1 Copyright 2013 by ASME

MODELING POZZOLANIC SYSTEMS FOR SUBSURFACE CEMENTITIOUS

SYSTEMS


Eduardus Koenders
COPPE-UFRJ / TU Delft
Rio de Janeiro, Brazil / Delft, The Netherlands
Camila Aparecida Abelha Rocha
COPPE-UFRJ
Rio de Janeiro, Brazil


Neven Ukrainczyk
TU Delft
Delft, The Netherlands
Romildo Dias Toledo Filho
COPPE-UFRJ
Rio de Janeiro, Brazil



ABSTRACT
The secondary pozzolanic reaction mechanism has been
modeled explicitly in the Delft hydration model Hymostruc.
The model calculates the progress of the hydration process as a
function of the particle size distribution, the water cement ratio,
the temperature and the cement and pozzolanic chemistry. The
consumption of portlandite due to the activation of the
pozzolanic materials is shown in detail. The numerical results
are validated by an experimental testing plan on G-cement and
8% of silica fume and a water to cementitious ratio of 0.44. The
simulated development of portlandite and degree of hydration
and the experimental results are in good agreement.

INTRODUCTION
The interest in modeling the hydration process of
pozzolanic-based cementitious systems has gained an enormous
attention. Especially for the offshore industry, pozzolanic
systems, using green supplementary materials like sugarcane
bagasse, rice husk ash, fly ash or silica fume, this could add
both to the performance of the mechanical performance and to
the footprint of the sustainable solution. Blended cement
systems turned out to have a significant positive effect on
reducing CO
2
emissions. Replacing cementitious clinker by a
pozzolanic material leads directly to a reduction of the
cementitious clinker mass which, on its turn, leads to a
corresponding reduction of the CO
2
production by the cement
industry. Nowadays, most blended cement systems in the
construction industry use Blast furnace slag as a pozzolanic
material. In The Netherlands, in general, slag replacements
exceed 65% and may increase to 80% of the cement content. In
Brazil, these numbers are a little lower, viz. 50% and is the
highest degree of replacement allowed. Optimizing these ratios
of blends can be very advantageous for the properties of the
internal hydration and the quality of the microstructure. An
advanced hydration model is needed to quantify these
properties. Therefore, in this paper the calculation principles of
the hydration model Hymostruc will be explained while also
accounting for the basic cementitious reactions and pozzolanic
reactions. The simulated results are compared with
experimental data received from lab tests on G-cement with
silica fume addition, at the LabEST laboratory of COPPE-
UFRJ.

HYDRATION MODELING
The main vision behind the hydration modeling approach is that
the primary silicate reactions produce CH and that the
secondary reaction uses the SiO
2
content of the pozzolans to
react and produce pozzolanic CSH. In this approach C
3
S and
C
2
S are the main silicate phases that produce most of the CH, a
necessary reaction product for the secondary pozzolanic
reaction to happen. Both the clinker phase and the pozzolanic
phase follow a certain particle size distribution (PSD) and are
taken into account in the modeling approach explicitly.
According to the Rosin-Ramler equation, the grading of the
particles can be calculated per single fraction. From the
materials individual PSD and the water to cementitious ratio of
the cement paste, the particle structure of the blended paste can
be calculated. A 3D impression of the initial 3D microstructure
is provided in Fig 1 where the grey particles represent the
anhydrous cement grains and the purple particles represent the
pozzolanic grains.
Proceedings of the ASME 2013 32nd International Conference on Ocean, Offshore and Arctic Engineering
OMAE2013
June 9-14, 2013, Nantes, France
OMAE2013-10916
2 Copyright 2013 by ASME

Fig 1. Virtual 3D microstructure of cement and pozzolans
before reaction has commenced.

From this 3D particle structure, the inter-particle spacings and
the paste density can be calculated for each fraction
individually. Based on this, the geometrical structure of the
paste is available for simulation. In Hymostruc the hydration of
the individual particles is modeled explicitly following both a
full 3D approach and a statistically-based cell concept [1]. A
cell is considered to be an elementary paste volume that
contains the volume of water and the volume of (blended)
cement grains up to a certain fraction. The cell density for three
different pozzolanic replacements is shown in Fig 2.


