Computational Modelling of Concrete Structures – Meschke, Pichler & Rots (Eds)

© 2018 Taylor & Francis Group, London, ISBN 978-1-138-74117-1

Fracture properties of cement hydrates determined from microbending

tests and multiscale modeling

J. Němeček, V. Šmilauer, J. Němeček & F. Kolařík

Faculty of Civil Engineering, Czech Technical University, Prague, Czech Republic

J. Maňák
Institute of Physics Academy of Sciences, Prague, Czech Republic

ABSTRACT: The paper shows experimental results received from bending tests performed on micro-
beams fabricated with focused ion beam milling. The micro-beams were bent by nanoindenter and load-
displacement curves recorded. From that, tensile strength and fracture energy were deduced for individual
cement paste constituents at the level of a few micrometers. The tensile strength of the C-S-H rich inner
product reached 700 MPa while the supremum of fracture energy was in the range 4–20 J/m2. The experi-
mentally obtained values served for verification of the multi-scale numerical model that was built for
scales starting from C-S-H globules (1–100 nm) to cement paste level (up to 1–100 μm). Simulation of
random packing of C-S-H globules reproduced well experimental data, yielding cohesive stress of the
globule as 2500 MPa. A weak size effect was found on the scale of C-S-H up to 1000 nm, signalizing
high ductility and weak strain localization. Further extension to cement paste was proposed, introducing
defects responsible for further strength reduction on scaling.

1 INTRODUCTION it is able to determine tensile strength of the individ-

Many material characteristics like elastic modulus,
tensile strength or fracture energy belong to basic
mechanical properties in fracture mechanics mod-
els. Traditionally, the properties are assessed on
centimeter to meter sized samples whose dimen-
sions are far above the size of microstructural
heterogeneities. Thus, microstructure-based pre-
dictions that take microlevel heterogeneity into
account need experimentation at a substantially
smaller scale, i.e. at the level of micrometers. More-
over, cementitious materials exhibit quasi-brittle
behavior on all considered scales. In this paper, we
focus our attention to the basic microscopic level
of cement paste which spans the range from 1 μm
to approximately 100 μm and which forms the
binder of all cementitious systems.
First, we introduce a unique experimental method
that allows cutting out a micrometer sized can-
tilever beam using the Focused Ion Beam (FIB)
milling technique from a heterogeneous composi-
tion of cement paste. High precision geometry of
the beams is reached with FIB. The beam is loaded
in bending with the help of a nanoindenter and
mechanical response is determined. Careful selection
of homogeneous-like regions allows assigning results
to dominant chemical phases, particularly the inner
product and the outer product that are rich of C-S-H
and Portlandite (CH) rich regions. From these tests,
ual phases and, in some cases, fracture energy needed
to break the cantilever. The experimental part is a
stepping stone for the development for up-scaling
and down-scaling models for fracture properties.
Thus, at second, we propose a three level numer-
ical model for prediction of cement paste tensile
strength. In the down-scaling direction, identifi-
cation of cohesion of a C-S-H globule was done.
Smeared crack model with strain-softening was
used in the framework of damage mechanics. In the
up-scaling direction, the tensile strength of C-S-H
products is described well in accordance with
experimental evidence gained on micro-beams. The
tensile strength of cement paste is further reduced
by internal defects whose size is beyond our experi-
ments as shown at the end of the paper.
2 EXPERIMENTAL PART
2.1 Samples and material microstructure
Samples of well hydrated cement paste were pre-
pared from pure Portland cement CEM-I 42,5R
with a standard chemical composition given by
Table 1. Water to cement ratio used for prepar-
tion of the paste was 0,4. Samples were casted into
small cylindrical moulds and stored in water for
7 years, thus the degree of hydration approaches
100%. Then, samples were cut into 5 mm thick

