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Elastic Properties of the Main Species Present in Portland Cement Pastes

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DOI: 10.1016/j.actamat.2008.12.007

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Acta Materialia 57 (2009) 1666–1674

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Elastic properties of the main species present in Portland cement pastes

H. Manzano a,*, J.S. Dolado a,b, A. Ayuela c
a
LABEIN-Tecnalia, Parque Tecnológico de Bizkaia, Edificio 700, 49160 Derio, Spain
b
Nanostructured and Eco-efficient Materials for Construction Unit, Associated Unit LABEIN-Tecnalia/CSIC, Spain
c
Unidad de Fı́sica de Materiales, Centro Mixto CSIC-UPV/EHU and Donostia Internacional Physics Center, PO Box 1072, San Sebastián/Donostia, Spain

Received 29 August 2008; received in revised form 4 December 2008; accepted 4 December 2008
Available online 8 January 2009

Abstract

The elastic properties of the most important phases present in cement pastes have been studied by force field atomistic methods. Cal-
culations reproduce the mechanical properties of crystalline species alite, belite and portlandite fairly well. The elastic properties of amor-
phous calcium–silicate–hydrate (C–S–H) gel are also explained in terms of the commonly used structural models 1.4 nm tobermorite and
jennite, once the intrinsic porosity and the silicate chain length are concurrently considered through the appropriate micromechanical
models. The findings conclude that bringing the atomic structure into contact with the mechanical properties of C–S–H gel may modify
the actual view of the gel.
Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Calcium–silicate–hydrate (C–S–H); Crystal structure; Elastic behavior; Atomic potentials; Nanostructure

1. Introduction Thus, the topic of this work is understanding their struc-

The cement matrix is a complex material with many
crystalline phases. Both unreacted species and hydration
products are present and agglomerated by an amorphous
product, the calcium–silicate–hydrate (C–S–H) gel. In
ordinary Portland cement, the raw materials are limestone
and clay. This implies a typical composition of clinkers
with 67% CaO and 22% SiO2 with mainly alite (C3S)
and belite (C2S) species, where in cement chemistry nota-
tion C stands for CaO, S for SiO2 and H for H2O. After
hydration of the clinker, the main components formed
are portlandite (CH) and C–S–H gel. The C–S–H gel is
the most important hydration product, up to 70% of the
final volume, and it is responsible for the cohesion and
mechanical properties of cement pastes. However, when
one considers the intrinsic porosity in cement pastes, these
properties are not only dependent on the C–S–H gel, but
also on the contribution of previous unhydrated species.
*
Corresponding author. Tel.: +34 946073300; fax: +34 946073349.
E-mail addresses: hmanzano@labein.es, hegoi.manzano@gmail.com
(H. Manzano).
tural and micromechanical characteristics and how they
are linked to the mechanical behavior of cements.
The mechanical properties of alite and belite have
been the object of different studies in synthetic and
in situ samples, as well as in the perfect stoichiometric
structures C3S and C2S. When measured with techniques
of nanoindentation and resonance frequency, the elastic
moduli of alite and belite are similar, with values
between 130 and 150 GPa [1,2]. Portlandite is also a
well-known mineral, and its mechanical properties have
been determined by many methods such as Brillouin
spectroscopy, X-ray spectroscopy and first-principles
atomistic calculations based on density functional theory
(DFT). Several nanoindentation measurements obtained
similar Young’s moduli (E) for portlandite: 36 GPa [2]
and 40 GPa [3]. These results are in agreement with (i)
the extrapolations of different samples to zero porosity,
E = 35.2 GPa [4] and E = 48 GPa [5], and also with (ii)
the values calculated by Monteiro and Chang [6], where
E ranges between 39.8 and 42.2 GPa after numerical
analysis of data measured by Brillouin spectroscopy [7]
and X-ray diffraction [8].

