15th International Congress on the Chemistry of Cement

Prague, Czech Republic, September 16–20, 2019

A simple model to predict C3S hydration kinetics

Frank Bellmann1,a, Jürgen Neubauer 2,b, Horst-Michael Ludwig1,c, Christoph Naber 2,d

1Institute for building materials, Bauhaus University Weimar, Weimar, Germany

2Department of mineralogy, University Erlangen-Nürnberg, Erlangen, Germany

[email protected]
[email protected]
c [email protected]
[email protected]

ABSTRACT
The hydration of tricalcium silicate with water is essential for the application of cements. Understanding
its basic mechanisms will allow its manipulation in a later stage. Currently existing models such as
C3S dissolution theory and C-S-H nucleation/growth theory are integrated in a computer code. The
model predicts rates of reaction, pore solution chemistry, interfacial dissolution- and growth rates, C3S
and C-S-H particle size, and surface area evolution during the first 24 hours of hydration. This model
approach is strictly based on chemical laws and does not rely on fitting parameters. The results are
compared to experimental data obtained in a collaborative study.
The simulation model captures C3S hydration kinetics qualitatively and quantitatively. Experimentally
obtained data for rates of reaction, pore solution chemistry, and BET are predicted within the
uncertainty of the experimental methods. It can be shown that different kinetic mechanisms are
operating simultaneously. The limiting kinetic step in the early stage of reaction is the nucleation and
growth of C-S-H, whereas the C3S dissolution is rate-limiting at later stages of hydration. This
underlines the experimental observation that the early hydration of C3S can be accelerated by the
addition of active C-S-H seeds.
The current model can be applied to the reaction of pure tricalcium silicate whereas the presence of
other phases such as tricalcium aluminate or gypsum strongly affects the reaction pattern. This results
in a modification of the basic mechanisms that will be integrated into the model in a later stage.
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

1. INTRODUCTION

There is a long tradition of experimental investigations related to tricalcium silicate hydration and this
process can be summarized by equation 1. Tricalcium silicate reacts with water to calcium hydroxide
and C-S-H which has a calcium/silicon-ratio of approximately 1.7 and a variable water content
depending on the drying conditions.

Ca3SiO5 + 3.9 H2O  1.7CaOSiO22.6H2O + 1.3 Ca(OH)2 (1)

It is generally agreed that a period of low chemical activity (called dormant period or induction period)
is observed before the main hydration period (Figure 1). Another peculiarity is the fact that the degree
of hydration after the main hydration period is relatively low (approximately 30-50% depending on the
fineness and other parameters). A number of models were suggested to explain the existence of an
induction period and most of these kinetic models fall into two main categories (BULLARD ET AL.). One
group of kinetic models assumes that the dissolution of tricalcium silicate is the critical kinetic step
during the early hydration and that a slow dissolution limits the reaction during the induction period.
The second group of models attributes the observation of an induction period to the slow nucleation
and growth of calcium silicate hydrate (C-S-H) as the main reaction product. This involves also the
formation of a passivation layer by an intermediate phase at the surface of tricalcium silicate. Both
hypotheses are tested in the current simulation to derive information about the basic mechanisms
governing the hydration kinetics of C3S.

A quantitative test of the aforementioned models requires knowledge of a number of kinetic properties
such as the interfacial dissolution rate of tricalcium silicate and the interfacial growth rate of C-S-H.
These parameters have to be combined with data for the specific surface area of tricalcium silicate
and C-S-H as a function of time and the surface area values depend on details of the microstructure.

15
rate [mW/g]

10
main hydration
period

5
induction
period

0
0 5 10 15 20
time [h]

Figure 1. Analysis of C3S-hydration kinetics by calorimetry

2. DETAILS OF THE COMPUTATION

It was assumed that pure tricalcium silicate with traces of free lime reacts with water at a water/solid-
ratio of 0.50. It is well known that the hydration of tricalcium silicate is a dissolution-precipitation
process. The kinetics of both steps depends on solution composition and surface area as discussed
by LASAGA:

a
n
rate  k0  Amin  e Ea / RT  aHH  g( I )  ni
 f (  r G)

i (2)
i
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

In this equation, k0 is a constant, Amin the surface available for dissolution or precipitation, Ea the
activation energy, I is the ionic strength of the solution, a the activity of an ion i and rG the change in
Gibbs free energy. The parameters related to solution composition can be integrated in an interfacial
rate (rinterface) which simplifies the aforementioned equation to:

rate  Amin  rinterface (3)