113
Table 1. Chemical composition of cement.
CaO SiO2 Al2O3 Fe2O3 MgO
wt.% 63.77 20.51 4.74 3.3 1.05
K 2O Na2O SO3 MnO free Ca
wt.% 0.95 0.15 3.07 0.09 0
Figure 1. Microstructure of cement paste.
slices and prepared with a metallographic proce-
dure (Němeček, Šmilauer, Polívka, & Jäger 2016)
to get a flat and smooth surface with the roughness
of several tens of nm. Such sufrace is suitable for
nanoindentation and FIB analyses. After polishing
samples were stored in an inert gas (argon) to limit
carbonation besides testing times when samples
were exposed to ambient lab humidity 20–40%.
At the level of hydrates (i.e. below 100 μm) the sam-
ples are characterized with a heterogeneous micro-
structure composing mainly of the inner and outer
products that are rich in C-S-H gels and amorphous
nano-crystallites of Ca(OH)2, then larger Portland-
ite crystals and a small portion of unhydrous grains
of clinker minerals, see Fig. 1. Also, the capillary
porosity with the main pore radii in the level of 10−2
−10−1 μm as measured by MIP (Němeček, Šmilauer,
Polívka, & Jäger 2016) is present at this scale.
2.2 SEM and FIB
After polishing samples were scanned and small
micro-beams prepared with the FIB technology.
FEI Quanta 3D FEG dual beam instrument com-
bining SEM and FIB was used for fabrication
of all samples. The FIB technique uses a finely
focused beam of gallium ions for precise milling of
microscopic samples with various geometries. For
our purposes, the sample geometry was chosen to
be a cantilever beam of 20 μm length and triangu-
lar cross-section with approximate dimensions of
3–4 μm in height and width. The final milling step
was done at an accelerating voltage of 30 kV and
TiO2
0
Figure 2. Microbeam fabricated in an outer product.
a current of 1 nA. Details on the fabrication can
be found in (Němeček, Šmilauer, Polívka, & Jäger
2016). After FIB milling, the micro-beams were
observed by SEM to scan their actual dimensions
and position in a particular microscopic phase. An
example of the milled beam is shown in Fig. 2.
2.3 Nanoindentation
Nanoindenter Hysitron Tribolab-700 system was
used for characterization of mechanical response
of micro-beams in two ways. First, standard
imprints were performed in the vicinity of the
beams to reveal elastic properties of the tested
phase. Secondly, the indenter was used as a load-
ing tool to bend cantilevers and record the force-
displacement diagram in the displacement control-
led regime. From the diagrams, both tensile strength
ft and fracture energy G fsup
u
have been calculated as
Fmax L h
ft = (1)
Iy 3
1 wmax
G fsup = ∫
u
Fdw
d (2)
Af 0
where Fmax is the maximum force measured by the
nanoindenter, L is the cantilever length, Iy the cross-
sectional second moment of inertia, h the height of
the triangular beam cross-section, wmax is the peak
deflection and Af is the fracture area (i.e. Af 12 bh
for the triangle). Note that the fracture energy was
computed as the supremum estimate based on the
assumption that the micro-beam behavior shows
neither snap-back nor softening and that the maxi-
mum force corresponds to the maximum energy
release rate with a limiting stablecrack propagation.
2.4 Results of microbending tests
Results of the micro-bending tests as recorded by
nanoindenter and recalculated into non-dimensional
114
 Chanvillard 2016). The basic assumption of the
model was that the tensile failure of C-S-H glob-
ules leads to progressive failure on higher scales.
At that time, downscaling approach identified
apparent uniaxial tensile strength of the C-S-HHD
as 107 MPa, which is almost 7 × lower than tensile
strength measured from microbending tests.
Recently, a molecular dynamics model of C-S-H
gel, formulated as cohesive polydisperse particles,
yielded tensile strength as C-S-HLD = 550 MPa and
C-S-HHD = 720 MPa (Davie & Masoero 2015).
Those values are comparable with microbend-
ing tests in Table 2, considering that outer prod-
uct contains certain portion of capillary porosity.
AFM nanoscale investigation of C-S-H cohe-
sion (modified C-S-HLD from alite hydration)
yielded 930 MPa, which is again comparable
with microbending results (Plassard, Lesniewska,
Pochard, & Nonat 2005).
In order to match current C-S-H experimental
data with the previous multiscale fracture model,
strength scaling needs further improvement. In this
regard, we propose three levels, see Figure 4, where
each level represents

Table 2. Results from nanoindetation and micro-

bending tests.