1359-6454/$34.00 Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2008.12.007
 Author's personal copy
H. Manzano et al. / Acta Materialia 57 (2009) 1666–1674
Regarding C–S–H gel, different nanoindenting tests
show the existence of two types of gels in terms of their
elastic properties: a low stiffness (LS) C–S–H gel with the
indentation modulus M  19 GPa and a high stiffness
(HS) variety with M  28 GPa [2,9]. This bimodal distribu-
tion in the indentation modulus fits perfectly with Jennings’
model [10,11]. In this model, globular 5 nm particles pack
themselves into a loose low density (LD) C–S–H gel with
a packing efficiency gLD = 64%, or into a high density
(HD) C–S–H gel with gHD = 74%. Several works [3,9] have
further advanced the correlation between LS–HS and LD–
HD varieties. They obtained the C–S–H indentation mod-
ulus using the back analysis procedure. These works iden-
tify the Jennings globule with a single crystal, which has an
indentation modulus Ms  60 GPa and a Young’s modulus
E  55 GPa [3,12]. These works provide strong evidence
for the existence of a unique C–S–H nanoparticle. The pic-
ture that emerges from coupling Jennings’ model with nan-
oindenting results is also supported by recent atomistic
simulations which found Young’s modulus for Hamid’s
structure (C/S = 1) to be E = 57.1 GPa [13].
The present work calculates the elastic properties of the
calcium–silicate-based species present in cement pastes
using an atomistic method. Specifically, bulk, shear and
Young’s moduli are calculated together with their Poisson
ratio. Although this method is appropriated for crystalline
phases, a direct calculation of the elastic properties of C–S–
H gel is impossible, owing to its unsettled atomic structure.
To overcome the problem, a starting point is taken using
the related crystalline structures of 1.4 nm tobermorite
and jennite. Then, well-known (nano)characteristics of
the C–S–H gels were applied to these crystals. Specifically,
intrinsic nanoporosity and the finite length of silicate
chains are accounted for. This scheme can reasonably bring
into contact the bulk crystalline properties with those of C–
S–H gels. This process adds new insights for C–S–H gels
into the links between structure and mechanical properties.
2. Force field methods
The calculations use the force field method [14]. The
atoms are represented as spheres, where their electronic
nature is taken into account implicitly with some parame-
ters, such as their charge and their radius. The interaction
between atoms is described by parameterized interatomic
potentials so the system energy can be traced back from
their position. The force field method gives accurate infor-
mation on structures, thermodynamic properties and
mechanical properties with a low computational effort.
The election of suitable potentials is the cornerstone of
any force field simulation. There are a large number of
published potentials for a wide range of systems. However,
there is no guarantee that certain potentials could properly
simulate structures different from the originals used to fit
them. The potentials are usually built up to describe the
interactions of atoms under a given neighborhood. Conse-
quently, the same atoms in different environments are
1667
expected to interact with each other in different ways.
Therefore, before any simulation, the employed sets of
potentials must be carefully checked with the experimental
data to assess their transferability.
The starting subset of interatomic potentials is the one
employed in Ref. [15] to simulate a tobermorite-like struc-
ture. Preliminarily, this scheme was used to describe the
mechanical properties of many crystalline-related C–S–H
phases [16]. The interactions between silicate ions are based
on the well-known potentials for zeolites [17–19]. The Si–O
interaction uses Buckingham potentials with a three-body
harmonic potential to simulate the bond hybridization.
The Ca–O ionic interactions are modeled by Buckingham
repulsive potentials [20]. The intermolecular interactions
between water molecules and other species are described
using Buckingham potentials, whereas the interaction
between different water molecules are described using a
Lennard–Jones potential. The intramolecular interactions
within water molecules are simulated with the Buckingham
potential and a three-body harmonic potential for the H–
O–H angle [21]. The coulomb interaction within water mol-
ecules has been subtracted. Thus, the charges of hydrogen
and oxygen atoms serve only to describe their interaction
with other atoms, and not to determine the structure in
water molecules. By eliminating this coulombic term first,
one drastically reduces the number of interactions that
must be computed and adds more flexibility to the config-
uration of water. The polarizability of oxygen atoms is
described by the core–shell approach [22]. In this model,
the atoms are treated as internal cores linked to external
massless shells. Both the core and the shell are linked by
a spring potential and have specific charges. It must be
noted that not all oxygen or calcium atoms are equal.
The environment surrounding a specific atom has a great
influence on its chemical behavior, bond distances, bond
strengths and other properties. Hence, the differences are
distinguished between atoms with different values for the
corresponding potential parameters (see Table 1). (Oxygen
atoms can be in water, hydroxyl groups, oxides or silicate
chains. Calcium atoms can be bonded to oxygen, water
or OH groups.)
The simulations were done with the GULP code [23].
The experimental data for the crystalline structures were
optimized by relaxing the unit cell parameters and the
atomic forces. The symmetries were eliminated once the
experimental full unit cells were generated to allow aniso-
tropic variations, even if the atoms were in specific symme-
try positions. The search of local minima followed the
Newton–Raphson procedure with the Broyden–Fletcher–
Goldfarb–Shannon (BFGS) [24] scheme to update the Hes-
sian. Then, the elastic constant tensor was calculated from
the second derivative matrix in the optimized structures.
The bulk (K) and shear (G) moduli were determined from
the elastic constants according to the averaged Hill defini-
tion [25]. The average Young’s modulus (E) and Poisson’s
ratio (t) were calculated through the standard relations for
isotropic media:
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1668 H. Manzano et al. / Acta Materialia 57 (2009) 1666–1674

