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Department of Civil and Environmental Engineering, Princeton University, Princeton, NJ, USA
Andlinger Center for Energy and the Environment, Princeton University, Princeton, NJ, USA
Universit Paris-Est, IFSTTAR, MAT, F-75732 Paris, France
d
Universit Paris-Est, Laboratoire Navier, Ecole des Ponts ParisTech, IFSTTAR, CNRS, F-77455 Marne-la-Valle, France
e
DGAC/STAC, F-94485 Bonneuil-sur-Marne, France
b
c
a r t i c l e
i n f o
Article history:
Received 12 February 2014
Accepted 3 October 2014
Available online xxxx
Keywords:
Carbonation (C)
Calcium-silicate-hydrate (C-S-H) (B)
Fly ash (D)
Microstructure (B)
Portland cement (D)
a b s t r a c t
Cement is a huge carbon dioxide producer. Supplementary cementitious materials can help reduce this outcome.
However, carbonation of these blended cements remains an active subject of research. Accelerated carbonation
tests (10% CO2, 25 C and 62% RH) are performed on y ash blended cement pastes. Experiments are performed
at varying ages of carbonation (1 to 16 weeks) to measure the evolution of the carbonation depth over time and
to quantify key parameters: thermogravimetric analysis (TGA), mercury intrusion porosimetry (MIP) and
gamma ray attenuation method (GRAM). The total porosity decreases with a rearrangement of the microstructure due to carbonation and the creation of big capillary pores for the paste with the highest contents of y
ash (60 vol.%). The C-S-H molar volume evolution during y ash-blended cement carbonation is calculated
using a method combining MIP, TGA and GRAM formerly successfully applied to OPC paste in a paper published
in the same journal.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
The worldwide cement industry accounts for at least 5 to 7% of the
anthropogenic CO2 emissions [1], hence solutions that reduce ordinary
Portland cement (OPC) content in concrete are needed in order to
decrease its environmental impact. Blended cements using supplementary cementitious materials (SCM) (such as y ash, slag, limestone,
metakaolin, silica fume) are increasingly being used in industry to
reduce the OPC content, but it is necessary to understand the long
term performance and durability of these materials in order to optimize
the whole life cycle. For this purpose, an evaluation of the durability of the
reinforced concrete structure including the effect of CO2 (carbonation) is
necessary.
Carbonation is the reaction of gaseous atmospheric CO2 with the
calcium-bearing phases of concrete and is known to cause a lowering
of alkalinity leading to the corrosion of the re-bars. The hydration products which are concerned by carbonation are mainly calcium hydroxide
(CH1) and calcium silicate hydrates (C-S-H). In this work, the inuence
of the substitution of y ash in clinker has been studied in order to
Corresponding author.
E-mail addresses: antoinem@princeton.edu (A. Morandeau),
mickael.thiery@aviation-civile.gouv.fr (M. Thiry), patrick.dangla@ifsttar.fr (P. Dangla).
1
It is recalled that according to the cement notations: C = CaO, H = H2O, S = SiO2, C
CO2 , A = Al2O3 and F = Fe2O3.
http://dx.doi.org/10.1016/j.cemconres.2014.10.003
0008-8846/ 2014 Elsevier Ltd. All rights reserved.
227
due to accelerated carbonation (10% CO2). This last article detailed all
the experimental protocols we used in the present work; hence this
article will present the experimental methods only briey.
In order to avoid early drying, sealed plastic bottles were used as
moulds for the preparation of the cement pastes. The plastic bottles
were: (i) lled in 3 steps and air was removed by vibrating the samples
between each step, (ii) sealed using a cork and paralm, and (iii) put in
an anti-segregation rotating system for 24 h. They were then left for at
least 6 months at 20 C before being subjected to carbonation. The y
ash-blended cement pastes were left for at least 11 months so that the
pozzolanic reaction had time to stabilize [25].
