International RILEM Conference on Material Science MATSCI, Aachen 2010 Vol.

II, HetMat 33
CHALLENGES IN MODELING CEMENTITIOUS MATERIALS
K. Scrivener, Laboratory of Construction Materials, EPFL, Switzerland
ABSTRACT: In order to meet the demands of sustainable development the range of
cementitious materials used will need to become more diverse. To master the use of this
range of materials, modelling has an essential role to play in linking composition and
processing to the final properties and performance. This paper describes some of the
challenges such modelling presents and progress made at the Laboratory of Construction
Materials at EPFL, based on the microstructural models ic [Bis09a, Bis09b] and AMIE
[Dun10].
1 INTRODUCTION
Concrete is the most used material on the planet and is the only material which can be
produced in sufficient quantities to meet the demands of the growing world population.
Intrinsically concrete has a low environmental footprint compared to alternatives (Table 1.1),
however the enormous volumes produced means that concrete accounts for some 5-8% of
man-made CO
2
emissions. Many routes exist to lower CO
2
emissions, but there is no single
magic bullet solution. Rather we must learn to use an increasingly diverse range of
materials optimised according to the raw materials available locally and the intended
application.
Table 1.1. Energy and CO
2
emissions of common materials [ICE09].
Materi al MJ/kg kgCO
2
/kg
Cement 4.6 0.83
Concrete 0.95 0.13
Masonry 3.0 0.22
Wood 8.5 0.46
Wood: multilayer 15 0.81
Steel: Virgin 35 2.8
Steel: Recycled 9.5 0.43
Aluminium: virgin 218 11.46
Aluminium recycled 28.8 1.69
Glass fibre
composites
100 8.1
Glass 15.7 0.85

The current use of concrete is based mainly on empirical knowledge from testing often at near
full scale. This, and justifiable demands for safety, mean that progress is slow and
incremental. To speed up the use of new and a more diverse range of materials, modelling
has a clear role to play; as has been well demonstrated in other fields of Materials Science.
For example it is now possible to make a virtual crash test of a new car with a model which
even incorporates the microstructure details of the porosity in the engine block from a
simulation of the solidification during casting!
34 SCRIVENER: Challenges in Modelling Cementitious Materials
In order to be reliable, models should be based on the real physical and chemical processes
linking the composition and processing of a material to its nano / microstructure and so to its
properties and performance this is the paradigm of Materials Science as shown in Fig. 1.1.
Properties
and
performance
MODEL
Nano/micro
structure
MODEL
Composition
and
processing

Fig. 1.1. Role of Models in linking composition and processing to microstructure and then this to
properties and performance: the Materials Science paradigm.
Due to their complexity and range of relevant length scales, modelling cementitious materials
poses particular challenges, which must be overcome if progress is to be made.
Fig. 1.2 shows a polished section of concrete imaged with backscattered electrons in the
SEM. The general features of the complex concrete microstructure can be identified
Aggregates, unhydrated cement, hydration products (mainly calcium hydroxide and C-S-H).
The complexity comes from the number of phases and their range of sizes. This originates
from the particle size distribution of the starting materials, which goes from under a micron to
tens of microns for the cement grains, through millimetres and centimetres for the aggregates.
The pores go from the nanometre range in the C-S-H gel to voids which may be in the
millimetre range. It is difficult to use classic multiscale approaches due to the continuous
dispersion of sizes.
parti al ly reacted
cement grai n
i nner C-S-H
outer or
undi fferenti ated
C-S-H
sand (aggregate)
cal ci um hydroxi de
(CH)
pores

Fig. 1.2. Microstructure of concrete.
International RILEM Conference on Material Science MATSCI, Aachen 2010 Vol. II, HetMat 35
2 EXAMPLES OF MODELLING
2.1 Kinetics and Microstructure
The first step in Material Science modelling is to simulate the microstructure from
information on the composition and processing of the material. The microstructure must be
sufficiently well represented to allow the model to then predict the desired behaviour. At
EPFL we work with a vectorial model for cement paste as this allows the wide range of
particle sizes to be represented without a lower resolution limit. The first version of the
model Integrated Particle Kinetics Model of Navi and Pignat [Nav96] was computationally
limited to the representation of a few thousand particles. The new implementation of the
model ic can deal with the hydration of several millions of particles in a typical 100 m box.
The first challenge addressed by ic [Bis09a,b] was a computationally efficient
implementation of the vector approach, but it was also realised that flexibility and easy
extensibility were essential features as to avoid regular development (even rewriting) due to
the complexity of cement and the gaps in our understanding of its chemistry coupled with
extensive research progress. This high level of flexibility also means that the model is ideally
suited to model the microstructural development of new cementitious materials. Figure 2.1
shows the basic design of ic [Bis09a]. Any number of reacting phases may be represented
with their correct particle size distributions. These phases react according to user defined
laws to give products which are deposited in the microstructure in different ways.
Simulations involving several million particles can be run in a matter of hours.

