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31 Cement and Concrete Science Conference Paper Number XX

Novel Developments and Innovation in Cementitious Materials
12-13 September 2011
Imperial College London, United Kingdom

Early hydration of tricalcium silicate

1,2 2 1
A. Bazzoni , M. Cantoni and K. Scrivener
1
Laboratory of construction materials, Swiss federal Institute of Lausanne
2
Interdisciplinary centre for electron microscopy, Swiss federal Institute of Lausanne

ABSTRACT

Recent studies in geochemistry [1] have shown that the mechanism of dissolution of minerals changes
significantly with the undersaturation of the solution and the defect density of the crystal. Based on model
proposed by Juilland [2], the mechanism of early hydration is further investigated.
In this work, reactivity of pure C3S was investigated using from the isothermal calorimetry. Heat treatment
was performed to evaluate the impact of both crystalline structure and defects on reactivity. Structural
modifications were followed by X-Ray powder diffraction.

monoclinic and R = rhombohedral [3]. Certain of

these polymorphs can be stabilized be introducing
1. INTRODUCTION
foreign ions in the structure. For example, Stephan
Recent work in geochemistry [1] has shown that et al. [4]-[6] have shown that magnesium oxide
the mechanism of dissolution of minerals changes (MgO), aluminum oxide (Al2O3) and iron oxide
significantly with the undersaturation of the solution (Fe2O3) can stabilize different polymorphs at
and the defect density of the crystal. Several different concentration. They have evidenced that
models have been proposed to explain the the reactivity of the different products vary with the
mechanism of hydration at early age. Juilland et al. type and amount of foreign ions. Thomson [7] et al.
[2] proposed a model to explain the mechanism of studied the effect of Mg ion incorporation on both
hydration at early age, based on the crystal structure and reactivity. They investigated the
dissolution theory: the formation of effect of annealing on the total amount of Mg
crystallographically controlled etch pits is a incorporated. They concluded first that at a level of
prominent feature of mineral surfaces. The 1.35 wt% of Mg incorporation a transition between
existence of these etch pits indicates that the triclinic and monoclinic form occurs and that the
process at the surface of certain minerals controls reactivity increases close to this transition. Second
the kinetics of dissolution and diffusion plays a that after annealing Mg is expelled from the lattice.
secondary role. According to the model [2], the The effect of ion incorporation can be modified by
early mechanism of hydration takes place in three heat treatment.
steps. When alite is in first contact with water,
This work has as an objective a better
there is a fast dissolution and hydroxylation of the
understanding of the mechanisms of hydration at
surface. A selective dissolution at defects and
early age. The early dissolution behavior is
creation of etch pits starts. As the concentration of
dramatically affected by the defect density of the
calcium ion in water increases, the undersaturation
crystal. The role of crystal structure and crystal
coefficient decreases. Second, there is a slow
defects will be further investigated in order the
dissolution until the calcium ion concentration
study the reactivity of alite.
reaches the supersaturation with respect to
portlandite. The dissolution processes by step
retreat, the lateral opening of etch pits. Finally, at
the supersaturation level, there is a massive
precipitation of hydrates. From this point, the
growth of hydrates controls the rate of dissolution.
Pure tricalcium silicate (Ca3SiO5, C3S) is known to
undergo 7 polymorphs modifications between
room temperature and 1500°C. These
modifications are reported to occur following the
sequence: T1 T2 T3 M1 M2
M3 R, with T = triclinic, M =
1
2. EXPERIMENTAL METHOD 3. RESULTS AND DISCUSSION
2.1 Synthesis 3.1 Effect of thermal treatment
Pure tricalcium silicate (Ca3SiO5, C3S) was The effect of the annealing time on the crystalline
synthetised in the lab. from a 3:1 stoichiometric structure of pure C3S is given in Figure 2:
mixture of calcium carbonate (CaCO3) and high
purity quartz powder (SiO2). Powders were
homogenized 24 hours in water and the blend was
dried at 100°C for 24 hours. The dried mass was
then pressed into pellets and burned at 1600°C
during 10 hours. The pellets were quenched in the
air after heating and finally grounded into powder.
The Figure 1 shows the different particle size
distributions of pure C3S:

Figure 2: Effect of the duration of the thermal

treatment at 650°C on the crystal structure of pure
C 3S
The treatment seems to have no impact on the
general crystal structure. Figure 3 shows detail of
the XRD spectra for the two specific windows of
identification [3] of the triclinic polymorph of pure
C3S:

Figure 1: Particle size distribution of pure C3S

2.2 Annealing
Samples of powder were annealed according to
parameters given in Table 1:

Sample Temperature Time Cooling

1  hour Figure 3: Effect of the duration of the thermal
650  °C
C3S 6  hour quench treatment at 650°C on the crystal structure of pure
850°C 1h C 3S