2.2. Pretreatment
After the sealed curing period (between 6 and 11 months, depending on the formulation), plastic bottles were cut in two pieces in order
to obtain two cylinders (height 60 mm, = 70 mm). The samples
were preconditioned prior to carbonation by covering each sample
with a self-adhesive aluminium foil over the lateral face and bottom
faces, so that all transport phenomena occurred unidimensionally. The
specimens were placed in a temperature-controlled oven at 45 C for
56 days. Finally, the specimens were stored for 56 days at 20 C and
62 5% RH over a saturated NH4NO3 solution. This last pretreatment
was used to accelerate the carbonation mechanism by controlling the
moisture content of the specimens as close as possible to the optimum
RH in the range of 40%70% [8,2629]. Note that the pretreatment duration was too short to obtain homogeneous RH in the samples, but these
heterogeneous moisture proles were quantied by gamma-ray attenuation measurement as reported in Section 3.2 and in [22].
Table 1
Formulations used in this work and water-to-binder ratio (cement and y ash), water-to-cement ratio, and volumic and mass fraction of y ash. The highest substitution ratio is out of
standards (cf. EN 206). The hydration degree is calculated using CH content (TGA). Porosity is measured either by MIP or by GRAM.
Characteristics
Units
CN
CN30
CN60
CP
CP30
vol.%
wt.%
0
0
0.45
0.45
30
23
0.45
0.64
60
51
0.45
1.13
0
0
0.6
0.6
30
23
0.6
0.86
Noncarbonated
Porosity (MIP)
Porosity (GRAM)
Hydration degree (TGA)
%
%
19.2 0.7
37.9 0.7
0.86 0.02
29.2 1.1
47.4 1.2
0.83 0.01
37.8 1.0
52.9 1.7
0.98 0.01
31.0 2.1
47.1 0.6
0.84 0.04
42.7
54.9 1.0
0.93 0.01
Carbonated
Porosity (MIP)
Porosity (GRAM)
%
%
12.3 1.1
30.2 1.1
23.4 2.7
36.0 0.8
36.4 1.2
46.5 0.9
23.1 3.1
36.5 1.3
34.2 2.1
48.8 0.8
228
to the so-called ink bottle effect, but as long as these limitations are
taken into account during interpretation of the results, the technique
is still valuable in making comparative assessments of the pore size
changes occurring in a given cementitious system [40], as it is the case
in this work.
2.4.4. Thermogravimetric analysis
Thermogravimetric analysis (TGA) has been carried out with a
Netzsch STA 449 F1 Jupiter coupled with a mass spectrometer (MS)
Netzsch QMS 403 C Quadrupole in order to determine the composition
of cementitious materials in terms of CH and CC. Samples were freeze
dried, ground with mortar and pestle, and sieved at 315 m. The heating
rate was 10 C/min from 20 C to 1100 C.
Note that the computed CH and CC molar contents are corrected by
subtracting the minimal value observed in each prole.
3. Results
CN
CN30
CN60
50
40
XC (mm)
40
XC (mm)
CP
CP30
50
30
30
20
20
10
10
0
0
10 12
t (days1/2)
t (days1/2)
(a)
(b)
10 12
Fig. 1. Carbonation depth XC as a function of the square root of time measured by phenolphthalein spray test.
0.4
0.4
1 week
2 weeks
4 weeks
8 weeks
16 weeks
0.3
-3
- 0 (g.cm )
229
0.3
0.2
0.2
0.1
0.1
0
-0.1
-0.1
-0.2
20
40
x (mm)
Fig. 2. Density evolution prole after 1 week,
4 different samples.
weeks,
20
40
x (mm)
weeks,
weeks and
20
40
x (mm)
20
40
x (mm)
20
40
x (mm)
-0.2
weeks of accelerated carbonation for the ve cement paste formulations. Each curve is the average value of
Fig. 3. Liquid water saturation evolution prole at the initial state, after week, weeks, weeks and
weeks of accelerated carbonation for the ve cement paste formulations plus a
non-carbonated (NC) control sample (dashed line) exposed to the same T and RH without CO2 for at least 16 weeks.
230
Fig. 4. Water content (in molL1 of porous material) evolution prole at the initial state, after week, weeks, weeks and
weeks of accelerated carbonation for the ve cement paste
formulations plus a non-carbonated (NC) control sample (dashed line) exposed to the same T and RH without CO2 for at least 16 weeks.
Given that carbonation also affects the evolution of the porosity, the
pertinent value to quantify a potential drying effect during the carbonation test is not Sw, but nw the molar content of free water molecules
per unit volume of porous material (molL1).
nw w Sw
w
Mw
Fig. 5. Porosity (water porosity) evolution prole at the initial state, after week, weeks, weeks and
weeks of accelerated carbonation for the ve cement paste formulations plus a
non-carbonated (NC) control sample (dashed line) exposed to the same T and RH without CO2 for at least 16 weeks.
