Proceedings of the Intern.

Conference on Ageing of Materials & Structures

AMS’14 Delft 26 – 28 May 2014, The Netherlands

Paper No. XXX (The number assigned by the Conf System)

The influences of CSH on the carbonation resistance of cement blended

with supplementary cementitious materials
Bei Wu *, Yong Zhang, Guang Ye
Delft University of Technology, Delft, The Netherlands

Abstract: The purpose of this work is to investigate the carbonation mechanism of C-S-H within
Portland cement and fly ash cement paste in terms of amount changes, silicate chain and nanoporosity
evolution during carbonation. Accelerated carbonation tests were performed at 3% CO2, 20 °C and
75±2% RH). The development of C-S-H due to carbonation were investigated by thermogravimetry
(TG), nitrogen adsorption and Fourier transform infrared spectroscopy (FTIR), respectively. Samples
from Portland cement and fly ash cement paste (w/b = 0,5) exposed to different carbonation ages from
4 to 8 weeks were collected for the above analysis. Combining experimental results, the C-S-H in fly
ash cement is more vulnerable to carbonation, which causes the worse carbonation resistance of
blended cement.
Keywords: SCMs, fly ash, CSH, accelerated carbonation

1 Introduction
Carbonation of calcium-bearing phases inside the concrete is the main deterioration process of open
infrastructure in district with high average annual relative humidity. The consequence of this ageing
phenomenon is the reduction of alkalinity, which makes the reinforcement easy to be corroded. In
general, calcium-bearing phases involving in carbonation could be hydration products like portlandite
(CH), calcium silicate hydrate (C-S-H) , as well as unhydrated cement clinkers like tricalcium silicate
(C3S), dicalcium silicate(C2S). Normally, the reactions between unhydrated cement and CO2 can be
ignored because their weak competition for CO2 in front of CH and C-S-H [1]. When comparing with
C-S-H, the carbonation of CH has a priority from thermo dynamical point of view [2]. When C-S-H
phase is still carbonating, CH carbonation slows down and stops. However in experiments the initial
rate of carbonation is quite similar [3]. If considering the long-term situation, CH is carbonated and
consumed very quickly in the early stage, then the C-S-H becomes a key role for the carbonation
resistance of cement paste.
Carbonation of C-S-H has been studied by many authors [3-5]. It agreed that a complex
decalcification-polymerization process of the C-S-H and the formation of amorphous silica gel
according to the following reaction occurs:
− −
Cx S y H z + x C → xC C + ySH t + ( z − yt ) H (1)
−
It is reclaim that, in cement notations, C = CaO, H= H2O, S = SiO2, A= Al2O3 and C =CO2. In
Portland cement paste, the C-S-H has a composition of ~1.5-1.9 C/S. The addition of supplementary
cementitious materials (SCMs) like fly ash results in the formation of a C-S-H with lower C/S, which
is generally agreed to have a tobermorite- like structure C0.83 S 2 H1.5 but with many defects, mainly in
bridging tetrahedron [6-8]. The formation of C-S-H with a low C/S leads to an increased uptake of
aluminium in the C-S-H, called C-A-S-H [9]. Therefore, in cement paste blended with SCMs like fly
ash, there are at least two types of C-S-H: C-S-H with high C/S from the hydration of C3S and
C2S(high Ca C-S-H), C-S-H with low C/S from the pozzolanic reaction(low Ca C-(A-) S-H). The
proportions of them are determined by the replacement level of SCMs, which is confirmed by the
thermodynamic modelling from B. Lothenbach et al [10].

