in ground granulated blast-furnace slag mortars as a
function of the curing period and the amount of ground granulated blast-furnace slag are proposed. This in-
formation will be useful to material and civil engineers in designing cement-based materials and planning the
required curing time depending on their ground granulated blast-furnace slag content.

1. Introduction 1.2. Carbonation chemical processes

1.1. Steel reinforced concrete failure by carbonation
Steel reinforced concrete structures need to be durable to ensure
that the intended service life is achieved [1]. The steel reinforcement
remains passivated due to the high alkalinity produced by the Portland
cement hydration but can be corroded if the pore solution pH drops as a
result of the carbonation process. Thus, reinforcement corrosion in-
duced by carbonation can play a significant role in a reinforced con-
crete structure's durability, particularly when carbonation is coupled
with chloride penetration [2]. Carbonation is a process produced by
several chemical reactions between the atmospheric carbon dioxide and
the calcium and alkali phases (Ca2+) in Portland cement-based mate-
rials. Such reactions produce different carbonates depending on the
reacting alkaline species [3]. Recently, several reviews on cement-
based materials carbonation have been published because reinforced
concrete structures carbonation is a serious concern due to the risk of
structural failure [4,5].
Carbonation is a chemical process consisting of the formation of
calcium carbonate (CaCO3) by a reaction of carbon dioxide (CO2),
calcium phases (Ca2+), and water (H2O) in Portland cement-based
materials. In a first step, carbon dioxide (CO2) dissolves in water (H2O)
according to Eq. (1). Then, it reacts with the calcium phases, mainly
calcium hydroxide (Ca(OH)2) as shown in Eq. (2). But also, calcium
bearing other phases such as C-S-H gel, ettringite, calcium aluminates,
tricalcium silicate (C3S) and dicalcium silicate (C2S) are affected by
carbon dioxide (CO2) reaction [6,7]. Ca(OH)2 initially reacts with CO2
more rapidly than C-S-H, but the rate of reaction decreases with time,
and is overtaken by C-S-H gel reaction rate [8,9]. Some researchers
[10,11] attribute this reaction rate slowdown to the formation of sev-
eral microcrystalline calcium carbonate layers around the reacting Ca
(OH)2 hexagonal crystals.
Chemical reaction of C-S-H gel with carbon dioxide (Eq. (3)) con-
sists of the calcium ions removal from the C–S–H gel leading to the
formation of several calcium carbonate polymorphs (calcite, aragonite
and vaterite [6,7,12] and silica gel [13,14]; thus, it becomes highly
porous (Eq. (3))). Particularly, formation of aragonite and vaterite is

∗
Corresponding author.
E-mail addresses: masanjuan@ieca.es (M.Á. Sanjuán), eestevez@loemco.com (E. Estévez), cg.argiz@upm.es (C. Argiz), dbarrio@loemco.com (D.d. Barrio).

https://doi.org/10.1016/j.cemconcomp.2018.04.006
Received 18 September 2017; Received in revised form 9 February 2018; Accepted 11 April 2018
Available online 12 April 2018
0958-9465/ © 2018 Elsevier Ltd. All rights reserved.
M.Á. Sanjuán et al. Cement and Concrete Composites 90 (2018) 257–265