Fig. 2.1. Schematic of the ic programme [Bis09a].
ic was used first to study the hydration of alite based on the data generated in the thesis of
Costoya [Cos08]. The approach was to synthesise alite (which unlike C
3
S has a grains similar
in size to cement) and separate the powder into fractions with, narrow particle size
distributions. This approach is important as it is very difficult to derive correct kinetic
behaviour from the full PSD as the complete reaction of small grains at short times makes it
impossible to differentiate between different kinetics at the particle scale. Bishnoi [Bis09b]
showed that while the acceleration part of the main heat evolution peak could be well fitted
with a boundary nucleation model (such as developed by Cahn [Cah56] and adapted by
Thomas for cements[Tho07] ), such a model could not capture the deceleration part of the
36 SCRIVENER: Challenges in Modelling Cementitious Materials
curve (Fig. 2.2a). In order to capture the decelerating part a radical suggestion was put
forward that the initial products grow quickly to fill the available space with a low density and
subsequently densify over time. This mechanism enabled excellent fits to the experimental
data to be obtained (Fig. 2.2b) across all the different particle size distributions, with the same
parameters for product nucleation and densification rates. The only parameter which needed
to be adjusted was that for the outward growth rate which was found to depend on the
distance between particles. This hypothesis and the simulation results are presented in detail
in [Bis09b].
Despite the radical nature of this hypothesis compared to conventional thinking, a loose, low-
density CSH, be observed in many micrographs [eg Ric99]. Quasi-elastic neutron
scattering and NMR relaxation measurements of pore-sizes, which do not entail sample-
drying, indicate that a larger than expected fraction of the water at this stage is close to the
surface of hydration products [Hal94][Fra02][McD07]

Fig. 2.2. a) left: failure of surface nucleation model to capture decelerating part of hydration
reaction: b) right: Good agreement between simulation and experiment for the case of
growth of a product with low density which subsequently densifies [Bis09b].
Recently Kumar [Kum10], has a mechanism to simulate the dissolution and induction periods
based on work by Juilland in our group [Jui10]. In Fig. 2.2 it can be seen that there is not a
good fit of the simulation to the experimental data in the first few hours. Initially, on addition
of water there is a high rate of reaction. The rate of reaction slows quickly to be followed by
the period of low heat evolution (the induction period) before the onset of the main hydration
peak. By analogy with recent findings and hypotheses in geochemistry this slow down in
reaction arises from the build up of ions in solution. In very dilute solutions, the dissolution
rate is fast as it is energetically possible to open up etch pits on the surface; as the
concentration increases the mechanism of dissolution changes to slow step retreat and this
may occur even when the solution is still many orders of magnitude below equilibrium
concentration. The implementation of this process allows the first part of the curve to be well
captured (Fig. 2.3) and it is found that the parameter related to the dissolution process are the
same across the range of particle sizes; for alite alone and in the presence of other phases and
even for alite in commercial cements. However these parameters are sensitive to temperature
and mixing intensity.
Furthermore it has been found that the same reaction mechanisms can capture the kinetics of
hydration of C
3
A with gypsum, mixtures of alite, C
3
A and gypsum and even commercial
Portland cements (Fig. 2.4), including considerations of the thermodynamics of the solution
phase. Remarkably it has been found that the fundamental kinetic parameters do not vary
significantly between systems.
International RILEM Conference on Material Science MATSCI, Aachen 2010 Vol. II, HetMat 37
Most importantly the kinetic simulations produce microstructures which can then be used to
compute behaviours. The microstructures have no lower resolution limit and are three
dimensional, Fig. 2.5. However, the structure of C-S-H itself is not explicitly represented.

Fig. 2.3. Simulations of reaction kinetics of alite with ic [Kum10].

Fig. 2.4. Simulations of alite, C
3
A gypsum mixture and a commercial cement.