*
Corresponding author at: Building 23, Stevinweg 1, 2628CN, Delft, The Netherlands
E-mail address: B.Wu@tudelft.nl
 Proceedings of the Intern. Conference on Ageing of Materials & Structures

AMS’14 Delft 26 – 28 May 2014, The Netherlands

Paper No. XXX (The number assigned by the Conf System)

It is accepted that the carbonation resistance of cement paste blended with SCMs is worse than
Portland cement and decreases with the increasing replacement level of SCMs. From the materials
point of view, first important reason is the lower CH content in blended cement , due to the pozzolanic
reaction and dilution effects. The other reason is possible from the C-S-H. As mentioned above, the C-
(A-) S-H with low C/S inside the blended cement paste has more defects and it is vulnerable to
carbonation.
The aim of this work is to provide more information of the aging of C-S-H under carbonation. Base
on the results from thermogravimetric analysis, Fourier transform infrared spectroscopy and nitrogen
adsorptiontests, the evolution of the C-S-H (content, silica chain structure and gel pore size) during
carbonation are studied in the case of CEM I cement paste and fly ash blended paste. By comparing
with the carbonation rates of different mixtures, a correlation between C-S-H types and carbonation
resistance of cement paste needs to be found, in order to explain the behaviour of blended cement
paste under carbonation from the C-S-H aspect.

2 Materials and method

2.1 Materials
Ordinary Portland cement (CEM I 425N, ENCI) was used to prepare cement paste. The SCMs used
here was fly ash (FA) and its replacement levels were 10% and 30% of cement in weight. Chemical
compositions of raw materials are listed in Table 1.

Table 1 Main chemical composition of cement and fly ash

CaO SiO2 Al2O3 Fe2O3 MgO K2O Na2O SO3 L.O.L
Cement 66,15 18,34 4,41 3,46 2,16 0,46 - 2,63 1,37
FA 5,61 49,79 31,81 5,38 1,05 0,90 0,18 0,49 2,35

2.2 Sample preparation

Cement pastes were casted in a HOBART mixer at the low speed for 1 minute and at the high
speed for 2 minutes with interval pause for 15 seconds. The samples were cast in the plastic bottles
with diameter of 50 mm. The bottles were filled in 3 steps and air was removed by vibrating for 10
seconds at each step before the bottles were sealed. Then, those bottles were fixed in the rotation
machine at a speed of 5-7 rpm for 24 hours to prevent bleeding. After that, a sealed curing was
performed for 105 days at 20◦C before the carbonation procedure. Two kinds of cement paste were
prepared, Portland cement paste (PC) and Fly ash cement paste. The replacement level of FA were
10% and 30%, which were labelled by FA10 and FA30 respectively. The water/ binder ratio of cement
pastes - was 0.5.
After curing, plastic bottles were cut into two pieces in order to obtain two cylinders (height = 40
mm, φ =50 mm, as shown in Figure 1). Both top face rims and bottom face of part B were re-sealed
with silicon sealant in order to obtain unidimensional carbonation condition. Then the samples were
put into a box regulated by CO2 concentration of 3%±0.2, at 20 ⁰C and 75% of relative humidity
(using a saturated NaCl solution). The carbonation ages were 28, 42 and 56 days.

Figure 1 Sample pretreatment

 Proceedings of the Intern. Conference on Ageing of Materials & Structures

AMS’14 Delft 26 – 28 May 2014, The Netherlands

Paper No. XXX (The number assigned by the Conf System)