200
60
55
50
40
35
30
25
20
15
10
5
0
CN
CN30 CN60
CP
CP30
Fig. 7. Total porosity (%) comparison measured by mercury intrusion (Hg) or by GRAM
(w) between the non carbonated (NC) and carbonated (C) states.
300
CN30
NC
C
w NC
Hg NC
w C
Hg C
45
porosity (%)
content are certainly due to the carbonation process itself, and not to a
process of redistribution of the moisture content within the specimens.
In Fig. 5, the porosity proles measured by GRAM (w) are presented. For the initial non-carbonated states, as the y ash content increases,
so does the porosity (comparison of CN, CN30 and CN60 for instance).
The initial porosity proles are evenly distributed, except for CN60.
Furthermore, the difference in the porosity between the initial and
nal control samples is at most 23%, which highlights that the variability from one sample to another is minimal compared to the effect of
carbonation.
As carbonation proceeds, the decreasing porosity proles indicate
a systematic clogging effect, even for CN60. This illustrates a wellidentied phenomenon for OPC systems where the formation of CC
clogs the pores since its molar volume is higher than the parent hydration products (CH and C-S-H). For CN60, the average non-carbonated
porosity decreases from 53% to 46% when carbonated. For CP30, it
decreases from 55% to 46%. It is also important to note that the carbonation reaction is stabilized for both CN60 and CP30 after 16 weeks
which makes it possible to dene an average porosity representing
the carbonated state (see Table 1). Indeed, a reduction in porosity
should lead to a decrease of the moisture transfer properties and a
slow down of the drying process during the course of the carbonation
test. On the contrary severe drying is observed for CN60 and CP30
when compared to non-carbonated control sample.
231
250
CN60
NC
C
250
CP30
NC
C
200
100
50
V/ log(rp) (mm3/g)
3
V/ log(rp) (mm /g)
V/ log(rp) (mm3/g)
150
200
150
100
0
10
100
1000
rp (nm)
(a)
10000
100
50
50
0
150
0
10
100
1000
rp (nm)
(b)
10000
10
100
1000
rp (nm)
(c)
Fig. 6. Average pore size distribution for non carbonated (NC) and carbonated (C) samples for CN30 (a), CN60 (b) and CP30 (c).
10000
232
nCaCO
3
nCH
nCaCO (CSH)
CN30 16 weeks
-1
CN30 4 weeks
CN30 2 weeks
0
0
10
20
30
40
50
0
0
10
x (mm)
20
30
40
50
10
x (mm)
20
30
40
50
x (mm)
Fig. 8. TGA results for CN30 after 2, 4 and 16 weeks of accelerated carbonation: molar content of portlandite nCH, of calcium carbonate nCC and of calcium carbonate issued from C-S-H
decalcication nCSH as a function of the sample depth.
CC
4.5
nCaCO
3
nCH
nCaCO (CSH)
4.5
CN60 2 weeks
4.5
CN60 4 weeks
3.5
3.5
2.5
2.5
2.5
1.5
1.5
1.5
0.5
0.5
0.5
3.5
10
20
30
x (mm)
40
50
10
20
30
x (mm)
40
50
CN60 40 weeks
nCaCO
3
nCH
nCaCO (CSH)
3
10
20
30
40
50
x (mm)
Fig. 9. TGA results for CN60 after 2, 4 and 40 weeks of accelerated carbonation: molar content of portlandite nCH, of calcium carbonate nCC and of calcium carbonate issued from C-S-H
decalcication nCSH as a function of the sample depth.
CC
at the edge of the sample after 4 and 16 weeks for CN30 and after 2
and 4 weeks for CN60. This conrms the results obtained by GRAM
(see Fig. 2) which shows a lower carbonation degree at the edge of
the specimen, mainly due a too low liquid water saturation in this
region as conrmed by Turcry et al. [49]. A lack of water near the surface
allows for faster diffusion of CO2 in the gas phase until the depth where
the carbonation reaction can occur, i.e. where water content is high
enough for CO2 dissolution. This residual portlandite may also be the
result of accelerated conditions since it is not always observed in the
case of naturally carbonated samples.