formed in highly decalcified C-S-H gel [9,13,15], i.e. in accelerated
carbonation testing where a high CO2 concentration is used. As result of
the C-S-H gel carbonation, the Ca/Si ratio drops approaching amor-
phous silica [6], therefore, this chemical reaction depends strongly on
the initial Ca/Si ratio of the C-S-H gel [7]. The more Ca/Si ratio, the
lower of C-S-H gel carbonation rate [14].
Also, ettringite and calcium aluminates may be carbonated at low
partial CO2 pressure, resulting in formation of gypsum, alumina gel
[16] and vaterite crystals [17].
CO2 + H2O → CO2 (g → aq) (1)
Ca(OH)2 (s → aq) + CO2 (g → aq) → CaCO3 (s) + H2O (aq) (2)
(CaO)x(SiO2)(H2O) + xCO2 → xCaCO3 + SiO2(H2O)y + (z - y) H2O
(3)
In carbonated anhydrous cement phases, it has been observed that
the number and size of the anhydrous cement phases such as tricalcium
silicate (C3S) and dicalcium silicate (C2S) decreases [18]. Their reac-
tions of with CO2 result in formation of CaCO3 and silica gel according
to Eq. (4) [18], where x = 2 for dicalcium silicate (C2S) and x = 3 for
tricalcium silicate (C3S).
xCaO·SiO2 + xCO2 + nH2O → SiO2 + nH2O + xCaCO3 (4)
The carbonation chemical reaction in Portland cement-based ma-
terials results in the building up of their microstructure and eventually
defines certain material properties such as mechanical strength and
carbon dioxide diffusivity [19]. In Portland cements without supple-
mentary cementitious materials, the CaCO3 formation causes pore
blocking which prevents further carbonation from occurring. This
might be attributed to the higher volume of the CaCO3 with regard to
the former Ca(OH)2, then a decrease in capillary porosity can be found
due to the precipitated CaCO3. Gruyaert et al. [20] suggested that
carbonation of blended cements leads to higher porosities which might
be attributed to the dissolution of C-S-H. Consequently, a reducing or
increasing porosity would cause a correspondent reducing or increasing
diffusivity. Therefore, in such cases, the application of the square root
of time equation becomes empirical.
1.3. Carbonation of blast furnace slag cements
Wrapping up, less Ca(OH)2 is available in blast furnace cements for
carbonation and a significant increase in big pores was found, then,
these facts change the nature and kinetics of the carbonation process
with regard to non-blended Portland cements.
1.4. Carbonation kinetic mechanism of cement-based materials
Many models have been proposed for depicting the carbonation
process in cement-based materials [2,3,8,9,16,19,29–45], which mainly
proceeds by diffusion. Then, to study the carbonation reaction rate, the
carbonation depth may be used to calculate the carbonation coefficient,
B, and the CO2 diffusion coefficient, D, according to Eqs. (5) and (6),
respectively [46,47]. The most widely kinetic model used in cement-
based materials is shown in Eq. (5); whereas the model given in Eq. (6)
is a solution to the Fick's second law of diffusion considering moving-
boundaries [48]. In this case, it is assumed that a chemical reaction
between the CO2 gas, the calcium phases (Ca2+), and water (H2O) is
produced by which the diffusing CO2 gas forms a new immobile che-
mical compound, the calcium carbonate (CaCO3) [48]. In the case of
most of the Portland cement-based materials, C2 = 0 and
Cx < < < C1. Cx is the CO2 concentration at discontinuity in kmol/m3
calculated as follows: Cx = %CaO x cement content in kg/m3 x hydra-
tion degree/56 = 2.898 kmol/m3.
Table 1 shows characteristic values of the carbonation coefficient, B,
and the apparent carbon dioxide diffusion coefficient, D, for different
quality levels of concretes [47]. Both of them are assumed to be con-
stant. However, they depend on several factors including environ-
mental relative humidity, pore size distribution (PSD), hydration de-
gree, CO2 concentration, binder composition and so on [3,12,23,24].
(5)
x=B t
0.5
where: B = carbonation coefficient (mm/s )
x = carbonation depth (mm)
t = natural carbonation exposure time (year)
x x2 x
CX − C1 t t t C1
= Π exp erf ≈
C2 − CX 2 D 4D 2 D CX (6)
3
where: Cx = CO2 concentration at discontinuity (kmol/m )

Blended cement production in Europe is increasing due to sustain- C1 = CO2 concentration in surroundings (kmol/m3) = 1.23·10−05.
ability concerns [21]. In particular, ground granulated blast-furnace C2 = CO2 concentration in the Portland cement-based material
slag (GGBFS) is one of the most frequently used additions in Europe and (kmol/m3) = 0.
their positive effects on concrete are well known. For instance, ground D = Apparent diffusion coefficient of the CO2 (m2/s)
granulated blast-furnace slag cements are recommended in aggressive
environments such as the marine environment in coastal areas [22]. Many authors reported that the square root model shown in Eq. (5)
Ground granulated blast furnace slag also can provide an adequate is capable of predicting accurately the cement-based materials carbo-
surface for the formation of nuclei of hydration products [23]. As a nation rate [30]. Then, it is one of the most used models in actual re-
disadvantage, cement-based materials made of ground granulated blast- inforced concrete structures design [1,9,15].
furnace slag have a weak carbonation resistance, especially when short An indirect model [32] to estimate the diffusion coefficient is based
curing periods are applied [24–27]. Then, it is of great importance to on the relative humidity and porosity, εp, of the concrete according to
optimize the blast-furnace slag amount allowed to be used in reinforced Eq. (7).
cement-based materials to ensure an adequate service life of reinforced
Dc (m2/s) = 1.64 × 10−6 × εp 1.8
× (1 – (RH/100)) 2.2
(7)
concrete structures.
During the hydration process of the constituting GGBFS of cement, a Another indirect estimation of the CO2 diffusivity based on the
C-S-H gel with a lower Ca/Si ratio is produced [23]. Thus, C-S-H gel concrete strength class, fck, was proposed in CEB-FIP Model Code [49]
decalcification might be expected in highly porous pastes, resulting in a as given in Eq. (8).
risk of carbonation shrinkage [20]. However, carbonation might not be
a risk for low-permeability blended pastes [28]. The carbonation rate
Table 1
increases in cement paste [28] and concrete [26] with increasing
Typical values of B and D [47].
amount of blast furnace slag. This may be attributed to rapid Ca(OH)2
depletion and the coarsening of the pore structure found in blast fur- Low quality Average quality Good quality
nace cement-based materials [20]. According to Borges et al. [28], the
B (mm/yr0.5) >9 5–9 <5
mechanism of carbonation is governed by the amount of Ca(OH)2 in D (x 10−7 m2/s) >4 0.5–4 0.5
blast furnace slag pastes prior to carbonation.