Outer product Inner product CH

E 24.9 ± 1.3 33.6 ± 2.0 39.0 ± 7.1

ft 264.1 ± 73.4 700.2 ± 198.5 655.1 ± 258.3
G fsup
u
4.4 ± 1.9 19.7 ± 3.8 19.9 ± 14.4
Figure 3. Results of micro-bending tests for individual
phases. n.t. 8 8 11

stress and relative deflection quantities are shown in Legend: E = Young’s modulus (GPa); ft = tensile strength
sup
u
(MPa); G f = supremum of fracture energy (J/m2),
Fig. 3. It can be seen in the figure that the beams
n.t. = number of evaluated tests.
behave approximately linearly up to the break and
the steep brittle fracture like unloading branch.
Althought the machine is depth controlled the sta-
bility of the post-peak control is not well maintained
and must be treated as approximate only. The tensile
strength is, therefore, captured well while the fracture
energy estimate was calculated as the supremum esti-
mate, Eq. 2. The results agree well with previously
obtained results of elastic properties of individual
cement paste constituents (Němeček, Králík, &
Vondřejc 2013) and also with energy calculations
derived from bulk nanoindentation (Němeček,
Hrbek, Polívka, & Jäger 2016).

3 MODELING PART

A four-scale fracture model was previously for-

mulated and validated for compressive strength of Figure 4. Three-level hierarchical multiscale model.
cement paste with w/c ∈ 0.157, 0.68 after approx- Microstructure images from E. Lachowski, P. Stutzman,
imately 1 day of hydration (Hlobil, Šmilauer, & D.P. Bentz et al.

