Materials and Structures, 1993, 26, 191-195

Computational materials science of cement-based materials*

E . J. G A R B O C Z I
Building and Fire Research Laboratory, Buildings Materials Division, 226/B348, National Institute of Standards and Technology,
Gaithersburg, Maryland 20899, USA

This paper describes recent research and theoretical results obtained for cement-based
materials using computational materials science techniques. Computer-generated
microstructure models are used to simulate the microstructure development during hydration,
and exact algorithms are applied to these models to compute experimentally verifiable
physical properties. Good agreement is found between experimental and simulation results.

1. I N T R O D U C T I O N its application to interracial zone microstructure in

mortar and concrete, section 4 describes computations
One of the fundamental tasks of materials science is to
of electrical conductivity/chloride diffusivity and their
quantitatively relate microstructure and properties, using
analysis using concepts from percolation theory, section 5
scientifically-based principles and not just empirical
briefly describes simulations of CH leaching and its effect
relationships. Empirical relationships are very useful, but
on transport properties, and section 6 concludes by
they are not the ultimate goal of materials science. The
discussing new research directions and the exciting
focus of the work described here is to use computational
possibilities for microstructural design of cement-based
materials science techniques to try to accomplish this
materials using this modelling approach.
goal for cement-based materials.
Cement-based materials, whether we are talking about
cement paste, mortar, concrete, or some new, high-tech 2. M I C R O S T R U C T U R E M O D E L O F C E M E N T
cementitious material, are composite materials that PASTE
exhibit complex randomness over a wide range of length
The microstructure model described here is for cement
scales. Concrete can be considered to be a mortar-rock
paste, where the fine nanometre structure of C - S - H has
composite, where the randomness in the structure is on
been ignored, and so C - S - H has been treated as a
the order of a few centimetres, the size of a typical coarse
uniform continuum material. Therefore we are working
aggregate. Mortar itself can be considered to be a cement
on the third of the four length scales mentioned above,
paste-sand composite, with random structure on the
that of a few micrometres.
order of a few millimetres. Cement paste can also be
The heart of our original microstructure model is using
considered to be a random composite material, made up
a digital image to represent an initial mixture of water and
of unreacted cement, C - S - H , CH, capillary pores, and
cement particles. The cement particles are considered to be
other chemical phases (standard cement chemistry
a single phase, similar to C3 S. Having the cement particles
notation is C = CaO, S = SiO 2 and H = H 2 0 ). The
made up of individual pixels allows random shapes to be
randomness in the cement paste microstructure is on the
represented, and allows for material redistribution to
order of a few micrometres. Finally, C - S - H is itself a
simulate microstructural development during hydration.
complex material, with random structure, as seen by Fig. 1 is a schematic illustration of how the model works.
neutron scattering [1], of the order of a few nanometres. Colour pictures of how the model works are available
This range of random structure from a few nanometres elsewhere [2,3]. Each cycle of the model has three steps.
( C - S - H ) to a few centimetres (concrete) covers seven
orders of magnitude in size. Therefore it is a large and
difficult task to try to theoretically relate microstructure Dissolution Diffusion Reaction
and properties for cement-based materials. In fact, it is
such a large and difficult task that it is hard to imagine Precipitates into solid
CSH upon contacting a
it being accomplished at all without the aid of a very 1.7 diffusing solid C3S or CSH surface
CSH species
large and fast computer. Dissolved
C3S p=xel
Over the last four years, we have made some progress in >--= Forms
the area of the transport properties and microstructure of
cement paste, using a novel microstructure model and Nucleates into solid CH or
-~ precipitates into solid CH
finite-difference algorithms applied to the model. Section 0.61 diffusing
upon contacting a solid
CH species CH surface
2 describes this microstructure model, section 3 describes
Fig. 1 Schematic diagram of the operation of the
*This paper is a non-verbatim written account of the 1992
Robert L'Hermite Medal lecture presented at the 46th General Council digital-image-based microstructure development model for
of RILEM, in Madrid, Spain, 1 October 1992. the hydration of C3S cement.
0025-5432/93 (~'.) RILEM
192
In the first step, all cement pixels in contact with water
are identified. Some of these are dissolved at random and
are then placed into the capillary pore space. For a given
cement type, there are fixed values of the ratios of product
volume to volume of cement consumed, although the
total volume of reaction products to volume of cement
consumed is roughly invariant, and is equal to about 2.3
[4]. How this volume is divided between products that
form on or near cement surfaces, like C - S - H , and
products that form in the pore space, like CH, differs for
each cement type, but not by much [4]. In this version
of our model, we explicitly follow C3S chemistry and
form 1.7 volume units of C - S - H and 0.61 volume units
of CH for every volume unit of cement consumed, and
place them in the capillary pore space. We believe that