Table 1
Potentials and parameters employed in this work*.
Species Charge core Charge shell Spring constant Ref.
Si 4.00 [17,18]
Cainter–intra–port 2.00 [20]
Ow 1.25 2.05 209.45 [21]
Osi 0.87 2.87 74.92 [17–19]
Ooh–port 0.87 2.27 74.92 [19]
Hw–oh–port 0.40 [21]
Water intramolecular potentials
Morse D (eV) a (Å2) H (Å) Cut off (Å)
Ow–Hw 6.2 2.22 0.924 0.0–1.4 [21]
Three-body harmonic k (eV rad2) h (°) Cut off 1–2–3 (Å)
Ow–Hw–Hw 4.2 108.69 0.0–1.2/0.0–1.2/0.0–2.4 [21]
1.4 nm tobermorite, jennite
Buckingham A (eV) q (A) C (eV Å6) Cut off (Å)
Si–O 1283.907 0.32052 10.66158 0.0–12.0 [17,18]
Si–Ooh 983.557 0.32052 10.66158 0.0–12.0 [17,18]
Si–Ow 983.557 0.32052 10.66158 0.0–12.0 [19]
Cainter–Osi 1090.4 0.3437 0.0–12.0 [20]
Cainter–Ooh 777.27 0.3437 0.0–12.0 [20]
Cainter–Ow 777.27 0.344 0.0–12.0 [20]
Caintra–Osi 1090.4 0.3437 0.0–12.0 [20]
Caintra–Ooh 1090.4 0.3437 0.0–12.0 [20]
Caintra–Ow 777.27 0.3437 0.0–12.0 [20]
Osi–Osi 22,764.0 0.32052 27.879 0.0–12.0 [17,18]
Osi–Ooh 22,764.0 0.149 13.94 0.0–12.0 [17,18]
Osi–Ow 22,764.0 0.149 0.149 0.0–12.0 [19]
Ooh–Ooh 22,764.0 0.149 6.97 0.0–12.0 [19]
Ooh–Ow 22,764.0 0.149 0.149 0.0–12.0 [19]
Ooh–Hw 311.97 0.25 0.0–12.0 [19]
Ow–Hw 396.0 0.25 0.0–12.0 [21]
Ow–Hoh 311.97 0.25 0.0–12.0 [19]
Morse D (eV) a (Å2) q (Å) Cut off (Å)
Ooh–Hoh 7.0525 3.1749 0.9428 0.0–1.4 [19]
Lennard–Jones A (eV Å6) B (eV Å12) Cut off (Å)
Ow–Ow 39.344.98 42.15 0.0–12.0 [21]
Three-body harmonic k (eV rad2) h (°) Cut off 1–2–3 (Å)
Si–O–Si 2.0972 109.47 0.0–1.8/0.0–1.8/0.0–3.2 [17,18]
Portlandite
Morse D (eV) a (Å2) q (Å) Cut off (Å)
Oport–Hport 6.2 2.22 0.924 0.0–1.4 [21]
Lennard–Jones A (eV Å6) B (eV Å12) Cut off (Å)
Oport–Oport 39.344.98 42.15 0.0–12.0 [21]
Buckingham A (eV) q (A) C (eV Å6) Cut off (Å)
Caport–Oport 777.27 0.3437 0.0 0.0–12.0 [20]
*
The subscripts indicate the atomic environments: oh, hydroxyl group; si, SiO4 group; w, water molecule; port, portlandite; inter, interlaminar atom;
intra, intralaminar atom.