258
M.Á. Sanjuán et al.
Table 2
Environmental requirement for minimum concrete cover (mm) according to
Ref. [50] in corrosion induced by carbonation.
Environmental requirement for minimum concrete Structural Class
cover (mm)
Exposure Class: Corrosion induced by carbonation S1 S2 S3 S4
XC1 - Dry or permanently wet 10 10 10 15
XC2 - Wet, rarely dry 10 15 20 25
XC3 - Moderate humidity 10 15 20 25
XC4 - Cyclic wet and dry 15 20 25 30
Dc (m2/s) = 10−7 × 10−0.025 fck
The International Federation for Structural Concrete (FIB) proposes
a full probabilistic method for the verification of service life design with
regard to carbonation induced corrosion in uncracked concrete [31].
This method takes into account some basic requirements with regard to
CO2 diffusion and concrete cover, which are comparable with those
already given in the European standard known as Eurocode 2 [50]. The
European standards series EN 1992 named as Eurocodes, deals with the
reinforced concrete structures design in civil engineering works and
buildings. In particular, the Eurocode 2 (EN 1992-1-1) describes the
requirements for safety, serviceability and durability of steel reinforced
concrete structures, considering the limit state concept. The minimum
concrete cover for reinforcement taking account of the carbonation
exposure class (XC), the structural class and a design working life of 100
years is given in Table 2 [50]. Exposure classes are identified by the
letter X followed by the initial letter of the deterioration mechanism to
which they refer, e.g. corrosion of reinforcement due to carbonation is
named XC.
Summing up, some carbonation models are based on the funda-
mental chemistry involved in concrete carbonation [32–34]. Also, more
complex mathematical modeling for the cement-based materials car-
bonation was developed extensively [9,32–37]. Some parameters of
these models are quite difficult to be determined because, in many
cases, they are time-dependant. The innovation of this paper deals with
the results obtained in natural carbonation conditions of ground
granulated blast furnace slag in a long-term test program.
In this work, the aim was to:
1. Set an upper limit for ground granulated blast-furnace slag content
in cement-based materials based on their carbonation resistance
useful for material engineers.
2. Set a minimum period of wet curing valid for real reinforced con-
crete structures useful when civil engineers consider the wet curing
time in building structures.
Finally, we develop two empirical mathematical models to estimate
the carbonation depth and the carbon dioxide diffusion coefficient in
blast-furnace slag mortars depending on the curing period and the
amount of blast-furnace slag.
2. Experimental
2.1. Materials and mortar preparation
Four commercial common Portland cements according to the
European standard EN 197–1:2011 [21,51] were chosen in this study.
One of these cements was a CEM I without any addition, while the other
three contains different amounts of ground granulated blast-furnace
slag (14.4%, 28.1% and 62.2%). Chemical analyses of SiO2, Al2O3,
Fe2O3, CaO, MgO, SO3 and free lime were performed according to the
European standard EN 196–2:2014 [52]. Chemical and physical prop-
erties are given in Tables 3 and 4, respectively. The testing mortars
Cement and Concrete Composites 90 (2018) 257–265
were prepared with distilled water and standardized sand (CEN-
Normsand, Germany) according to the European standard EN
196–1:2016 [53]. The cement/sand ratio was 1/3 and water/cement
ratio 0.50. After 24 h with 99% relative humidity, mortars were de-
molded, and then, they were cured under water for zero, one, three,
seven, 14 or 28 days. Thereafter, mortars were tested for natural car-
S5 S6
bonation using a phenolftalein indicator solution which was prepared
20 25 by dissolving 1 g of phenolphthalein powder in a 100 ml solution of
30 35 70 ml ethanol and 30 ml of distilled water [54].
30 35 Tables 3 and 4 show the chemical and physical properties of four
35 40
commercial cements used in practice in civil works and building
structures. All of them present similar specific gravity (3.0–3.2 kg/m3),
However, the setting time is clearly influenced by the ground granu-
(8)
lated blast-furnace slag content. The higher amount of ground granu-
lated blast-furnace slag, the longer final setting time. With regard to the
chemical composition, the increase of ground granulated blast-furnace
slag in the cement leads to an increase of SiO2 and Al2O3, and a de-
crease of CaO.
2.2. Natural carbonation testing
Two alternative methods are allowed in the technical specification
CEN/TS 12390–10 [55] for natural carbonation testing. In the first one,
the mortar is exposed to the natural exterior environment under shelter
from rain conditions; whereas in the second one, it is held in a climatic
chamber by maintaining a controlled CO2 concentration of
0.035 ± 0.005%, a temperature of 20 ± 2 °C and a relative humidity
of 65 ± 5%. In the present work, the first procedure has been chosen.
Measurement was taken at 24 months of natural exposure after the
curing period under water of zero, one, three, seven, 14 or 28 days. It
should be noted that a previous curing at 100% RH was provided for the
first 24 h when remained in the moulds. All the specimens were sawn
up into 20 mm slices, for each test age. The sawn cut is suitable for
carbonation testing given reliable results by which to determine the
carbonation depth [20].
The depth of carbonation was measured on the freshly sawn surface.
This sawn surface was cleared immediately of dust and loose particles
after breaking. Afterwards, it was sprayed with a fine mist of the phe-
nolftalein indicator solution. In some cases, when only a weak col-
ouration or none at all appeared on the treated surface, the spray test
was repeated after half-hour.
2.3. Flexural and compressive strength
Flexural and compressive strength tests were performed on mortars
at two and 28 days according to the European standard EN 196–1:2016
[53] by using an IBERTEST-AUTOTEST 200-10-5 wc model hydraulic
press with a loading rate of 2400 ± 200 N/s. The 40 × 40 × 160 mm
mortar specimens were cured under water at 20.0 ± 1.0 °C. Flexural
strength was tested on three specimens for each mortar type; then, six
samples were obtained which were used for compressive strength
testing.
3. Results and discussion
3.1. Compressive and flexural strength
Compressive and flexural strengths at 2 and 28 days of mortars
made of blended cements CEM II/A-S 42.5 N, CEM III/A 42.5 N and
CEM III/B 32.5 N-LH/SR in comparison to CEM I 52.5 R-SR 3 are shown
in Figs. 1 and 2, respectively.
The compressive strength at 28 days decreases when the ground
granulated blast-furnace slag content increases in the cement in
agreement with other researchers [20]. Nevertheless, different cement
compressive strength makes difficult to attribute the different results
only to the GGBFS content. This change happens in mortars with about
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M.Á. Sanjuán et al. Cement and Concrete Composites 90 (2018) 257–265