the capillary pore structure produced by the model,
however, is more general than just that of a pure C3S
paste, because of the good agreement between various
computed properties of the model and experimental
results on Portland cement pastes [5].
In the second step of the cycle, all those pixels dissolved
in the pore space that are destined to become either
C - S - H or CH undergo random walks through the pore
space. Reaction and product formation occur in the third
step. Dissolved pixels that are destined to become C - S - H
react and turn into solid C - S - H when they run into
either unreacted cement or previously formed solid
C - S - H gel. Dissolved pixels that are destined to become
CH, on the other hand, on every step of their random
walk have a probability, which depends on their total
number in solution, of spontaneously stopping and
forming the nucleus of a crystal. If another wandering
CH pixel runs into such a nucleus, it sticks on and causes
the crystal to grow.
When all dissolved species have been consumed, new
cement surfaces in contact with water are identified, and
a new cycle of dissolution, diffusion and reaction begins.
The model will continue to a preset degree of hydration,
or until either all cement is hydrated (a slow process), or
until there are no more cement surfaces in contact with
water. In real materials, hydration could continue via the
diffusion of water throughthe layers of C - S - H that cover
unreacted cement, which is not allowed for in our model.
We can typically reach 85-90% of hydration for a given
water/cement ratio with the present model rules.
Recently we have tried to build more of the real,
complex chemistry of Portland cement into the model,
in order to be able to simulate and study the effect of
chemical admixtures on early hydration, and study the
microstructure at the set point more carefully [6,7]. For
that version of the model, we use a combination of
back-scattered scanning electron micrographs and
pixel-by-pixel X-ray maps to uniquely identify each
phase in a given Portland cement. We then use the
resulting colour-coded image as a starting point for
hydration simulation, where now a separate set of
dissolution-diffusion-reaction rules is formulated for
each chemically distinct phase, similar to the rules for
C3S described earlier.
Garboczi
3. INTERFACIAL Z O N E M I C R O S T R U C T U R E
An immediate application of the microstructure model
can be found in studying the microstructure of the
interfacial zone in mortar and concrete. The characteristic
features seen in this region are (i) higher capillary porosity
than in the bulk and generally bigger pores, and (ii) higher
CH volume fractions than are seen in the bulk. These
features are typically seen in the cement paste volume
that is within 50 p.m of an aggregate surface.
Using the microstructure model, two major causes of
this interfacial microstructure can be identified, neither
of which depends on bleeding. They are (i) the particle
packing effect [8] and (ii) the one-sided growth effect [9].
The particle packing effect arises from the fact that
particles cannot pack together as well near a flat edge as
in free space. Since the typical aggregate is many times
larger than the typical cement particle, locally the
aggregate edge appears flat. This inefficient packing
causes less cement and higher porosity to be present
initially near the aggregate surface, and so even after
hydration this condition persists. The width of the
interfacial zone will then scale with median cement
particle size [10]. This is the main contribution to the
interfacial zone microstructure, but not the only one.
The one-sided growth effect arises in the following way.
Consider a small region of capillary pore space located
out in the bulk paste part of a mortar or concrete. On
the average, there is reactive growth coming into this
small region from all directions, since the cement particles
are originally located randomly and isotropically. Now
consider a similar small region of capillary pore space,
but located very near an aggregate surface. Reactive
growth is coming into this region from the cement side,
but not from the aggregate side [9].
Mineral admixtures like silica fume and fly ash can
also be incorporated into the model, and their effect on
interfacial zone properties simulated [11]. We have found
that the two main variables of importance are particle
size, and reactivity with calcium hydroxide. The size of
the mineral admixture controls the width of its packing
effect at the aggregate edge, with smaller admixtures
allowing better packing nearer to the aggregate edge. The
reactivity controls how much calcium hydroxide can be
consumed, and converted to C - S - H . Assuming adequate
dispersion, we have shown, using the model, that the
effectiveness of a mineral admixture in improving t h e
interfacial zone microstructure increases as its reactivity
increases and its size decreases ]-11-]. Colour pictures of
some of these simulations can be found in Bentz and
Garboczi [2] and detailed comparisons with experi-
mental measurements in Bentz et al. [12].
Properties of the aggregate can be studied as well, such
as the effect of porous and/or reactive aggregates. Bentz
et al. [10] present results of the model for the effect of
these variables on the interfacial zone microstructure. We
have found it possible to explain the influence of each of
these material variables on the interfacial zone
microstructure in terms of the particle packing effect and
Materials and Structures 193

the one-sided growth effect. These ideas then serve as a (a) [ I I I I I I I I

1.01
useful theoretical framework to unify analysis of how
cl
material variables affect interracial zone microstructure U.l
[10]. 0.8
III
Z
Z
O 0.6