9G sizes large enough to be seen with nanoindentation measure-

E¼ ð1Þ
3 þ G=K ments, and the measured elastic properties are compared
with the computed results. Secondly, the complex C–S–H
and gel is examined by applying a homogenizing sub-micro-
3  2G=K scopic model with defects in the involved crystalline compo-
m¼ ð2Þ nents, which are 1.4 nm tobermorite and jennite (Fig. 2).
6 þ 2G=K
3.1. Highly ordered phases present in cement pastes
3. Results and discussion
3.1.1. C3S
The results are presented in two different sections. First, The computed values for the cell parameters are shown
C3S, C2S and portlandite are studied (see Fig. 1). They are in Table 2. The unit cell parameters are in good agreement
present in the cement matrix as crystalline structures with with the experiments [26] with errors <2.5%. The atomic
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H. Manzano et al. / Acta Materialia 57 (2009) 1666–1674 1669

Fig. 1. Geometries of crystalline phases. Optimized structures of: (a) C3S in the xz plane; (b) C2S in the xz (right panel) and the yz plane (left panel); (c)
portlandite in the xz plane. Silicon tetrahedra are in dark purple, calcium atoms in large orange spheres, oxygen atoms in small red spheres/sticks, and
hydrogen atoms in light white sticks. (For interpretation of color mentioned in this figure the reader is referred to the web version of the article.)

Fig. 2. Crystals related to C–S–H gel: optimized structures of: (a) 1.4 nm tobermorite; (b) jennite. The left and right panels are the projections in the xz
and yz planes, respectively. The atom labels are given as in the previous figure. Additionally, water molecules are indicated by joined sticks.

arrangement and the coordination tetrahedra do not
change greatly from the input experimental coordinates
(see Fig. 1a). Also the computed values for the mechanical
properties are in agreement with the experimental data
given in Table 3. There are no direct experimental measure-
ments of the bulk (K) and shear moduli (G) for this clinker
phase. Young’s modulus (E) was determined by nanoin-
dentation measurements with a result of E = 135 GPa
[1,2]. Using resonance frequency techniques and extrapo-
lating the results of samples with different porosities to zero
porosity, a slightly larger value of E = 147 GPa was
obtained [1]. The theoretical result of E = 138.9 GPa is
between these two experimental values and in very good
agreement. The computed Poisson ratio, t = 0.28, is also
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1670 H. Manzano et al. / Acta Materialia 57 (2009) 1666–1674

Table 2
Cell parameters of highly ordered phases present in cement pastes; the differences between experimental data and the computed values are also shown.
Alite (C3S) Belite (b-C2S) Portlandite (CH)
Exp. [26] This work % Error Exp. [28] This work % Error Exp. [29] This work % Error
a (Å) 33.08 33.45 +1.13 5.50 5.51 +0.16 3.59 3.55 1.17
b (Å) 7.02 7.12 +1.39 6.76 6.92 +2.44 3.59 3.55 1.17
c (Å) 18.50 18.91 +2.24 9.32 9.94 +6.58 4.91 4.94 +0.72
a (°) 90 90 0.0 90 90 0.0 90 90 0.0
b (°) 94.1 94.9 +0.81 94.1 94.0 0.17 90 90 0.0
c (°) 90 90 0.0 90 90 0.0 120 120 0.0

Table 3
Bulk (K), shear (G) and Young’s moduli (E) in GPa together with their Poisson ratio (t) for the crystalline phases present in cement pastes.
K G E m
Exp. This work Exp. This work Exp. This work Exp. This work
Alite (C3S) – 103.0 – 54.5 147–135 [1,2] 138.9 0.30 [27] 0.28
Belite (b-C2S) – 111.0 – 53.1 140–130 [1,2] 137.9 0.30 [27] 0.30
Portlandite (CH) 39.65 [6] 31.1 16.36 [6] 13.4 40.3 [3], 36 [2] 35.2 0.30–0.325 [6] 0.31

close to the estimated averaged value of t = 0.30 for all this anisotropic effect with values of Ex = Ey = 93.6 and
phase constituents in the clinker [27]. Ez = 32.8 GPa.

