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Acta Materialia 67 (2014) 8194
www.elsevier.com/locate/actamat
Department of Civil and Environmental Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong
b
Department of Civil Engineering Henan Polytechnic University, Henan, China
Received 14 July 2013; received in revised form 12 November 2013; accepted 11 December 2013
Available online 24 January 2014
Abstract
Calcium silicate hydrate (C-S-H) is the most important hydration product of cement-based materials. In the nanostructure of C-S-H,
structural water molecules are distributed in the interlayer region and determine the mechanical performance of C-S-H gel. In this study,
C-S-H gels with dierent water contents expressed as the water/Ca ratio are characterized in the light of molecular dynamics. In order to
study the inuence of the water molecules, the structures of 12 C-S-H gel samples with water/Ca ratios from 0 to 0.95 are investigated. It
is found that the penetration of water molecules transforms the C-S-H gel from an amorphous to a layered structure by silicate depolymerization as the water content gradually increases. The structures are then tested for mechanical properties by simulated uniaxial tension and compression. The mechanical tests associated with structural analysis reveal that the structural water molecules can greatly
weaken the stiness and the cohesive force by replacing the ioniccovalent bond with unstable H-bond connections. By studying the tensile failure mechanism of C-S-H gels at dierent humidity levels, the disconnecting role of the structural water molecules is comprehensively interpreted. Because the interlayer water molecules prevent reconstruction of the bonds between the Caw and the silicate chains, the
plasticity of the C-S-H gels is reduced signicantly in the change from a dry state to a saturated state. In addition, the compressive
strength of a C-S-H gel in the saturated state is much larger than the tensile strength. This provides molecular evidence for the tensile
weakness of cement paste.
2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Calcium silicate hydrate (C-S-H); Water/Ca ratio; Molecular dynamics; Uniaxial tension/compression test
1. Introduction
When Portland cement reacts with water, cement
hydrates are produced. Calcium silicate hydrate (C-S-H)
gel is the dominant cement hydrate, and hence it determines the binding force of the cement paste. For the whole
service life of a cement paste/concrete, the interaction
between water and C-S-H gel determines the mechanical
properties and durability of cement-based materials. On
the one hand, the initial water content of the cement paste,
or water-to-cement ratio, inuences the microstructure of
Corresponding authors.
the cement hydrates [1]; on the other hand, the water molecules, as essential elements of C-S-H gel, are sensitive to
the surrounding environment and humidity [2]. For example, when immersed in water, C-S-H gel is very likely to
reach a saturated state, while the structural water of the
C-S-H may be missing in the case of a re.
In order to understand the role of water in C-S-H gel, it
is necessary to investigate the intrinsic structure and
mechanical performance of the gel at dierent humidity
levels. The molecular structure of C-S-H has been studied
for more than half a century, particularly using a variety
of experimental techniques, including nuclear magnetic
resonance (NMR) imaging [3], X-ray diraction [4] and
small-angle neutron scattering (SANS) [5], and C-S-H is
now widely believed to be the analogue of the layered
1359-6454/$36.00 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.actamat.2013.12.016
82
minerals tobermorite [6,7] and jennite [8]. Based on experimental data, Pellenq et al. [9] employed the molecular
dynamics method to construct a C-S-H model that can
describe well the structural, dynamical and mechanical
properties of cement at the nanoscale. Because the model
is based on previous experimental results, it has been
widely accepted in the nanoscale simulation eld and is
dened as a realistic model. The CSHFF force eld
[10] was developed to describe the interaction between
atoms in cement systems, and this force eld demonstrated
good transferability in simulating cement-based materials.
Water molecules, essential constituents in C-S-H gel,
have been investigated since the birth of the realistic model. Pellenq et al. [9] simulated the stressstrain relation of
C-S-H gel in resisting shear force. By comparing the
mechanical performance of dry and wet C-S-H gels, it
was concluded that, during the loading process, large displacements of water molecules in wet C-S-H gels weaken
the shear strength and result in unrecovered deformations.