The interfacial rates for dissolution and precipitation depend on solution composition which is
changing during hydration. This implies that the solution composition is an important parameter that
needs to be included in a simulation of hydration kinetics. It is assumed here that the sample of
tricalcium silicate contains traces of free lime which results in a calcium concentration of approximately
12 mmol/l in the pore solution due to the dissolution of free lime. The calcium ion concentration is
increasing during hydration as tricalcium silicate dissolves and C-S-H with a calcium/silicon-ratio of 1.7
is formed indicating that some calcium is accumulated in solution until it can precipitate in the form of
calcium hydroxide. The silicon concentration in solution is much lower than the calcium concentration.
It was first demonstrated by JENNINGS that the solution composition in the first hours is clustered
around a curve B in the phase diagram. This was corroborated and extended in a recent paper by
SOWOIDNICH ET AL. and curve B was fitted by the following equation:


Si µmol/l   1.8856  1  e0.0128Ca mmol/l  
2.1366
(4)

According to equation 4, silicon concentration can be predicted from the calcium concentration during
the first hours of hydration including the induction period and also the first part of the main hydration
period as long as the degree of hydration is relatively low. However, a deviation from curve B is
observed at higher degrees of hydration and the solution composition gradually decreases from curve
B to curve A as shown by DAMIDOT & NONAT. Curve A is the solubility curve of C-S-H and a number of
models is available to fit the solubility of this hydration product. Our computations are based on the
solubility constants and Ca/Si-ratios for a model including 3 different compositions currently
established by BULLARD & SCHERER.

β1= {Ca2+}0.80  { H3SiO4-}  {OH-}0.60/1.4310-7 (5)

β2= {Ca2+}1.00  { H3SiO4-}  {OH-}1.00/1.5910-9 (6)
β3= {Ca2+}1.81  { H3SiO4-}  {OH-}2.62/2.4710-14 (7)
βtot= β1 + β2 + β3 (8)

The aforementioned equations can be used to predict the silicon concentration as long as the solution
composition is resting on curve B (metastable hydration product) or curve A (stable hydration product)
but much less data is available for the transition from curve B to A during the main hydration period.
We have assumed that the silicon concentration and thus the supersaturation decreases after the
maximum of the main hydration period and this decrease is connected to the degree of C3S surface
covering. It is clear that such assumptions strongly affect the solution composition and thus the
interfacial dissolution rate of C3S and the interfacial growth rate of C-S-H as these depend strongly on
solution composition. Any shortcoming in our assumption about the transition of curve B to curve A will
thus also affect the predicted rates of reaction and need to be corrected as soon as more experimental
data about the evolution of solution composition during the main hydration period is reported from
experimental studies.

2.1 tricalcium silicate dissolution

The dissolution of the starting material depends on the interfacial dissolution rate and the surface area
of tricalcium silicate (equation 3).

The surface area of the initial material was calculated from the particle size distribution analyzed by
laser light scattering (Figure 2). Such data applies only to the initial state before hydration and the
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

surface area changes during hydration as a result of particles size reduction, surface roughening and
deposition of hydration products on the surface. The reduction of the particle diameters during
hydration was addressed by the shrinking core model. This implies that the thickness of the dissolved
layer is the same for all particles independent from the initial particles size. It is assumed that all
particles have a spherical shape which is maintained during hydration with a reduction of the size of
the anhydrous core. The degree of hydration can be computed from the ratio of the volume of the
dissolved shell to the initial volume of the particle for a given shell thickness and the result summed for
all particle sizes. Repeating this computation for a number of shell thicknesses provides a plot of
remaining C3S surface area relative to the degree of hydration as shown in Figure 3. The data points
in this figure were fitted by equation 9 which applies to the sample with the particles size distribution
from Figure 2 and was integrated in the kinetic model to account for the reduction of the surface area
of tricalcium silicate during hydration. It is evident that this result is based on computations and
relevant experimental data describing such an evolution has not been reported yet. The data in Figure
3 is related to the total surface area of tricalcium silicate during hydration but SEM studies have shown
that the surface becomes progressively covered by C-S-H during the main hydration period which
reduces the surface available for dissolution. It can be assumed that only a fraction of the total surface
area is uncovered and can dissolve freely. The degree of surface covering was estimated by NABER ET
AL. as a function of hydration time. Initially, the surface is fully uncovered as no C-S-H is present after
mixing with water. The share of free surface decreases during the accelerating period until the C3S
surface is fully covered at a time that is close to the peak of the main hydration period. This is
addressed in the simulations by computing a degree of surface covering which is used to reduce the
surface area available for dissolution.