0C t i
4. T R A N S P O R T P R O P E R T I E S AND O
Z
PERCOLATION THEORY O
0.4
O O 0.45 w/c
We have found the ideas of percolation theory to be very <
r O 0.50 w/c
u.. A 0.60 w/c
helpful in understanding the relationship between the 0.2
v 0.70 w/c
random microstructure of cement-based materials and
their transport properties. The main concept of 0 I I I I I I
0 0.2 0.4 0.6 0.8 1.0
percolation theory is connectivity. Picture some sort of
DEGREE OF HYDRATION
structure being built up inside a box by randomly
attaching small pieces to a central core. Percolation
(b) I I I I I
theory attempts to answer the question: at what point
1.0
does the structure span the box? An alternate form of
this question, for a random structure that already
0.8
spans the box, is: if pieces of the structure are removed LU
at random~ when will it fall apart? The percolation Z
Z
threshold is defined by the value of some parameter, say OO 0 . 6
9
volume fraction, right at the point where the structure Z
_o O [] 0.35 w/c
either achieves or loses continuity across the box. i - 0.4 O O 0.45 w/c
o
.< <> 0.50 w/c
These ideas can be applied to cement paste, for n" 9" 0.60 w/c
IJ_ <>
example, where the random structure being considered 0.2 v 0.70 w/c
[]
is now a particular material phase, and the 'box' is a
macroscopic sample. Immediately after mixing, the solid I I I I
phases are discontinuous, and so the freshly mixed paste 0.2 0.4 0.6