Table 3
Chemical compositions of cements determined according to EN 196–2:2014 [52] (%).
Cement SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O LOI IRa Cl−

CEM I 52.5 R-SR 3 21.73 3.67 4.31 66.12 1.32 3.00 0.49 0.57 1.12 0.19 0.01
CEM II/A-S 42.5 N 23.24 5.74 2.46 61.82 2.29 2.83 0.46 0.59 – – 0.05
CEM III/A 42.5 N 24.55 6.42 2.14 57.14 3.00 2.80 0.40 0.50 0.91 0.21 0.05
CEM III/B 32.5 N-LH/SR 29.66 8.06 2.16 51.08 4.82 2.53 0.30 0.37 0.77 0.38 0.05

a
Insoluble residue determined by the Na2CO3 method (European standard EN 196–2:2005).

10% up to 28% of ground granulated blast-furnace slag, but became
very significant (30%) with 62.2% of ground granulated blast-furnace
slag (Fig. 1). On the contrary, the compressive strength at two days
strongly depends on the fineness. Given that, CEM III/B 32.5 N-LH/SR
with 62.2% of ground granulated blast-furnace slag and a specific
surface area of 5024 cm2/g presents a similar compressive strength at
two days (30.5 MPa) than CEM II/A-S 42.5 N with 14.4% of ground
granulated blast-furnace slag and a specific surface area of 4229 cm2/g
(31.6 MPa). It should be taken into account that these cements are
factory made and, therefore, both the amount of ground granulated
blast-furnace slag and the fineness of the final cement have been opti-
mized.
Flexural strength at two days follows the same trend as compressive
strength, except for CEM III/B 32.5 N-LH/SR, which has the same
flexural strength as CEM I 52.5 R-SR 3 (8.3 MPa) as result of the very
high specific surface area of 5024 cm2/g. On the other hand, flexural
strength at 28 days is slightly enhanced by the ground granulated blast-
furnace slag amount (Fig. 2).
3.2. Carbonation depth and weight evolution
Figs. 3 and 4 show the depth of carbonation at two years of the
mortars with ground granulated blast-furnace slag (14.4%, 28.1% or
62.2%) in comparison to CEM I. It is evident both the effect of the
ground granulated blast-furnace slag content in the mortar and the wet
curing periods. The more ground granulated blast-furnace slag and the
less curing period, the more carbonation depth. The effect of a short
curing time is more significant in high slag content mortars as reported
elsewhere [24]. However, there were no significant differences with
regard to CEM I 52.5 R-SR 3 and CEM II/A-S 42.5 N when they are
cured for more than seven days. Carbonation reaction occurs when
carbon dioxide in air dissolves in the mortar pore solution and reacts
with calcium hydroxide leading to precipitation of calcium carbonate
crystals on the pores surface (see Fig. 3).
Fig. 4 shows the depth of carbonation at two years of mortars made
of ground granulated blast-furnace slag cured for zero, one, three,
seven, 14 and 28 days. High ground granulated blast-furnace slag
(62.2% ground granulated blast-furnace slag, CEM III/B 32,5 N-LH/SR)
replacement leads to a higher carbonation than control mortar without
additions as shown in Fig. 4. There is an almost linear relationship
between carbonation depth and the ground granulated blast-furnace
slag content in mortars cured for one day or without any curing time.
This trend is becoming smothering as the curing period is increased.
Mortars cured for seven, 14 and 28 days presented the lowest carbo-
nation depths after two years of natural exposure sheltered from rain.
Accordingly, a curing time of seven days could be established as a
threshold level to set a minimum curing time for mortar with a content
of ground granulated blast-furnace slag higher than 28%; whereas a
curing time of three days could be enough for cement-based materials
with less than 28% blast-furnace slag [7]. Similarly, increased sus-
ceptibility to carbonation was reported in elsewhere [20]. This is
probably due to rapid depletion of CH.
Phenolftalein colour change is a result not only of the Ca(OH)2
