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31 st Cement and Concrete Science Conference Novel Developments and Innovation in Cementitious Materials 12-13 September 2011 Imperial College London, United Kingdom

Paper Number XX

Early hydration of tricalcium silicate

A. Bazzoni 1,2 , M. Cantoni 2 and K. Scrivener 1

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 C 3 S 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.

1. INTRODUCTION

Recent work in geochemistry [1] has shown that the mechanism of dissolution of minerals changes significantly with the undersaturation of the solution and the defect density of the crystal. Several models have been proposed to explain the mechanism of hydration at early age. Juilland et al. [2] proposed a model to explain the mechanism of hydration at early age, based on the crystal dissolution theory: the formation of crystallographically controlled etch pits is a prominent feature of mineral surfaces. The existence of these etch pits indicates that the process at the surface of certain minerals controls the kinetics of dissolution and diffusion plays a secondary role. According to the model [2], the early mechanism of hydration takes place in three steps. When alite is in first contact with water, there is a fast dissolution and hydroxylation of the surface. A selective dissolution at defects and creation of etch pits starts. As the concentration of calcium ion in water increases, the undersaturation coefficient decreases. Second, there is a slow dissolution until the calcium ion concentration 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 (Ca 3 SiO 5 , C 3 S) is known to undergo 7 polymorphs modifications between room temperature and 1500°C. These modifications are reported to occur following the

sequence: T 1

M 2

R, with T = triclinic, M =

following the sequence: T 1 M 2 R, with T = triclinic, M = T 3
following the sequence: T 1 M 2 R, with T = triclinic, M = T 3
following the sequence: T 1 M 2 R, with T = triclinic, M = T 3

T 3

the sequence: T 1 M 2 R, with T = triclinic, M = T 3 T
the sequence: T 1 M 2 R, with T = triclinic, M = T 3 T

T 2

M 1

T 1 M 2 R, with T = triclinic, M = T 3 T 2 M

M 3

1

monoclinic and R = rhombohedral [3]. Certain of these polymorphs can be stabilized be introducing foreign ions in the structure. For example, Stephan et al. [4]-[6] have shown that magnesium oxide (MgO), aluminum oxide (Al 2 O 3 ) and iron oxide (Fe 2 O 3 ) can stabilize different polymorphs at different concentration. They have evidenced that the reactivity of the different products vary with the type and amount of foreign ions. Thomson [7] et al. studied the effect of Mg ion incorporation on both structure and reactivity. They investigated the effect of annealing on the total amount of Mg incorporated. They concluded first that at a level of 1.35 wt% of Mg incorporation a transition between triclinic and monoclinic form occurs and that the reactivity increases close to this transition. Second that after annealing Mg is expelled from the lattice. The effect of ion incorporation can be modified by heat treatment.

This work has as an objective a better understanding of the mechanisms of hydration at early age. The early dissolution behavior is dramatically affected by the defect density of the crystal. The role of crystal structure and crystal defects will be further investigated in order the study the reactivity of alite.

2. EXPERIMENTAL METHOD

2.1 Synthesis

Pure tricalcium silicate (Ca 3 SiO 5 , C 3 S) was synthetised in the lab. from a 3:1 stoichiometric mixture of calcium carbonate (CaCO 3 ) and high purity quartz powder (SiO 2 ). 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 C 3 S:

the different particle size distributions of pure C 3 S: Figure 1: Particle size distribution of

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

 

650 °C

1

hour

 

C3S

6

hour

quench

850°C

 

1h

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.

3. RESULTS AND DISCUSSION

3.1 Effect of thermal treatment

The effect of the annealing time on the crystalline structure of pure C 3 S is given in Figure 2:

structure of pure C 3 S is given in Figure 2: Figure 2: Effect of the

Figure 2: Effect of the duration of the thermal treatment at 650°C on the crystal structure of pure

C 3 S

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

C 3 S:

[3] of the triclinic polymorph of pure C 3 S: Figure 3: Effect of the duration
[3] of the triclinic polymorph of pure C 3 S: Figure 3: Effect of the duration

Figure 3: Effect of the duration of the thermal

treatment at 650°C on the crystal structure of pure

C 3 S

The polymorph of the pure C 3 S is not changed after the thermal treatment.

The effect of annealing temperature for 1 hour of treatment on the crystalline structure of pure C 3 S 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 thermal treatment on the crystal

Figure 4: Effect of the temperature for 1 hour of thermal treatment on the crystal structure of pure

C3S

of thermal treatment on the crystal structure of pure C3S Figure 5: Effect of the temperature
of thermal treatment on the crystal structure of pure C3S Figure 5: Effect of the temperature

Figure 5: Effect of the temperature for 1 hour of

thermal treatment on the crystal structure of pure

C 3 S

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 C 3 S 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 bigger peak can correspond to a variation of the 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 C 3 S is given in Figure 6 and Figure 7:

of the pure C 3 S is given in Figure 6 and Figure 7: Figure 6:

Figure 6: Effect of the duration of the thermal treatment at 650°C on the reactivity of pure C 3 S

3

treatment at 650°C on the reactivity of pure C 3 S 3 Figure 7: Effect of

Figure 7: Effect of the temperature for 1 hour of thermal treatment on the reactivity of pure C 3 S

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

induction

treatment

effect of thermal periods:

on

the

the induction treatment effect of thermal periods: on the Figure 8: Effect of the duration of

Figure 8: Effect of the duration of the thermal treatment at 650°C on the induction period

of the thermal treatment at 650°C on the induction period Figure 9 : Effect of the

Figure 9 : Effect of the temperature for 1 hour of 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 temperatures. Secondly the heat produced during the induction period is lower for treated samples, with the same dependence to the duration and the 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 C 3 S 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 C 3 S 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 C 3 S 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 C 3 S, 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 C 3 S with Mg and Al in order to evaluate the impact of these ions on the reactivity of alite.

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[1]

Lasaga A.C. and Lüttge. A., Science,

291:2400–2404, 2001 Juilland, Early hydration of cementitious systems, these EPFL, 2009 H.F.W.Taylor, Cement Chemistry. Thomas Telford

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4

[7]

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[8]

of The American Ceramic Society 58:54-57, 1975 Bigaré M., Guinier A., Mazieres C., Regourd M., Yannaquis N., Eysel W., Hahn T., Woermann E., J. Amer. Ceram. Soc 50 :609-619, 1967