www.mrs.

org/publications/bulletin

contact angle), and to the cross sectional

Why Does Concrete area A of the liquid bridge. Under equilib-

rium conditions, rK is determined by the
vapor pressure, whereas the bridge vol-
ume and area depend on the average cur-
vature and the surface roughness of the

Set?: The Nature of grains. As the vapor pressure increases,

the area increases, but the meniscus radii
also increase, so that cohesion goes through
a maximum. In sand totally saturated with

Cohesion Forces in water, cohesion is again vanishingly

small, because all the internal menisci dis-
appear and the material turns to slurry.
Can this simple argument be applied to

Hardened Cement- clay- and cement-based materials? Yes, to

some extent.4 A wall of clay-rich earth or
hardened concrete always contains a sig-
nificant fraction of liquid water from the

Based Materials capillary condensation of water vapor in

the intergranular pores. Clay particles
the glue of earth (see the article by
Houben et al. in this issue of MRS Bul-
Roland J.-M. Pellenq and Henri Van Damme letin)are much smaller than sand grains,
and this increases both the strength and
the number of capillary bonds in the
Abstract material. However, the sensitivity of earth
Unlike other porous materials such as sandstone, brick, or porous glass, the cohesion to relative humidity is much
interatomic bonding continuity of cement-based materials like concrete is far from more limited than that of sand, which sug-
obvious. When scrutinized at the micro- or nanoscopic level, the continuity of the gests that other forces may complement
ioniccovalent bonding in the solid phase is interrupted almost everywhere by water capillary forces.
molecules or liquid water films. The same situation is found in set plaster.Yet, plaster and
When it comes to concrete, it is obvious
that additional interactions must be in-
cementitious materials are able to withstand stresses of the same order of magnitude as
volved. Cement is able to set under water,
rocks. Molecular simulation studies and direct-force measurements by atomic force
and its cohesion is only moderately sensi-
microscopy provide strong arguments for predicting that short- and medium-range
tive to relative humidity. In addition, if
surface forces mediated by partially or totally hydrated calcium ions are the essential capillary or van der Waals forces were the
components of cement strength, with additional contributions from van der Waals and main forces ensuring the cohesion of hard-
capillary forces. This provides a clue for understanding the nano- and mesostructure of ened cement, then any silicate with a
cement-based materials and new levers for improving their properties. roughly similar composition and particle
size distribution would have, at the same
Keywords: atomic-scale simulations, cement, cohesion forces, concrete, construction density, a comparable cohesion. This is not
materials, porosity. confirmed by common experience. What
then is the mechanism of cement cohe-
sion? Should hardened cement be consid-
Introduction ered a porous and partially crystalline
What is the difference between a one- In dry sand, cohesion is vanishingly sol-gel network owing its strength to the
meter-high sand castle on a beach, a seven- small, and building even the smallest ver- continuity of ioniccovalent bonding? Or
story earthen building in Yemen, and a tical wall out of dry sand is virtually im- is it better described as a packing of
1000-foot-high concrete and steel skyscraper possible. An avalanche starts and flows nanoparticles interacting by means of
in Shanghai? Their height! Indeed, but in until the slope reaches equilibrium. If the water-mediated surface forces? Recent
terms of elementary granular-material surrounding air contains water vapor, some molecular simulation studies confirmed
mechanics going back to Coulomb in 1773,1 cohesion may be detected in the sand, due by atomic force microscopy (AFM) meas-
the difference comes from cohesion, C, to microscopic capillary bridges between the urements suggest that both pictures are
that is, the internal stress that, together with asperities in contact on the rough surface probably correct.
intergranular friction, prevents a granular of the grains.3 Then, building a vertical
material from dividing in two and sliding wall is still risky but feasible, up to mod- Hydration and Setting
along a failure plane when subjected to a erate heights. For a small liquid bridge (as The setting of cement is not, as some-
force (e.g., its own weight).2 In its simplest compared with the grain size), the attrac- times believed, a drying process; in fact, it
form, the failure criterion reads tive capillary force is related to the Laplace is the exact opposite.5 This is a major dif-
pressure across the air/water meniscus, ference from earth hardening. When ce-