is a viscous liquid. The solid phase is then built up CAPILLARY POROSITY

through random growth of reaction products, and at
some point becomes continuous across the sample. This
percolation threshold is then a rigorous theoretical
definition of the set point, which will tend to occur earlier
in hydration than measured by the Vicat needle test, for
example, since the needle could break through a
percolated but still weak mixture.
A percolation threshold that is more important for
transport processes is the point at which the capillary
pore space loses continuity. At this point, 'fast' transport
of water or ions through the relatively large capillary
pore system would end, and transport would then be
regulated by the much smaller C - S - H gel pores. Using
the model, this threshold can be investigated.
Fig. 2a shows the 'fraction connected' of the capillary
pore space versus degree of hydration for several
water/cement ratios. The quantity 'fraction connected' is
defined as the volume fraction of capillary pores that
make up a connected path through the sample, divided
by the total volume fraction of capillary pores. Immedi-
ately after mixing, the cement particles are isolated, and
so the connected fraction of the capillary pore space is
unity. As hydration occurs, small pockets of pore space
can be trapped between particle clusters, and thus the
connected fraction decreases gradually. At some point,
large clusters of pore space become isolated and the
'connected fraction' goes to zero as connectivity is lost.
This process can be seen in the data for all the
water/cement ratios plotted, except for 0.6 and 0.7. We
have found in the model that water/cement ratios of 0.6
Fig. 2 (a) Connected fraction of capillary pore space plotted
against the degree of hydration for several different
water/cement ratio simulated cement pastes; (b) the same
data for the connected fraction of the capillary pore space
but now plotted against the capillary porosity for several
different water/cement ratio simulated cement pastes.
and above always have a continuous (or percolated)
capillary pore system. This prediction is in good
agreement with the limited experimental results available
[13]. It is clearly seen in Fig. 2a that as the water/cement
ratio decreases below 0.6, less and less hydration is
required to close off the capillary pore system.
In order to try to unify the previous results, we have
re-plotted all the data from Fig. 2a in Fig. 2b, but now
against capillary porosity. All the connectivity data now
fall on one curve, and it is clearly seen that there is a
common percolation threshold at a critical value of
capillary porosity of about 0.18. Even the 0.6 and 0.7
water/cement ratio data fall on this curve, and now it is
clear why these pastes always have an open capillary
pore space: there is not enough cement present originally
to be able to bring the capillary porosity down to the
critical value, even after full hydration. This common
percolation threshold for cement paste, which of course
will have some small sensitivity to cement particle size
distribution and degree of dispersion, implies that there
are now three regions of behaviour for the transport
properties of cement paste.
194
The first region is early in hydration, where the
capillary pore space is fully percolated. These pores are
much larger than the C - S - H gel pores (which are also
fully connected fairly early in hydration [4]) and so
dominate the transport. As the capillary porosity
decreases, the capillary pores also become smaller, and
so the second region is an intermediate region, for
porosities around the percolation threshold, where pure
capillary pore paths have about the same influence on
flow as hybrid paths that are made up of isolated capillary
pockets linked by C - S - H gel pores. Below the critical
capillary porosity, all flow must now go through C - S - H
gel pores, but the flow is still dominated by the hybrid
paths, not just pure C - S - H gel pore paths. If this were
not true, then after a certain point, transport properties
would begin going up with increasing hydration, since
more C - S - H was being formed. This is not the case [4].
The microstructure model has been used to compute
the diffusivity of cement paste by solving Laplace's
equation in the simulated microstructure with a finite
difference method [14-]. Computational results confirm
the above microstructural picture, and compare reason-
ably well with experimental measurements [7,143.
When considering how to take these results for cement
paste and apply them to predicting the transport
properties of concrete, it is necessary to again consider
the interfacial zone pores and their connectivity. Since
interfacial zones are known to contain large pores, they
can offer 'fast' transport pathways for ions and water.
Recent work has shown, using what is known as a 'hard
core/soft shell' percolation model, that in a typical
concrete or mortar, the interfacial zone pores are almost
certainly connected across a given sample (percolated),
so they may indeed have an important effect on transport
properties [15-].
5. CALCIUM HYDROXIDE L E A C H I N G
Changes in transport properties over time are important
for predictions of service life and durability under various
environmental conditions. For example, it is thought that
the chloride diffusivity and thickness of the concrete cover
are the main determinants of the service life of a reinforced
structure exposed to chloride in the environment [-16].
Simple service life models can be made, if the values of the
chloride diffusivity of the concrete cover and the critical
chloride content needed for initiation of corrosion are
known. But what if the pore structure of the concrete and
hence its transport properties are changing over time?
We have examined one simple example of this
possibility by simulating the leaching of calcium
hydroxide, and computing its effect on chloride
diffusivity. A cement paste microstructure is 'grown' in
the computer, and then calcium hydroxide is progress-
ively dissolved using an algorithm similar to that used
to dissolve cement in the hydration simulation. As the
calcium hydroxide dissolves, new capillary pore space is
created. At each stage of dissolution, the diffusivity is
computed and compared with the original, unleached
Garboczi
value. Using the percolation concepts explained above,
it is then clear that large changes in diffusivity can occur
during leaching only when the capillary pore space of a
paste is originally disconnected, but becomes re-
connected as the critical threshold for capillary pore space
percolation is again attained or exceeded [17]. This
reference discusses this topic in greater detail, including
the concept of a critical amount of silica fume replacement
required to prevent the re-percolation of the capillary
pore space. The point to b e emphasized here is that
percolation concepts can give good insight into the