Fig 2. Cell density for three different pozzolanic replacements.

Based on the cell concept, hydration products representing the
inner and outer C-S-H gel that is formed by each individual
fraction can be calculated. The outer expansion of the particles
is calculated according to the so-called particle expansion
mechanism (Fig 3) [1,2]. The expansion mechanism describes
the outer growth of a spherical central particle with diameter x,
while embedding the cement and



Fig 3. Schematic impression of expansion mechanism [3].

pozzolanic particles smaller than the central particle in the
expanding shell. The volumetric outer expansion of the
particles V
c
ou,ex,x,j
and V
p
ou,ex,x,j
with diameter x at time j and an
outer volume V
c
ou,x,j
and V
p
ou,x,j
can be calculated by means of a
geometrical leading to the following equations for cement
(sup. c) and pozzolan (sup. p), respectively [1-3]:

( ) ) ( ) ( ) ( 1
, , , ;
, ;
, ; ,
p
j x
c
j x
c
j x ou
c
j x ou
c
j x ex ou
f f
v
v
< <
+
=
o o o _ ,

(1)

( ) ) ( ) ( ) ( 1
, , , ;
, ;
, ; ,
p
j x
c
j x
p
j x ou
p
j x ou
p
j x ex ou
f f
v
v
< <
+
=
o o o _ ,

(2)

where is the density of the shell surrounding a central particle.
The factors f(
c
<x,j
) and f(
p
<x,j
) are the contributions accounting
for the volumetric effect due to the potential particle expansion

c
and
p
for cement and pozzolans, and the degree of hydration
for cement grains
c
<x,j
and for pozzolanic grains
p
<x,j
,
according to:

{ }
c
j x
c c
x
c
j x
v f
, ,
) 1 ( 1 ) (
< < <
+ = o u o (3)

{ }
p
j x
p p
x
p
j x
v f
, ,
) 1 ( 1 ) (
< < <
+ = o u o (4)

and where
c
<x
and
p
<x
are the volumetric contributions of both
cementitious materials. With these equations the basis for
expansion of the cementitious (C
3
S and C
2
S) and the
pozzolanic fraction of SiO
2
can be calculated forming the
morphology of the developing microstructure. From the three
individual hydrating phases, i.e C
3
S, C
2
S and SiO
2
, the molar
volumes per gram can be calculated for each fraction. This
algorithm implicitly accounts for the effect that smaller
Pozzolan
3 Copyright 2013 by ASME
particles will hydrate faster than the bigger particles and show a
much rapid increase of the degree of hydration in comparison
with the coarser cement particles. However, in terms of mass,
the finer pozzolanic fractions contribute less, which also holds
for the development of the degree of hydration of the blended
system. In the model the degree of hydration of the blended
system
s
is calculated according to:
p
j p
c
j c j s
m m t o o o o + = = ) ( (5)
where m
c
is the mass fraction of the cement and m
p
the mass
fraction of the pozzolan. The incremental evolution of the
degree of hydration of the cement is calculated from the four
Bogue phases, i.e. C
3
S, C
2
S, C
3
A and C
4
AF, individually and
based on their mass representation of the phases in the cement
clinker according to:

C
3
S:
3 3 3
3
3 3
, 1 , 1 ,
,
1 1
C S C S C S
x j x j x j C S
x j c c
x x
r r
o o o
o

( ( + A
A =
( (
( (

(6)
C
2
S:
2 2 2
2
3 3
, 1 , 1 ,
,
1 1
C S C S C S
x j x j x j C S
x j c c
x x
r r
o o o
o

( ( + A
A =
( (
( (

(7)
C
3
A
3 3 3
3
3 3
, 1 , 1 ,
,
1 1
C A C A C A
x j x j x j C A
x j c c
x x
r r
o o o
o

( ( + A
A =
( (
( (

(8)
C
4
AF:
4 4 4
4
3 3
, 1 , 1 ,
,
1 1
C AF C AF C AF
x j x j x j C AF
x j c c
x x
r r
o o o
o