  C, (1) ment is mixed with water, it undergoes a
PLaplace
(2LV cos )/rK , (2) dissolution reaction generating calcium,
where
and  are the shear and normal silicate, and aluminate ions in the intersti-
stresses on the sliding plane, respectively, (where LV is the air/water surface ten- tial solution. New products (hydrates)
and  is the friction coefficient. sion, rK is the meniscus radius, and  is the then precipitate when their solubility limit

MRS BULLETIN/MAY 2004 319

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 Why Does Concrete Set?: The Nature of Cohesion Forces in Cement-Based Materials
is reached and after a nucleation period
that is (improperly) called the dormant
period.6 The most important products (for
Portland cement, for example) are calcium
silicate hydrate (C-S-H) and calcium hy-
droxide (Portlandite). This dissolution
diffusionprecipitation process has been
known since le Chatelier.7 It can be mod-
eled by cellular automata algorithms,8 and
it yields, as expected from the physics of
these phenomena,9 geometrically complex
interfaces. As the hydration reaction pro-
ceeds, more and more anhydrous material
is converted into hydrates, with a decrease
in the porosity, since the volume of hy-
drates (including interlayer water) is more
than twice the initial anhydrous volume.10
Two important mechanical events occur
during hydration (Figure 1). The first is a
simple coagulation of the slurry, due to
the high ionic strength of the aqueous
phase.11 It occurs almost immediately, at
virtually zero hydration, once the cement
is mixed with water. The coagulated net-
work has a poor mechanical strength and
may be destroyed by vigorous mixing. It
is nevertheless strong enough to give the
slurry a measurable shear modulus (Fig-
ure 1) and yield stress, which impedes
workability. Fortunately, coagulation may
be prevented by the use of polymer dis-
persants12 (see the article by Flatt et al. in
this issue). The second and more impor-
tant event is setting. This appears to occur
by a continuous reinforcement process at
the contact areas, leading at some point to
mechanical percolation. At this point, the
shear modulus is in the gigapascal range
(Figure 1). However, only a few percent of
the anhydrous cement has been trans-
formed into C-S-H and other hydrates.13
Figure 1. Time evolution of the complex
shear modulus, G*, of a cement slurry
prepared at a water/cement (by weight)
ratio of 0.80, without (left curve) and
with (right curve) addition of a
dispersant.12 The horizontal line
indicates the minimum significant
detection level.
320
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A Debated Issue:The Structure
and Microstructure of C-S-H
The hydrates give cohesion to hardened
cement. All of the hydrates play a role in
this cohesion, but in Portland cement, the
most important is undoubtedly C-S-H.
Unfortunately, the structure of this hy-
drate is not well documented.
Structure
C-S-H is a nonstoichiometric com-
pound. The average Ca/Si ratio in ordi-
nary hardened cement paste is around 1.7.
Local values, measured by analytical scan-
ning transmission electron microscopy,
fluctuate from 0.6 to 2 or more.14,15 The rea-
son is that the Ca/Si ratio in C-S-H is ther-
modynamically controlled by the calcium
ion activity in equilibrium with it.5
C-S-H is widely recognized to have a
layered crystal structure, akin to that of
the minerals tobermorite or jennite, with a
layer thickness in the subnanometer
range.5,16 This morphology is hardly rec-
ognizable in real hardened cement
paste (as distinguished from synthetic to-
bermoritic C-S-H, obtained from mixing
silica and CaO at moderate temperature),
but it becomes evident from x-ray diffrac-
tion and from direct transmission electron
microscopy (TEM) observations of C-S-H
prepared by reacting colloidal silica with
lime (Figure 2).
High-resolution 29Si, 1H, and 17O nuclear
magnetic resonance (NMR), x-ray absorp-
tion spectroscopy, IR spectroscopy, and
Raman spectroscopy17 give considerable
information on the structure of the layers.
It is accepted that their two-dimensional
backbone is a double plane of Ca2+ ions Figure 2. (a) Model of calcium silicate
6- or 7-coordinated by central O 2 ions, to hydrate (C-S-H) at Ca/Si
0.66, with a
which disordered silica chains are grafted central double layer of calcium ions
connected on each side to chains of
