Construction and Building Materials 40 (2013) 1012–1020

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Construction and Building Materials

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How to assess the hydration of slag cement concretes?

Aveline Darquennes a,⇑, Bernard Espion b, Stéphanie Staquet b
a
Laboratoire de Mécanique et Technologie (LMT), ENS Cachan, CNRS UMR 8535, UMPC, PRES UniverSud Paris, Cachan, France
b
Department of Building, Architecture and Town Planning (BATir), Université Libre de Bruxelles (ULB), Brussels, Belgium

h i g h l i g h t s

" Adiabatic calorimetry, TGA and SEM were used to characterize the hydration.
" Slag addition affects seriously the hydration advancement at early age.
" Chemically bound water method predicts well of the hydration degree evolution.
" The final hydration degree of slag is higher when the slag content increases.
" Mechanical properties are better estimated by models based the hydration degree.

a r t i c l e i n f o a b s t r a c t

Article history: Addition of slag modifies the hydration process of cement and the evolution of the mechanical properties
Received 14 February 2012 of concrete. In this study, the advancement of hydration was monitored for concretes with different blast-
Received in revised form 12 September 2012 furnace slag contents using several techniques such as adiabatic calorimetry, thermogravimetry and anal-
Accepted 25 September 2012
ysis by scanning electron microscopy. Results show clearly the slowdown of the hydration for slag
Available online 29 December 2012
cement concretes. A fundamental parameter describing the hydration process and the evolution of the
microstructure, named the degree of hydration, is quantified for the slag cement concretes. It appears
Keywords:
that the method based on the evolution of the chemically bound water gives the most reliable evolution
Degree of hydration
Chemically bound water
of the hydration degree. The knowledge of this parameter allows predicting correctly the evolution of
Portlandite compressive strength and Young modulus at early age for concretes with high slag content using an ana-
Calorimetry lytical model based on the degree of hydration.
Mechanical properties Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Nowadays, various civil engineering structures (e.g. highways,
bridges, tanks, etc.) are realized with slag cement concretes. In-
deed, slag cement presents several advantages comparing to Port-
land cement: its production requires less energy and emits a
smaller amount of carbon dioxide in the atmosphere [1]; it is char-
acterized by a lower hydration heat and permeability and a better
resistance to sulphate attacks [2,3]. Nevertheless, slag addition
modifies the kinetics of cement hydration [4] and the evolution
of the mechanical properties. Thus, it can lead to an early cracking
of concrete under restraint conditions [5] and jeopardize the dura-
bility and the functionality of the structure. It is therefore crucial to
be able to understand and to quantify the hydration of slag cement
concretes as it influences their mechanical properties.
The hydration process is a complex phenomenon that can be
described by the hydration reactions of the cement constituents
⇑ Corresponding author. Tel.: +33 1 47 40 53 69; fax: +33 1 47 40 74 65.
E-mail address: aveline.darquennes@ens-cachan.fr (A. Darquennes).
(C3A, C2S, etc.). These reactions differ in their kinetics, while being
mutually interdependent. In simplified models found in the litera-
ture, cement hydration is often described as a single hydration
reaction characterized by a global degree of hydration. This global
hydration degree is defined as the ratio between the hydrated ce-
ment content at a time t and the initial anhydrous cement content.
It is an intrinsic parameter that allows monitoring the physical and
chemical processes during the cement hardening phase and it de-
scribes the development of the microstructure of the cementitious
material.
The determination of the hydrated cement being a difficult task,
it is often substituted by the anhydrous cement content deter-
mined using X-ray or scanning electronic microscopy (SEM) analy-
sis [6]. Because of the great number of experimental results
needed, other parameters are also often measured (e.g. liberation
of heat, content of chemically bound water, chemical shrinkage,
portlandite content, strength, etc.) [7]. Although these methods
are largely used to describe cement hydration [8–10], and few
experimental data on the quantification of the concrete hydration
degree can be found in the literature [11,12]. Cement and concrete

0950-0618/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.09.087
 A. Darquennes et al. / Construction and Building Materials 40 (2013) 1012–1020 1013

pastes have different degrees of hydration [13]. This is partially due Table 3
to the paste inhomogeneity in concrete [14] and the fact that the Chemical composition of slag and clinker.