( ( + A
A =
( (
( (

(9)
Analogue to this, the evolution of the degree of hydration of the
pozzolanic particles can be calculated with a similar approach
Therefore, for a system with dominating pozzolanic SiO
2

particles the degree of hydration
p
is calculated according to:
3
, 1 ,
3
1 ,
,
2 2 2
2
1 1
(
(

A +

(
(

= A

p
x
SiO
j x
SiO
j x
p
x
SiO
j x SiO
j x
r r
o o o
o (10)
In these equations
x
is the actual depth of the water (reaction)
penetration front,
x
is the incremental increase of the
penetration front within a particular period of hydration time
and r
c
the radius of the clinker particle, and r
p
is the radius of a
pozzolanic particle. With these set of equations and with the
formulations of the chemical silicate reactions the amount of
phases consumed (C
3
S, C
2
S, C
3
A, C
4
AF, SiO
2
and H
2
O), and
the amount of phases produced (C-S-H and CH) during
hydration of a blended system can be calculated as a function of
time and as a function of the degree of hydration.


Fig 4. Schematic representation for the shell (containing binder
particles = cement and pozzolan) surrounding a central cement
particle (left) and a central pozzolan particle (right).

INTEGRATED PARTICLE KINETICS
As said, in Hymostruc the 3D microstructure is simulated using
the particle expansion mechanism (Fig. 3) where the particles
are modeled as expanding spheres following the kinetics of eq
(1). In this equation K
0
is the basic rate of hydration of the
individual cement or pozzolan particles, F
1
is the Arrhenius
function and the O
i
account for the state of water in the
microstructure during hydration. The last part in the equation
accounts for the change of the reaction process from phase
boundary to diffusion controlled and also accounts for the
temperature effect F
2
on the morphological growth of the C-S-
H gel. The water penetration into an individual reacting particle
with time can, therefore, be described as with the following
equation called Basic Rate Equation (BRE):

|
| |
o
o
o
(
(

O O O =
A
A
+
+
1
2 2
,
2 2 1 3 2 1 0
1
1 ,
) ( ) (
j x
tr
j
j x
F F F K
t
(11)
where Ao
,j+1
represents the penetration depth of the reaction,
developed in the upcoming incremental time step At
j+1
, while
o
tr
and o
x,j
are the transition thickness and the thickness of the
product layer, respectively. Finally, accounts for the change
from phase boundary to a diffusion controlled reaction, |
1
and
|
2
are three empirical constants [2]. The first reduction factor
O
1
refers to the hydration of the embedded and still
incompletely hydrated cement and/or pozzolanic particles
situated in the shell of either cement or pozzolanic particles.
The still incomplete hydrated cement or pozzolanic particles
embedded in the shell of a central cement or pozzolanic particle
(Fig 4) may withdraw a certain amount of the water needed for
further hydration of the central cement or pozzolan particle.
This means that the rate of hydration of the central cement
and/or pozzolanic particles is affected by the embedded and
still incomplete hydrated cement and/or pozzolanic particles,
which means that the kinetics of the particles is depending on
its particular position in the microstructure. It makes the rate of
hydration unique for each hydrating particle in the system. For
the cell concept as presented in this paper, this mechanism is
considered per fraction while for the fully 3D kernel this

Cement Pozzolan
4 Copyright 2013 by ASME

Fig 4. Effect of O
1
on the rate of reaction for different central
hydrating cement particles x with diameters 20, 40 and 110 m
and embedded cement particles for a w/c ratio of 0.4.
mechanism is considered on an individual particle level. This
makes each particle a unique object. The reduction factor O
1
for
the central cement particle (Fig 4, left) can be described
according to the following formulation:
p
j x em p
c
j x em c
c
j x
c
j x
w m w m w
w
, ; , ; ,
,
1
A + A + A
A
= O (12)
Where w
c
x,j
, w
c
em;x,j
and w
p
em;x,j
, are the incremental water
consumption of the central cement particle, by the embedded
cement particles and by the embedded pozzolanic particles,
respectively. Furthermore, m
c
and m
p
are the mass fractions of
the embedded cement and pozzolanic particles of all particles
with a diameter smaller than the central particle considered.