on each side (Figure 2). These composite
silica tetrahedra. (b)Transmission
layers stack along the [001] direction, sep- electron microscopy (TEM) image of
arated by water molecules, Ca2+ ions, and C-S-H prepared by reaction of lime with
possibly OH ions. amorphous silica at Ca/Si
1 (from
In tobermorite, with Ca/Si
0.66, the Reference 32). (c) High-resolution TEM
chains are infinite and run parallel to the micrograph of the hydrated region in a
b axis. Two interlayer distances are ob- real, dense, C-S-H paste (adapted
served, 1.1 nm and 1.4 nm, the difference from Reference 43). AM, NC, and
arising from additional water molecules. MSOR indicate amorphous,
nanocrystalline, and mesoscopically
Two models have been proposed for the
ordered regions, respectively. The
1.1 nm form. In Hamids model,18 the re- distance between layers is 1.5 nm.
peating units along the chains are the so-
called dreierketten, with two pairing
tetrahedra linked to the CaO polyhedra by
sharing edges with them, and one bridg- Merlinos structure,19 the lamellae are linked
ing tetrahedron pointing away from the by bridging SiOSi bonds, generating cavi-
CaO polyhedra layer (Figure 2). All of the ties analogous to those found in zeolites.
oxygen atoms involved in the dangling Up to Ca/Si
1.5, C-S-H may be con-
bonds of the silicate chain are protonated as sidered a defective tobermorite structure.
hydroxyl groups, so that the structure is Above Ca/Si
1, the degree of polymer-
neutral. No chemical bonds exist between ization of the silica chains decreases. Ion-
adjacent lamellae. The interlayer is occupied ization of the hydroxyl groups of the
by water molecules. On the contrary, in dangling bonds generated by this chain
MRS BULLETIN/MAY 2004
 Why Does Concrete Set?: The Nature of Cohesion Forces in Cement-Based Materials
shortening maintains the negative charge
of the layers and the number of Ca2+ ions
in the interlayer space. Above Ca/Si
1.5,
the structure of C-S-H is controversial.
Three main models have been proposed,17
which are either a solid solution with Port-
landite, a nanophase mixture of tobermorite-
and jennite-related units, or a defective
tobermorite further modified by the re-
placement of SiO2 units by Ca(OH)2. It is
this ill-defined, ill-organized, charged, hy-
drated, and layered material that is the
cornerstone of the strength of most of our
buildings, bridges, and roads.
Microstructure
The widespread use of the term C-S-H
gel expresses our inaptitude to qualify
the way that the individual lamellae and
their aggregates fill space. X-ray diffrac-
tion techniques are of little help, which is
a clear sign that the in-plane extension of
the lamellae and the stacking order are
both very limited. High-resolution TEM
shows very little local order in ordinary
cement at early ages, and even in well-
cured, high-density samples, the coher-
ence lengths remain small (see the article
by Vernet in this issue).
Direct observation by AFM of the C-S-H
nanoparticles grown on smooth silica sur-
faces at the solid/lime solution interface
reveals the formation of discrete, elon-
gated 5-nm-thick, disk-shaped particles
with a long axis on the order of 60 nm.20
Each particle is an aggregate of a few C-S-H
lamellae. Globular units of similar size
(
60 nm) are observed by bright-field TEM
observation of ultrathin sections of mature
hydrated calcium silicate pastes.21,22 Al-
though it is not known if these are univer-
sal features, this size is probably about
right for the typical size of locally compact
stacks of C-S-H lamellae.
1, respectively.35,44
The microstructure at larger length scales
is also a controversial question. AFM ob-
servation shows that on silica substrates,
as C-S-H nucleation and growth proceeds,
large assemblies of the basic units form.23
These assemblies grow both laterally, par-
allel to the substrate surface, and axially,
perpendicular to the surface. This bidirec-
tional character of growth was also ob-
served in the dispersed state by soft x-ray
microscopy.24 On a substrate, lateral growth
is always faster, but the ratio of axial over
lateral growth rates depends on the lime
concentration in the solution.23
Such detailed observations cannot be
performed on real dense pastes, but nu-
merous models have been proposed on the
basis of indirect data such as surface area
and porosity determinations.25 The most
recent model26 assumes the existence of