4. Discussion
4.1. Quantication of the available calcium content
As expected, the initial CH content in the NC samples is lower when
y ash is substituted in the cement (see Fig. 10a). This is due to not only
the dilution effect (lowering of the clinker content), but also the effect
of the pozzolanic reactions (which consume CH). In the case of CN60,
there is almost no portlandite in the NC state. The main source of calcium
is C-S-H, conrmed by the TGA proles.
Whatever the formulation, carbonation of C-S-H and CH is not instantaneous. This is highlighted by the broad calcium carbonate prole
(see Figs. 8 and 9). Due to calcium carbonate coating around CH crystals
all the portlandite will not be dissolved during carbonation [29]. This
phenomenon is also observed in natural conditions [50]. By subtracting
the minimal remaining CH content in the carbonated samples from
the initial CH content of NC materials we quantify the calcium content
available from CH carbonation. This amount is added to the calcium content in the C-S-H (assessed through a hydration model [51] using
Papadakis's work [52] and the cement oxide composition) in order to
calculate the theoretical total available calcium content. In Fig. 10a, we
compared it to the total experimental CC content when the carbonation
reaction is stabilized. We are clearly missing calcium (yellow bar higher
than green bar). This illustrates that all the calcium in the C-S-H is
not available for carbonation. Since the carbonation state is stabilized
(e.g. after 40 weeks of accelerated carbonation for CN60, see Fig. 9), it
is assumed that this difference is not due to kinetics effect, but mostly
13
11
-1
Content (mol.L ) (TGA + model)
12
attributed to the fact that (i) the ner water-saturated gel pores are
hardly accessible to carbon dioxide by aqueous diffusion and that
(ii) C-S-H can suffer an accessibility reduction that does not lead to
their total carbonation. Note that Visser [53] considers that all calcium
is available for carbonation and that experimental results showing the
contrary either correspond to not well carbonated samples or are due
to accelerated carbonation side effects. In this work, an almost carbonation state has been reached, this presence of non carbonated C-S-H
may thus be explained by the accelerated conditions.
In the following section, we will try to quantify the a priori amount
of calcium available and thus the amount of C-S-H that is theoretically
available for carbonation as a function of the total calcium content
deduced from the cement oxide composition. We need hypothesis on
the C-S-H carbonation mechanism. The rst one being that the inner
product (or high density C-S-H) will not carbonate. The second idea is
to consider that the more porous C-S-H gel is the only one which can
be easily reached by carbon dioxide. MIP results on blended cement
pastes (on CN60 and CP30 where macropores were created during
carbonation) also support the idea that pozzolanic C-S-H carbonates
easily. Fig. 10b presents the experimental total CC content compared
to the addition of three contributors to calcium release in carbonation:
(i) the carbonated CH content (assessed by TGA), (ii) the low density
C-S-H content (assessed according to [54]) and (iii) the pozzolanic
C-S-H content (hydration model [51] using Papadakis work [52]).
The gure shows that the calcium content from CH + LD-C-S-H +pozzolanic C-S-H (see Fig. 10b) is higher than the total experimental calcium content from CC (green bars): the hypothesis stating that all
pozzolanic C-S-H are readily carbonated or that all of the low density
C-S-H are accessible to carbon dioxide is thus not fully satisfactory
for all ve formulations. For CN, CN30 and CN60, this approach appears
correct, but it does not hold true for CP and CP30. The experimental
results show that not all the C-S-H is able to carbonate, even for the
high w/b formulations, and that the LD-C-S-H hypothesis including
pozzolanic C-S-H is only relevant for low w/b ratios. It may also be
due to (i) the fact that for high w/b ratios, the LD-C-S-H model overestimate the real quantity of C-S-H that has a low density, or (ii) simply
because this classication cannot be applied to carbonation since it is
based on nitrogen sorption experiments (the size of nitrogen molecules
13
nCa in CH
nCa in CSH (model)
nCa CSH + CH
Total CaCO3 (exp)
10
9
8
7
6
5
4
3
2
1
0
233
12
Total Ca (exp)
CSH-LD model
11
10
9
8
7
6
5
4
3
2
1
0
CN
CN30 CN60
(a)
CP
CP30
CN CN30 CN60 CP
CP30
(b)
Fig. 10. Calcium content in molL1 of porous material. Comparison between (i) available calcium in CH (TGA) for carbonation, (ii) total calcium in C-S-H (hydration model) (iii) total
amount of calcium available a priori (iv) nal CC when the carbonation reaction is stabilized (a). In (b) is illustrated the comparison between (i) the nal CC (carbonated) and (ii) sum
of the available calcium in CH (TGA) for carbonation, in LD-C-S-D and in the pozzolanic C-S-H (see Section 4.1).
