Transactions on Engineering Sciences vol 4, 1994 WIT Press, www.witpress.

com, ISSN 1743-3533

Numerical simulation of hydration and

microstructural development of
cement-based composites
K. van Breugel
Faculty of Civil Engineering, Delft University of
Technology, Delft, The Netherlands

ABSTRACT

A computer-based numerical model is presented which simulates hydration and

microstructural development in Portland cement-based composites. The model,
called HYMOSTRUC, predicts hydration curves as a function of the particle size
distribution and chemical composition of the cement, the water/cement ratio and
the actual reaction temperature. The influence of microstructural development,
i.e. the formation of interparticle contacts, on the rate of hydration is modelled
explicitly. Parameters used for quantification of particle interactions are dis-
cussed in view of their correlation with strength development. The potential of
the model to allow for the effect of the reaction temperature on the relationship
between strength and microstructural properties is briefly discussed.

INTRODUCTION

One of the major aims of materials science is to link properties with the charac-
teristic features of the microstructure. This holds in general, and also for a ce-
ment-based composite like concrete. On the meso-level concrete can be consi-
dered as a three-phase material, consisting of a porous cement paste matrix, the
aggregate (0.5 to 30 mm), and a matrix-aggregate interfacial zone with a thick-
ness of about 10 to 50 |iim. The matrix, on its turn, is a composite of still unhy-
drated cores of cement particles, different types of reaction products like needle
shaped silicate hydrates and calcium hydroxide (CH) and pores of different
sizes as schematically shown in figure 1. The characteristics of the microstruc-
ture depend on, among other things, the type of cement, particle size distribu-
tion of the cement, the water/cement ratio and the temperature at which the re-
action products have been formed. For a realistic image representation of the
microstructure of the cement paste and for linking of the materials properties
with this microstructure an enormous computer would be required, if it were
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240 Composite Material Technology IV

plastic phase setting stage basic skeleton "stable" skeleton

Figure 1: Formation of reaction products and build-up of microstructure [1]

possible at all [2]. For the time being an exact description of reality must be
considered beyond our capability. There is no doubt, however, that with the a-
vailability of powerful computers computer-based models have a great potential
to simulate this complex reality with an ever increasing exactness [3]. In this
paper such a computer-based simulation model will be presented. For this mo-
del a statistical approach has been adopted, with emphasis on the stereological
aspect of microstructural development in cement-based composites.

2 NUMERICAL SIMULATION OF HYDRATION AND MICROSTRUCTU-

RAL DEVELOPMENT

Basic features of the simulation model

In the computer-based simulation model called HYMOSTRUC, the acronym for
HYdration, Morphology and STRUCtural development, the effects of the particle
size distribution and the chemical composition of the cement, the water/cement
ratio OQ and the reaction temperature on the rate of hydration are dealt with.
Unlike most previously proposed models the effect of physical interactions be-
tween hydrating cement particles on the rate of hydration of individual cement
particles is modelled explicitly. For numerical evaluation of the intensity of
particle interaction due attention had to be given to the stereological aspect, i.e.
the spatial distribution of the cement particles in the paste.

Stereological aspects In HYMOSTRUC cement particles are considered to be dis-

tributed homogeneously in the cement-water system. An arbitrary particle is
considered to be located in the centre of a cell "l" (Figure 2). The cell "l" is
defined as a cubic space in which the central particle has a diameter x and fur-
ther consists of I/NX times the original water volume and 1/N% times the vol-
ume of all particles with diameter smaller than x JLUTI, N% being the number of
particles with diameter x pm in a certain paste volume.

On contact with water cement particles start to dissolve under formation of

reaction products. These product are formed partly inside and partly outside the
original surface of the cement particles. In this way the cement particles exhibit
an outward expansion, thereby coming in contact with neighbouring particles.
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Composite Material Technology IV 241

This process is shown

schematically in figure
3. For the assumed ho- cell I
mogeneous spatial distri-
bution it is relatively
easy to determine the
amount of cement found
in a fictitious shell with
thickness d surrounding
a cement particle with
diameter x pm. For this
purpose a shell density
factor Csh;x,d has been Figure 2: Cell concept - schematic [4].
defined, viz. (bottom
part of figure 3):

cement volume in spherical shell with thickness d

(1)
total shell volume

Going from the periphery of particle x in outward direction the shell density
gradually increases from zero just at the outer periphery of the anhydrous par-

shed density
factor fshix.d

Figure 3: Interaction mechanism for expanding particles [4].

Upper-left: free expansion; Upper-right: embedding of particles, several itera-
tion steps. Bottom part: Course of shell density factor Csh-xd-
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242 Composite Material Technology IV

tide to the paste density , with = [l+coQ.p^]", p^ being the specific

mass of the cement (For details, see ([4]).

For the particle size distribution of the cement the Rosin-Ramler distribution

G(x) = 1 - exp(-bx ) [g] (2)

has been adopted, with x [jim] the particle diameter and b and n constants
which are determined so that G(x o) = 1 g.