Fig 5. Schematic representation of the pore volume distribution
as a function of the pore diameter.

Fig 6. Effect of O
2
on the rate of reaction process versus the
degree of hydration for different water to cement ratios.

The second reduction factor O
2
refers to the water shortage in
the pore system and its associated effect on the partial emptying
of the pores and locally ceasing of the hydration process [1,2].
When considering this concept in view of the addition of the
pozzolanic phase, the microstructural parameters that are
affected by the cement as well as the pozzolanic reaction are
both the volume of capillary water V
cap
(bounded by hydration)
and the actual pore volume V
por
(solidification of the
microstructure due to C-S-H production). The effect of the
water shortage in the pore system O
2
can be calculated from the
free pore wall area A
wat,
relative to the total pore wall area A
por,
or from the minimum pore
0
and maximum pore
por
diameters
in the system and the diameter of those pores that are still
completely filled with water
wat
according to:

o
o
o
o
|
|
| |
| |
o
o
,
,
0 ,
0 ,
2
) (
) (
wat
por
por
wat
por
wat
A
A

= = O (11)
The pore diameters in equation (11) change with progress of the
hydration process, which makes O
2
also a function of the
degree of hydration . A pore model (Fig 5) can be used to
calculate these diameters during hydration and MIP
measurements can be conducted to validate this model.
The last reduction factor O
3
refers to the amount of water
available to accommodate the ions that develop during the
chemical reaction of cement and pozzolans (Fig 6). The
reduction of the amount of water in the hydrating paste is
considered to cause a shortage of water for the ions to move
through the microstructure and react to another phase. This so-
called water shortage concept also causes a reduction of the
rate of hydration due to the consumption of water by cement
and pozzolans and can be calculated according to:
wbr
m w m w wbr
p
p
j p c
c
j c

= O
o o
3
(12)
5 Copyright 2013 by ASME

Fig 6. Effect of O
3
on the reaction process versus the degree of
hydration for different water to cement ratios.
where wbr is the water to binder ratio, m
c
and m
p
the mass
fractions of cement and pozzolans respectively. The factors
wc

and w
p
refer to the water to cement ratio that at which either the
cement or the pozzolanic phase is completely hydrated if al
cementitious has hydrated (=1). For both cement and
pozzolan a factor 0.4 can be adopted.
With the basic rate equation as described in a simple form with
eq. (9), the formulations of the water dependency (O
1
to O
3
),
and the Arrhenius equation F
1
for the temperature dependency
of the reactions, the integrated kinetics approach can be applied
to all particles that are part of the particle size distribution
including both the cement and pozzolanic particle fractions.
The calculation procedure should account for the incremental
increase of the hydration process and associated changes in the
microstructure, capillary water and the chemistry. Figure 7
shows an schematic overview of the different calculation steps
that are considered in the calculation of the cement reactions.
To include the secondary pozzolanic reactions in the model,
both the cement chemistry and the secondary pozzolanic
reactions have to be described explicitly. For the cement
reactions the following reaction equations are considered [3]:
/
C S ( ( / ) )H C SH ( ( / ))CH
b C S x
b C S x b C S + + + (13)
where b = 2 or 3 represents reaction of C
3
S or C
2
S, respectively.
For the numerical calculations in this paper C/S = 1.8 and x = 4
is adopted. Reactions of aluminate-bearing clinker minerals are
represented by the following sequential chemical reaction
schemes:
3 2 6 3 32
C A+3CsH +26H C As H (14)
3 6 3 32 4 12
C A+0.5C As H +2H 1.5C AsH (15)
3 3 6
C A+6H C AH (16)
4 2 6 3 32 3
C AF+3CsH +30H C As H +CH+FH (17)
4 6 3 32 4 12 3
C AF+0.5C As H +6H 1.5C AsH CH FH + + (18)
4 3 6 3
C AF+10H C AH +CH+FH (19)
When all gypsum is consumed ettringite transforms to
monosulfate according to eqs. (15 and 18). After both gypsum
and ettringite are consumed, the remaining aluminates react
according to eqs. (16 and 19). For a dominating SiO
2
secondary
pozzolanic reaction the following relation for the chemical
reaction holds:

xCH + S + (y-x)H C
x
SH
y
(20)

where the CH produced by the cement reaction reacts with the
SiO
2
content of the pozzolan and water to a C-S-H gel. For
pozzolans with a high content of amorphous SiO
2
, this C-S-H
gel has about the same structure as the C-S-H gel formed by the
cement reactions.