2.3 Test method

Carbonation depth (Xc) was determined by phenolphtalein spray test. The specimens used for the
phenolphtalein test were split in two half-cylinders. Phenolphthalein was sprayed upon both exposed
fresh surfaces. About 10 points along the 50 mm diameter exposed surface were chosen to measure the
carbonation depth. After the spray test, the carbonated and noncarbonated part were separated.
Samples for microanalysis were collected from area at least 1mm from the carbonation front. The
reason is that the carbonation can have happened at greater depths than which was indicated by the
phenolphalein test [11-14]. Collected samples from both carbonated and noncarbonated parts were
immersed into liquid nitrogen for 3-4 min to stop further hydration. Then those specimens were
immediately put into a vacuum freeze-dryer under −24°C, at 0.1 Pa [15]. The drying procedure would
take at least 4 weeks until the weight loss was less than 0.01%.
Thermogravimetric analysis (TGA) is used to determine the amounts of CH and CaCO3 by
detecting the sample mass loss during heating samples from 40-1100°C at 10°C/ min. The samples
after drying were ground into powder<75 μm. The mass of powder samples was 30-50 mg. TGA were
carried out in the Netzsch STA 449 F3 Jupiter coupled with a mass spectrometer (MS) Netzsch QMS
403 C Quadrupole under a dry argon atmosphere, in order to identify with the more accurate
temperature range related to the emissions of H2O or CO2.
Fourier transform infrared spectroscopy (FTIR) coupled with attenuated total reflectance (ATR)
technique enables examination of samples directly in the solid or liquid state without further
preparation. In this research, the FTIR spectra were collected over the wavelength range of 4000 to
400 cm-1 at a resolution of 4 cm-1using TM 100 Optical ATR-FTIR spectrometer. The samples were
grinded into powders with same fineness as those used for TGA test, spread on the testing plate (ATR
crystal) and pressed to obtain good contact.
Nitrogen adsorption isotherm is a method for estimating the pore volume and area distribution by
using the BJH model [16]. Nitrogen adsorption tests were conducted by using Gemimi VII 2390 with
a relative pressure range from 0.05~0.98.

3 Results and discussion

3.1 Phenolphtalein spray test-carbonation depth(Xc)
Figure 2 shows the time evolution of Xc for cement pastes PC, FA10 and FA30 with w/b =0,5. A
square root of time relation passing through the origin has been used to fit Xc data. As expected, PC
paste is more resistant to carbonation than that of FA cement paste. The more the FA introduced into
cement paste, the higher the rate for the Xc development. This conclusion is in good agreement with
other researchers [17-19].

Figure 2 Carbonation depth determined by the phenolphthalein spray test on PC, FA10, FA30 pastes (w/b = 0,5) after total
56 days of carbonation vs. Square root of time

3.2 TGA-MS coupled test results

The TGA-MS results for cement paste before and after carbonation is shown in Fig. 3. By using MS,
the ion currents of different gases are recorded, providing gas information during the TGA. In the
TGA cure of noncarbonated sample,the weight loss in the range of 40-400°C is normally related to the
 Proceedings of the Intern. Conference on Ageing of Materials & Structures

AMS’14 Delft 26 – 28 May 2014, The Netherlands

Paper No. XXX (The number assigned by the Conf System)

dehydration of C-S-H [20, 21], part of the carboaluminate hydrates [22], AFm and AFt [23] phases, as
well as to the emission of physically-bound water [21]. This is confirmed by the mass spectrum of
H2O( see Figure 3a). There is a minor peak around 150°C in the mass spectrum of , indicating the
presence of monocarbonate [24]. Coupled with MS results, the mass loss related to CH
dehydroxylation usually occurs in the range of 450-550 °C [21, 25] The main decarbonation of CaCO3
is in the range of 600-900 °C[21, 26], even though the second minor peak in the mass spectrum of
CO2 indicates that the start point of the decarbonation of CaCO3 is around 500 °C. This can be also
observed in the TGA-MS of carbonated sample( see Figure 3b). The test results of carbonated sample
also show that nearly all the CH are converted to CaCO3. Weight loss due to the dehydration of CH
and decarbonation of CaCO3 are determined by a graphical technique[27]. The technique makes a
correction for the concurrent dehydration of other compounds.

100 1.8E-9 100

a PC,Hydrated for 105d 4.5E-11 b PC,Hydrated for 105d, 2.8E-10

4E-11 1.6E-9 carbonated for 42d 1E-10 2.6E-10

95 2.4E-10
95
2.2E-10
3.5E-11

Ion Current (A)

1.4E-9
Ion Current (A)
90 CO2 2E-10
Mass (%)

90
Mass(%)
3E-11 1.8E-10
CO2 85 H2O
1.2E-9 1.6E-10
85 2.5E-11
H2O 1.4E-10
80
1E-9 1E-11
80 2E-11 1.2E-10
75
1E-10
75 8E-10 70
100 200 300 400 500 600 700 800 900 1000 1100 100 200 300 400 500 600 700 800 90010001100
Temperature (°C) Temperature (°C)
Figure 3 TGA-MS results for cement paste w/b = 0.5: (a) PC, before carbonation; (b) PC, carbonated for 42d