Fig. 2.5. Simulated microstructure: unhydrate cement dark grey, C-S-H grey and calcium
hydroxide, bright grey.
38 SCRIVENER: Challenges in Modelling Cementitious Materials
2.2 Mechanical Properties
The primary requirement for most concrete is to support load. Therefore the most important
property is compressive strength. Despite the simplicity of the compressive strength tests, the
actual process of compressive failure of a material is very complex and not yet possible to
model explicitly. However it is generally accepted that strength is a function of the elastic
modulus, which can be more easily modelled. Of course it is well accepted that the primary
factor determining mechanical strength is the total amount of capillary porosity. Fig. 2.6
below shows a typical plot which can be found in the literature. Although the general trend to
higher strength with decreasing porosity is clear, it is important to realise that this correlation
is completely inadequate from a practical point of view. If we look at an average porosity of
around 20% we see that the scatter of strength values varies by a factor of 3! At present the
reasons for this large scatter are very unclear. Of course there are intrinsic errors in the
measurement of both porosity and strength, but these are much less than the observed scatter.
From a Materials Science perspective one expects that this must be related to the spatial
arrangement of the porosity. To date most attempts to model elastic properties have not shed
much light on the reasons for this dispersion. Bary et al [Bar08, Bar10] showed that the
results from most analytical schemes converge for low porosities.

Fig. 2.6. Strength porosity relationship from [Jen91], typical of many to be found in the literature.
From a practical point of view the area of most interest is the early age strength development,
which is the area most sensitive to the substitution of clinker by supplementary cementitious
materials. The recently competed thesis by Chamrova [Cha10] explored the possibility of
numerically modelling elastic properties from the ic model at low degrees of hydration, via
the FEM method. As previously observed the critical phenomenon at this stage is the
connectivity between the hydrating cement grains. Fig. 2.7 shows the huge impact of
considering all particles, or just those connected. The percolation threshold is very sensitive
to the resolution of the model and, even with the increasing power of computers it will never
be possible to represent the finest features in the cement paste microstructure on the scale of
the RVE (representative volume element. Nevertheless despite the numerical limitations, the
model illustrated well the potential impact on elastic properties of microstructural features
such as the clustering of the cement grains and the number of calcium hydroxide crystals
(Figs. 2.8 & 2.9).
International RILEM Conference on Material Science MATSCI, Aachen 2010 Vol. II, HetMat 39

Fig. 2.7. Impact of connectivity of prediction of elastic modulus [Cha10].

Fig. 2.8. Impact of cement grain clustering on prediction of elastic modulus [Cha10].

Fig.e 2.9. Impact of number of calcium hydroxide crystals on prediction of elastic modulus
[Cha10].
40 SCRIVENER: Challenges in Modelling Cementitious Materials
The impact of the correct microstructural arrangement is also apparent in the work of Dunant
on modelling the alkali silica reaction [Dun10]. This model, at the paste aggregate level using
AMIE, considers ASR as occurring at reactive sites embedded in a non-reactive matrix,
corresponding to the situation observed experimentally with the aggregate types of interest,
Fig. 2.10. This model can correctly capture the dependence of expansion on the amount of
reaction, unlike the case where ASR is considered to occur only at the aggregate paste
interface.

Fig. 2.10. Model (left) and real microstructure (right) for concrete affected by ASR [Dun10].
These examples illustrate how appropriate models can illuminate different mechanical
behaviours, despite the limitations of resolution. In order to delve further into the impact of
microstructure of mechanical properties we are now limited as much be good quantitative
descriptions of the microstructures of new cementitious materials as by the available models.
2.3 Durability
The term Durability encompasses a vast array of phenomena many of which are not fully
understood. However, common thread linking many processes related to the degradation of
concrete is the transport of fluid, gas or ions through the porous network of concrete. Here
the main challenges are to represent the porous network of a RVE at sufficient resolution. As
described above this is almost impossible when the smallest size of interest is an ion and the
RVE is on the order of 100 m or more.
However, recently Kumar [Kum10b] has shown that it is possible to simulate absorption
desorption of water directly from the ic model, with no fitting parameters, by considering
explicitly the addition of water molecules layer by layer to the solid surfaces produced by the
hydration process. Fig. 2.11, shows some results from this work. The very good agreement
between the model and the simulation is extremely encouraging to be able to simulate
transport in partically saturated conditions (which is usually the case in the field). In the
present case features such as the surface roughness of the C-S-H of the shrinkage of this phase
were not considered suggesting that such effects has a comparatively minor effect of the
isotherms.
International RILEM Conference on Material Science MATSCI, Aachen 2010 Vol. II, HetMat 41

Fig. 2.11. Simulations of absorption desorption isotherms form ic [Kum10b].
3 CONCLUSIONS
This paper presents several examples of modelling cementitious materials. Despite the
challenge of capturing small features at the level of the RVE the progress is quite
encouraging. Such modelling based on mechanism rather than the encapsulation of empirical
data holds great promise to understand and predict the behaviour of the increasingly diverse
range of cementitious materials which must be used in the future is the environmental
footprint of concrete is to be reduced.
ACKNOWLEDGMENT
The authors thank the members of LMC, EPFL who contributed to the research reported here:
Shashank Bishnoi, Aditya Kumar, Mercedes Costoya, Alexandra Quennoz, Cyrille Dunant,
Patrick Juilland.
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