Fig 7. Schematic representation of the cement reaction process.

For other compositions of pozzolans this may change. The
amorphous SiO
2
content in pozzolans can change significantly
and depend on the type of material. Table 1 gives an overview
of the amorphous SiO
2
content of pozzolans.



6 Copyright 2013 by ASME
Table 1: SiO
2
content in pozzolans.
Pozzolan Content SiO
2
[% m/m]
Slag 35-40
Silica fume 84 98
Fly-ash 40-65
Sugarcane bagasse 42-49 coarse
34-43 fine
Rice husk ash >85%

The pozzolans that dominate in amorphous SiO
2
is silica fume
and also rice husk ash shows a relatively high SiO
2
content.
Later in this article the model will be validated by using silica
fume as a pozzolan.

EXPERIMENTS
The reference cement is composed only of the mixture of CEM
G cement, while the blend was produced with partial
replacement of Portland cement by 8 % mass of SF. The water
to cement ratio was 0.44. The curing of hydration was
conducted at a temperature of 20 C. In order to test the model
for simulating the hydration of blended pozzolanic systems the
numerical results are compared with laboratory experiments by
means of the development of the amount of calcium hydroxide
CH. The amount of CH liberated during hydration is
determined by TGA TA Instruments SDT Q600, measuring the
mass loss near 430 C. From these experiments the CH data
liberated during plain paste and blended paste hydration after
different ages were obtained. The results are used for
preliminary testing of the numerical model for hydration
blended cement.

DISCUSSION OF RESULTS
All thermogravimetric (TG) measurements showed a mass loss
at a low temperatures caused by the dehydration of CSH and
aluminate phases [4], loss at around 400
o
C due to the
dehydration of Ca(OH)
2
, a mass loss around 600 C attributed
to the decomposition of poorly-crystallized carbonated product.
An example of TG experimental data curve for PC hydration
after 28 days is given in Figure 8. In the TG the mass loss
around 400
o
C was related to the stoichiometry of the Ca(OH)
2

de-hydroxylation as obtained from TG analysis employing a
tangential approach [5]. The result was related relatively to the
mass of binder obtained after firing at 1000
o
C. Figure 9 shows
the development of portlandite (CH) as a function of time. Two
data points series are plotted, corresponding to the reference
and blended paste (where cement was replaced by 8 mass % of
SF). For the hydration of reference cement paste the quantity of
CH produced increases continually with the hydration time. In
blended system, however, the CH quantity reaches a maximum
(at 7 days), which is still much lower than the quantity reached
by reference cement paste hydration, and begins to decrease
with further hydration (Fig. 9). These results are consistent with
the reaction of SF with CH (Eq. 20) produced by the hydration
of clinker (silicate phases, Eq. 1). Ca(OH)
2
is consumed and
used for the formation of pozzolanic C-S-H.


Fig 8. An example of TG experimental data for PC hydration
after 28 days.

This chemical process affects, therefore, also the amount of C-
S-H formed as well as the microstructure development. In Fig 9
it can be also observed that at early ages, until 1 day of
hydration, the reference cement has a lower content of CH than
the blended one, while after 1 day the situation is reversed, the
reference cement has now a higher amount of CH than the
blended one. Until 1 day of hydration SF acts as an accelerator
(filler) only, while later the effect of pozzolanic reaction is
visible by a high CH consumption. The obtained results are in
accordance with literature. Dobson et al. [6] also found by the
NMR experiments

Fig 9. Comparison of hydration simulation against
experimental results for calcium hydroxide of reference and
blended paste hydration (water/binder ratio is 0.44 and the
replacement of silica fume is 8 %).