Youssef et al. [11] investigated the structural and dynamic
features of water molecules in C-S-H gels. Due to the
highly hydrophilic nature of calcium silicate sheets, Hbonds constructed between the non-bridging oxygen and
water are very strong. Therefore, water molecules constrained in the gel demonstrate a glassy nature: the tetrahedral spatial structure is distorted and the diusion rate is
signicantly reduced. Ji et al. [12] utilized ve classic water
models, SPC, TIP3P, TIP4P, TIP4P05 and TIP5P, to simulate calcium silicate hydrate. They concluded that SPC
and TIP5P accurately describe the intrinsic properties of
C-S-H gel, with SPC (exible) being more computationally
ecient. Recently, Bonnaud et al. [13] interpreted the cohesive force of C-S-H gel by analyzing the uid pressure of
the water molecules and the counter-ions in the interlayer
region. Under dierent humidity conditions, they found
that the cohesive force mainly results from negative pressure caused by the interaction between interlayer calcium
atoms and the calcium silicate sheets. Even though this
work took the amount of water in the C-S-H gel into consideration, the molecular structure of the calcium silicate
sheet was assumed to remain unchanged under dierent
humidity conditions. This assumption, ignoring the structural evolution due to the water eect, needs to be further
investigated.
Previous research on C-S-H gels can be categorized into
two classes: molecular structure analysis and thermodynamics investigation. Few eorts have been made to investigate the evolution of mechanical properties with water
content variation. In particular, the tensile strength of CS-H gels at the nanoscale, considered as the most essential
property of construction material, has not been studied so
far. The aim of this paper is to bridge the relationship
between the morphology and the mechanical performance
of C-S-H gels in dierent humidity conditions. On the
one hand, the structural feature evolution can be characterized by analyzing the silicate chain morphology and
chemical bonds in dierent water contents. On the other
22
Space in z direction
21
20
19
0.0
83
0.2
0.4
0.6
0.8
1.0
Water/Ca ratio
84
Fig. 3. Snapshots of the molecular structures of C-S-H gel samples from the dry state to the saturated state: (a) water/Ca = 0; (b) water/Ca = 0.5; (c)
water/Ca = 0.95. The red and white sticks corresponding to water molecules. (For interpretation of the references to color in this gure legend, the reader
is referred to the web version of this article.)
Fig. 4. Density proles of Cas, Si, Ow, Caw atoms: (a) water/Ca = 0; (b) water/Ca = 0.5; (c) water/Ca = 0.95.
into the branch structure and develops along two dimensions (y and z directions). Similarly, the Q3 species has also
been detected experimentally in the mineral analogue of C [21], which contains no water
S-H gel, i.e. tobermorite 9 A
molecules. On the other hand, as shown in Fig. 5b, when
the water/Ca ratio reaches 0.3, two dimers and one monomer can grow together to develop a long silicate chain
across the interlayer region. Even though the Q3 species
disappears due to the increasing water content, silicate
chains can still grow in two dimensions. The polymerization process is the evolution from short silicate chains
(Q0, Q1) to long chains (Q2).
From the analysis in this section, it can be seen that, in
the C-S-H gel, water molecules can isolate the neighboring
calcium silicate chains and prevent further polymerization
of defective silicate structures. The depolymerization role
of the water molecules has been explained in previous
silica synthesis simulations [22]. The hydration of cement,
which produces C-S-H gel, is based on the solgel reaction
in the presence of calcium ions. Water molecules associated with the non-bridging oxygen atoms in silicate
chains prevent connections between isolated silicate structures, and cause decay in the polymerization process. In
the case of low water/Ca ratio, a further polymerization
process contributes to the formation of the amorphous
silicate morphology and weakens the layered structure
of C-S-H gel.
85
Fig. 5. Morphology change of silicate chain: (a) polymerization in the dry sample; (b) polymerization in the sample with water/Ca = 0.3; (c) morphology
of the silicate chain in the saturated state.
Cas-Os
Cas-Ow
Caw-Os
Caw-Ow
CN of Ca
0
0.0
0.2
0.4
0.6
0.8
1.0
Water/Ca ratio
2. 0
Os-Hw
Ow-Hw
1. 5
RDF (O H)
86
1. 0
0. 5
0. 0
0
10
Distance (Ang)
O s -H w
Ow-Hw
H-bonds/water
1. 6
1. 2
0. 8
0. 4
0. 0
0.2
0.4
0.6
0.8
1.0
Water/Ca
87
88
C (t)
0. 8
0. 6
0. 4
Si-O
Ca-O
Caw-O
Caw-Ow
Ow-Hw
Hw-O
0. 2
0. 0
0
200
400
600
800
1000
Time (Ps)
Ow
Caw
Cas
Si
MSD (Ang )
0
0
200
400
600
800
1000
Time (Ps)
89
Fig. 15. Stressstrain relations of 12 samples under uniaxial tension loading along the z direction.