5 100

80
4
concentration [Vol.-%]

surface area [%]

60
3

40
2
20

1
0
0 10 20 30 40
0
degree of hydration [%]
0 10 20 30 40 50
particle diameter [µm]

Figure 2. particle size distribution of Figure 3. decrease of the surface area during
tricalcium silicate hydration predicted from the shrinking core
model

relative surface area %  100  e 0.071degree of hydration(%) (9)

The last parameter affecting the evolution of the surface area during hydration (surface roughening)
was not considered in the computations as there is no reliable experimental data available for
simulation. Based on particle size reduction and surface covering, the evolution of the surface
available for dissolution was computed. The rate of reaction can be calculated when the surface area
at a given time is multiplied by the interfacial dissolution rate according to equation 3. This interfacial
dissolution rate depends primarily on solution composition which can be expressed in form of an ion
activity product for tricalcium silicate:

ln(IAPC3S) = ln({Ca2+}³  {H3SiO4-}  {OH-}5) (10)

The impact of solution composition and thus of IAP C3S was analyzed experimentally and the results
displayed in Figure 4 suggest an almost linear trend in the range of solution compositions relevant for
hydration of tricalcium silicate and can be approximated by the following equation:
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

rinterface,diss = 0.3  ln(IAPC3S) + 12 (11)

In summary, a combination of equations 3, 4 and 9-11 allows a prediction of the dissolution rate for
each time step during hydration and this computation is based on the following assumptions:

 The surface area of tricalcium silicate decreases due to particle size reduction (shrinking core
model) and surface covering (formation of C-S-H).
 The interfacial dissolution rate depends from the solution composition.

The computation provides the dissolution rate of tricalcium silicate in units of µmol/(sgC3S) which can
be translated into rates observable by calorimetry using a value of 124 kJ/mol for the heat of
hydration.

2.2 C-S-H growth

Similar to dissolution, also the growth of C-S-H depends on the surface area and the interfacial rate
(equation 3). The surface area of C-S-H is increasing from virtually zero after mixing with water to
relatively high values exceeding 3 m²/g during the main hydration period. SEM investigations have
indicated that the shape of the hydration products formed during the accelerating stage can be
approximated by a semi-ellipsoid which is used in these simulations. This refers to the outer product,
whereas the formation of a gap between the dissolving C3S-grain and the outer product C-S-H is not
considered here. It is clear that such a process is highly relevant for the kinetics after the first day but
there is hardly any data or model available to describe the transport of water and ions through the
inner product layer and it is thus not included in this simulation.

40
Ca=12 mmol/L
35 Ca=20 mmol/L
growth rate [nmol C-S-H/(m²s)]

Ca=21 mmol/L
30 Ca=28 mmol/L

25

20

15

10

0
0 10 20 30 40
βtot

Figure 4. Interfacial dissolution rates of Figure 5. Analysis of C-S-H growth rates at

tricalcium silicate depending on solution different calcium concentrations based on
composition (reprinted from BELLMANN ET AL. experimental data from BELLMANN & SCHERER
2015 with permission from Elsevier)

The surface area of the outer product C-S-H particles depends on the size and number of these semi-
ellipsoids. Both parameters are increasing with time. The number of C-S-H particles depends on the
nucleation rate of C-S-H which was estimated in an experimental study of tricalcium silicate hydration
suggesting a number of approximately 135 particles/(hµm²). Although being a rough estimation, this
nucleation rate can be used to predict the number of C-S-H particles present at a given time step
relative to the surface area of tricalcium silicate. The volume and surface area of the individual semi-
ellipsoids is calculated from the radius and the length of the C-S-H particles which is increasing during
hydration. It is observed by SEM that the length grows much faster than the radius which is
considered here by a change of the aspect ratio (radius/length-ratio) linearly in the first hours:

aspect ratio= C-S-H length/C-S-H radius = 1.1  hydration time + 1 (12)

 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

Radius and length are increasing during each time step and this increase was estimated following an
approach suggested by GARRAULT-GAUFFINET & NONAT. The absolute C-S-H growth rate in nmol/time
step and g C3S is computed from the surface area of C-S-H at the beginning of the time step and the
interfacial growth rate. This amount of C-S-H is translated in a volume of C-S-H (227 g/mol, 2 g/cm³)
which is the volume of C-S-H formed in the considered time step. The volume at the end of the time
step is the sum of the initial volume and the volume increase during the time step. Length and radius
of the C-S-H particles at the end of the time step are obtained from the volume at the end of the time
step, the number of C-S-H particles and the aspect ratio. This results in a continuous increase of C-S-
H size, surface area and volume during the acceleration period. These C-S-H particles nucleate and
grow on the surface of tricalcium silicate thus isolating a part of this surface from the surrounding
solution. Absence of homogeneous nucleation of C-S-H directly in the solution is assumed in this
model. The degree of surface covering at a given time step is computed from the number and basal
radius of the C-S-H particles relative to the surface area of tricalcium silicate. It is assumed in this
computation that all C-S-H particles have an identical size and thus represent the mean size of these
semi-ellipsoids.