microstructure-transport property relationships in com-
plex porous materials like cement-based materials, even
when the microstructure is changing with time.
6. NEW RESEARCH DIRECTIONS
AND CONCLUSIONS
An exciting area that we are just starting to consider is
that of elastic simulations. Treating each pixel in our
digitized microstructure as a finite element, and assigning
each pixel elastic properties according to its phase
identification, we can apply an arbitrary strain and then
solve the elastic equations for the stress everywhere.
Using these results, we have produced two-dimensional
stress maps [7], showing how different parts of a cement
paste microstructure carry a given load, and can predict
the elastic moduli of cement paste as a function of degree
of hydration and capillary porosity. We plan to combine
this new elastic algorithm with our previous interfacial
zone microstructure simulations, and study load transfer
between matrix and aggregate. We can also treat cement
paste as a uniform continuum, embed sand particles in
it, and study the effective elastic moduli of mortar as a
function of sand volume fraction and particle size
distribution.
Another really exciting possibility for this kind of
computational materials science approach is in the area
of microstructural design. W h a t this means is using
computer simulation to decide if a certain kind of
microstructure could give improved performance by
actually building it in the computer and computing its
properties. An example might be if someone has an idea
how to modify the cement manufacturing process to
produce elongated cement particles with an aspect ratio
of 10:1. Cement paste made from such a particle could
easily be simulated, and its properties predicted. If these
looked favourable, it might then be worthwhile for the
would-be inventor to work on his modified cement
manufacturing process. Another example might be
producing cement grains with certain phases tending to
appear more on the surface, or a blended cement with a
certain composition. Again, such cement pastes could be
simulated, and properties computed. Possible areas of
application are wide, and became wider still as we develop
simulations of new properties and build more chemical
and structural information into our simulations. We will
continue to carefully check predicted properties against
experimental results, and simulated microstructures
Materials and Structures
against real microstructures, to be sure that our
computations are giving accurate predictions of the
properties of real materials.
ACKNOWLEDGEMENTS
I would like to thank the R I L E M General Council and
the Jury members for awarding me the 1992 Robert
L'Hermite Medal. There are many others who have
shared in this work, and I would like to acknowledge
them as well. First of all, the original version of the
digital-image-based cement paste microstructure model
was developed at N I S T by my colleague Dale Bentz, and
almost all the work described above was carried out in
collaboration with him. Second, I would like to
acknowledge Hamlin Jennings, who, while at NIST,
developed the first real cement paste microstructure
model incorporating a simulation of reactive growth via
hydration, which was an inspiration for our later work.
And third, I would like "to acknowledge Professor
Wittman and his collaborators' work in 'numerical
concrete'. Their idea of applying a finite-element
algorithm to a microstructural image, a diagram of which
graced the cover of Materials and Structures for several
years, foreshadows the work I have described. In
addition, I would like to acknowledge all my other
collaborators: P. E. Stutzman, K. A. Snyder, N. S. Martys,
R. T. Coverdale, B. R. Christensen, T. O. Mason, A. R.
Day, M. F. Thorpe, D. N. Winslow and M. D. Cohen. I
would also like to thank the National Science
Foundation Center for Advanced Cement-Based Mater-
ials for partial funding of nearly all the work described
above. Finally, I would like to thank J. R. Clifton and
G. J. Frohnsdorff for much encouragement, and for their
long-term commitment to, and support of, the modelling
of cement-based materials.
REFERENCES
1. Allen, A. J., Oberthur, R. C., Pearsons, D., Schofield, P.
and Wilding, C. R., 'Development of the fine porosity
and gel structure of hydrating cement systems', Phil.
Ma 9. B 56(3) (1987) 263-288.
2. Bentz, D. P. and Garboczi, E. J., 'Computer modelling of
cement-based materials', Cray Channels 14 (1992) 12-16.
RESUME
Etude de mat~riaux ~ matrice de ciment par les techniques
de simulation appliqu~es/i la science des mat6riaux
Cet article d&rit les r~sultats th~oriques dYtudes r~centes
de matbriaux ~ matrice de ciment au moyen des techniques
de modklisation appliqukes ~ la science des matkriaux.
On a utilisb des modules de microstructure obtenus
par ordinateur pour simuler le dkveloppement de la
195
3. Hall, C., 'Looking at cement hydration', Oilfield Rev. 3(2)
(1991) 4-6.
4. Bentz, D. P. and Garboczi, E. J., 'Percolation of phases
in a three-dimensional cement paste microstructure
model', Cem. Contr. Res. 21 (1991) 325-344.
5. Garboczi, E. J. and Bentz, D. P., in 'Materials Science of
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6. Bentz, D. P., Coveney, P. V., Garboczi, E. J., Kleyn, M. F.
and Stutzman, P. E. 'Cellular automaton simulations of
cement hydration and microstructure development,
Modellin9 & Simulation in Mater. Sei. & Engn9,
submitted.
7. Garboczi, E. J. and Bentz, D. P., 'Computational materials
science of cement-based materials, Mater. Res. Soe. Bull.
in press.
8. Scrivener, K. L. and Gartner, E. M. 'Microstructural
gradients in cement paste around aggregate particles' in
'Bonding in Cementitious Composites', edited by S.
Mindess and S. P. Shah (Materials Research Society,
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9. Garboczi, E. J. and Bentz, D. P., J. Mater. Res. 6 (1991)
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88(5) (1991) 518-529.
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15. Snyder, K. A., Winslow, D. N., Cohen, M., Bentz, D. P.
and Garboczi, E. J., 'Percolation and pore structure in
mortars and concretes', Cem. Concr. Res. in press.
16. Clifton, J. R. and Knab, L. I., 'Service life of concrete',
Internal Report NISTIR 89-4086 (National Institute of
Standards and Technology, Gaithersburg, MD, 1989).
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space percolation and diffusivity', Mater. Struct. 25
(1992) 523-533.
microstructure pendant l'hydratation, et on applique des
algorithmes exacts fi ces modOles afin de calculer les
propriktbs physiques vbrifiables exp&imentalement. On
trouve une bonne concordance entre les r~sultats
expkrimentaux et ceux obtenus par simulation. Cet article
est une adaptation de la confOrence pr&ent& • l'occasion
de la remise de la MOdaille Robert L'Hermite, lots de la
46dine ROunion du Conseil Gkn&al de la R I L E M ~t
Madrid, le l er octobre 1992.