aggregates disrupt the packing of cement particles [15]. It is there- Oxides (%) Slag Clinker
fore necessary to determine the degree of hydration of the concrete CaO 39.8 66.1
material to correctly predict its compressive strength or its autog- SiO2 34.4 19.0
enous shrinkage... Al2O3 11.5 5.4
The aim of the present experimental study is to characterize the MgO 9.3 0.8
SO3 3.1 1.8
hydration process of concretes with different slag contents, to
quantify the evolutions of their hydration degree (concrete hydra-
tion degree) and the degree of their pozzolanic reaction. Classical
experimental techniques (calorimetry and thermogravimetry), Table 4
usually used for mortar or cement pastes, are therefore adapted Hydraulicity factors.
for these purposes. The importance of the quantification of the Factors Equations Value of the
concrete hydration degree is illustrated by using two analytical studied slag
models to predict the compressive strength and Young modulus Chemical modulus ðCaO þ MgOÞ 1.43
SiO2
of the studied concretes. Hydraulic factor ðCaO þ MgO þ Al2 O3 Þ 1.76
SiO2
Solubility factor R CaOAl2 O3 0.217
ðSiO2 þ Al2 O3 Þ2
2. Materials Langavant ratio C 20 þ CaO þ Al2 O3 þ 0:5MgO  2SiO2 7.19
Ih ratio CaO þ 1:4MgO þ 0:56Al2 O3 1.72
SiO2
Three cements were used in the experimental campaign presented hereafter: a
Tetmayer modulus CaO
þ MgO Al2 O3
40 þ 102
1.84
Portland cement CEM I 52.5 N and two blended cements, namely CEM III/A 42.5 LA 56
SiO2
60
and CEM III/B 42.5 HSR LA. They differed on their slag content while their clinker
and slag were of the same origin. The blended cements (CEM III/A and CEM III/B)
contained 42% and 71% of slag respectively and had similar specific areas and den-
sities (Table 1). The respective concretes are indicated in this paper as CEM I, CEM
III/A and CEM III/B. Their water–binder ratio (w/b) and the binder (clinker + slag) Langavant ratio, the Ih ratio and the Tetmayer modulus. In this study the Langavant
content were kept identical and equal to 0.45 and 375 kg/m3 respectively. Six dif- ratio indicated a slag of ordinary hydraulicity, while the other two ratios a slag of
ferent fractions of aggregates were used. Details on the concrete mixture propor- good conductivity. Notice that slag reactivity depends also on other factors such
tions are given in Table 2. as geometry properties, temperature and alkali environment [19].
The origin of the slag can significantly influence the results [16]. The chemical
features of slag (used in this study and provided by cement manufacturer) were
measured. An X-ray diffraction analysis showed that the slag used was character- 3. Testing procedure
ized by a vitreous appearance and different crystalline phases (merwinite Ca3-
Mg(SiO4)2, akermanite Ca2Mg(Si2O7), gehlenite Ca2Al(AlSi)O7 and rankinite 3.1. Adiabatic calorimetry
Ca3Si2O7). Some of these crystals, such as the merwinite crystals, improve the slag
reactivity by increasing the aluminium oxide (Al2O3) content [17]. The percentages
of its main compounds (calcium, silicon, aluminium, etc.) were determined by X-ray Cement hydration reaction is exothermic. Quantification of the
fluorescence (Table 3) to estimate the reactivity, solubility and hydraulicity of the heat release was done using calorimeters. The majority of these de-
slag (Table 4). The chemical modulus and the hydraulic factor characterize the slag vices is designed for cement or mortar specimens. However, it is
reactivity [2]. These ratios define the acid or basic character of the slag and are used
known that cement paste data should only be used when compar-
as acceptance criteria in cement production (they should be higher than 1 and 1.4
respectively [18]). The slag used in this study had a basic character and matched the ing cements; for heat calculations in concrete it is necessary to test
above acceptance criteria. Slag quality is considered adequate if the ratio of slag sol- concrete specimens [20]. An adiabatic calorimeter was designed in
ubility in a basic solution (R) is higher than 0.18. This condition was also verified. the laboratory of the BATir department at the Université Libre de
Finally, slag hydraulicity can be characterized using different relations [17]: the Bruxelles [21] to determine the heat release of slag cement con-
cretes during the hardening phase. This kind of calorimeter has a
good sensibility in measuring the low heat release of cementitious
Table 1 materials with mineral additions. Moreover, it is suitable for quan-
Cements characteristics. tifying the heat production of slag cement concretes in massive
Cements CEM I 52.5 CEM III A 42.5 CEM III B 42.5 concrete structures (e.g. dyke, dam).
Clinker content (%) 95 58 27 The general principle of an adiabatic calorimeter is that heat ex-
Slag content (%) / 42 71 change is avoided by keeping the environment around the sample
Limestone filler content (%) / / 2 at the same temperature as the hydrating concrete mixture. The
Specific area (m2/kg) 445 447 477 new device (Fig. 1) consists of a copper cylindrical tank with water
Density (kg/m3) 3.09 3.01 2.93
circulation (3). An insulating air layer (2) separates the sample
(volume = 30.4 l) (1) from the tank (3). In order to obtain adiabatic
conditions, temperature regulation was controlled by thermocou-
