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Carbonation of Blended Binders Containing Metakaolin

Article  in  RILEM Bookseries · January 2015

DOI: 10.1007/978-94-017-9939-3_4

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Carbonation of Blended Binders
Containing Metakaolin

R. Bucher, M. Cyr and G. Escadeillas

Abstract The pozzolanic materials are often recommended for their very good
durability in aggressive environment. Unfortunately, this is not always true and
particularly in the case of carbonation by the atmospheric CO2. Although cement
replacement by pozzolanic materials causes a decrease in pore size, the pozzolanic
reaction consumes portlandite and decreases the protection potential against CO2
ingress. This is the case for most pozzolanic materials, including metakaolin. The
aim of this study is first to confirm the literature results of carbonation by using
flash metakaolin in partial replacement of cements (CEM I, CEM II A-LL and CEM
II A-V). Then the concretes with a metakaolin are compared with concretes based
on standardized cement in order to assess the carbonation depth of metakaolin-
based concretes and concretes used today in the building construction. Even though
the cement replacement of CEM I and CEM II A-V by metakaolin increases the
carbonation depth, results are not the same with the CEM II A-LL cement. The
interaction of metakaolin with the cement limestone filler can explain this better
performance, certainly because the hemicarboaluminate allows slowing down the
CO2 propagation through the matrix.

1 Introduction

The carbonation of concrete is usually slowed down by the reaction of CO2 with
Portlandite. It means that supplementary cementing materials (SCM) that consume
the Portlandite could lead to an increase in the carbonation depth, especially if the
permeability of the concrete is not reduced by the pozzolanic reaction. Results from
the literature showed that a replacement of 25 % of Portland cement by metakaolin
(MK) could lead to a carbonation depth of 9 mm instead of 2 mm after 28 days of
accelerated test (50 % CO2, 20 °C and 65 % RH) [1]. These results can be
correlated with those of Kim et al. [2], who showed that accelerated carbonation

R. Bucher (&)
M. Cyr
G. Escadeillas

LMDC, UPS—INSA Toulouse, Toulouse, France
e-mail: bucher.raph@gmail.com

© RILEM 2015 27
K. Scrivener and A. Favier (eds.), Calcined Clays for Sustainable Concrete,
RILEM Bookseries 10, DOI 10.1007/978-94-017-9939-3_4
28 R. Bucher et al.

(5 % CO2, 30 °C and 60 % RH) led to an increase of 56d-carbonation depth by

40–70 % when 5–10 % of MK was used in replacement of the cement. The
carbonation depth could even be increased by 370 % for replacement rate of 20 %.
Similar results were found by McPolin et al. [3] for replacement rates of 10 % (5 %
CO2, 20 °C and 65 % RH).
The aim of this paper is:
• To assess the effect of MK against CO2 ingress, in comparison with commercial
cements with and without SCM. Commercial blended cements (conform to EN
197-1) are actually accepted in the industry for all exposure classes, including
for corrosion due to carbonation. It could be thus interesting to situate the
combination CEM I—MK with cements containing mixtures of clinker and
SCM such as slag and/or fly ash.
• To evaluate the consequence of the increase in the carbonation depth in terms of
lifespan time.

2 Materials and Methods

2.1 Materials

Two reference cements without SCM were used (>95 % clinker): one normal CEM
I and one low-C3A CEM I (named PM-ES in France). In order to compare the
behavior of matrices containing MK with those of commercial blended cements,
several other cements conform to EN 197-1 [4] were used: one CEM II/A-LL (16 %
of limestone filler), one CEM II/B-LL (22 % of limestone filler), one CEM II/A-V
(15 % of fly ash), one CEM III/A (62 % of GGBS) and one CEM V/A (22 % of fly
ash and 22 % of GGBS). The MK used in this study came from a flash-calcination
process [5], i.e. that dehydroxylation (at around 700 °C) of powdered kaolinite clay
was made within a few tenths of a second. The purity of the MK was around 50 %,
the main impurity being quartz. More characteristics of this MK can be found
elsewhere [1]. MK was used in replacement of fractions of the following cements:
CEM I, CEM II/A-LL and CEM II/A-V. The mixtures assessed in this study are
summarized in Table 1.

2.2 Methods

Compressive strength was measured at 28 days on three replicate 10 cm cubes.