carbonation, which is present in the pore solution and portlandite, but
also such chemical process is produced in other calcium bearing other
phases such as C-S-H gel, ettringite, calcium aluminates, tricalcium si-
licate (C3S) and dicalcium silicate (C2S) [6,7]. In particular, ettringite
and calcium aluminates may be carbonated leading to gypsum, alumina
gel [16] and vaterite crystals formation [17]. As shown in Fig. 3,
ground granulated blast-furnace slag cementitious materials have a
weak carbonation resistance, particularly in short wet curing periods
[24–27].
After two years of natural carbonation, weight gain is observed in
mortars containing from 0% to 14.4% of ground granulated blast-fur-
nace slag, then, the weight gain is similar between 14.4 and 28.1% and,
finally, it decreases sharply up to 62.2% (Fig. 5). The weight variation is
mainly due to the carbonation process where calcium carbonate is
formed leading to a weight increase. Also, this process is developed in
parallel with the water which is formed within the hydration and
pozzolanic reactions. Such water evaporation acts in the opposite way
reducing the final weight. This process is combined with the dissolution
rate of Ca(OH)2 and the water amount generated due to the develop-
ment of the carbonation process [29]. Also, the hydration and pozzo-
lanic reactions play a key role in the resulting weight balance. Summing
up, the presence of a high amount of ground granulated blast-furnace
slag results in a final reduction of the mortar weight after two years of
natural carbonation. This finding is in agreement with the higher por-
osity found in carbonated blended cements [20].
3.3. Carbonation coefficient
Carbonation results have been modeled according to Eq. (3), where
B is the carbonation coefficient. This parameter depends on the mortar
quality and environmental factors. Many civil engineers use this simple
model [9,36], based on diffusion laws, to predict the initiation period of
reinforcement corrosion induced by carbonation of the concrete cover,
where only the CO2 transport through the pores is considered and the
whole carbonation process is viewed as a CO2 diffusion and chemical
reaction process.
Fig. 6 presents the carbonation coefficient, B (mm/yr0.5), calculated
from Eq. (5). The carbonation coefficient results calculated at 2 years
can be divided into two main groups, the first one is composed of CEM I

Table 4
Physical properties of cements.
Cement Specific gravity (kg/m3) Initial setting time (min) Final setting time (min) Volume expansion (mm) Specific surface Blaine (m2/kg)

CEM I 52,5 R-SR 3 3.2 160 205 0.0 5656

CEM II/A-S 42.5 N 3.1 235 275 0.0 4229
CEM III/A 42.5 N 3.0 285 325 0.0 4365
CEM III/B 32,5 N-LH/SR 3.0 270 365 0.0 5024

260
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Fig. 1. Compressive strength at 2 and 28 days of mortars made of ground granulated blast-furnace slag. From left to right, blended cements CEM II/A-S 42.5 N, CEM
III/A 42.5 N and CEM III/B 32.5 N-LH/SR in comparison to CEM I 52.5 R-SR 3.

and CEM II/A-S cements while the second one is composed of CEM III/
A and CEM III/B ones.
In Portland cements CEM I, calcium carbonate formation causes
pore blocking which reduce the carbonation progress. This fact is due to
the higher volume of the CaCO3 with regard to the former Ca(OH)2.
However, carbonation of blended cements leads to higher porosities
[20].
Unexpectedly, results of mortar carbonation after one day of curing
are nearly the same and follow the same trend as those obtained in
mortars without curing. However, it is necessary to take into account
that mortars without curing under water have got a curing at 100% RH
while remained in the moulds for the first 24 h. This means that one day
of curing is not enough. In both cases, a linear relationship between
carbonation depth and blast-furnace slag content was found.