In order to monitor the deterioration extent of C-S-H during carbonation, the weight loss due to the
dehydration of C-S-H was calculate. Although the temperature range for the dehydration of C-S-H in
cement paste is debatable [21, 28, 29]in present research, 180-300 °C is selected as the main
dehydration temperature of C-S-H. The water loss in this range will represent the C-S-H content inside
the cement paste before and after carbonation. The amount of water loss in the range of 105 - 220°C
are also calculated for comparison. The calculation results are shown in Figure 4.
Apparently, the water loss from the dehydration of C-S-H decreases with the carbonation time,
which means part of the C-S-H is carbonated by CO2. The C-S-H content in FA cement paste
decreases more after carbonation. Moreover, if increasing the FA content, the deterioration of C-S-H
by carbonation goes faster.

Figure 4 Evolution of water loss percentage from C-S-H dehydration with carbonation time (a:180-300 °C ;b:105-220°C)

The total amounts of carbonates mainly consists of two parts; one part is from the carbonation of
CH and another part is from the carbonation of CSH. As mentioned above, the CH and CaCO3
contents can be calculated from the TGA curves. As the CH is totally converted to carbonates, the
carbonates from CH is calculated based on the CH content in the sample before carbonation. The
 Proceedings of the Intern. Conference on Ageing of Materials & Structures

AMS’14 Delft 26 – 28 May 2014, The Netherlands

Paper No. XXX (The number assigned by the Conf System)

differences between total amounts of carbonates and those from CH is the carbonates content from
CSH. All the calculated results are illustrated in Figure 5. In all the mixtures, the amounts of
carbonates from CSH increase with carbonation time. In the same carbonation time, the carbonates
amounts from CSH increase with the replacement level of FA. It means there are more C-S-H in the
FA blended system carbonated in the same age. The reason is that those C-S-H(low Ca C-(A-) S-H)
produced from the pozzolanic reaction inside the FA cement paste is easier to be carbonated. There
higher the replacement level of FA, the more the low Ca C-(A-) S-H. Therefore, the amounts of CSH
carbonated in the same time are much higher in the FA blended cement paste. This is consistent with
the results by calculating the water loss from the dehydration of C-S-H.
100
95

1646
Transmittance (%)

3644
90

1475
1418
85
80
75

875
70

955
65 PCH105D
4000 3500 3000 2500 2000 1500 1000
Wavenumbers (cm-1)
Figure 5 CaCO3 content related to C-S-H carbonation vs. Figure 6 Mid-FTIR spectra of cement paste (PCH105D:
replacement level of FA at same carbonation time Portland cement paste hydrated for 105 days)

3.3 ATR-FTIR test results

A typical Mid-FTIR spectra of cement paste is shown in Figure 6. The band at 955 cm-1 can be
assigned to Si-O stretching vibrations of the Q2 tetrahedra, and it shifts toward lower frequency with
increasing C/S ratio ≤ 1.2, indicating progressive depolymerisation of the silicate chains [30, 31]. The
bands in the range of 1400-1500 cm-1 correspond to the asymmetric stretching (v3) of CO32- , and the
weak shoulder at ~875 cm-1 is due to the out-of-plane bending (v2) of CO32-. The 3600 cm−1 band can
be mostly attributed to less strongly hydrogen-bonded interlayer water molecules and any CaOH sites,
the intensity of which will decrease after carbonation. The band at 1640 cm−1 is due to H–O–H
bending vibration of molecular H2O. In the following, only the band around 955 cm-1 will be
discussed.
After carbonation for 28 d, the frequency of bands in the FTIR spectra of PC, due to Si-O
stretching vibrations of the Q2 tetrahedra, shifts to higher frequency, from 955 to 992 cm-1, as
illustrated in Figure 7a. This shifting in the spectra of FA30 (see Figure 7b) is from 956 to 1029 cm-1.
This shifting tendency indicates the polymerisation of the silicate chains and the reduction of Ca/Si
ratio in C-S-H because of the carbonation.
By prolonging the carbonation time to 42 d, both the frequency and the intensity of this band
increases in the spectra of PC. It means further decomposition of C-S-H exists in the Portland cement
paste with the increasing carbonation time. However, in the spectra of FA, only the intensity increases,
at least in this research. This means decalcification-polymerization process of the C-S-H in FA cement
paste nearly stops after 28 days’ carbonation.
In the mid- IR spectra of C-S-H with portlandite and C-S-H with silica gel, the band assigned to Si-
O stretching vibrations of the Q2 tetrahedra are at 958 and 1056 cm-1, respectively [30]. By comparing
with the results in this research C-S-H loses Ca and decomposes to silica gel during the carbonation.
The C-S-H with low C/S in the FA cement paste is more vulnerable to carbonation and quicker to be
decomposed into silica gel. That is why the band in mid-IR spectra indicating the Q2 tetrahedra won’t
make further shift after certain carbonation time.
 Proceedings of the Intern. Conference on Ageing of Materials & Structures