The interfacial growth rates required in the aforementioned computation are based on a recent
experimental study (Figure 5) and are predicted using 13.

rinterface,growth = 0.013  βtot  [Si] (13)

where βtot is the supersaturation with respect to C-S-H and [Si] is the silicon concentration in solution
in units of µmol/l. As with the dissolution rate, the growth rate is computed in units of nmol/(sgC3S)
which can be translated into calorimetric units by multiplication with the heat of hydration.

Dissolution and precipitation rates are calculated during each time step from initial values for calcium
concentration, C3S and C-S-H surface area, degree of surface cover, number of C-S-H nuclei etc. at
the start of that time step. Both processes change the solution composition and the amount and
surface area of the solid phases during the time step and the modified parameters at the end of the
time step serve as input data for the following time step. Nucleation of calcium hydroxide was
assumed to start at a calcium concentration of 35 mmol/l which is then reducing to 30 mmol/l.

3. RESULTS AND DISCUSSION

The results of the computations can be compared to experimental data and the most important
experimental tool in this regard is calorimetry or related methods providing the evolution of the rate of
reaction over time. Beside reactivity, the results obtained by simulation should match experimental
data for pore solution chemistry, supersaturation, C-S-H surface area, shape and number of C-S-H
particles etc.

The hydration of the tricalcium silicate sample from Figure 2 was simulated and two lines are
computed and plotted in Figure 6 which refer to dissolution and precipitation, respectively. It is evident
that dissolution (dashed line) is much faster than precipitation in the first hours. This is due to the fact
that tricalcium silicate has a high surface area that is not covered by C-S-H implying that C3S can
dissolve very fast. On the other hand, the growth of C-S-H is very slow as the surface area of C-S-H is
very low in the first hours. The concentration of calcium and silicon in the pore solution can rapidely
increase as dissolution is much faster than growth. Dissolution comes to a halt at curve B which is the
solubility of an intermediate hydrate phase (TAYLOR, SOWOIDNICH ET AL., JENNINGS, RODGERS ET AL.,
GUTBERLET ET AL., GARTNER & GAIDIS, NABER ET AL., BELLMANN ET AL. 2010.) which has been termed
product B in the literature. This intermediate hydrate phase forms a protective layer and the solution
concentrations would increase to much higher levels when such a layer would not exist. There is
hardly any chemical activity during the induction period as the precipitation is very slow and the
solution in equilibrium with the intermediate hydrate phase. It can be concluded that the global
hydration process is limited by the slow nucleation and growth of C-S-H in the induction period. When
the main hydration period starts, the precipitation of C-S-H becomes faster as the number and size of
C-S-H is increasing which results in a higher surface area of this hydration product. The C-S-H surface
area is multiplied with the interfacial growth rate according to equation 3 but the latter remains more or
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

less constant in the first hours. This implies that the strong increase in C-S-H surface area is
responsible to the higher growth rates in the main hydration period. The dissolution rate is decreasing
over time as the C3S surface area becomes smaller and covered by C-S-H. As indicated in Figure 6,
dissolution and precipitation rates cross after approximately 10 hours and the precipitation of C-S-H is
faster than the dissolution of C3S after that point. This is based on the fact that the surface area of C-
S-H has strongly grown whereas that of C3S is reduced. It is evident that C3S cannot dissolve fast
enough as C-S-H can precipitate and this slows the whole process down which depends after the
crossing of the curves on the dissolution of C 3S. The faster precipitation can also decrease the
solution concentrations which affects the interfacial rates.