ples embedded in the sample (1). A thermostatic bath measured
Table 2
the temperature of the fluid circulating in the six compartments
Concretes mixtures proportions.
of the tank to ensure a homogeneous temperature in the device.
Composition (kg/m3) CEM I CEM III/A CEM III/B Homogeneity was checked with PT-100 sensors placed in each
Cement 375 375 375 compartment. Thermal exchange between the calorimeter and
Water 164.6 166.95 164.9 the environment was limited by the insulation surrounding the de-
Total water 169 169 169 vice. The experimental device was validated comparing tempera-
Admixture 5.63 2.63 5.25
Sand 0/0.5 492 492 492
ture measurements on Portland cement concrete obtained with
Sand 0.5/1 126 126 126 the calorimeter from the Magnel Laboratory at Ghent University
Sand 1/3 104 104 104 [22].
Limestone 2/6 311 311 311 For the calorimetry tests, the initial temperature h0 of the con-
Limestone 6/10 438 438 438
crete specimens was equal to 20 °C. The test duration was about a
Limestone 10/14 415 415 415
week. Beyond that period, the temperature of the sample reached
1014 A. Darquennes et al. / Construction and Building Materials 40 (2013) 1012–1020
Fig. 1. Adiabatic calorimeter and scheme of a cross section with a concrete sample (1), an insulating air layer (2) and a fluid circulation (3) (dimensions in mm).
its maximal value. The cumulative liberated heat Q can be calcu-
lated from the temperature gradient using Eq. (1) [23,24]. In this
relation, the specific heat of concrete cc was kept constant and
equal to 1000 J/kg °C [24]. In reality, this parameter varies with
the advancement of the hydration reaction, the temperature and
the cement type [25,26]. For the studied concrete mixtures, the de-
crease in specific heat with the advancement of the hydration reac-
tion was counterbalanced by the temperature increase during the
adiabatic test [25]. The choice of a constant value for the specific
heat is therefore considered reasonable. Notice that concrete
density also changes with the hardening.
q mentary results to characterize the slag effect on the nature and
Q ðtÞ ¼ cc ðhðtÞ  h0 Þ
C
where q is the density (kg/m3) and C is the cement content (kg/m3).
3.2. Thermogravimetry
Mortar samples from the concretes were analysed using Differ-
ential Thermal Analysis (DTA) and Thermogravimetry (TGA). The
samples were kept at 20 °C and 90% relative humidity (RH) until
the stop of the hydration. This was carried out using two solvents
(ethanol and ether) at different ages: 3, 6, 9 and 24 h; 2, 3, 7, 28, 90
and 365 days. Before the test, the samples were crushed. The tests
were performed under helium atmosphere over the temperature
range 20–1000 °C with a heating rate of 10 °C/min.
From these experiments, the portlandite (Ca(OH)2) and chemi-
cally bound water (w) contents were determined using the sample
mass loss Dm(t) at the temperature intervals 400–600 °C (Eq. (2))
and 145–1000 °C (Eq. (3)) respectively. The temperature threshold
between the evaporation of free water and the beginning of the
chemically bound water departure was equal to 145 °C. The mass
loss between 600 °C and 880 °C corresponds to the decarbonation
of CaCO3.
jDm400 C!600 C ðtÞj MCaðOHÞ2
mCaðOHÞ2 ðtÞ ¼  ð2Þ
mc M H2 O
jDm145 C!1000 C ðtÞj  jDm600 C!880 C ðtÞj
wðtÞ ¼
mc
where mc is the cement mass in the mortar sample from concrete
(kg), MCaðOHÞ2 and MH2 O are the portlandite and water molar mass
(kg/mol) respectively.
3.3. SEM
Concrete fracture surfaces were analysed by scanning electron
microscopy (SEM). A JEOL 6100 microscope was used to compare
the morphology of the hydration products at 2, 3, 7 and 28 days.
Before the SEM tests, the samples were coated with carbon as con-
ducting material. The purpose of these tests was to obtain supple-
ð1Þ the evolution of the hydration products.
4. Experimental results and discussion
4.1. Hydration process of slag cement concretes
4.1.1. Evolution of the heat flow
The advancement of the hydration reaction can be observed by
looking at the evolution of the heat flow (first derivative of the
cumulative liberated heat curve). For the studied concrete mix-
tures, it exhibited four stages: an initial, a dormant, an acceleration
and a deceleration stage (Fig. 2).
The initial period is characterized by a first high peak related to
heat dissolution. Then, the hydration reaction goes through a dor-
mant period characterized by a minimal heat flow. This phase,
named often in the literature ‘‘induction period’’, is longer for
CEM III/B (6.67 h) than for CEM III/A (4.5 h) and CEM I (5.25 h)
which behave in a similar way. During this phase, no reaction
seems to take place. Nevertheless, a layer of calcium silicate hy-
drates (C–S–H) is formed superficially around the cement grains
[27] and the calcium concentration increases progressively. This
last observation was also confirmed by resistivity measurements
[28].
After the initial period, the setting process is initialized and the
acceleration period begins. The third phase starts when the con-
centration of Ca2+ and OH ions in the solution becomes critical.
The ions saturation causes the precipitation of portlandite (CH)
ð3Þ
and the formation of new hydration products (C–S–H and ettring-
 A. Darquennes et al. / Construction and Building Materials 40 (2013) 1012–1020 1015