115
• Level 1: CSH. C-S-H globules are intermixed
with gel pores
• Level 2: Cement paste. Level 1 acts with capil-
lary porosity, other hydration products, unre-
acted clinker, unreacted SCMs.
• Level 3: Defects. Level 2 is enriched with defects
in the form of cracks and air voids.
3.1 Material model for compressive and
tensile failure
Material model describing compressive of tensile
failure at each level is based on fracture/damage
mechanics. Damage mechanics uses the concept
of an equivalent strain, ε, as a descriptor of dam-
age evolution. Damage becomes initiated when the
equivalent strain, ε, exceeds strain at the onset of
cracking, ε0 = ft/E, where E is the elastic modulus.
The Rankine criterion for tensile failure defines ε as
σ1
ε = , σ1 > 0 (3)
E 1924).
where σ1 is the maximum positive effective prin-
cipal stress of undamaged-like material. Figure 5
elucidates the mechanism.
Under uniaxial compressive stress, crack initia-
tion occurs under a different mechanism. A homo-
geneous material experiences only one negative
principal stress and deviatoric stresses. Cracking
in diagonal, shear band zone, is often encountered
on cementitious specimens, however, the physi-
cal mechanism is again tensile microcracking in
voids and defects in the underlying microstructure
(Bažant & Planas 1998, pp. 297). Such a behavior
has already been described in the work of Grif-
fith (Griffith 1924), and McClintock and Walsh
(McClintock & Walsh 1962), and we briefly review
this theory and extend it with an equivalent strain
to be used in the framework of damage mechanics.
Figure 5. Crack evolution during (a) uniaxial tensile
stress and (b) compressive stresses. The material contains
randomly oriented elliptical voids with negligible area.
116
It is assumed that a material contains randomly
oriented 2D elliptical flat voids with various aspect
ratios m = b/a. The voids have a negligible area and
only represent stress concentrators and internal
defects in a material. Under macroscopic biaxial
stress, the maximum tensile stress among all voids,
m ⋅ ση, appears on a critically inclined elliptical
void under a critical angle ψ
σ 3 σ1 σ1 1
cos 2ψ = , ≥− (4)
2( 3 1 ) σ 3 3
−(σ 1 − σ 3 )2
m ⋅ση = (5)
4(σ 1 + σ 3 )
Crack formation occurs when the tangential
tensile stress, m ⋅ ση, equals to the tensile strength
of the matrix. Since ση and the crack geometry,
m, cannot be measured directly, it is reasonable to
relate their product to the uniaxial macroscopic
tensile stress, σ 1, as proposed by Griffith (Griffith
m ⋅ση
σ1 = (6)
2
The material starts to crack when σ 1 equals to
the uniaxial macroscopic tensile strength ft. Note
that the tensile strength of the homogeneous
matrix (intrinsic strength) and the crack geometry
remain unknown separately and we can assess only
apparent macroscopic tensile strength ft.
Plugging Equation (5) into Equation (6) and
further into Equation (3) leads to the definition
of the equivalent strain, ε , under compression-
dominant loading
1 −(σ 1 σ 3 )2
ε = ⋅ (7)
E 8(σ 1 + σ 3 )
An interesting feature of the Griffith model is
that the ratio of the uniaxial compressive-to-tensile
strength equals to 8
| fc | = ft (8)
This can be verified when plugging σ1 = ft into
Equation (3) which leads to ε = ft /E . Plugging
σ1 = 0, σ3 = −8ft into Equation (7) leads to the same
equivalent strain.
Since the equivalent strain may arise from the
Rankine of Griffith criterion, it is necessary to
compare both Equations (3) and (7) and to select
the higher equivalent strain. Since the damage
evolution law has a small effect on the computed
macroscopic strength simple linear softening is
assumed in the simulations. The linear cohesive
law takes the form

⎛ w⎞
σ = ft ⎜1 − ⎟ (9)
⎝ wf ⎠

where w is a crack opening and wf is the maximum

crack opening at zero stress. According to the
formulation of the isotropic damage model, the
uniaxial tensile stress obeys the law

σ ( ω )E ε. (10)

with ω being the isotropic damage parameter,

ω ∈ 0;1 . Figure 6. Unit cells for C-S-HLD and C-S-HHD, 20 × 20 ×
Let us consider the fracture energy in mode I, 40 brick elements (size 100 × 100 × 200 nm).
Gf, and the effective thickness of a crack band h,
which corresponds to the finite element size in
the direction of the maximum principal strain
(Bažant & Planas 1998). This ensures objec-
tive results, independent on finite element size
(Jirásek & Bažant 2002). Notice that w hωε
and wf = 2Gf/ft. The evolution of isotropic dam-
age is obtained by combining Equations (9) and
(10).
−1
⎛ ε ⎞ ⎛ hE ε 02 ⎞
ω = 1 − 0 ⎟ ⎜1 − ⎟ (11)
⎝ ε ⎠ ⎝ 2G f ⎠

3.2 Model for fracture properties of C-S-H

globules Figure 7. Tensile strength scaling in C-S-H gel with
various packing density of globules.
Nanoindentation experiments carried out previ-
ously (Constantinides & Ulm 2004) identified
elastic properties of C-S-H and limit packing den-
sities as ηC-S-HLD = 0.63 and ηC-S-HHD = 0.76 (Con-
stantinides & Ulm 2007). Our model used 2D
and 3D images for different packing densities.
Figure 6 provides such examples for C-S-HLD and
C-S-HHD.
In order to match uniaxial tensile test, periodic
boundary conditions occur on horizontal surfaces
and uniform static boundary conditions with zero
normal stress belong to vertical surfaces. Vertical
eigenstrain loads 2D unit cell and uniaxial macro-
scopic tensile stress recovers.
Figure 7 displays the evolution of the C-S-H
tensile strength with regards to packing density,
as determined from 200 × 200 nm microstructures.
Fracture energy 2 J/m2 was assigned to the globule. Figure 8. Tensile strength scaling on C-S-HLD gel
Analytical approximation reads. depending on size of microstructure.