Table 1: Annealing parameters

The effect of the annealing on the crystalline
structure was studied by X-Ray powder diffraction.
The reactivity of the treated powders was followed
by differential calorimetry.
The polymorph of the pure C3S is not changed
after the thermal treatment.
The effect of annealing temperature for 1 hour of
treatment on the crystalline structure of pure C3S is
given in Figure 4. The detail of the XRD spectra for
the two specific windows of identification of the
triclinic polymorph in Figure 5:

2
 Figure 4: Effect of the temperature for 1 hour of Figure 7: Effect of the temperature for 1 hour of
thermal treatment on the crystal structure of pure thermal treatment on the reactivity of pure C3S
C3S
The effect of thermal treatment can be identified in
two points: the length of the induction period and
the height of the main hydration. Since no
structural modification could be identify in the XRD
spectra, the slight increase of the main hydration
peak can be attributed to the slight increase of the
peak intensities in the XRD spectra.
Figure 8 and Figure 9 show more in detail the
effect of thermal treatment on the induction
periods:

Figure 5: Effect of the temperature for 1 hour of

thermal treatment on the crystal structure of pure
C 3S
Again, the treatment seems to have no impact on
the crystal structure and the form of the polymorph.
According to the XRD spectra, no significant
structural modification of the C3S could be
observed, neither for the duration of treatment, nor
for the temperature of thermal treatment. However
the treated samples exhibit slightly higher peaks.
As each peak in the X-Ray powder diffraction
spectra corresponds to a family of planes, this Figure 8: Effect of the duration of the thermal
bigger peak can correspond to a variation of the treatment at 650°C on the induction period
unit cell parameters [8]. This increase of the peak
can also be attributed to a modification of the
crystallites size. The impact of the thermal
treatment on the reactivity of the pure C3S is given
in Figure 6 and Figure 7:

Figure 9 : Effect of the temperature for 1 hour of

Figure 6: Effect of the duration of the thermal
treatment at 650°C on the reactivity of pure C3S
3
thermal treatment on the induction period
There are three modifications of the induction
period. Firstly after thermal treatment, the induction
period is extended. This effect is more marked for
longer duration of thermal treatment and for higher [7] Thomson R.A., Killoh D.C., Forrester J.A., Journal
temperatures. Secondly the heat produced during of The American Ceramic Society 58:54-57, 1975
the induction period is lower for treated samples, [8] Bigaré M., Guinier A., Mazieres C., Regourd M.,
with the same dependence to the duration and the Yannaquis N., Eysel W., Hahn T., Woermann E., J.
Amer. Ceram. Soc 50 :609-619, 1967
temperature of treatment. Ultimately at the end of
the induction period, the bump tends to disappear.
According to crystal dissolution theories, the longer
induction period and the lower heat released can
be attributed to lower dissolution rate during the
step retreat regime. Indeed, the thermal treatment
has as an effect to reduce the defect density on
the surface of C3S grains, which results in a lower
etch pit density in the first stage of dissolution,
which results in a slower step retreat process. Also
when the dissolution is controlled by step retreats,
slower dissolution results in a lower evolution of
heat. The same phenomena were observed by
Juilland [2] on heat treated alite.
The bump in the acceleration part is attributed to a
massive precipitation of portlandite when the
calcium concentration reaches the supersaturation
degree of portlandite. For untreated samples,
dissolutions rates are high and the calcium
concentration reaches rapidly the supersaturation
degree. When C3S is thermally treated, dissolution
rates decrease and the supersaturation degree is
reached more slowly. There is a massive
precipitation of portlandite, but the system is more
in an equilibrium state. However, this is speculative
and requires further investigation.

4. CONCLUSION
The effect of thermal treatment on the crystal
structure and the reactivity of pure C3S have been
investigated. It has been shown that the thermal
treatment at various temperatures and duration
has a little influence on the crystal structure of pure
C3S, but has an influence on the overall reactivity.
The major modification is in the induction period.
This modification of the induction period was
attributed to a lower dissolution rate, due to a
slower step retreat process.
The same investigations are running for doped C3S
with Mg and Al in order to evaluate the impact of
these ions on the reactivity of alite.

REFERENCES
[1] Lasaga A.C. and Lüttge. A., Science,
291:2400–2404, 2001
[2] Juilland, Early hydration of cementitious systems,
these EPFL, 2009
[3] H.F.W.Taylor, Cement Chemistry. Thomas Telford
nd
2 edition, London, 1997
[4] Stephan D. and Wistuba S., J. Eur. Ceram. Soc.
26:141-148, 2006
[5] Stephan D, Njooh Dikoudou S., Raudaschl-Sieber
G., Materials and Structures 41:1729-1740, 2008
[6] Stephan D, Njooh Dikoudou S., Raudaschl-Sieber
G., Thermochimica Acta 472:64-73, 2008