234
is slightly smaller than carbon dioxide), (iii) one part of the pozzolanic
C-S-H is not carbonated or, (iv) because the distinction between low
and high density C-S-H is too simple to picture the real diversity in
the C-S-H structure. It is also important to note that the initial CS ratio
of the C-S-H has an inuence on its ability to release calcium [55,56]
and that the lower the CS is, the less likely the C-S-H will be releasing
calcium (threshold value of CS = 0.75 corresponding to an increasing
structural disorder in the C-S-H structure).
Fly ash contains aluminium, and it may be pertinent to evaluate
the impact of the hypothesis neglecting solid phases other than CH
and C-S-H (AFm, AFt and hydrogarnet C3AH6). Indeed, carbonation of
hydrogarnet produces hydrated aluminium oxide and CC [57] and
carbonation of ettringite produces CC, gypsum, hydrated aluminium
oxide and releases water [58]. We can easily conclude that a small
part of CC measured by TGA comes from the carbonation of these last
phases. The amount of calcium that we assume available in C-S-H for
carbonation is even lower than the amount we quantify because we
include a small part of CC coming from these secondary solid phases.
This reinforces the previous conclusion stating that C-S-H does not
fully carbonate.
4.2. Porosity evolution vs. chemical changes
For CN (w/b = 0.45 CEM I), it has been shown [22] that CH and C-S-H
contribute to the formation of CC. If one considers that the porosity variation is only due to CH (CH) and C S H (CSH), this variation can
1
37 cm3 mol stands
be expressed as proposed in Eq. (2) where V CH
CC
for the molar volume of the calcium carbonate formed by CH carbonation
(mainly calcite), and VCH = 33 cm3 mol1 is the CH molar volume. The
calcium carbonate content produced by CH carbonation, nCH comes from
CC
TGA and comes from GRAM.
CH
CH
CH CSH nCC V CC V CH CSH
14
w
Hg
from Ca(OH)2
12
- (%)
10
8
6
4
2
0
CN CN30CN60 CP CP30
Fig. 11. Porosity variation measured by mercury intrusion (Hg) or by GRAM (w) between
the non carbonated (NC) and carbonated (C) states and contribution to CH carbonation to
this porosity evolution.
0.04
-1
VCSH(initial)-VCSH (L.mol )
poro G to ATG
CN
CN30
CN60
CP
0.03
235
0.02
0.01
0
References
-0.01
0
0.4
0.8
1.2
1.6
CSH
Eventually, combining Eqs. (3), (4) and the fact that CS nCSH nCSH
Ca ,
we get Eq. (5) which allows plotting of the evolution of the C-S-H molar
volume at a given carbonation time t, VCSH(t), as a function of the C-S-H
decalcication state quantied by the macroscopic CS (see Fig. 12). We
clearly see that, in this case, the trend followed by CN and CP (no y
ash) is not obvious for CN30 and CN60.
The molar volume variation of classic C-S-H and pozzolanic C-S-H
might not be the same. The uncertainties are also important and it is
hard to obtain an investigation of the full range of CS since the y-ah
blended samples carbonates quickly.
0
CSH
CSH B CSH
nCC @V CC
1
C
C
t t
S 0
S
C
V CSH t V CSH t 0 A
5. Conclusion
Methods have been developed in order to combine TGA, MIP and
GRAM measurements. Following a previous study on OPC based cement
pastes and mortars. We have monitored carbonation of y-ash blended
cement pastes.
For blended carbonated pastes, when the substitution ratio is high
(above 30%) combined with a high water to binder ratio (above 0.6),
the pastes develop coarser capillary pores which allows for extensive
drying to occur, even if the total porosity decreases. The moisture transfer properties change and the materials can easily dry, especially water
released by carbonation of the hydration product. This can be even more
problematic for durability concerns that are not limited to carbonation
by increasing the speed of chloride or sulfate penetration in concrete.
This is not the case for OPC based cement paste where the whole
range of pores is clogging, and thus free water is not easily transported.
236
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