90
Fig. 16. Stressstrain relations of 12 samples under uniaxial compression loading along the z direction.
the saturated state, the compressive strength of the C-SH gel is about twice as large as the tensile strength. It
should be noted that, at the macrolevel, the cement paste
is strong in compression and weak in tension. The
discrepancy between the compressive and tensile behavior
of C-S-H gel at the nanolevel gives molecular insight into
the tensile weakness of cement paste.
3.2.3. Structural analysis
In order to support the discussions on the relation between
mechanical properties and chemical bonds, structural analysis is required. The strain-correlated function (SCF) is used
to describe the variation in chemical bonds in comparison
with the original structure during the tensile process. The
SCF can be interpreted as a TCF in the presence of strain
loading, and is dened in a similar way to TCF as
65
60
55
50
(a)
45
0.0
0.2
0.4
0.6
0.8
1.0
0.8
1.0
Water/Ca ratio
(b)
0.0
0.2
0.4
0.6
Water/Ca
(c)
0
0.0
0.2
0.4
0.6
0.8
1.0
water/Ca
Ce
91
92
0.8
0.8
0.6
0.6
C ( )
C ()
1.0
0.4
0.4
Cas-Os
Si-Os
Caw-Os
0.2
0.0
0.0
0.2
0.2
(a)
0.4
0.6
0.8
Strain (Ang/Ang)
0.0
0.0
Cas-Os
Si-Os
Caw-Os
0.2
(b)
0.4
0.6
0.8
Strain (Ang/Ang)
Fig. 18. SCFs of CaO, SiO and CawO bonds in dierent states: (a) dry state; (b) saturated state.
Fig. 19. Molecular structural evolution of C-S-H gel in resisting tensile loading in dierent states (the strains from top to the middle and the bottom are
small, moderate and large, respectively): (a) dry state; (b) saturated state.
93
Fig. 20. Molecular structural evolution of C-S-H gel in resisting compressive loading in dierent states (he strains from top to the middle and the bottom
are small, moderate and large, respectively): (a) dry state; (b) saturated state.
This structural analysis proves that the hydrolytic weakening found in the silicate composite also occurs in C-S-H
gels. In the dry sample, in the interlayer region, the coordinated atoms of Caw are Os and CawOs connections have a
high potential energy. In addition, even though the breakage of local CawOs bonds occurs, Ca atoms can immediately reconstruct the chemical bonds with neighboring Os.
The reconstruction of the chemical bonds contributes to
the recovery of small defects in the elastic region. Nevertheless, in the saturated sample, interlayer Ow atoms substitute
partial Os atoms and form unstable CawOw bonds. Due to
the disjoining inuence of the water molecules, the broken
CaO connection cannot be reconstructed as easily as in
dry C-S-H gel. Therefore, saturated C-S-H gel has a more
brittle structure.
4. Conclusion
By considering the molecular dynamics, the structure,
dynamics and mechanical performance of C-S-H gels at
dierent states have been investigated. The following
conclusions can be drawn from this study.
(1) Structurally, as the water content increases, the penetration of the water transforms the C-S-H gel from an
amorphous to a layered structure. Meanwhile, the
bridging bonds between the calcium silicate sheets
vary from only CawOs bonds to a combination of
CawO bonds and H-bonds. That is to say, the presence of water molecules weakens the stability of the
chemical bonds in the system.
(2) The morphology and chemical bond variation
induced by the water determine the mechanical
properties evolution. Both the stiness and the
cohesive force are reduced with increasing water
content.
(3) In the tensile loading process, the amorphous dry
sample, due to the stretching of the silicate branch
and the breakage of the CasOs bonds, demonstrates
high stiness, high strength and plasticity in the
post-failure stage. In contrast, in the saturated state,
the much weaker CawOs bonds and H-bonds play
major roles in the loading resistance, which leads
to lower stiness and strength, and makes the gel
more brittle.
94
Acknowledgements
Support from the China Ministry of Science and Technology under grant 2009CB623200 is gratefully acknowledged.
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