Particle expansion and interaction mechanism

In order to obtain a workable algorithm for the determination of the interaction
between hydrating and expanding cement particles the following assumptions
were made:
1 . Particles belonging to the same fraction hydrate at the same rate.
2. The ratio v between the volumes of the reaction products, or gel, and the
reactant is a function of the curing temperature. So v = v(T), with de-
creasing values at elevated temperatures (see also [4]).
3. Reaction products precipitate in the close vicinity of the cement particles
from which they are formed (based on [5]).
4. Dissolution and expansion of the cement particles occur concentrically.
The simplifications which are introduced here are, to a large extent, inherent
to the statistical approach that was adopted. For a more extensive justification
of these simplifications reference is made to [4].

An arbitrary stage in the hydration process of a central particle x is shown

schematically in the upper part of figure 3. At a certain time, say t, the degree
of hydration of particle x is a . For the corresponding penetration depth 8^.^ :
of the reaction front it holds:

The volume of outer product of particle x corresponding with the degree of hy-
dration a, follows from:

with v% the volume of particle x in its anhydrous state. If no cement would be

found in the spherical outer shell when it is tilled up gradually with outer pro-
duct of the expanding particle, the outer radius R^ of particle x would be:

For the thickness 8^ of the outer shell it would follow:

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Composite Material Technology IV 243

5ou;x,j = ROU;X,J ~ ^ (6)

In reality a certain amount of cement will be present in the outer shell. The vol-
ume of the cement in a shell with thickness 8^.^, called the directly embedded
cement volume v^.^j, is determined by multiplying the shell volume v^.%
with the corresponding shell density factor Q^ do (with dq = 8^.%:):

The volume of the embedded cement, which is partly hydrated, will cause an
additional expansion A8^. of the outer shell of particle x. This additional ex-
pansion, on its turn, results in an increase of the amount of embedded cement.
The amount of cement found in the shell with thickness A8^. is called the
indirectly embedded cement volume. The total volume of directly and indirectly
embedded cement can be calculated analogously to the procedure for the deter-
mination of the directly embedded cement (formulae (1) and (7)), albeit that the
shell density factor is a little higher now because of the increase of the thick-
ness of the outer shell (Figure 3, bottom part: sh;x,d, > Gsh;x,do)- The increase
of the amount of embedded cement, on its turn, causes another additional in-
crease of the outer shell, etc. This expansion mechanism can be written in the
form of a geometrical series. Algebraic evaluation results in workable expres-
sions for the thickness of the outer shell of particle x and for the total thickness
of the layer of reaction products at time tj, viz. 8%: (figure 3), as well as for the
amount of cement embedded in the outer shell or particle x. Adding of the a-
mounts of cement embedded in the outer shells of all free particles in the sys-
tem yields the amount of cement involved in the interaction process at time t .

Rate or penetration of the reaction front

The rate of penetration of the reaction front in an individual cement particle x
at time tj is computed with the "basic rate formula" viz. (in a reduced form):

5 M Pi ^

with A8^-x i+i the increase of the penetration depth in time step At^, KQ(.) the
basic rate Factor [|um/h], 8^0) the transition thickness [jim], being the total
thickness of the product layer 8 at which the reaction for the particle in view
changes from a boundary reaction (X = 0) into a diffusion controlled reaction
(A, = 1). The model parameters K^(.) and 8^(.) turned out to be a function of
the chemical composition of the cement [4]. (3j is an empirical constant.

The factor Qj = QJ(X,OJ) accounts for the effect of water withdrawal by the
embedded and still hydrating particles on the rate of penetration of the reaction
front in the central particle x. The factors ^ = ^((Xj) and Og = Q^(a ) are re-
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244 Composite Material Technology IV

duction factors, allowing for the distribution and the amount of capillary water
in the pore system of the hydrating paste, respectively, and are a function of the
degree of hydration. The function F^(.) accounts for the effect of the reaction
temperature on the rate of operating processes and mechanisms. For this func-
tion the Arrhenius function is used, in which the activation energy written as
a function of the degree of hydration OC:, the reaction temperature T: and the ce-
ment composition, i.e. the CgS content. A second temperature function p2(.) ac-
counts for the effect of the curing temperature on the morphology and density
of the reaction products: the higher the temperature, the lower the v-value [4].

RESULTS OBTAINED
WITH HYMOSTRUC degree of hydration (X

Simulation potential of
the model
The potential of HYMO-
STRUC to simulate the
effects of the particle
size distribution and the
curing temperature on
the rate of hydration is
illustrated in figures 4 0.0
and 5. In these figures 20 50 100 200 5001000
measured hydration val- time [hrs]
ues are indicated with Figure 4: Measured and calculated degree of
discrete points, whereas hydration for fine and coarse cement [4]. Ex-
the calculated values are perimental data for three cement types [6].
given with solid lines.
The clinker composition
is indicated in the le-
degree of hydration (X
gends of the figures. In
all tests Portland cement
was used.

