12th WSEAS International Conference on SYSTEMS, Heraklion, Greece, July 22-24, 2008

Application of the Exponential Kinetic Model in the Hydration of

Cements Produced According to EN 197-1
TSAMATSOULIS DIMITRIS
Halyps Building Materials S.A., Italcementi Group
17th Klm Nat. Rd. Athens Korinth
STATHOULOPOULOU CHRISTINA , PRELORENTZOS LOUIS
TEI of Athens, Department of Physics, Chemistry and Materials Technology
Ag. Spiridonos and Pallikaridi, 12210, Egaleo, Athens
GREECE

Abstract: - The heat of hydration of four cement types complying with EN 197-1 is investigated in the present
study by fitting an exponential model to experimental data taken in a maximum period of around one and half
years. It is demonstrated that the finely ground limestone, accelerates the clinker hydration by also enhancing
its total hydration degree. A large amount of pozzolane inhibits firstly the hydration, but after approximately
seven days the pozzolanic reaction starts. In addition a combination of the two compounds, leads to a
synergetic effect. Most of the models parameters are correlated with the cements chemical analysis. Therefore
the mathematical models form a useful tool to predict the heat of hydration of any cement containing the same
raw materials and can be utilized for cement composition design purposes.
Key-Words: - Hydration, Kinetics, Cement, Clinker, Model, Simulation

1 Introduction

2 Experimental

The aim of the research is the longterm kinetic

study of the hydration rates of cements conforming
to the EN 197-1:2000 standard, produced in
industrial scale. A reliable tool to study the cement
hydration is the heat of hydration based on the
solution method according to the EN 196-8:2005.
One additional reason for the systematic usage of
this method and the respective fitting of the results
to kinetic models is that in spite of the existence of
extended literature about the heat of hydration of
CEM I or the clinker compounds [1, 2, 3] the same
systematic investigation is not observed for cements
derived from co-grinding of several components
such as the EN 197-1 conforming cements. However
during the last years the heat of hydration study of
cements containing several main components is
developing [4, 5, 6]. A significant objective of the
study is to apply mathematical simulations, fitting
the existing experimental data, having as mush as
possible technical character and being easily
verified. The application of these models renders
easier the assessment of the effect of the different
main components on the hydration behavior of the
cements during their curing. The exponential kinetic
model is fitted to heat of hydration experimental
data derived from cements containing pozzolane and
limestone as main compounds in their composition,
except clinker and gypsum. The measurements are
extended to a period more than one year.

ISBN: 978-960-6766-83-1

2.1 Materials and Analysis

The tests were performed using four cement types.
The main cement components, except the gypsum,
are shown in the table 1. For each type several
samples were tested, provided from the Halyps
cement plant, in order to have a more realistic
picture of the cement variance, belonging to the
same type and produced by the same production
unit. The cement types and samples codification is
also presented in Table 1. The physical and chemical
characteristics of the cements are shown in Table 2.
The Blaine measurement is performed according the
EN 196-6:1994. The residues at 40 microns, R40,
are measured using air jet sieving. The loss on
ignition (LOI) and the insoluble residue are
measured according EN 196-2:2004.

2.2 Experimental Procedure

The experimental measurement of the heat of
hydration followed the EN 196-8:2005, e.g. heat of
solution method. The procedure includes the
measurement of the heat of solution of the initial
cement samples as well as of the hydrated products
in a hydrofluoric and nitric acid mixture for different
curing ages. The cement paste has a water/cement
ratio equal to 0.4. The curing temperature is

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maintained constant at 200.2 C. For the dry

cement samples and the hydrated ones, loss on
ignition (LOI) measurements was also executed.

t
H = H 1 exp

t0

Table 1.Cement types utilized and codification

%Clinker and Code
other main
components
I 52.5 N
>95%
1
II A-L 42.5 R
80% - 94%
2, 2B, 2C
limestone
II B-M (P-L)
65% - 79%
3, 3B, 3C
32.5 N
pozzolane,
limestone
II B-P 32.5 N
65% - 79%
4, 4B, 4C, 4D
pozzolane
Table 2. Cements
characteristics
1
3510
Blaine,
cm2/gr
7.5
%R40
2.86
LOI, %
0.34
Insoluble
Residue,
%
3.42
SO3 , %
3
4090
Blaine,
2
cm /gr
9.5
%R40
12.32
LOI, %
6.86
Insoluble
Residue,
%
2.28
SO3 , %
4
3320
Blaine,
2
cm /gr
9.5
%R40
5.28
LOI, %
18.39
Insoluble
Residue,
%
2.96
SO3 , %