3.1.2. C2S 3.2. Cementitious C–S–H gel

The computed cell parameters for belite (Table 2) are
close to the experimental values [28], except for the c axis,
which increases 0.6 Å. Nevertheless, this expansion is
negligible regarding the atomic arrangement (shown in
Fig. 1b) and the crystal properties. The silicate tetrahedron
orientation and the coordination of Ca+2 ions reproduce
the experimental data. Both the computed Young’s modu-
lus (E = 137.9 GPa) and Poisson ratio (t = 0.30 GPa) are
also in good agreement with the experimental data. Note
that the experimental Young’s moduli are 130 and
140 GPa, obtained with nanoindentation and frequency
resonance, respectively [1,2]; and their t ratio values are
estimated as 0.30 [27], as shown in Table 3.
3.1.3. Portlandite
After relaxing the experimental input parameters, the
unit cell of portlandite keeps the trigonal symmetry (see cell
parameters a and b between layers in Fig. 1c). The output
cell dimensions are in agreement with experimental data
[29], and their differences are slightly >1%, as listed in
Table 2. The present calculated value for Young’s modulus
is E = 35.4 GPa, close to the value obtained experimen-
tally. Furthermore, Monteiro and Chang [6] obtained the
values of the bulk and shear moduli together with their
Poisson ratio. The present calculated values for these mag-
nitudes are smaller, but they are also in agreement with the
experimental data, as shown in Table 3. The elastic proper-
ties of portlandite crystals have also been calculated by first
principles using DFT [30]. In such work, Young’s moduli
in the axis directions of the unit cell are anisotropic because
of the layered structure of portlandite, with Ex = Ey = 89.0
and Ez = 38.6 GPa. Although not discussed here, it should
be mentioned that the present calculations also reproduce
3.2.1. Mechanical properties of tobermorite and jennite
Much of the actual knowledge about C–S–H gel is due
to its comparison with some crystals, specifically 1.4 nm
tobermorite and jennite (Fig. 2). Both 1.4 nm tobermorite
and jennite have a sheet-like structure of Ca–O layers
ribbed by silicate chains. These chains where the Si–O tet-
rahedra repeat themselves every three units follow the dre-
ierketten arrangement. In 1.4 nm tobermorite, two of these
tetrahedra are intimately connected to the Ca–O layer
(called pairing tetrahedra), and the remaining one is ori-
ented to the interlaminar space (called the bridging tetrahe-
dron). The final stoichiometry (Ca5Si6O16(OH)27H2O with
Ca/Si ratio 0.83) was resolved in Ref. [31] along with its
exact crystalline structure. Jennite has a similar structure,
with two differences. First, only half the oxygen atoms
belonging to the Ca–O layer are linked to the silicate
chains, whereas the rest are bonded to OH groups and to
an extra Ca–O sheet. Secondly, the spatial arrangement
of silicate chains is slightly different owing to this extra
sheet that bridges the tetrahedra and partially connects
them to the Ca–O layers (see Fig. 2). The stoichiometry
(Ca9Si6O18(OH)65H2O with a Ca/Si = 1.5) and its crystal-
line structure were determined in Ref. [32].
The crystalline structures of 1.4 nm tobermorite and jen-
nite were optimized. The cell parameters and structures
after optimization are shown in Table 4 and Fig. 2. The
small variation in the volume of both species is 3.5%,
mainly due to the cell expansion in the z axis and the per-
pendicular direction to the layers. This expansion can be
attributed to the shielding effect that the interlayer water
molecules made in the dispersive and coulombic attraction
between different sheets. Concerning mechanical proper-
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H. Manzano et al. / Acta Materialia 57 (2009) 1666–1674
Table 4
Cell parameters for highly ordered phases, 1.4 nm tobermorite and jennite, related to C–S–H gel; the differences between experimental data and computed
values are also shown.
1.4 nm tobermorite
Exp. [31] This work
a (Å) 6.74 6.76
b (Å) 7.42 7.34
c (Å) 27.99 29.15
a (°) 90 90
b (°) 90 90.3
c (°) 123.3 122.9
ties, Poisson’s ratio (t) for both 1.4 nm tobermorite and
jennite are in reasonably agreement with the experimental
data for C–S–H gel [33]. This agreement can be explained
because t is related to the ratio between elastic moduli.
However, the calculated Young’s moduli (E) of tobermor-
ite and jennite are 49.9 and 56.0 GPa, respectively, which
are much larger than those of experimental findings for
C–S–H gels, with E  16–25 GPa [3,9]. The calculations
of both bulk (K) and shear (G) modulus with values of
44.8 and 40.2 GPa, respectively, are also overestimating
the experimental data of C–S–H gels. It was found experi-