two types of aggregates, compact and
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loose. On the other hand, there is now a
considerable body of evidence from a va-
riety of techniques (small-angle x-ray and
neutron scattering,21,2729 mercury intru-
sion,21 image analysis,21 and NMR relax-
ometry30) that, at high degrees of hydration,
the texture exhibits scale-invariant (fractal)
properties on length scales from at least
the nanometer to the micrometer scale. This
is not in contradiction with the existence
of two types of C-S-H aggregates. Disor-
dered growth processes may lead either to
surface or to mass fractal structures, de-
pending on the rate-limiting step and on
the confinement conditions.9,22
Which Forces?
The previous section indicates that there
are probably two length scales at which
the sources of cohesion have to be sought.
One is the subnanoscale of interlayer dis-
tances within the lamellae stacks and the
contact points between stacks. The other is
the mesoscale of interwall distances in the
fabric of the stacks.
Cohesion at the Subnanoscale
Only atomic-level simulations are rele-
vant at this small length scale. Two meth-
ods have recently been applied to the
computation of the interlayer cohesion en-
ergy of tobermorite-like C-S-H.31,32 The first
involves the minimization of the potential
energy of a pair of tobermoritic C-S-H
lamellae with variable Ca/Si ratios, in-
cluding the interlayer calcium ions, water
molecules, and OH groups, using a set of
semiempirical interatomic potentials suit-
able for oxides. This allows for the compu-
tation of structural (all atomic positions),
mechanical (moduli), vibrational (density
of states), and thermodynamic (energy,
entropy, free energy) data to be compared
with experimental values. In the second
approach, starting from all the atomic po-
sitions thus determined, the nature of all
the interatomic bonds (ionic, covalent,
ioniccovalent), including intra- and inter-
lamellar atomic species, was determined
by a quantum chemical ab initio method,
using the HartreeFock method to solve
Schrdingers equation.
The potential energy minimization was
applied to Hamids and to Merlinos struc-
ture. Hamids structure is a Rietveld re-
finement that presents tobermorite as
independent layers; Merlinos structure
is a Rietveld refinement that presents it
as chemically linked layers; thus, the
two structures have a priori different me-
chanical properties. A relaxed configuration
of Hamid-type tobermoritic C-S-H at
Ca/Si
0.83, with 4 H2O molecules per
unit cell, is shown in Figure 3. Surpris-
ingly, the calculations show that both
Figure 3. A relaxed configuration of
tobermorite-like C-S-H (Hamids
structure), after potential-energy
minimization, at Ca/Si
0.83 with four
H2O molecules per unit cell in the
interlamellar space. Hydrogen atoms
are white, oxygen atoms are red, layer
calcium ions are dark grey, interlayer
calcium ions are light grey, and silicon
atoms are yellow-brown. Note the short
distance between the interlayer calcium
ions and the closest oxygen atom from
the neighboring layer.
structures have almost the same energy at
0 K, which suggests that the electrostatic
interaction between the charged lamellae
and the interlayer calcium ions (Hamids
structure) is as strong as a covalent
SiOSi bond (Merlinos structure).
The Youngs modulus of Hamids struc-
ture (Ca/Si
1), calculated from the ma-
trix of elastic constants, is 57.1 GPa at 0 K.
This has to be compared with the values
(16 GPa33 and 17 GPa34) obtained using ul-
trasonic methods and also the 20  2 GPa
and 31  4 GPa values obtained recently
by nanoindentation measurements for
Ca/Si 1 and Ca/Si
The quantum approach indicates that the
attractive contribution of electronic disper-
sion interactions (van der Waals forces) is
about 20% of the cohesion energy. Impor-
tantly, the partial electronic charge on the
atoms does not depend on the interlamel-
lar distance, which means that the nature
of the inter- and intralamellar bonds re-
mains unchanged. The ionic character of
the bonds in the lamellae is close to 60%.
The charge on the interlamellar calcium ions
is 1.38, which is slightly higher than for
the ions within the lamellae (+1.29), but is
still much lower than the value expected
for a purely ionic bond. If the ions were to-
tally hydrated and free to diffuse in a dif-
fuse electric double layer, they would