Physical
2

and
2

3590

3400

11.0
6.62
1.50

12.0
7.07
1.01

7.5
6.52
0.30

2.90

2.77

2.60

3B

3C

3880

4060

12.5
10.62
5.90

9.0
12.27
5.58

2.79

2.12

4B

4C

4D

3620

3460

3890

8.0
5.43
19.20

11.0
4.77
20.03

6.5
5.51
15.03

2.85

2.73

2.28

(1)

4 Results and Discussion

4.1 Fitting the kinetic models
For each cement type the optimum parameters were
derived and presented in Table 3. Figure 1 and
Figure 2 show the experimental heats of hydration
as well as the predicted ones using the model for all
the cement types.

3440

Where: H = the heat of hydration, in cal/gr, in time t,

in days, H = the totally released heat, when t ,
n = a model parameter and t0 = the time needed for
the released energy to reach the 63.2% of the
maximum. The parameters of the model are fitted to
the experimental results, to give the minimum
residual error, sres, by applying a non-linear
regression technique.

chemical
2

Figure 1.Experimental and model results.

3 Kinetic Model
The experimental data are fitted to the exponential
Avrami Erofeev exponential model as used by
Aloia et al. [7] and it is described by the equation
(1):

ISBN: 978-960-6766-83-1

Figure 2.Experimental and model results.

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The residual errors are found in the region 5.8 8.1

cal/gr, comparable to the reproducibility of the EN
196-8 method represented by a value of 4.3 cal/gr
and taking into account that the experimental
procedure was extended to a period of more than
one year.
Table 3.Model optimum parameters
I 52.5 N II A-L II B-M
42.5 R 32.5 N
149.7
120.8
H (cal/gr) 157.6
t0 (days)
n
sres

10.6
0.275
7.1

8.3
0.296
7.2

15.6
0.507
5.8

clinker ratios are also demonstrated. The heat ratios

correspond to the left vertical axis, while the clinker
ratios to the right one.
(v) For each cement type the calculations are
extended up to the time of the models field of
application, e.g. the maximum time where
experimental data exist.

II B-P
32.5 N
118.9
8.4
0.73
8.1

Concerning the Figure1 the limestone high strength

cement, CEM II A-L 42.5 R, presents behavior very
similar to the CEM I 52.5, in spite of the
significantly lower clinker content. Only in longterm a small difference appears, not significantly
different from the model residual errors. CEM II BM (P-L) 32.5 N releases a lower amount of heat in
correspondence with its lower clinker content. CEM
II B-P 32.5 N initially presents a lower heat of
hydration comparing to CEM II B-M (P-L) 32.5 N,
because of the higher pozzolane content, but after a
period of 7-10 days the heat evolved is significantly
higher than this of the composite cement, due to the
reaction of the pozzolane with the liberated calcium
hydroxide. A more detailed investigation of these
results follows.

Figure 3.Clinker and heat of hydration ratios as

function of time
Some significant conclusions can be extracted from
these two figures:
The ratio of the heat of hydrations of the CEM II
A-L 42.5 to CEM I 52.5, H2/H1, remain always
higher than the corresponding clinker ratios. The
above means that the presence of the finely ground
limestone activates the clinker and accelerates its
hydration. This result occurs up to a period of at
least one and half years. This fact implies that a
clinker fraction not reacting up to more than one
year in the case of CEM I 52.5 is hydrated because
of the limestone dispersion inside the mortar in the
case of the CEM II A-L 42.5. As time increases, the
ratio of the heats of hydration decreases slowly.
Concerning the ratio of heats of CEM II B-P 32.5 to
CEM I 52.5, H4/H1, initially up to a period of 7 days,
this ratio is lower than the clinkers ratio, due to the
high pozzolane content. After this period, the heats
ratio exceeds the clinker ratio, because of the
reaction of the pozzolane silica with the calcium
hydroxide liberated from the clinker. The evolution
of the ratio H4/H1 as a function of time, passes from
a maximum, probably because the clinker contained
in this cement type is coarser than contained in
CEM I 52.5 and as a result a fraction remains nonhydrated. The case of CEM II B-M (P-L) 32.5 is
found between the previously mentioned cases.
Initially H3/H1 < C3/C1, but H3/H1 > H4/H1. A reason
for the first inequality is the pozzolane presence.
The second inequality has to be attributed to the
activating action of the limestone to the clinker.