Fig. 2. Heat flow evolution. Fig. 3. Chemically bound water evolution.

ite). It ends at the second peak that appears at 14.58 h, 20.25 h and Table 5
27.9 h for CEM I, CEM III/A and CEM III/B. However, the heat flow Portlandite content (%).
evolution of CEM III/B shows a change in the slope at about Age (days) CEM I CEM III/A CEM III/B
13.5 h corresponding to the beginning of the acceleration period
0.25 5.1 3.7 4.2
of the pozzolanic reaction [3]. Notice that the maximal heat flow 1 15.3 8.5 4.4
is lower for the slag cement concretes than for CEM I: it is equal 2 19.1 13.7 7.5
to 13.95 J/gh, 8.98 J/gh and 6.49 J/gh for CEM I, CEM III/A and 3 19.2 16.7 8.2
CEM III/B respectively. This phase is followed by the deceleration 7 19.3 16.9 11.9
28 19.5 17.1 15.1
and steady state periods during which the hydration rate is
relatively low.

4.1.2. Formation of hydration products

As mentioned previously, two experimental techniques were
used to analyse the formation of hydration products: thermogravi-
metry and SEM. The first one allows quantifying the evolution of
the chemically bound water (w) and the portlandite (Ca(OH)2).
Chemically bound water comes from portlandite, C–S–H gel,
ettringite and other hydrates. The second one is useful to charac-
terize the formation and morphology of the hydration products.
During the first day, the chemically bound water content
evolves faster for CEM I than for the slag cement concretes (<5%)
(Fig. 3). After the first day, it increases significantly for CEM III/A.
Beyond the third day, the behaviour becomes similar for these
two types of concrete. The acceleration of the hydration process
of CEM III/A is confirmed by the fact that its slag particles are sig-
nificantly hydrated. Portlandite content is also found similar for
CEM I and CEM III/A (Table 5). Consequently, their hydration seems
well advanced at 3 days in comparison with the hydration of CEM
III/B. This observation was also confirmed by SEM. Indeed, the ce-
ment matrix of CEM I and CEM III/A is dense and their main hydra- Fig. 4. Hydration products of CEM I at 2 days.
tion products are C–S–H (Fig. 4) and portlandite (Fig. 5). However,
no portlandite crystals are observable for CEM III/B (Fig. 6). This is
probably related to its low content of portlandite (Table 5) due to analysis showed that the Ca/Si ratio decreased when measure-
its consumption by the pozzolanic reaction to product additional ments were done close to the slag particles. For example, this ratio
C–S–H. was found equal to 2.97, 3.10, 4.70 and 6.65 on the slag particle,
At 7 days, the studied concrete mixtures are characterized by a the slag side, the slag-hydration products interface and on the
similar chemically bound water value (Fig. 3). The portlandite con- hydration products respectively. Therefore, slag dissolution is fol-
tent of CEM III/B increases, but always stays inferior to that of CEM lowed by a migration of its compounds. With the advancement
I and CEM III/A. As for CEM III/A, the large dissolution of slag par- of the hydration, the quantity of hydration products continuously
ticles confirms the acceleration of the hydration reaction of CEM increases, in particular for CEM III/B. This is the reason why the ce-
III/B (Fig. 7). In Fig. 7, it seems that the hydration of slag particles ment matrix of the studied concrete was dense and packed at
is dissolution controlled. This was confirmed by a chemical analy- 28 days.
sis performed at different places of the slag cement concrete ma- The analysis of the formation of hydration products using differ-
trix using the Energy-Dispersive X-ray technique (EDX). The ent experimental techniques shows clearly the slowdown of the
1016 A. Darquennes et al. / Construction and Building Materials 40 (2013) 1012–1020