Carbonation depth after 28 days of curing was highlighted with a pH indicator
(phenolphthalein) on split 7*7*28 cm prisms. Three replicate samples and 10
measurements per sample were made for each concrete formulation. Natural
Table 1 Mixture proportions of concrete
Materials (kg/m3) Cement MK Fine aggregates Coarse aggregates Water W/B HRWRA (%) Air (%) Slump (cm) Compressive
strength (MPa)
CEM I 280 0 738 1149 167 0.60 0.6 2.3 17.5 49.0
CEM I PMES 280 0 738 1149 167 0.60 0.5 1.8 18.5 –
CEM II/A-LL 280 0 738 1149 147 0.53 1.5 1.3 16.0 53.7
CEM II/A-V 280 0 738 1149 147 0.53 1.5 1.6 18.0 51.4
CEM II/B-LL 368 0 738 1149 170 0.46 0.6 2.1 19.0 44.0
CEM III/A 280 0 738 1149 167 0.60 0.5 1.7 17.0 48.2
CEM V/A 280 0 738 1149 147 0.53 1.5 1.6 18.0 48.3
Carbonation of Blended Binders Containing Metakaolin

CEM I 15 238 42 738 1149 167 0.60 1.0 1.9 17.0 47.4
CEM I 20 224 56 738 1149 167 0.60 1.3 2.0 18.0 52.9
CEM I 25 210 70 738 1149 167 0.60 1.3 1.9 17.5 49.1
CEM II/A-LL 15 238 42 738 1149 147 0.53 2.5 1.7 15.0 64.7
CEM II/A-V 15 238 42 738 1149 147 0.53 2.5 1.6 14.5 47.3
Fresh and hardened properties
29
30 R. Bucher et al.

carbonation was measured after 2 years and accelerated carbonation testing was
performed according to XP P18-458 [6], i.e. exposition of the concrete for 70 days
in a chamber (4 % CO2, 20 °C, 50 % RH) after a pretreatment of 14 days at 20 °C
and 50 % RH.

3 Results

Figure 1 presents the carbonation depth results for all the concretes in accelerated
(a) and natural (b) conditions. The graphs include the main reference cements
(black bars: CEM I, CEM II/A-LL and CEM II/A-V), the same cements with MK
(grey bars), and the other reference blended cements (hollow bars). The shaded
zones stand for the carbonation depths between the best and worst commercial
cements in terms of carbonation. It can be seen that the CEM I always led to the
lower carbonation, while the CEM V gave the higher carbonation depth, both in
accelerated and natural conditions. It seemed obvious here that the pozzolanic
reaction involved in the CEM V hydration was unfavorable to the carbonation of
the concrete.
As expected, the use of MK as replacement of CEM I systematically led to an
increase in the carbonation depth, but the values remained in the same order of
magnitude than other commercial blended cements (hollow bars). If these increases
are accepted in the case of commercially available blended cements, they probably
should also been acceptable for blended mixtures made of CEM I or CEM II with MK.
Similar results were obtained when MK replaced a fraction of CEM II/A-V (fly
ash cement), probably due to a higher consumption of the Portlandite by MK
(decrease of the lime reserve). Only the replacement of 15 % of CEM II/A-LL by
MK led to a slight decrease of the carbonation depth when compared to the ref-
erence. The compressive strength of this mixture was higher than the other con-
cretes. Moreover, it can be noted that the good compatibility between MK and
limestone filler in ternary blended binders has already been reported by Antoni et al.
[7], who highlighted the formation of hemicarboaluminates in such matrices. These

(a) Main references Other references Ref + MK

(b) Main references Other references Ref + MK

25 Carbonation of commercial cements 6

Carbonation depth

Carbonation depth

Carbonation of commercial cements

20 5
4
15
(mm)

(mm)

3
10
2
5 1
0 0
CEM I PM-ES

CEM I PM-ES
CEM I

CEM II/A-LL

CEM II/A-V
CEM II/A-LL 15

CEM II/A-LL 15
CEM II/A-V 15

CEM II/A-V 15
CEM I
CEM III/A

CEM III/A
CEM I 15
CEM I 20
CEM I 25

CEM I 15
CEM I 20
CEM I 25
CEM V

CEM V
CEMII/B

CEMII/B
CEM II/A-LL

CEM II/A-V

Fig. 1 Carbonation depth of concretes cured 28 days, after a 70 days of accelerated carbonation,
and b 2 years in natural conditions
Carbonation of Blended Binders Containing Metakaolin 31

hydrates tend to be transformed into calcite when the CO2 concentration increases
[8], meaning that they could play the role (as Portlandite) of CO2 pump in clinker-
limestone filler-MK mixtures. This could help reducing the CO2 ingress in this
ternary blended matrix.

4 Lifetime Span Regarding Carbonation

In order to compare the effect of MK on the rate of CO2 ingress in the concrete, a
predictive carbonation model (Eq. 1) was used [9]. This model allowed us to
calculate the carbonation depth as a function of time (a given time corresponding to
the service life of a structure), and thus to compare the carbonation state of the
different cements (blended or not) studied in the precedent section. This model was
fitted on the experimental points from natural carbonation.
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u 2
D0CO2
P0
t
u
xc ðtÞ ¼ t   n  
up
C2
 n  ð1Þ
R
T
1 þ b
C2
PPatm0
nþ1
PPatm0 þ Q1

with:
P0 pressure of CO2 at the concrete surface (Pa)
R universal gas constant (J/mol/K),
T temperature (K)
β fitting parameter independent of the material
C2 number of moles of calcium in C-S-H for the material considered (mol/l of
cement paste) (calculated with chemical data of cement and the C/S ratio of
the C-S-H)
xc(t) carbonation depth (m)
t time (s)
Patm atmospheric pressure at the concrete surface (Pa)
φp fraction of paste in the concrete (liter of cement paste per liter of concrete or
mortar)
n fitting parameter independent of the material
Q1 number of moles of calcium initially contained in portlandite, Aft and Afm
(mol/l of cement paste) (calculated with chemical data of cement and
stoichiometric formulas)
D0CO2 coefficient of CO2 diffusion in carbonated zones (m2/s) (fitted)