4.2 Influence of the cement composition on

the heat of hydration
As it is indicated from the cement nomenclature,
except for clinker and gypsum the composite cement
contain as well limestone and pozzolane. For a
known average analysis of these raw materials, the
composition of each cement sample is calculated
[8]. Afterwards the next working steps follow:
(i) For each cement type the average composition is
found over all the samples. Thus, the following
variables are considered: %Clinker I 52.5 = C1,
%Clinker II A-L 42.5 R = C2, %Clinker II B-M (PL) 32.5 N = C3, %Clinker II B-P 32.5 N = C4.
(ii) For each cement type, the heats of hydration are
characterized with the same indices, e.g. H1, H2, H3,
and H4.
(iii) The clinker ratios C2/C1, C3/C1, C4/C1 and the
corresponding heat of hydration ratios, H2/H1,
H3/H1, H4/H1, for different curing times are
calculated.
(iv) The ratios of heat of hydration are plotted as
function of time in Figure 3. In the same figure the

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After a period of 14 days, H3/H1 becomes higher

than C3/C1, because of the pozzolanic reaction as
well as of the limestone activation. After 7 days
curing H3/H1 < H4/H1, because of the additional heat
resulting from the pozzolanic reaction, taking place
more intensively in the case of the CEM II B-P 32.5
which contains higher pozzolane fraction than the
CEM II B-M (P-L) 32.5.
The results verify that in the case of the cements
containing limestone the hydration is accelerated.
More specifically Kakali et al. [9], mention that the
C3S reaction is accelerated. The above activation
liberates faster Ca(OH)2. In case that the
composition contains pozzolane, the reactive silica
reacts with the calcium hydroxide and the reaction
of the clinker phases occurs more to the right side.
Therefore a synergetic effect exists between
limestone and pozzolane. Firstly limestone acts to
the clinker, then and in parallel with the first action,
pozzolane reactive silica consumes the Ca(OH)2
produced. These phenomena lead to a higher total
hydration degree of the clinker than occurs in the
case of CEM I which remains partially nonhydrated. Except for the other benefits, mineral
components as limestone and pozzolane and their
synergetic behavior, drive to a more rational use of
energy [6].

H = 169.8 3.05 LOI 1.97 Insol. Re s.

(3)

Std _ Err = 3.5 R = 0.982

n = 0.215 + 0.0113 LOI + 0.0248 Insol . Re s.
Std _ Err = 0.037

(4)

R = 0.985

Figure 4.Parity plot of the data fitted to the eq. 3

1.0
0.9

n Lin. Regr.

0.8
0.7
0.6
0.5
0.4
0.3
0.2

4.3 Influence of the cement composition on

the model parameters

0.1
0.0
0.0

The correlation of the model parameters H, n with

the chemical analysis of the different cement types
is investigated. Two cement characteristic properties
were considered: The LOI and the insoluble residue
related with the limestone and pozzolane contents
respectively. It has to be noticed that the average
LOI of the limestone is 43%, while the average
insoluble residue of the pozzolane is 81%. The n
exponent is generally connected with the rate of
hydration and given by the formula (2) below.
1

H

d ln ln1
H

n=
d ln(t )

0.4

0.6

0.8

1.0

n Model

Figure 5.Parity plot of the data fitted to the eq. 4

The model values and the calculated ones from the
previous equations appear in parity plot format in
the Figures 4 and 5. In spite the low number of
experimental points, the equations (3), (4) indicate
that the totally released heat and the models
parameters are strongly related with the cement
composition expressed via the two main chemical
analyses characterizing the added minerals. The
practical advantage of this kind of relations is that
for any cement composition of the same raw
materials, if the chemical analysis is made, the
parameters H and n can be estimated, in the case
that the product fineness is found in the same region
of the tested cements. Then by measuring the heat of
hydration at only one or two early curing times, the
parameter t0 can be derived and the heat of hydration
at any curing time can be estimated. Obviously the
above offers a benefit concerning the effective
cement composition design.