3.4. Carbonation diffusion coefficient

Fig. 3. Depth of carbonation after two years of natural carbonation of mortars
As expected, the carbon dioxide diffusion coefficient calculated made of ground granulated blast-furnace slag and cured under water for 0, 1, 3,
according to Eq. (6) shown in Fig. 7 follows the same trend as the 7, 14 or 28 days: a) CEM III/B 32.5 N-LH/SR; b) CEM III/A 42.5 N; c) CEM II/A-
carbonation coefficient shown in Fig. 6. Nevertheless, comparing the S 42.5 N; d) CEM I 52.5 R-SR 3.
carbon dioxide diffusion coefficient of the different mortars, it is more
evident the strong influence of the curing time and ground granulated
blast-furnace slag content. Wet curing periods of at least three days are
recommended for all the cementitious materials, particularly those in-
corporating ground granulated blast furnace slag in the mix.
From Fig. 8, it is clear that the obtained CO2 diffusion coefficients
are ten times the values obtained from the application of the CEB-FIP
Model code formula, Eq. (8). The explanation for this difference is
found in the fact that the experimental results have been obtained in
mortars and the CEB-FIP Model code formula is given for concretes.
However, some studies [44] have reported smaller differences between
mortar and concrete natural carbonation when equivalent cement
content was considered. Also, it has been reported that the CO2 buffer
Fig. 4. Depth of carbonation at two years of mortars made of ground granulated
capacity might be the governing parameter for the carbonation re-
blast-furnace slag cured for zero, one, three, seven, 14 and 28 days.
sistance of mortar and concrete, expressed by the w/CaOreactive.

Fig. 2. Flexural strength at 2 and 28 days of mortars made of ground granulated blast-furnace slag. From left to right, blended cements CEM II/A-S 42.5 N, CEM III/A
42.5 N and CEM III/B 32.5 N-LH/SR in comparison to CEM I 52.5 R-SR 3.

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Fig. 5. Weight increase of mortars made of ground granulated blast-furnace slag cured for zero, one, three, seven, 14 and 28 days after two years of natural
carbonation after two years of natural carbonation.

Therefore, similar conclusions have been obtained in mortar and con-

crete with the same CO2 buffer capacity [44]. In the present paper, as
mortar with cement:sand:water ratio of 1:3:0.5 has been tested, then, a
concrete with equivalent buffer capacity should have a cement content
of about 550 kg/m3.
Some authors have considered concrete as a two-phase composite
composed of mortar matrix and aggregate [56–58]. Apparently, trans-
port properties of concrete would decrease with the increase of ag-
gregate content, i.e. the apparent chloride diffusion coefficient [59],
among other diffusion coefficients. Also, it was reported that aggregate
distribution and aggregate shape have a negligible influence [60]. Ac-
cording to López et al. [61], the mortar approach leads to a rapid op-
timization of mix proportions including different types of cements. Fig. 7. Carbon dioxide apparent diffusion coefficient, D (m2/s), calculated ac-
Given that, carbonation of CEM III/A 42.5 N mortars was performed to cording to Eq. (6).
study the influence of low-alkalinity cement-based materials on corro-
sion of reinforcing steel [62]. carbonation coefficients are 1.3, 1.9 and 1.3 times higher, respectively,
The carbonation coefficient generally increases with the amount of in ground granulated blast-furnace slag mortars than in plain mortars.
cement replacement by ground granulated blast-furnace slag. However, In agreement with other authors [24,26], the fastest carbonation
over 14.4% of cement replacement, the carbonation rate of ground rate is produced in ground granulated blast-furnace slag cement-based
granulated blast-furnace slag mortars decreases sharply as the wet materials exposed to dry environments. These data are a consequence of
curing period increased. The highest carbonation rate is obtained in the the higher capillary porosity found in blast-furnace slag mortars and
mortar with 62.2% of ground granulated blast-furnace slag and the their lower alkaline reserve [15]. Serdar et al. [62] reported a decrease
lowest in mortars without addition for all the range of wet curing time in capillary porosity in the case of carbonation of plain mortar produced
studied (zero, one, three, seven, 14 and 28 days). by the clogging of pores by precipitation of calcium carbonate; while in
The absence of wet curing provides a concrete carbonation coeffi- the case of mortar with ground granulated blast-furnace slag, an in-
cient 3.5 times higher when 62.2% of ground granulated blast-furnace crease in capillary porosity was found by carbonation. These results
slag is used in relation to concretes without addition. It should be re- show that curing conditions in real structures are quite different to the
membered that different the commercial cement used in the tests pre- required curing conditions for blast-furnace slag mortars (longer per-
sented different compressive strength levels and fineness. For wet iods of curing time are needed).
curing periods of zero, one, three, seven, 14 and 28 days such

Fig. 6. Carbonation coefficient, B, calculated from carbonation depths measured at two years of mortars made of ground granulated blast-furnace slag cured for zero,
one, three, seven, 14 and 28 days.