mentally that K = 18 GPa [34]. To the best of the authors’
knowledge, the shear moduli of C–S–H gel have not been
measured, although an approximated value obtained after
a homogenization analysis gives G  9.7 GPa [9]. The cal-
culated G values are 19.0 and 22.1 GPa for 1.4 nm toberm-
orite and jennite, respectively, which are again significantly
larger than those in the experiments.
The disagreement between experimental and theoretical
values has been traditionally attributed to (nano)porosity-
related effects. The intrinsic values for the Young’s modu-
lus of C–S–H gel have been estimated by reverse analysis
based on micromechanical models. The Mori–Tanaka
(MT) model gives E  47 GPa [35], and the self-consistent
(SC) model gives E  65 and 60 GPa [3,12]. These values
compare well with the prediction reported by Pellenq and
Van Damme (E = 57.1 GPa) [13]. The experimental values
are also in agreement with the computed data for 1.4 nm
tobermorite (E = 48 GPa) and jennite (E = 56 GPa). How-
ever, several experimental studies by 29Si nuclear magnetic
resonance show that the chain length has discrete values
following the 3n  1 rule: those formed with n = 2, 5 and
sometimes 8 silicon tetrahedra are especially stable [36–
38]. Consequently, the picture drawn is still incomplete,
and the situation is far more complex and intriguing. As
advanced in a preliminary work [16], it seems dubious (or
at least not completely justified) that the intrinsic mechan-
ical properties of solid C–S–H particle could be directly
correlated with those of perfect crystalline structures.
3.2.2. Tobermorite-like and jennite-like structures with
shortened silicate chains
There is overall agreement that the silicate chain struc-
ture of C–S–H gel is formed by the omission of bridging
tetrahedra [39,40]. Based on this statement, the authors
1671
Jennite
% Error Exp. [32] This work % Error
+0.29 10.57 10.63 +0.56
1.09 7.26 7.34 1.10
+4.14 10.93 11.13 +1.82
0.0 101.3 102.7 +1.38
+0.33 97 93.9 3.19
0.32 109.7 110.1 +0.36
built a bulk material of tobermorite-like species (T), and
jennite-like species (J), formed by dimeric (T2, J2), penta-
meric (T5, J5) and octameric (T8, J8) chains. The omission
of bridging tetrahedra in jennite does not change the total
charge of the unit cell when one eliminates a silicon atom
(+4) and two oxygen atoms (2). In the case of tobermor-
ite, one has to remove a silicon atom (+4), an oxygen (2)
and an OH group (1). With this procedure, the system
would gain one electron. To return the unit cell to its neu-
tral state, two possibilities have been considered. In the first
case, the extra charge has been compensated by saturating
half of the terminal oxygen atoms of silicate chains with H,
so that they form terminal OH groups (species denoted by
TOHn). In the second case, the necessary number of calcium
atoms has been introduced in the interlayer space to coun-
terbalance the charge (TCan).
The relaxation of these new tobermorite-like and jen-
nite-like structures with defects leads to small changes in
their structure. For tobermorite-like species, the main
change is the movement of interlayer Ca ions towards the
vacancy left after removing the bridging silicon tetrahe-
dron. For jennite-like structures, the absence of bridging
tetrahedra implies a slight atomic rearrangement in the
Ca–O layer. The new terminal oxygens, previously bonded
to the silicon bridging atom, now enter in coordination
with this Ca–O layer, and change the orientation of the sil-
icate chains. This possibility of charge compensation makes
the Ca interlayer atoms remain in their positions. The large
atomic rearrangement in jennite-like structures does not
happen in those based in tobermorite.
The mechanical properties for these shortened species
are listed in Table 5. As expected, the mechanical proper-
ties of both species increase as the chain length increases,
owing to the stability given by the longer silicate chains
attached to the Ca–O layers. The main improvement in
the elastic properties is due to the incorporation of the first
bridging tetrahedron, which merges two dimer structures
into a pentamer. This suggestion is supported by the
non-lineal relationship between the mechanical properties
and the chain length. The mechanical properties have the
largest change between dimers and pentamers, whereas
the rise from pentamers to octamers is smaller. For
tobermorite-like species, the structures with pentamer
chains have almost the same properties as their infinite
crystals. For jennite-like structures, the mechanical proper-
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1672 H. Manzano et al. / Acta Materialia 57 (2009) 1666–1674