have a charge of 2. Furthermore, the dis-
tance between the interlamellar calcium
ions and the oxygen atoms of the lamellae
is very close to the CaO distance within
321
 Why Does Concrete Set?: The Nature of Cohesion Forces in Cement-Based Materials
the lamellae. This indicates that the inter-
layer calcium ions are linked to the lamel-
lae by a strongly ioniccovalent bond.
Cohesion at the Mesoscale
Computation of the wall-to-wall inter-
action between C-S-H surfaces in water-
filled pores, at distances comparable to the
electric double-layer thickness, could be
a priori performed by the same methods as
those just described, but the computa-
tional cost would be prohibitive. A more
realistic approach is to use Monte Carlo simu-
lations in the so-called primitive model
framework (Figure 4). The primitive
model treats the surfaces as homoge-
neously charged walls, water as a dielec-
tric continuum, and the ions as charged
hard spheres. Neglecting van der Waals
interactions, the z component of the inter-
action pressure P can be written as the
sum of three terms:36
PtotalD
PelecD  PcontactD
 PidealD.
The first term is the force resulting from
the sum of all the ionion, ionlamella,
Figure 4. Configuration used to
calculate double-layer interactions by
Monte Carlo simulation, using the
so-called primitive model. Two uniformly
charged walls are separated by a
dielectric continuum in which hydrated
ions are free to move. In the
overwhelming majority of possible
configurations, the distribution of ions is
neither symmetrical with respect to the
midplane nor homogeneous along the
vertical axis. The excess of ions in some
places leads to a deficit in other places.
This generates strongly attractive
electrostatic forces that may overcome
the osmotic repulsion. D is the interlayer
separation; di is the counter-ion
diameter.
322
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and lamellalamella coulombic interac-
tions through a plane at z
0. It is ob-
tained from the z derivative of the energy.
This term is always attractive (negative).
The second, repulsive term is the hard core
contact pressure, which is a consequence
of using ions with a finite and realistic
size. It is proportional to the number of
ions in contact (collisions) through the
central plane. The third term is the re-
pulsive osmotic pressure, (0)kT, due to
the kinetic contribution of the confined ions
(k
Boltzmanns constant; T
temperature).
When this method is applied to surfaces
with a low surface charge density (in the
1 charge/nm2 range) and monovalent
counterions, the results are in excellent
agreement with the PoissonBoltzmann
(PB) treatment (which is the basis of the
double-layer interaction in the classical
DLVO* theory). However, with higher
charge densities and divalent ions, large
deviations from the standard PB treatment
are obtained at short separations.37 For some
(3) realistic values of the parameters, a net at-
tractive interaction may even be obtained.
The reason for this difference is that in
the PB treatment of two identically charged
surfaces with an intervening electrolyte
solution, the two halves of the cell are
symmetrical and both are neutral, so that
no electric field emerges from one cell into
the other. In a real system, the over-
whelming majority of instantaneous ionic
configurations do not achieve this ideal
situation (Figure 4). On average, the electric
field generated by one half of the lamellar
system is still zero in the other half, but for
every configuration, there is a spatially
varying field. The charges of the second
half respond to this instantaneous field by
adopting configurations of lower energy,
different from the mean-field configura-
tion. These correlated polarizations of the
ionic clouds, not taken into account in the
classical PB treatment, are automatically
considered in a Monte Carlo simulation.
They give rise to a van der Waals-type
force, much in the same way as correla-
tions between fluctuating electronic dipoles
give rise to the London dispersion force.
This has been confirmed by an analytical
treatment.38
Ionic correlations can explain the re-
stricted swelling of Ca-exchanged mont-
morillonite, a swelling clay that forms
cohesive lamellar stacks even in dilute
suspensions.39 It is only recently that a pa-
rameter range broad enough to cover the
*DLVO is the name given to a widely accepted