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Fig. 8. Carbon dioxide apparent diffusion coefficient, Dc (m2), calculated ac-

cording to Eq. (6) versus that calculated according to Eq. (8).
Fig. 9. Carbonation depth estimation according to Eq. (9).

3.5. The modeling of slag mortars carbonation

One of the most widely assumptions considered in carbonation

models is the homogeneity of the cement-based material. Nevertheless,
the properties that determine the carbonation rate change from the
outer surface named skin of the concrete, to the bulk concrete close to
the reinforcement in actual reinforced concrete structures. Therefore,
the square root model should be regarded as an upper limit for carbo-
nation estimation because it overestimates carbonation depth in cases
where the cement-based material is exposed to wet periods [15,22].
Two empirical mathematical models, the first one to estimate the car-
bonation depth and the second one to estimate the carbon dioxide
diffusion coefficient in blast-furnace slag mortars have been obtained.
Both of them are based on Eq. (9) with the parameters shown in
Table 5. Both models have a good correlation coefficient (r2 = 0.98).
Figs. 9 and 10 show the response surfaces of the models. Fig. 10. Carbon dioxide diffusion coefficient estimation according to Eq. (9).
b e
Z=a+ +
(1 + ((X − c )/ d )2) (1 + ((Y − f )/ g )2) furnace slag at two years. The carbonation depth increases sharply
h when ground granulated blast-furnace slag content increases in mortars
+
((1 + ((X − c )/ d )2) ∗ (1 + ((Y − f )/ g )2)) (9) cured for one day or without any curing time. This trend becomes
smoother as the wet curing time is increased. Fig. 9 shows that mortars
where: X = Slag content (%) cured for seven, 14 and 28 days presented the lowest carbonation
depths after two years of natural exposure sheltered from rain. This fact
Y = Curing time (days) supports the proposal of a minimum curing time of seven days for ce-
Z = Carbonation depth, B (mm), or carbon dioxide apparent diffu- ment-based materials with a content of ground granulated blast-furnace
sion coefficient Dco2 (×10−8 m2/s) slag higher than 28%. On the other hand, a curing time of three days
a, b, c, d, e, f, g, h = Constants could be enough for cement-based materials with less than 28% blast-
furnace slag [7].
Both models follow the same trend (Figs. 9 and 10). Fig. 9 shows the Adjusted r2 values show the accuracy of the modeled systems. In
depth of carbonation of mortars made of ground granulated blast- these cases, adjusted r2 values are 0.974 and 0.970 for the carbonation
depth estimation and for the carbon dioxide diffusion coefficient esti-
Table 5 mation equations, respectively. These values mean that the accuracy of
Data set for Eq. (9). Eq. (9) is 97.4% and 97.0%, respectively, indicating that there were in a
Property Carbonation depth Carbon dioxide apparent diffusion good agreement between the experimental and the predicted values.
(mm) coefficient (×10−8 m2/s) Therefore, these models provide reasonable predictions as some car-
bonation of cement-based material models generated elsewhere
X Slag content (%) Slag content (%)
Y Curing time (days) Curing time (days) [32–37].
Z B (mm) Dco2 (×10−8 m2/s) Analysis of variance (ANOVA) was further carried out to check the
adequacy of both models. The ANOVA for carbonation depth and
a 0.5233 2.0628 carbon dioxide diffusion coefficient models are listed in Table 6, re-
b 7.7538 14.5100
c 66.9404 61.7560
spectively. From the ANOVA analysis, the F-values of 132.472 and
d 59.7835 34.3687 114.755, respectively, and Prob > F of 0.0 in both cases, implied that
e −8.3101 −25.9994 both models were significant. In any case, the validity of the model
f 0.2713 0.4182 should be contrasted with new experimental data.
g 1.7017 1.1477
h 21.2113 119.1436
3.6. Reinforced mortar service life assessment
r2 Coef Det 0.9830 0.9804
DF Adj r2 0.9740 0.9700
Fit Std. Error 0.6987 4.1915 Carbonation process plays a key role in the chemical reactions and
the steel corrosion damage in reinforced concrete structures [29]. We

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Table 6 environment containing 0.03% CO2. To determine whether corrosion