AMS’14 Delft 26 – 28 May 2014, The Netherlands

Paper No. XXX (The number assigned by the Conf System)

100 100 FA30H105D

95 PCH105D 95 FA30H105DC28D
PCH105DC28D FA30H105DC42D
90 90
PCH105DC42D

1478
1416
1475

Transmittance (%)
1418
Transmittance (%)

85 85
80 80
75 75

CO32-(v3)
70

Si-O stretching ( Q2)

70

Si-O stretching ( Q2)

992
65

1440
955
65

1000

CO32-(v2)
60 60
1412

1027
956

CO3 (v2)
CO32-(v3)
55 55

875 2-
50
50

1409
875
b
1408

45
40 a 45
180017001600150014001300120011001000 900 800 700 180017001600150014001300120011001000 900 800 700
Wavenumbers (cm-1) Wavenumbers (cm-1)
Figure 7 Shifting of bands at ~955cm-1 in mid-FTIR spectra of Portland cement paste (a), and 30% FA cement paste (b)
due to carbonation (H105D: hydrated for 105 days; C28D: carbonation for 28 days; C42D: carbonation for 42 days)

3.4 Nitrogen adsorption

By using BJH method, the pore size distributions in the range of 2-37 nm are calculated from the
nitrogen adsorption test results, as shown in Figure 8. In this scale, the pores are mainly from the gel
pores of C-S-H. As mentioned in Jennings ‘work, the nitrogen can only penetrate into low density (LD)
C-S-H. Therefore, the pores in this scale mainly belong to the gel pores of LD C-S-H, which are
divided into three kinds according to the Globule C-S-H models [32]. That would be inter globule
pores (IGP, ≤ 1nm), small gel pores (SGP = 1-3 nm) and larger gel pores (LGP = 3-12nm).

a b c

Figure 8 The evolution of accumulative pore volume and pore size distributions (2-37 nm) of Portland cement paste (a),
10% FA cement paste (b) and 30% FA cement paste (c) with carbonation time (H105D: hydrated for 105 days; C28D, C42D,
C56D: carbonation for 28, 42, 56days)
In the pore size distribution curves of cement paste before carbonation, there are two main peaks,
which are at ~4 nm and ~28nm (Fig. 8a). The second peak can be assign to the larger gel pore of LD
C-S-H. After carbonation, the size of the larger gel pores increases. That is because the decomposition
of C-S-H to silica gel. The decalcification of C-S-H leads to a C-S-H with a molar volume smaller
than a non-carbonated C-S-H and to a smaller C/S [3]. This changes in FA cement paste is more
obvious, especially for FA30. The peak of larger gel pores moves out of the nitrogen test limitation, to
the capillary pore area. This also proves that the C-S-H in FA cement paste is easier to be carbonated.