It can be summarized that the simulation results in Figure 6 demonstrate that nucleation and growth of
C-S-H is the critical kinetic step triggering the kinetics during the induction period and up to the
maximum of the main hydration period. After that maximum, the hydration kinetics depends on the
dissolution of C3S as the critical kinetic step during the later stage of the main hydration period. This is
shown in Figure 7 when a simulation curve is shown that consists of two branches from Figure 6. This
is the C-S-H growth branch in the first 10 hours and the C3S dissolution branch after the maximum.
Also plotted in Figure 7 is experimental data related to the hydration of the C3S sample from Figure 2
at a water/solid-ratio of 0.50 showing that the simulated hydration kinetics are in agreement with the
experimental results.

60 30
calorimetry rate from simulation
dissolution
calorimetry rate from QXRD
of C3S
heat release rate [J/(gh)]
heat release rate [J/(gh)]

calorimetry (experimental data)

40 20

20 precipitation 10
of C-S-H

0 0
0 5 10 15 20 0 5 10 15 20
Time [h] Time [h]

Figure 6. Dissolution and precipitation rates Figure 7. Comparing the simulation results to
calculated for the hydration of tricalcium experimental data from the analysis of the
silicate referring to the sample from Fig. 2 degree of hydration by QXRD and calorimetry

There is a high number of simulation studies in the literature that are able to reproduce the calorimetric
curve and show even better agreement than Figure 7. However, the strength of the current model is
that no fitting parameter is involved and other parameters such as solution composition and surface
area are included which have a true physical meaning and can be analyzed. Related data is shown in
Figure 8 and 9 for the evolution of the calcium and the silicon concentrations during hydration at a
water/solid-ratio of 0.50. Hydration starts at a calcium concentration of 12 mmol/l which was adjusted
by the free lime concentration dissolving after contact with water (Figure 8). The calcium concentration
increases over the following hours reaching the critical supersaturation with respect to calcium
hydroxide after approximately 2 hours and the calcium concentration falls rapidly after this nucleation
event and stays constant for the remaining time. This is in agreement with the experimental data
obtained at the same water/solid-ratio but the calcium concentration rises faster than predicted. The
nucleation of portlandite is also reflected by the experimental data. There is a decrease in calcium
concentration after the maximum of the main hydration period which is not included in the simulation
as there is no relevant data or model available for the simulation of calcium hydroxide growth details.

A similar agreement between measured and computed concentration is also observed for silicon
(Figure 9). The very low initial calcium concentration corresponds to a relatively high initial silicon
concentration as evident from the solubility product of the metastable hydrate phase reflected in
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

equation 4. Silicon falls as calcium increases and this pattern is observed in simulation and
experiment. The decrease of the silicon concentration after the maximum of the main hydration period
is related to a change from curve B to curve A in the phase diagram which is difficult to predict as
there is no clear description of such a transition available in the literature in terms of degree of
hydration or surface covering. The latter parameter was used in the present simulation. It can be
summarized that the basic pattern of the evolution of the ion concentration can be predicted by the
simulation but the quantitative agreement can be improved as soon as reliable models for the
aforementioned details become available from experimental studies.

50 150
Ca-concentration [mmol/L]

Si-concentration [mmol/L]
40

100 silicon concentration in simulation

30 silicon concentration in alite paste

20
50
calcium concentration in simulation
10 calcium concentration alite paste

0
0
0 5 10 15 20
0 5 10 15 20
Time [h]
Time [h]

Figure 8. Evolution of the calcium Figure 9. Evolution of the silicon

concentration during hydration concentration during hydration

The supersaturation with respect to C-S-H and the ion activity product for tricalcium silicate can be
computed from the concentrations in Figures 8 and 9 for simulation and experiment. A relatively good
agreement was observed for the concentrations which results in a similar agreement for the
supersaturation with respect to C-S-H (Figure 10) and the ion activity product for C3S (Figure 11).
There is a tendency to a higher supersaturation with respect to C-S-H during the main hydration
period relative to the induction period and the final period which is due to a higher calcium
concentration in the main hydration period and an increasing distance between curves A and B at
elevated calcium concentrations.

40
Time [h]
-38
supersaturation C-S-H

0 5 10 15 20
30

-40
20
ln(IAPC3S)

-42
10
supersaturation CSH in simulation
-44 ion activity product of C3S in simulation
supersaturation CSH in alite paste
0 ion activity product of C3S in alite paste
0 5 10 15 20
-46
Time [h]

Figure 10. Evolution of the supersaturation Figure 11. Evolution of the ion activity product
with respect to C-S-H during hydration of C3S during hydration
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

10 1,5
surface area in simulation

C3S surface area [m²/g sample]

surface area from BET total surface area
surface area [m²/g sample]

8 uncovered surface area

1,0
6

4
0,5

0 0,0
0 5 10 15 20 0 5 10 15 20
Time [h] Time [h]