200 400 600 800 1000
80
85
90
95
100
CaCO
3
T
G
,

%
Temprature,
o
C
Ca(OH)
2

0.01 0.1 1 10 100
0.00
0.05
0.10
0.15
0.20
Hydration time, days
C
H
,

g

/

g

b
i
n
d
e
r
Experimental:
Reference CemG
SF 8%
Simulation:
Reference CemG
SF 8%
7 Copyright 2013 by ASME
that the presence of SF particles greatly accelerates the
hydration of C
3
S during first 24 h. The fundamental
understanding of the acceleration of the clinker (PC) hydration
in the presence of the silica is still not yet clearly defined. The
causes may be attributed to the thickness and densification of
the shell of hydration products forming around the dissolving
clinker particles. The acceleration of early hydration of PC
could be ascribed to the fineness of the SF particles that would
provide preferential nucleation sites.

SIMULATIONS
In order to test the potential of the model to simulate the
hydration of blended pozzolanic systems the output results are
compared with the obtained experimental data. For modeling
purposes it was assumed that the cement has a mineralogical
composition of 60 mass % of alite (C
3
S), while hydration
reactions of other phases (C
2
S, C
3
A and C
4
AF) were neglected.
For modeling we used Rosin-Ramler distribution curve. The
reactive (amorphous) constituent of the SF is assumed to be 95
% of the SiO
2
content. Each individual hydration reaction
kinetics for C
3
S and SiO
2
was modeled according to BRE (Eq.
11) with a corresponding set of kinetic input parameters (K
nucl.
,
K
0
,
tr
, and
1
). Kinetic parameters used for reference C
3
S and
blended hydration system employed for hydration simulation
are given in Table 2, whereas the input parameters for the
particle size distribution (PSD) for both cement and silica fume
are described in Table 3.The free outer growth of the particle
expansion can be calculated according to stoichiometry and
densities of components in the reaction equation. The
expansion factor for C
3
S reaction, in this first approach, was
considered to be
c
= 2.2, thus assuming both C-S-H and CH
reaction products to grow in the shell around the C
3
S particles.
Recently, in the 3D kernel, separate nucleation and growth of
CH particles in a free capillary pore space was implemented,
thus allowing a more realistic microstructural description as
regards to this issue, however with a high price on
computational efficiency. For the pozzolanic reaction the
expansion factor of
p
= 3.77 is used [7]. In the blended model
the volumetric expansion related to the C
3
S reaction is effected
by the pozzolanic reaction due to the consumption of CH, and
therefore the value 2.2 must be corrected in each time
increment in order to consider the interaction with the
pozzolanic reaction. Furthermore, it should be noted that the
particle size distribution of the cement and silica fume are
considered as independent phases.

Table 2: Reaction kinetic parameters
System Phase K
0
,
m/h

tr
,
m

1

Reference C
3
S 0.09 6 2
Blended C
3
S 0.13 13 4
SF 0.002 1 4

Table 3: PSD input values for C
3
S and SF particle.
Phase n b Blaine,
m
2
kg
-1

Range,
m
Fraction
width,
m
Cem G 1.101 0.0267 320 1 - 90 1
SF 2.00 0.04 - 1 - 10 1