4 Conclusions
In the paper, the carbonation mechanism of cement paste blended with FA is studied by using TGA,
FTIR and nitrogen adsorption. The evolution of the content, silica chain and nano porosity of C-S-H
due to carbonation are discussed The influence of C-S-H type on the carbonation resistance of cement
paste blended with FA are found. The main conclusions are as follow:
 Proceedings of the Intern. Conference on Ageing of Materials & Structures

AMS’14 Delft 26 – 28 May 2014, The Netherlands

Paper No. XXX (The number assigned by the Conf System)

- The rate of carbonation (indicated as carbonation depth (XC)) in cement paste blended with FA
is greater than that in Portland cement paste. This value increases with the increase of
replacement level of FA.
- At the same carbonation time, the amount of C-S-H carbonated by CO2 increases with the
increase of replacement level of FA by calculated from TGA results.
- From FTIR results the decalcification-polymerization process of the C-S-H in FA cement
paste nearly stops after 28 days’ carbonation, which means the C-S-H is more vulnerable to
carbonation comparing with Portland cement paste.
- The larger gel pores of C-S-H in cement paste blended with 30% nearly moved to capillary
pore area, indicating the massive changes of C-S-H due to carbonation
Combination of TGA, FTIR and nitrogen adsorption techniques to investigate the C-S-H behaviour
exposed to carbonation have provide another clue to study the influence of SCMs on the carbonation
resistance of cement paste. The C-S-H with lower C/S or C-A-S-H are more vulnerable to carbonation.
The proportion of this type of C-S-H increases with the increase of replacement level of SCMs, which
makes the carbonation resistance of cement paste even worse.

Acknowledgement
The authors are grateful for the help from technicians and experimental supports from Microlab, Delft
University of Technology.

References
[1] M. Peter, A. Muntean, S. Meier, M. Böhm, Competition of several carbonation reactions in concrete: a
parametric study, Cement Concrete Res, 38 (2008) 1385-1393.
[2] F. Glasser, T. Matschei, Interactions between Portland cement and carbon dioxide, in: Proceedings of the
ICCC Conference, 2007.
[3] A. Morandeau, M. Thiery, P. Dangla, Investigation of the carbonation mechanism of CH and CSH in terms
of kinetics, microstructure changes and moisture properties, Cement Concrete Res, 56 (2014) 153-170.
[4] L. Black, C. Breen, J. Yarwood, K. Garbev, P. Stemmermann, B. Gasharova, Structural features of C–S–H
(I) and its carbonation in air—a Raman spectroscopic study. Part II: carbonated phases, J Am Ceram Soc, 90
(2007) 908-917.
[5] V.r.L. Zdeneˇk Sˇauman, Long-term carbonization of the phases 3CaO.Al2O3.6H2O and
3CaO.Al2O3.SiO2.4H2, Cement Concrete Res, 2 (1972) 12.
[6] I. Richardson, The nature of CSH in hardened cements, Cement Concrete Res, 29 (1999) 1131-1147.
[7] X.D. Cong, R.J. Kirkpatrick, O-17 MAS NMR investigation of the structure of calcium silicate hydrate gel, J
Am Ceram Soc, 79 (1996) 1585-1592.
[8] X.D. Cong, R.J. Kirkpatrick, Si-29 MAS NMR study of the structure of calcium silicate hydrate, Adv Cem
Based Mater, 3 (1996) 144-156.
[9] I. Richardson, G. Groves, The incorporation of minor and trace elements into calcium silicate hydrate (C
S H) gel in hardened cement pastes, Cement Concrete Res, 23 (1993) 131-138.
[10] B. Lothenbach, K. Scrivener, R. Hooton, Supplementary cementitious materials, Cement Concrete Res, 41
(2011) 1244-1256.
[11] G. Villain, M. Thiery, G. Platret, Measurement methods of carbonation profiles in concrete:
thermogravimetry, chemical analysis and gammadensimetry, Cement Concrete Res, 37 (2007) 1182-1192.
[12] A. Rahman, F. Glasser, Comparative studies of the carbonation of hydrated cements, Adv Cem Res, 2
(1989) 49-54.
[13] Y. Lo, H. Lee, Curing effects on carbonation of concrete using a phenolphthalein indicator and Fourier-
transform infrared spectroscopy, Building and environment, 37 (2002) 507-514.
[14] M. Thiery, G. Villain, P. Dangla, G. Platret, Investigation of the carbonation front shape on cementitious
materials: effects of the chemical kinetics, Cement Concrete Res, 37 (2007) 1047-1058.
[15] G. Ye, Experimental study and numerical simulation of the development of the microstructure and
permeability of cementitious materials, (2003).
[16] L.G. Joyner, E.P. Barrett, R. Skold, The determination of pore volume and area distributions in porous
substances. II. Comparison between nitrogen isotherm and mercury porosimeter methods, Journal of the
American Chemical Society, 73 (1951) 3155-3158.
[17] V.G. Papadakis, Effect of supplementary cementing materials on concrete resistance against carbonation
and chloride ingress, Cement Concrete Res, 30 (2000) 291-299.
 Proceedings of the Intern. Conference on Ageing of Materials & Structures