Micro structural features

and strength develop-
ment
The amount of cement
that is involved in the
formation of interparti- 0.0
cle contacts, i.e. the em- 20 50 100200 5001000
bedded cement volume, time [hrs]
was assumed to be a
Figure 5: Effect of curing temperature on the rate
measure for the strength.
of hydration in isothermal experiments [4].
Figure 6 seems to sup-
Experimental data [9].
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Composite Material Technology IV 245

port this assumption. In this compressive strength f^ [MPa]

80
figure the compressive strength temp. wcr
is presented as a function of the 70 - [-c] 0.4 0.5
20 a /
60 ~ 32 o * :
calculated amount of embedded
cement per jarn^ paste. Pastes 50 44 A A
were made with water/cement 40 r
ratios 0.4 and 0.5, whereas cu- 30
ring temperatures varied be- 20 ^
tween 20 and 44C. The effect 10 /
of temperature was taken into
account by reducing the ratio 5 10 20 ^ 50 100 200 5C
Vem [/um^/g paste](*10^)
between the volumes of the re-
action products and the anhy- Figure 6: Strength as a function of the
drous cement. This turns out to amount of embedded cement v^ [4].
result in an unambiguous rela-
tionship between strength and
amount of embedded cement. em;x,j

Another confirmation of the

reasonableness of the assump-
tion that strength is correlated
with the intensity of the inter-
particle contacts is can be de-
duced from figure 7. In this fig- Figure 7a: Embedded centre-plane area
ure the relative increase in ^em-xi of particle x - schematic [4].
strength is presented as a func-
tion of the degree of hydration compressive strength l%l
120
together with the relative in-
crease of the embedded centre- 100 -H-
plane area, i.e. the summarized
centre-plane area of all embed- 80
ded cement particles (see figure
la). The proportional increase in 60
strength was deduced from ex-
perimental data of Powers [7] 40
and Fagerlund [8]. In figure 7b
20
three sets of curves are shown,
viz. for water/cement ratios 0.3,
0.4 and 0.7. A relatively good 0 20 40 60 80 100
degree of hydration
agreement of curves referring to
the three water/cement ratios relative embedded centre-plane area
suggest a good correlation be- relative strength after Powers [7]
relative strength after Fagerlund [8]
tween strength development and
the relative increase in the a-
Figure 7b: Relative increase in strength
mount of embedded cement.
and in embedded centre-plane area [4].
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246 Composite Material Technology IV

CONCLUDING REMARKS

Computer-based simulation programs are powerful tools with which huge files
of data concerning chemical, physical and stereological aspects of hydration and
microstructural development of cement-based composites can be made accessi-
ble and operational for engineering practice. The model presented in this paper
is an example of a model that can be used at the personal computer level. The
step-wise calculation procedure of the model makes it possible to consider a
large number of non-linear phenomena and mechanisms from which we would
have to refrain if we would stick to an analytical "closed solution" approach.
Although the model is still in its early stage of development it has already
added to our knowledge of cement-based composites and has been used for
practical engineering purposes as well. Preliminary results have been obtained
already regarding simulation of microstructural features of the matrix-aggregate
interfacial zone [4]. From those and other results it is justified to conclude that
computer-based simulation models, together with experimental work, will push
forward our understanding of hydration and microstructural development in ce-
mentitious materials. This can be considered as a first and necessary step before
reliable numerical predictions can be made of deliberate material modifications,
i.e. of tailoring of cement-based composites.

REFERENCES

1. Locher, F.W. "Erstarren von Zement: Reaktion und Gefiigeentwicklung." Ze-

ment, Kalk, Gips, No. 10, pp.435-442, 1976.
2. Wittmann, F.H. "Properties of hardened cement paste." Proceedings of the
7th. International Congress on the Chemistry of Cements. Paris, Vol.1, Sub-
theme VI-2, pp.VI-2/1-14, 1980.
3. Garboczi, E.J., Bentz, D.P. "Computer-Based Models of the Microstructure
and Properties of Cement-Based Materials. Proceedings 9th. International Con-
ference on the Chemistry of Cements, New Delhi, Vol.VI, pp. 1-15, 1992.
4. Breugel, K. van. Simulation of hydration and formation of structure in har-
dening cement-based materials. PhD Delft University of Technology, Meinema,
Delft 1991.
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PhD University of Karlsruhe, 1976.
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Heft 8, pp.283-285, 1976.
8. Fagerlund, G. "Relations between the strength and the degree of hydration
or porosity of cement paste, cement mortar and concrete." Seminar on Hydra-
tion of Cement, Copenhagen, p. 56, 1987.
9. Lerch, W., Ford, C.L. "Long-term Study of Cement Performance in Con-
crete." Journal of the American Concrete Institute, pp.745-795, 1948.