MODEL VALIDATION
The modeling approach presented in this paper is a valuable
tool that can be employed to test hypothesis on fundamental
mechanisms involved in pozzolanic hydraion systems. Here the
model was tested and validated against a limited amount of
experimental data. The validation of the multicomponent
kinetic model coupled with the evolving 3-D microstructure
incorporating pozzolanic fillers calls for a comparison of the
evolution of the component fractions (e.g. reactants and
hydration products) over time with the equivalent experimental
data. For crystalline phases, quantitative X-ray diffraction
appears to be the most straightforward means for obtaining
phase quantification. This would be particularly useful for the
PC minerals and crystaline hydration products such as CH.
SEM/image analysis is also a useful technique for analyzing
real microstructures at various hydration ages.
Thermogravimetric analysis provides data on the water released
at different temperatures, from which one can quantitatively
estimate the CH content of pozzolanic pastes.
29
Si NMR [8] is
the only direct method for obtaining the reactivity of
amorphous silica. Combination of this techniques will be used
in future studies in order to validate and further improve the
pozzolanic modeling approach presented here. When
considering the development of the chemical phases the mass
of calcium hydroxide (CH) per gram of cement can be
calculated with the model and the results compared with
experimental data. Figure 9 shows the development of CH as a
function of time for both the reference and blended paste and
the results are compared with laboratory experiments. The
pozzolanic reaction between CH liberated by the C
3
S phases
and the secondary reaction with water and SiO
2
phase turned
out to lead to a reduction of CH. Calcium hydroxide is
consumed and used for the formation of pozzolanic C-S-H.
This chemical process affects, therefore, also the amount of C-
S-H formed in the microstructure. Good agreement with
experimental data could be reached for both systems. From the
simulated and experimental results it can also be observed that
for blended system the amount of CH in system reduces after 7
days of hydration. Justnes [8], Papadakis [9], and Yajun and
Cahyadi [10] show for different silica fume blended systems
that the CH content liberated after hydration may reach a
maximum and depending on the amount of replacement and
water binder ratio may even reduce to zero amounts indicating
the potential influence of pozzolanic reactions in paste. Our
simulation results indicated that for 25 % addition of SF the CH
reached the zero value after 65 days of hydration. Figure 10
shows the degree of hydration for both the plain paste and the
blended system. The results show the hydration of the clinker
8 Copyright 2013 by ASME


Fig 10. Simulation of a degree of hydration reactions of
reference and blended cement paste with 8 % silica fume (SF).

phase C
3
S and the hydration of the pozzolanic phase SiO
2
. In
the model algorithm, these phases are independent meaning that
unique behavior of these phases is explicitly described which is
a true necessity for modeling pozzolanic hydration. The model
accounts for the effect of SF addition on the acceleration of PC
kinetics. The increase in the kinetics of PC hydration due to SF
addition was considered in this paper by increasing the C
3
S
kinetic parameter from 0.09 to 0.13. The proposed model is
flexible to simulate the simultaneous hydration reactions of a
multicomponent system. More experimental data on kinetics of
PC and SF reactions are needed in order to draw further
conclusions. Figure 11 depicts the evolution of the simulated
avarage Ca/Si molar ratio of the overall C-S-H hydration
product with hydration time. The Ca/Si molar ratio starts to
decrease when the pozzolanic reaction is activated at

Fig 11. Simulated avaraged Ca/Si molar ratio of the overall C-
S-H hydration product.
about 9 h, because of the precipitation of C
1.1
SH (20) while PC
precipitates C
1.8
SH (13). Moreover, the model is capable of
simulating the further decrease in Ca/Si ratio that could happen
when there is not a sufficient amount of CH available in the
system.

CONCLUSION
The pozzolanic model described in this paper shows the
potential to use growing spheres numerical simulation models
to simulate pozzolanic reactions in blended cement systems.
The model is implemented in the simulation model Hymostruc
and integrated in the 3D kernel. The simulated results show
good agreement with obtained experimental data, achieved
from TGA laboratory experiments for CH liberation during
hydration of blended paste systems as measured in the LabEST
laboratorium in at COPPE-FRJ in Rio de Janeiro. Further
testing of the multi-component hydration kinetics model
incorporating other types of reactive pozzolanic fillers requires
a comparison of the simultaneous evolution of the reactants and
associated hydration products, and more systematic
experimental data.
ACKNOWLEDGMENTS
This work was financially supported by the COPPE-UFRJ,
M&E at TU Delft, and the Marie Curie Actions EU grant FP7-
PEOPLE-2010-IEF-272653-DICEM
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fume blended cement hydration , M and S 37, 397-404.

0.01 0.1 1 10 100
0.0
0.2
0.4
0.6
0.8
1.0
D
e
g
r
e
e

o
f

r
e
a
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t
i
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Hydration time, days
Reference:
C
3
S
Blended:
SF
C
3
S

0.01 0.1 1 10 100
1.60
1.65
1.70
1.75
1.80
Hydration time, days
A
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a
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C
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