Table 5
Calculated bulk (K), shear (G) and Young’s moduli (E) in GPa and their Poisson ratio for the tobermorite-like and jennite-like species.*
Ca/Si ratio K G E m
TOH2 1.25 26 14 35.61 0.27
TOH5 1.00 33.7 18.5 46.92 0.27
TOH8 0.94 36.8 19.1 48.85 0.28
TCa2 1.50 25 15.7 38.95 0.24
TCa5 1.10 33.9 18.7 47.39 0.27
TCa8 1.00 47.8 18.5 49.16 0.33
T1 0.83 44.8 19 49.94 0.31
J2 2.25 23.9 13.8 34.72 0.26
J5 1.80 31.8 18.4 46.27 0.26
J8 1.69 37.8 21 53.16 0.27
J1 1.50 40.2 22.1 56.03 0.27
Exp. data C–S–H gel 0.7–2.3 [40] 18 [34] 9.7 [9] 19–28 [9] 0.25 [33]
*
T denotes tobermorite; J, jennite. The subscripts OH and Ca refer to the charge used compensation method (see text). The end number is the chain length
n, where n is the number of silicon atoms.

ties are not close to the crystal ones when using the penta-
mer chains, and one must look to the values of octamer
chains. This finding could be explained by the bridging tet-
rahedra playing a more active role here in the stabilization
of Ca–O layers than in tobermorite. The differences
between the tobermorite-like species balanced by OH
(TOH) groups and by Ca ions (TCa) are also examined.
The added calcium ions take the place of removed silicon
with air void inclusions. Thus, the mechanical properties of
C–S–H gel are written as a function of those values for
solid phases (i.e., those of the Tn and Jn structures) and
of certain packing factors (g) which are related to the gel
porosity (p) through the equation g = 1  p. Within the
SC approach [43], the bulk and shear moduli of C–S–H
gel (KC–S–H gel and GC–S–H gel) are given in the following
expressions:

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
GC–S–H gel 1 5 3 1 2
¼  ð1  gÞ  r0 ð2 þ gÞ þ 144ð1  r0  480g þ 400g2 þ 408r0 g  120r0 g2 þ 9r20 ð2 þ gÞ ð3Þ
G0 2 4 16 16

tetrahedra and hold together, giving continuity to the sili-

cate chains. Nevertheless, there is no significant improve- 4gG
ment in the mechanical properties, which change from K C–S–H gel G0
¼ 4G
ð4Þ
E = 35.6 GPa to E = 38.9 GPa in the case of dimers. This K0 Goþ3ð1gÞr0
effect is even less important in the case of longer chains.
where g is the packing factor, K0 and G0 are the bulk and
In addition, it was observed that the Ca/Si ratios increase
the shear modulus of crystalline species, and r0 is a param-
from 0.83 in tobermorite and 1.5 in jennite to values in
eter defined as the ratio K0/G0. In the MT approach [44],
the range between 0.94 and 2.25, respectively. This rise is
the bulk and shear modulus are written as
in agreement with the ideas in Refs. [41,42]: the higher
Ca/Si ratio of C–S–H gel with respect to tobermorite and K C–S–H gel 1a
¼g ð5Þ
jennite crystals is due to the omission of bridging tetrahe- K0 1  ag
dra and the incorporation of extra Ca ions to balance the GC–S–H gel 1b
charge, which was the authors’ procedure to build the ¼g ð6Þ
G0 1  bg
highly ordered phases related to C–S–H gel.
where g is again the packing factor, and a and b are two
To sum up this section, in the present simulations there
parameters dependent on the bulk and the shear modulus
is a noticeable disparity between the mechanical properties
of crystalline species (K0 and G0):
of T2 and J2 and those with longer tobermorite- and jen-
nite-like structures (T5, J5, T8 and J8). 3K 0
a¼ ð7Þ
ð3K 0 þ 4G0 Þ
3.2.3. Mechanical properties of C–S–H gel
ð6K 0 þ 12G0 Þ
Following Refs. [3,12], the properties of the Tn and Jn b¼ ð8Þ
crystals are scaled up to those of C–S–H gel using the ð15K 0 þ 20G0 Þ
homogenization procedure of the SC and the MT micro- Thus, the values obtained for both models are applied to
mechanical models. Here the C–S–H gel is pictured as a Eqs. (1) and (2), and Young’s modulus and Poisson’s ratio
composite made of a solid phase (the Tn and Jn structures) are recalculate. For a better comparison with the
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H. Manzano et al. / Acta Materialia 57 (2009) 1666–1674 1673