Fig. 5. Hydration products of CEM III/A at 2 days.
Fig. 6. Hydration products of CEM III/B at 3 days, principally ettringite needles.
Fig. 7. Dissolution of slag at 7 days for CEM III/B.
hydration for slag cement concretes. This difference in the behav-
iour between Portland and slag cement concretes is due to the poz-
zolanic reaction and it is intensified for increasing slag quantities.
It also reveals that slag cement hydration produces the same
hydration products as in Portland cement, but in different
quantities.
4.2. Hydration degree of slag cement concretes
According to the previous experimental results, slag addition
modifies the hydration reaction evolution, particularly during the
first week and for high slag content. To determine its effect on
the evolution of the mechanical properties, it is important to quan-
tify the hydration evolution by means of the hydration degree.
From the evolution of the liberated heat and the chemically
bound water content, the evolution of the hydration degree can
be estimated using Eqs. (4) and (5). The values of the chemically
bound water content w1 and the liberated heat Q1 corresponding
to a complete cement hydration can be found using Eqs. (6) and
(7), expressed in terms of the hydration heat and the chemically
bound water content of the cement components. Nevertheless,
these relations are adequate only for Portland cement concretes.
Bogue’s relations [29], often used to determine the percentage of
cement constituents, are not applicable to cements with mineral
additions. No equivalent relations are proposed for slag cements,
because their hydration is more complex due to the coexistence
of the hydration of clinker and the reaction of the mineral admix-
tures. Notice also that the Bogue method is reported not accurate
and several modifications are proposed in the literature [29,30].
Major points of difference refer to the extent to which the effect
of minor constituents and the burning and cooling processes dur-
ing manufacturing of the cement are taken into account [31].
Moreover, the proposed values of wi and qi differ in the literature
[7]. These differences are due to the applied measuring methods
or to the extent to which the effect of minor compounds and/or
the presence of glass are considered.
wðtÞ
aðtÞ ¼ ð4Þ
w1
QðtÞ
aðtÞ ¼ ð5Þ
Q1
w1 ¼ w1 ð%C3 SÞ þ w2 ð%C2 SÞ þ w3 ð%C3 AÞ þ w4 ð%C4 AFÞ ð6Þ
Q 1 ¼ q1 ð%C3 SÞ þ q2 ð%C2 SÞ þ q3 ð%C3 AÞ þ q4 ð%C4 AFÞ ð7Þ
  a 
s
xðtÞ ¼ x1 exp  ð8Þ
t
where (. . .) is the content of cement major constituents, w1,2,3,4 is
chemically bound water of individual cement constituents, q1,2,3,4
is heat of hydration of individual cement constituents, x is hydra-
tion degree, chemical bound water content or liberated heat, x1 is
ultimate value of the corresponding parameter, s, a is the parame-
ters controlling respectively the intercept and the curvature of the
plot in logarithmic scale.
Several models exist in the literature to determine the liberated
heat and chemically bound water content for complete cement
hydration. De Schutter [32] proposed to consider the value of the
liberated heat ad infinitum as its maximum value. The progress
of the hydration reaction and the evolution of its specific parame-
ters can also be estimated with the Three-Parameter Equation
(TPE) [8,33] (Eq. (8)). In the following, this last approach is adopted
to extrapolate the values of the ultimate hydration heat and
chemically bound water content. The three parameters (x1, s and
a) of the TPE were determined from the experimental tests
(Table 6).
Notice that Eqs. (4) and (5) provide the evolution of the hydra-
tion degree from the beginning of the reaction (0) to the end of the
 A. Darquennes et al. / Construction and Building Materials 40 (2013) 1012–1020 1017