Figure 12. Evolution of the surface area during Figure 13. Evolution of the surface area of C3S
hydration during hydration

Also the surface area was computed as the sum of the surface area of C-S-H and the uncovered
fraction of the remaining C3S surface area which can be compared to results obtained by N2-BET
(Figure 12). A relatively close agreement is observed in the first 5 hours but a relatively large gap
exists between simulation and experiment at later times. This difference is based on the continuing
growth of C-S-H to relatively long needles in the simulation which is confirmed by SEM but not
reflected in the BET data. It can be assumed that this gap is related to the intergrowth of C-S-H
particles and the fine pores between these particles cannot be assessed by nitrogen molecules.

The surface area of tricalcium silicate starts to decrease at the beginning of the main hydration period
due to a reduction of the particle sizes as predicted from the shrinking core model (Figure 3) which is
shown by the thick line in Figure 13. In parallel, the remaining surface area becomes covered by C-S-
H reducing the surface area available for dissolution (thin line in Figure 13). The uncovered surface
area approaches zero after the maximum of the main hydration period inducing a decrease of the rate
of reaction. There is no experimental data available to test the results of the simulation in Figure 13.

150 1.000
nucleation density [n/µm²]
size C-S-H particle [nm]

800

100
length 600
radius
400
50

200

0 0
0 5 10 15 20 0 5 10 15 20
Time [h] Time [h]

Figure 14. Evolution of mean length and radius Figure 15. Evolution of the nucleation density
of the C-S-H semi-ellipsoids during hydration during hydration

The size and number of C-S-H particles is another result of the computation which cannot be
confirmed by experimental data. The nucleation density is the number of C-S-H particles on the
surface of tricalcium silicate formed by heterogeneous nucleation. It starts almost linearly dictated by
the nucleation rate of 135 nuclei/(hµm²) and levels off at approximately 900 particles/µm² when the
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

surface area is fully covered shortly after the maximum of the main hydration period (Figure 15). At the
same time, the mean length of the C-S-H particles grows to approximately 120 nm and the radius to
approximately 20 nm. It is likely that slightly other values will be computed when reliable models
become available for the prediction of C-S-H size and nucleation density.

It can be summarized that the current simulation is able to predict a number of properties relevant for
the kinetics of tricalcium silicate hydration during the main hydration period. This is also confirmed for
the computation of the degree of hydration as shown in Figure 16.

40
DoH alite paste (QXRD)
DoH in calorimetry
degree of reaction [%]

30 DoH in simulation

20

10

0
0 5 10 15 20
Time [h]

Figure 16. Comparing the simulation results for the evolution of the degree of hydration to
experimental data from QXRD and calorimetry

4. CONCLUSIONS

The kinetics of tricalcium silicate hydration was simulated in this study and the following conclusions
can be derived:

 The rate controlling step in the first hours up the maximum of the main hydration period is the
nucleation and growth of C-S-H, whereas the dissolution of C3S is rate controlling after the
maximum.

 Simulation of the dissolution process is based on the shrinking core model and heterogeneous
nucleation of C-S-H on the surface of tricalcium silicate. Precipitation of C-S-H is predicted
from the number and size of C-S-H particles. Both processes also involve interfacial rates
depending on solution composition.

 The model in this study can predict the evolution of rates of reaction, degree of hydration, pore
solution chemistry, surface area of solid phases and micro-structural properties such as the
size of C-S-H and degree of surface covering. There is good agreement with experimental
data for most properties which have been analyzed.

 It is evident that the hydration kinetics is dominated by the evolution of the surface areas for
tricalcium silicate and C-S-H which are strongly affecting the rates of reaction- more than any
other parameter. These surface areas itself depend on micro-structural details. Surprisingly,
there is only very limited data reported in the literature for such properties (Thomas et al.). The
simulation is free from fitting parameters but depends critically on micro-structural parameters
such as the shape of the C-S-H particles. It can be expected that the current simulation can be
improved as soon as these gaps are filled.
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

5. ACKNOWLEDGEMENTS

Most of the experimental data shown in this study was provided by C. Naber prior to publication.

6. REFERENCES

Bellmann F, Scherer G (2018). Analysis of C-S-H growth rates in supersaturated conditions. Cement
and Concrete Research, Volume 103, pp 236-244.

Bellmann F, Damidot D, Möser B, Skibsted J (2010). Improved evidence for the existence of an
intermediate phase during hydration of tricalcium silicate. Cement and Concrete Research, Volume
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