(2)

For each cement type, the LOI and insoluble residue

of all the measured samples are taken into account.
Then each pair of these independent variables is
associated with the corresponding model parameter
of the respective cement type. This technique is
selected to have a more exact estimation of the
regression standard error and the following
equations are extracted.

ISBN: 978-960-6766-83-1

0.2

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12th WSEAS International Conference on SYSTEMS, Heraklion, Greece, July 22-24, 2008

5 Conclusions

Proceedings of the Fourth International

Symposium, 1960, pp. 429-465..
[2] Preece, S.J., Billingham, J., King, A.C., On the
initial stages of cement hydration, Journal of
Engineering Mathematics, Vol. 40, 2001, pp. 4358.
[3] Park, K., Noguchi, T., Plawsky, J., Modeling of
hydration reactions using neural networks to
predict the average properties of cement paste,
Cem. Concr. Res., Vol. 35, 2005, pp. 1676-1684
[4] Escalante, J.J., Gomez, L.Y., Johal, K.K.,
Mendoza, G., Mancha, H., Mendez, J.,
Reactivity of blast-furnace slag in Portland
cement blend hydrated under different
conditions, Cem. Concr. Res., Vol. 31, 2001, pp.
1403-1409.
[5] Feng, X., Garboczi, E.J., Bentz, D.P., Stutzman,
P.E., Mason, T.O., Estimation of the degree of
hydration of blended cement pastes by a
scanning electron microscope point-counting
procedure, Cem. Concr. Res., Vol. 34, 2004, pp.
1787-1993.
[6] Bonavetti, V., Donza, H., Menendez, G.,
Cabrera, O., Irassar, E.F., Limestone filler
cement in a low w/c concrete: A rational use of
energy, Cem. Concr. Res., Vol. 33, 2003, pp.
865-871.
[7] Aloia, L.D., Ghanvillard, G., Determining the
apparent activation energy of concrete Ea
numerical simulations of the heat of hydration of
cement, Cem. Concr. Res., Vol. 32, 2002, pp.
1277-1289.,
[8] Tsamatsoulis, D.C., Calculation of cement
composition
and
uncertainty
analysis,
Proceedings of Congress of Concrete, Kos,
2002, Volume A, pp. 263-270.
[9] Kakali, G., Tsivilis, S., Aggeli, E., Bati, M.,
Hydration products of C3A, C3S and Portland
cement in the presence of CaCO3, Cem. Concr.
Res., Vol. 30, 2000, pp. 1073-1077

In the present study a simulation of the heat released

during the hydration of CEM I 52.5 as well as of
Portland cements type II is performed. All the
cements are industrially produced according to the
EN 197-1:2000. The experimental study is extended
for a maximum period of one and half years. The
model residual errors are found in a region less than
two times the reproducibility of the measurement
method followed. Therefore the model can be
considered as valid and able to describe the process.
The long-term experimental study and the
acceptable fitting of the data allow the extraction of
conclusions as regards the cements performance and
more
specifically
their
main
compounds
interactions.
The ratios of the released heats are compared
with the corresponding clinker ratios, by considering
as reference the CEM I 52.5 N. The limestone acts
as an accelerator of the clinker hydration, by also
enhancing the total degree of the clinker hydration.
As a result the liberated heat of the CEM II A-L
42.5 R does not differ significantly from this of the
CEM I 52.5 N, during the test period. The addition
of elevated pozzolane amount initially inhibits the
hydration. Due to the pozzolanic reaction, after a
period of seven days, the ratio of the heats of
hydration exceeds the corresponding clinker ratio.
Cement containing significant amounts of limestone
and pozzolane combine the advantages of both
materials giving rise to a synergy effect. These
products have an advantage over the CEM I,
because for a similar performance need less energy
to be produced.
By using simple linear regression, a good fit is
found between the models parameters and the
cement characteristics which define the limestone
and pozzolane content. For any cement composition
containing the studied raw material of known
chemical analysis, a very limited number of heat of
hydration tests are needed to calibrate the rest of the
parameters. Consequently, the heat of hydration at
any curing time can be predicted, based on the
models with acceptable accuracy.

6 Acknowledgment
This research was coo-funded by E. U. (75%) and
the Greek Government (25%). Thanks are due to the
Halyps Building Materials SA for supplying the
materials.
References:
[1] Copeland, L.E., Kantro, D.L., Verbeck, G.J.,
Chemistry of Hydration of Portland Cement,

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