Table 6 this relation and the known value of chemically bound water w ad
Parameters for TPE determined with the chemically bound water content and the infinitum, a more accurate value of Q ad infinitum can be esti-
liberated heat.
mated. These values are equal to 396 J/g, 418 J/g and 380 J/g for
Ultimate Values for chemically Values for liberated CEM I, CEM III/A and CEM III/B respectively and they are slightly
hydration bound water content w(t) heat Q(t) superior to the ones presented in Table 6. Using these values, the
degree (–)
w1 (–) a (–) s (h) Q1 (J/g) a (–) s (h) evolution of the hydration degree based on the cumulative liber-
CEM I 0.72 0.26 0.55 27.34 285 1.75 12.97 ated heat is closer to the one based on the chemically bound water
CEM III/A 0.85 0.31 0.51 50.11 290 0.98 19.40 content [21]. In conclusion, the method based on the chemically
CEM III/B 0.93 0.30 0.47 90.13 237 1.23 23.15 bound water content gives a better estimation of the evolution of
the hydration degree.
According to the previous analysis, the hydration degree evolves
reaction (1, complete hydration). In reality, cement hydration can faster for CEM I than for the slag cement concretes. Using the meth-
stop earlier, after several months depending on the Water/Binder od based on the chemically bound water, the degree of hydration at
(W/B) ratio and the type of curing [34]. For example, the hydration 3 days is found equal to 0.40, 0.37 and 0.31 for CEM I, CEM III/A and
of a Portland cement is generally considered complete for sealed CEM III/B respectively. At 7 days, it is similar for CEM I and CEM III/A.
concretes characterized by a W/B ratio superior to 0.42 [35]. If Notice that the value of the hydration degree of CEM I at 1000 h is
moisture exchanges are taking place between concrete and its sur- close to that proposed by Oh and Cha [38] and Torrenti [39] for a
roundings, this ratio decreases and becomes equal to 0.36 [36]. Portland cement concrete kept at 20 °C. Nevertheless, the ultimate
For concrete with mineral additions, a relation providing the value is higher for the slag cement concretes (Table 6).
ultimate value of the hydration degree (Eq. (9)) was suggested by
Schindler and Folliard [37]. It is based on Mill’s relation [38] taking
4.3. Degree of the pozzolanic reaction
into account that cement hydration stops when the space between
particles becomes too small for deposition of new hydration prod-
The degree of the slag reaction (hydraulic and pozzolanic reac-
ucts. Moreover, this relation considers the effects of mineral addi-
tions) is an important parameter for modelling the hydration reac-
tions. This relation is used hereafter to predict the ultimate
tion of slag cements and their microstructural development. It can
hydration degree of the studied concrete mixtures.
be determined by measuring the quantity of unreacted slag in the
1:031 W paste. Nevertheless, the necessary experimental techniques (e.g.
C
a1 ¼ þ 0:50pFA þ 0:30pslag 6 1 ð9Þ selective dissolution method) are complex and their validity is of-
0:194 þ WC ten questioned [4]. A simple method based on the portlandite con-
where C is the cement, pFA is fly ash content, pslag is the slag content. sumption is followed hereafter to quantify the degree of the
Fig. 8 shows the evolution of the hydration degree for the three pozzolanic reaction.
studied mixtures based on Eqs. (4), (5), and (9). Comparison of the Table 5 shows that the portlandite content increases faster for
different methods (based on the chemically bound water and the CEM I. This is due to the consumption of calcium hydroxide (CH)
liberated heat) shows that the ultimate value of the hydration de- by slag to form new hydration products (e.g. CSH gel) [40]. From
gree is reached earlier (at about 1000 h) when using the cumula- the experimental data (Table 5), it is evident that the CH produced
tive liberated heat. This difference is related to an erroneous by the hydration of slag cement is less than the CH produced by the
estimation of the ultimate value of the cumulative liberated heat Portland cement hydration. Based on this observation, the varia-
due to the short measurement period (up to 7 days). The value of tion of the CH content can be used as a measure of the degree of
chemically bound water w ad infinitum is more accurate as mea- the pozzolanic reaction. The degree of the pozzolanic reaction aslag
surements were realized from 3 h to one year old specimens (Eq. can be estimated from Eq. (10), where the ultimate value of port-
(8)). For each studied mixture, a (slightly) nonlinear relation based landite CH(w1) is calculated using a relation between portlandite
on the experimental results can be determined between the cumu- and the chemically bound water evolution [8] (Fig. 9).
lative liberated heat Q and the chemically bound water w [8]. From CHPC ðwÞ  CHðwÞ
aslag ðwÞ ¼ ð10Þ
CHðw1 Þ