Analysis of variance (ANOVA) for the carbonation depth estimation model (top) due to carbonation is a risk for the concrete reinforced structure, these
and carbon dioxide diffusion coefficient estimation model (bottom). values must be compared to the minimum cover thickness given in
Source Sum of Squares DF Mean Square F Statistic P>F Table 2 for XC environments, which are related to corrosion induced by
carbonation. Since the natural carbonation sheltered from rain tests
Regression 452.6021 7 64.6574 132.472 0.00000 were performed at 60% RH, XC3 environment applies (Table 2). These
Error 7.80932 16 0.4881
values were compared to the ones of Table 7. Considering a S5 struc-
Total 460.4114 23
tural class, a minimum cover thickness of 30 mm is applicable as the
Source Sum of Squares DF Mean Square F Statistic P>F lower threshold within its life span.
The carbonation depths after 50 years for CEM I 52.5 R-SR 3 cured
Regression 14113.201 7 2016.1716 114.755 0.00000
from zero to 28 days are acceptable for environments containing 0.03%
Error 281.1098 16 17.5694
Total 14394.311 23 CO2, while these of CEM II/A-S 42.5 N and even CEM III/A 42.5 N are
acceptable only when the wet curing time is at least of seven days. As
the ground granulated blast-furnace slag increases up to 62.2% (CEM
Table 7 III/B 32.5 N-LH/SR), longer curing periods can limit the carbonation
Carbonation depth in mm estimated for 50 years (Natural carbonation sheltered depth, but not to an extent that the corrosion risk could be controlled.
from rain, XC3 environment according to Table 2). Considering a S5 structural
class, a minimum cover thickness of 30 mm is required. 4. Conclusions
Cement Curing time (days)
Carbonation of cement-based materials is a chemical process influ-
0 1 3 7 14 28 enced by the cement type. Based on the experimental results, a number
of conclusions can be drawn:
CEM I 52.5 R-SR 3 25.1 23.5 23.5 20.8 21.0 17.8
CEM II/A-S 42.5 N 43.4 38.8 31.6 24.7 25.1 21.8
CEM
CEM
III/A 42.5 N
III/B 32.5 N-LH/SR
68.0
100.0
49.4
100.0
42.5
55.9
33.3
46.4
29.1
42.7
30.0
40.8
• Carbonation rate increases with increasing ground granulated blast-
furnace slag content in mortars and with decreasing wet curing
time. Then, a minimum curing time of seven days is established as a
threshold level for mortar with a content of ground granulated blast-
have conducted both laboratory research on natural carbonation and furnace slag higher than 28%; whereas a minimum curing time of
modeling studies on natural carbonation in an attempt to evaluate two three days could be enough for cement-based materials with less
key design parameters such as slag content and wet curing period with than 28% blast-furnace slag. These results might change if a dif-
regard to their relation to carbonation rate, to produce an accurate ferent water/cement ratio is used.
service life design estimation. The results presented in this section are
applicable to mortar only.
• Service life estimation with regard to carbonation was performed
depending on the slag content and curing time. The higher amount
The reinforcement corrosion process can be roughly divided into of blast-furnace slag, the lower service life.
two periods of time named initiation period and propagation period
[46]. The initiation period of the reinforcement corrosion process may
• Empirical mathematical models to estimate the carbonation depth
and the carbon dioxide diffusion coefficient in blast-furnace slag
be defined as the time until the reinforcement becomes depassivated. As mortars depending on the curing period and the amount of blast-
soon as the reinforcement concrete cover is carbonated, the reinforce- furnace slag have given good predictive results.
ment is considered depassivated.
The square root model is based on diffusion laws and is used to All the above results are in fact the requirements that engineers
predict the initiation period of reinforcement corrosion induced by have to take into account when they are designing building structures
carbonation of the concrete cover. made of ground granulated blast-furnace slag cement-based materials.
According to the Model Code 2010 [31], the predicted depth of Curing time must be planned depending on ground granulated blast-
carbonation at the end of the expected service life has to be compared furnace slag content in cement-based materials.
with the concrete cover. This leads to the materials engineers to obtain
a servicelife estimation in case of carbonation induced corrosion. Acknowledgements
In both Eurocode 2 [50] and EN 206, concrete compressive strength
is used as indirect measure of concrete durability, on the basis of the This research did not receive any specific grant from funding
assumption that higher compressive strength is reached by a less porous agencies in the public, commercial, or not-for-profit sectors.
concrete and, therefore, such less porous concrete is able to provide a
higher reinforced concrete durability. However, this assumption is not Appendix A. Supplementary data
true because it does not take into account the chemical composition of
the cement involved in the carbonation process. Supplementary data related to this article can be found at http://dx.
According to Table 2, the minimum concrete cover goes from 10 to doi.org/10.1016/j.cemconcomp.2018.04.006.
40 mm depending on the Structural Class in environments classified as
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