experimental data, the indentation modulus (M) of C–S–H
gels is calculated using
E the change in indentation modulus with the packing, espe-
M¼
ð1  m2 Þ
Both SC and MT models are applied with two packing fac-
tors. The g values are 0.64 for the LD-C–S–H gel and 0.74
for the HD-C–S–H gel. The indentation modulus of C–S–
H gels (MC–S–H gel) as a function of the length of Tn and Jn
crystals is displayed in Fig. 3a and b for the SC and the MT
scheme, respectively. The triangles indicate low packing
g = 0.64, while the squares indicate high packing
g = 0.74. The experimental ranges found in Ref. [9] for
LS-C–S–H and HS-C–S–H gels are also shown as
shadowed areas. For both micromechanical models, the
stiffness depends clearly on the packing factor and the
silicate chain length. As expected, the indentation modulus
increases with the packing factor and with the silicate chain
length. Moreover, it is remarkable that both models cap-
ture the range measured for LS- and HS-C–S–H gels.
The main difference between both schemes depends on
ð9Þ cially for the SC model. Within the SC scheme, the packing
factor is the main reason for the change from the LS region
to the HS one. In comparison, the MT gap between the LS
and HS regions can be crossed by changing the silicate
chain length. Several conclusions can be drawn, in spite
of the micromechanical model employed. The HS-C–S–H
gel is composed only of highly polymerized silicate chains.
From the present results, T2 and/or J2 units can never par-
ticipate in the HS arrangements. Additionally, the short sil-
icate chains are always involved in the description of LS-C–
S–H gel. Whether present or not, longer chains in the LS-
C–S–H gel cannot be fully elucidated from the present sim-
ulations, as they provide a different conclusion, depending
on the micromechanical model employed. Further detailed
correlations between experiment and theory will require
additional C–S–H measurements and calculations.

4. Conclusions
a 35
J This work investigated, through force field atomistic
TCa simulations, the elastic properties of the most important
Indentation Modulus (M) GPa

TCa
30 TOH
phases present in Portland cement pastes. The following
TOH
J
HS were proved.
J
25 TCa
TCa TCa
TOH (i) The lattice parameters of studied crystalline species
TOH TOH
J J (C3S, C2S and CH) are in agreement with the exper-
20 TCa imental results. This agreement corroborates the suit-
TOH LS
J ability of the method and the transferability of the
15 potential parameters. The predictions for their
η = 0.64) mechanical properties are also in agreement with
MT (η
(η = 0.74) the experimental data obtained by nanoindentation
10 MT
and other techniques, such as Brillouin spectroscopy
2 3 4 5 6 7 8 and frequency resonance.
Silicate Chain Length (n) (ii) Simulations have shown that the mechanical proper-
ties of 1.4 nm tobermorite and jennite (usually
b 35 employing structural models of CSH gel) are about
twice as great as those of C–S–H gel. Nevertheless,
J when applying characteristics such as intrinsic poros-
Indentation Modulus (M) GPa

30
TCa TCa HS ity and the finite chain length of the C–S–H gel to the
TOH
TOH crystals, the mechanical properties decrease and reach
25 J values in excellent agreement with nanoindentation
TCa
measurements for C–S–H gels.
20 TOH J (iii) Though the elastic properties of C–S–H gels have
J TCa TCa been traditionally explained in terms of solely poros-
TOH LS
TOH ity-related effects, simulations show that the silicate
15 TCa J
chain length also matters. In fact, the results indicate
TOH that the longer the silicate chains, the better the
J
SC (η = 0.64)
10 SC (η = 0.74) mechanical properties.
(iv) Interesting linkages are suggested between the atomic
2 3 4 5 6 7 8 structure and the mechanical properties of LS- and
Silicate chain length (n) HS-C–S–H gels. According to the simulations, the
Fig. 3. Indentation modulus vs silicate chain length for: (a) SC microme- mechanical properties of HS-C–S–H gel can only be
chanical model; (b) MT model. Squares indicate HD values (g = 0.74); explained if it consists of pentamers and/or larger sil-
triangles indicate low densities (g = 0.64). icate units. Unfortunately, the simulations cannot
 Author's personal copy
1674 H. Manzano et al. / Acta Materialia 57 (2009) 1666–1674
unequivocally determine the units which make up the
LS-C–S–H gel. Further work combining experiment
and theory must be done in order to clarify this
situation.
Acknowledgements
This work was supported by the Basque Government
through the NANOMATERIALS Project (IE05-151) un-
der the ETORTEK Program (NANOMAT), Spanish Min-
isterio de Ciencia y Tecnologı́a (MCyT) of Spain (Grant
No. Fis 2004-06490-C03-00 and MONACEM Project)
and the European Network of Excellence NANO-
QUANTA (NM4-CT-2004-500198). The computing re-
sources of the Donostia International Physics Center
(DIPC) and those of the Supercomputation Center of Gali-
cia (CESGA) are gratefully acknowledged.
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