where CHPC is the portlandite content for a Portland cement con-

crete and CH is the portlandite content for a slag cement concrete.
Fig. 10 presents the evolution of the degree of the pozzolanic
reaction as a function of the CEM III/A and CEM III/B hydration de-
gree. The pozzolanic reaction of CEM III/A starts earlier in accor-
dance with the observations of the calorimetry measurements
(Fig. 2). It increases faster for CEM III/B and its ultimate value is
higher. From these results, it appears that the degree of the pozzo-
lanic reaction depends on the slag content. This behaviour is prob-
ably related to the water/clinker ratio. Its larger value for CEM III/B
allows a faster release of OH ions needed for the slag dissolution.
Furthermore, a greater number of slag particles are in contact with
the pores and their alkali solution. As shown by the portlandite
content (Table 5), this process begins earlier (<12 h) and evolves
faster for CEM III/B than for CEM III/A.

5. Application

Fig. 8. Evolution of the degree of hydration determined with the methods based on Two analytical models, the first one based on the Eurocode 2
the chemically bound water content (w) and the liberated heat (Q) evolution. model [41,42] (EC2) and the second one on the models of Rostásy
1018 A. Darquennes et al. / Construction and Building Materials 40 (2013) 1012–1020

Fig. 9. Evolution of the portlandite content as function of the chemically bound

water content. Fig. 11. Evolution of the compressive strength (fc) and the Young modulus (E) as
function of time: experimental results and prediction of EC2 model.