theory describing pairwise interactions be-
tween colloidal microparticles, advanced inde-
pendently in the 1940s by Derjaguin and
Landau and by Verwey and Overbeek.
case of C-S-H hydrates has been investi-
gated. Pellenq et al.40,41 explored charge
densities from less than 1 charge per 2 nm2
to 1 charge per 0.2 nm2. The pressure was
calculated for separation distances from 1
to 5 hydrated ionic diameters.
One or more attractive pressure wells
were obtained with Ca2+ ions in the inter-
layer space. For charge densities similar to
montmorillonite clay, the pressure well is of
the order of 10 atm at a separation distance
of 1.4 nm (Figure 5), in agreement with the-
ory.35,36 But for charge densities of 1 charge
per 0.33 nm2, the depth of the well in-
creases to 600 atm at a separation of 0.7 nm
(Figure 5), which is more than one order of
magnitude larger than the van der Waals
pressure at the same distance. These are the
most attractive conditions. At still higher
charge densities, repulsive-contact interac-
tions in the crowded interlayer space start
to compensate the electrostatic attraction.
Remarkably, the charge density at which
the maximum attractive pressure is ob-
tained corresponds to that of a C-S-H
lamella with all of its OH groups ionized.
The existence of strong noncontact at-
tractive forces was confirmed by direct-force
measurements using a C-S-H-covered
AFM tip and a C-S-H flat surface.42 When
the tipsubstrate system was immersed in
a sodium chloride or hydroxide solution,
only long-range repulsive forces were
Figure 5. Isobaric contour map for two
negatively charged surfaces with
calcium counterions in water. The
surface charge density for a fully ionized
C-S-H surface (0.03 e /nm 2)
corresponds to the deepest attractive
pressure well (lightest blue area). The
interlayer distance D/d is expressed in
units of hydrated calcium-ion diameters.
The zero pressure line is the locus of
equilibrium positions. Numbers inside
the graph are expressed in atm. Blue
regions indicate negative pressure: the
system will want to contract (i.e., reduce
its interlamellar separation) to recover
equilibrium (P
0). Redorange
regions indicate positive pressure: the
system will want to expand to recover
equilibrium.
MRS BULLETIN/MAY 2004
 Why Does Concrete Set?: The Nature of Cohesion Forces in Cement-Based Materials
measured, as expected from DLVO theory.
But when it was immersed in a lime solu-
tion in chemical equilibrium with the
C-S-H, a strongly attractive force, much
larger than the expected van der Waals
forces, was detected at distances of 25 nm.42
These direct-force measurements bring
further evidence that noncontact attractive
forces of an ionic and electrostatic nature-
contribute to the cohesion in cement.
The Next Frontier
The picture that emerges from this short
overview of calcium silicate hydrate cohe-
sion is that of a multifactorial property,
with both short- and meso-range attrac-
tive interactions. Some of these interac-
tions are not specific, like capillary and
van der Waals forces. But the main ones
(ioniccovalent and ion correlation forces)
are very intimately related to a unique
combination of features found in C-S-H: a
high layer charge, divalent counterions,
and water in the interlayer space. Interest-
ingly, this combination is also found in an-
other family of cement hydrates, namely
the mono-sulfoaluminates, but with op-
posite charges (positive layers, divalent
interlayer anions). This suggests that the
same conclusions may apply for the cohe-
sion of those hydrates.
So far, the strength of concrete has been
increased essentially by reducing its poros-
ity through optimizing the size distribu-
tion of the aggregates and filling the
residual porosity of the hydrated cement
phase with mineral fillers such as silica
fume. There are reasons to believe that the
next source of improvement will lie in the
fine-tuning of the hydrates themselves
and of the different parameters that drive
short (ioniccovalent bonding) and long
(ionic correlation) interactions.
Acknowledgments
This research was part of a joint collec-
tive program of the Centre National de la
Recherche Scientifique (CNRS) and the
Association Technique de lIndustrie des
Liants Hydrauliques (ATILH). The authors
are grateful to all of the participating col-
eagues for a very stimulating collaboration.
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