The results of the calculations are given on Fig. 2, up to an age of 50 years of

natural exposure to CO2. This age corresponds to a normal lifespan of an ordinary
structure [10]. The increase in the MK content (15–25 % in replacement of CEM I)
could lead to +9 to +14 mm more carbonation when compared to the CEM I
reference. However:
32 R. Bucher et al.

Fig. 2 Application of the 30

26,0 mm
model of natural carbonation

Carbonation depth (mm)

25
for mixtures based on CEM I, 22,8 mm
21,0 mm
CEM I + MK, CEM II/A, 20 20,1 mm
CEM II/A-LL + MK, and
CEM III 15 CEM II/A-LL
12,8 mm
12,2 mm
10 11,8 mm
CEM II/A-LL 15

0
0 10 20 30 40 50
Natural carbonation times (years)

• The carbonation depths should be around the ones of commercially blended

cements (e.g. CEM III/A and CEM V/A). It could be noted that interesting
results are obtained for ternary blended cements (clinker + filler + MK), since
the carbonation could be as low as the CEM I.
• The maximum depth after 50 years should be much lower than the 50 mm
usually requested to protect the steel rebars in real structures [1]. Moreover, this
model calculated only the time of CO2 ingress, without taking into account the
time necessary for the corrosion to begin, or the time needed for the structure to
be ruined due to the corrosion. It means that SCM (including MK) should
protect the steel bars at least for the lifespan of the structure.

5 Conclusions

The following conclusions can be drawn from this study:

• The replacement of CEM I and CEM II/A-V (based on fly ash) by metakaolin
leads to an increase in the carbonation depth of concrete.
• The carbonation depths of MK concretes are in the same order of magnitude
than the ones of commercially available blended cements.
• The combination CEM II/A-LL + MK (i.e. ternary mixture composed of clinker,
limestone filler and metakaolin) seems to be beneficial to the reduction of
carbonation (both accelerated and natural).
• The calculation of the carbonation depth after 50 years of natural exposition
shows that all SCM concretes (including MK) are still acceptable in terms of
carbonation, especially when considering the concrete cover protecting the steel
bars.
 Carbonation of Blended Binders Containing Metakaolin 33

References

1. San Nicolas, R.: Approche performantielle des bétons avec métakaolins obtenus par
calcination flash, Thesis in french (Toulouse, 2011)
2. Kim, H.S., Lee, S.H., Moon, H.Y.: Strength properties and durability aspects of high strength
concrete using Korean metakaolin. Constr. Build. Mater. 21, 1229–1237 (2007)
3. McPolin, D.O., Basheer, P.A.M., Long, A.E., Grattant, K.T.V., Sun, T.: New test method to
obtain pH profiles due to the carbonation of concretes containing supplementary cementitious
materials. J. Mater. Civ. Eng. 19, 936–946 (2007)
4. EN 197-1, ‘Cement-Part 1: composition, specifications and conformity criteria for common
cements’ (2001)
5. Salvador, S.: Pozzolanic properties of flash-calcined kaolinite: a comparative study with soak-
calcined products. Cem. Concr. Res. 25, 102–112 (1995)
6. XP P18-458.: Tests for hardened concrete-Accelerated carbonation test-Measurement of the
thickness of carbonated concrete (2008)
7. Antoni, M., Rossen, J., Martirena, F., Scrivener, K.: Cement substitution by a combination of
metakaolin and limestone. Cem. Concr. Res. 42, 1579–1589 (2012)
8. Damidot, D., Stronach, S., Kindness, A., Atkins, M., Glasser, F.P.: Thermodynamic
investigation of the CaO-Al2O3-CaCO3-H2O closed system at 25 °C and the influence of
NaO. Cem. Concr. Res. 24, 563–572 (1994)
9. Hyvert, N., Sellier, A., Duprat, F., Rougeau, P., Francisco, P.: Dependency of C-S-H
carbonation rate on CO2 pressure to explain transition from accelerated tests to natural
carbonation. Cem. Concr. Res. 40, 1582–1589 (2010)
10. Karimpour, M., Belusko, M., Xing, K., Bruno, F.: Minimising the life cycle energy of
buildings: review and analysis. Build. Environ. 73, 106–114 (2014)

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