AMS’14 Delft 26 – 28 May 2014, The Netherlands

Paper No. XXX (The number assigned by the Conf System)

[18] C.D. Atiş, Accelerated carbonation and testing of concrete made with fly ash, Constr Build Mater, 17
(2003) 147-152.
[19] K. Sisomphon, L. Franke, Carbonation rates of concretes containing high volume of pozzolanic materials,
Cement Concrete Res, 37 (2007) 1647-1653.
[20] N. Richard, Structure et propriétés élastiques des phases cimentières base de mono-aluminate de calcium,
in, 1999.
[21] A. Noumowé, Effet des hautes températures (20 °C–600 °C) sur le béton, in: Institut National des Sciences
Appliquées, 1995.
[22] E. Nonnet, N. Lequeux, P. Boch, Elastic properties of high alumina cement castables from room
temperature to 1600 C, Journal of the European Ceramic Society, 19 (1999) 1575-1583.
[23] Q. Zhou, F. Glasser, Thermal stability and decomposition mechanisms of ettringite at< 120 C, Cement
Concrete Res, 31 (2001) 1333-1339.
[24] B. Lothenbach, G. Le Saout, E. Gallucci, K. Scrivener, Influence of limestone on the hydration of Portland
cements, Cement Concrete Res, 38 (2008) 848-860.
[25] G. Platret, Suivi de l’hydratation du ciment et de l’évolution des phases solides dans les bétons par analyse
thermique, Caractéristiques microstructurales et propriétés relatives à la durabilité des bétons Méthodes de
mesure et d’essai de laboratoire Méthodes d’essai, (2002).
[26] P. Grattan-Bellew, Microstructural investigation of deteriorated Portland cement concretes, Constr Build
Mater, 10 (1996) 3-16.
[27] B.K. Marsh, R.L. Day, Pozzolanic and cementitious reactions of fly ash in blended cement pastes, Cement
Concrete Res, 18 (1988) 301-310.
[28] G. Khoury, Compressive strength of concrete at high temperatures: a reassessment, Mag Concrete Res, 44
(1992) 291-309.
[29] L. Alarcon-Ruiz, G. Platret, E. Massieu, A. Ehrlacher, The use of thermal analysis in assessing the effect of
temperature on a cement paste, Cement Concrete Res, 35 (2005) 609-613.
[30] P. Yu, R.J. Kirkpatrick, B. Poe, P.F. McMillan, X. Cong, Structure of Calcium Silicate Hydrate (C‐S‐H):
Near‐, Mid‐, and Far‐Infrared Spectroscopy, J Am Ceram Soc, 82 (1999) 742-748.
[31] P.F. McMillan, G.H. Wolf, B.T. Poe, Vibrational spectroscopy of silicate liquids and glasses, Chemical
Geology, 96 (1992) 351-366.
[32] H.M. Jennings, Refinements to colloid model of CSH in cement: CM-II, Cement Concrete Res, 38 (2008)
275-289.