strength (fcm28) and the secant elastic modulus (Ecm28) at 28 days

determined experimentally, and the coefficients depending on the
cement type (Eqs. (11) and (12)). In this study, CEM III/A is consid-
ered as ‘‘normal hardening’’ (s = 0.25) and CEM III/B as ‘‘slow harden-
ing’’ (s = 0.38) according to literature [44]. These parameters alone
are not sufficient to simulate the low evolution of the compressive
strength for CEM III/B, a behaviour related to its low C3S content
[45] and its hydration reaction [46]. Furthermore, the hydration of
slag cement concretes depends on the breakdown and dissolution
of the glassy slag structure by hydroxyl ions released during the
hydration of the clinker and on the alkali content in cement [17].
The advancement of the slag reaction depends strongly on the con-
tent of portlandite produced by the clinker reaction.
Following these observations, it appears that the advancement
of the hydration reaction influences strongly the evolution of the
mechanical properties (i.e. strength and Young modulus). This is
the reason why several authors [11,43,47,48] proposed models
based on the hydration degree in order to predict the evolution
Fig. 10. Evolution of the degree of the pozzolanic reaction.
of the mechanical properties.
rffiffiffiffiffiffi!!
28
[43] and De Schutter [11], are used to predict the evolution of the fcm ðtÞ ¼ fcm28 exp s 1  ð11Þ
t
concrete mechanical properties (compressive strength and stiff-
ness) as a function of time and as a function of the degree of hydra-
 0:3
tion respectively. Predictions are compared to the experimental fcm ðtÞ
Ecm ðtÞ ¼ Ecm28 ð12Þ
results [5]. Compressive strengths and static elastic moduli were fcm28
measured on three cylindrical samples of several ages (diameter
Ø = 100 mm, height h = 200 mm for the strength tests and Eqs. (13) and (14) are used hereafter to predict the evolution of the
h = 350 mm for the moduli tests) kept at 20 °C and 90% R.H. The compressive strength and the secant elastic modulus as functions of
average standard deviation is equal to 0.58 MPa and 0.63 GPa for the hydration degree. Several parameters (Table 7) had to be deter-
the compressive strength and the Young modulus respectively. No- mined from the experimental results: the compressive strength
tice that the slag cement concretes are characterized by a low (m1) and Young modulus (m4) at ultimate hydration degree, the
strength at early age and strength at 28 days exceeding that of hydration degree (m2) corresponding to the development of a sig-
the Portland cement concrete (Fig. 11). A similar evolution is ob- nificant strength [48,49]. The parameters m3 and m5 are fitted from
served for the Young modulus. In this case, the modification of the experimental results. Notice that m2 is located after the final
kinetics appears after the 7th day.
Comparison of the experimental results with the results ob- Table 7
Parameters of Eqs. (13) and (14).
tained with the analytical model based on Eurocode 2 shows that
the mechanical properties of CEM I and CEM III/A are well pre- CEM I CEM III/A CEM III/B
dicted during the first month (Fig. 11). However, the stiffness m1 (MPa) 75.508 78.900 81.980
and compressive strength of CEM III/B are significantly overesti- m2 (–) 0.146 0.156 0.139
mated during the first days. The compressive strength of CEM III/A m3 (–) 0.479 0.569 0.676
m4 (MPa) 48623 48899 49379
and CEM III/B is also significantly overestimated after 100 days. The
m5 (–) 0.203 0.174 0.169
reason is probably related to the model parameters: the compressive
 A. Darquennes et al. / Construction and Building Materials 40 (2013) 1012–1020
Fig. 12. Evolution of the compressive strength (fc) and the Young modulus (E) as
function of the degree of hydration: experimental results and model prediction.
setting of the studied mixtures [5]. Its value is close to that pro-
posed by Taplin [48].
 m3
aðtÞ  m2
fcm ðaÞ ¼ m1
1  m2
 m5
aðtÞ  m2
Ecm ðaÞ ¼ m4
1  m2
With this model, the evolutions of the mechanical properties are
well described for all the studied mixtures (Fig. 12) and they are
found similar. The difference on the behaviour between the Port-
land and the slag cement concretes observed on Fig. 11 representing
the evolutions of the mechanical properties with respect to the age,
is therefore due principally to a difference on the hydration process.
Supplementary tests are however needed to generalize relations 13
and 14 for concretes with different types and percentages of slag
and to propose relations for the parameters m1–5.
6. Conclusions
In this study, an experimental program is performed to investi-
gate the advancement of the hydration reaction for concretes hav-
ing different slag percentages and to quantify the evolution of their
hydration degree. This last parameter allows predicting the evolu-
tion of their mechanical properties. The main results are summa-
rized hereafter:
 Three experimental techniques (calorimetry, thermogravimetry
and SEM) applied on the concrete samples indicate that the
addition of slag leads to a slowdown of the hydration reaction,
particularly during the first week. This behaviour is intensified
with the increase in slag as shown with CEM III/B. The delay
of the hydration of the slag cement concretes is clearly identi-
fied on their heat flow curve. The hydration products of slag
cement concretes are similar to that of the Portland cement
concrete, but their quantities vary.
 Based on the measurement of the chemically bound water and
the liberated heat value, the evolution of the hydration degree
can be predicted for slag cement concretes using the Three
Parameter Equation. The method based on the chemically
bound water seems to be more adapted when measurements
are realized on long lasting experiments.
1019
 For the tested specimens the hydration degree evolved faster for
the Portland cement concrete at early age. This behaviour chan-
ged at long term and the final value of the hydration degree
increased with the slag content. The evolution of the hydration
degree of slag, determined from the evolution of portlandite,
was influenced by the slag content. It evolved faster and its final
value was higher when the slag content increased. It is related
to the water/clinker ratio of the studied concrete mixtures.
 The Eurocode 2 model allows determining the evolution of the
compressive strength and the elastic modulus of CEM I and CEM
III/A during the first 28 days. For an important slag content (e.g.
71%), the mechanical properties are overestimated at early age.
This is due to the fact that the model does not take into account
the pozzolanic reaction of slag and its dependence on the clin-
ker reaction. The use of a model based on the evolution of the
hydration degree resolves this problem. With this type of
model, it appears that the differences in the evolution between
the mechanical properties of Portland and slag cement con-
cretes are principally due to their hydration process. However,
further results are needed to propose relations valid for con-
cretes with different types and contents of slag.
Acknowledgements
This research is partially financed by the Belgian National Foun-
dation for Scientific Research (FRFC), which is gratefully acknowl-
ð13Þ
edged. The authors would also like to thank Professor Marie-
Paule Delplancke-Ogletree for her valuable contribution to this
study.
ð14Þ
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