⎛ 1.293( glob
g
13.011
− 1) ⎞ where instrinsic cohesion of a globule was found
ft ,0 ft ,glob exp ⎜ ⎟ (12) as ft,glog = 2500 MPa. This yields tensile strength
⎝ ηglob ⎠ ft ,0C-S-HLD = 247.6 MPa and ft ,0C-S-HHD = 489.3 MPa,

117
being comparable with molecular dynamics data
and microbending tests.
Further, we explored strength scaling with the
size of a unit cell. In perfectly plastic materials
and parallel configuration of load-bearing phases,
no size effect occurs as opposed to brittle materi-
als or to serial configuration. Weak size effect was
found on C-S-HLD up to 1000 nm signalizing that
C-S-H globules are ductile enough to redistribute
stress during strain softening (Figure 8). Weak sta-
tistical size effect occurs after 1000 nm signalizing
random nature of C-S-H packing with increasing
brittleness.
3.3 Model for level of cement paste
Ordinary cement paste with low w/c attains flexu-
ral strength up to approximately 12 MPa (Taplin
1959). This can be significantly increased by hot-
cured, compacted cement pastes with amorphous
C-S-H where compressive strength 690 MPa
was reached (i.e. the tensile strength of about
690/8 = 86 MPa can be assumed) (Gouda & Roy
1976). It was shown previously that significant
decrease of strength from C-S-H to paste level
is caused by presence of capillary porosity, spa-
tial gradient of C-S-H, and stress concentra-
tion around elastic inclusions (unreacted cement
clinker, crystalline hydration products, unreacted
supplementary cementitious materials) (Hlobil,
Šmilauer, & Chanvillard 2016). However, those
effects are still insufficient for strength scaling
from C-S-H to cement paste. Thus, further reduc-
ing mechanisms happen. They can be in the form
of interfaces (Qian, Schlangen, Ye, & van Breugel
2012) or additional defects introduced at level 3.
Defects at level 3 can arise from several causes;
shrinkage during water consumption, rearange-
ment of hydrates, internal stresses etc. It is obvi-
ous that size of those defects must lay above the
size of our experimental cantilever beams, i.e.
above ≈5 μm. LEFM can estimate the bottom
size of internal defects if considered as a crack of
length a in perfectly brittle material. For illustra-
tion, let us consider cement paste with E = 15 GPa,
Gf,CSH = 2 J/m2, ft = 10 MPa
EG
G f CSH
ft = , (13)
πa
EG
G f CSH 15 ⋅ 109 ⋅ 2
a= ≈ = 95 ⋅ 10 −6 m.
π ft 2
π (10 ⋅ 106 )2
Such estimation is consistent with (Ghebrab &
Soroushian 2010) who used a ≥ 50 μm arguing that
large portlandite crystals are responsible for stress
concentration and crack propagation. However,
simulations need to prove this hypothesis and vali-
date experimental data.
4 CONCLUSIONS
The following conclusions can be drawn on experi-
mental and numerical parts:
• Micro-bending tests on beams prepared with
FIB give access to local fracture properties of
cement paste constituents. Tensile strength
of inner product, outer product and CH were
found in the range of 260–700 MPa. Supremum
of fracture energies lie in the range 4–20 J/m2 for
the respective constituents.
• Cohesion of C-S-H globule was identified as
2500 MPa. When intermixing C-S-H globules
with gel porosity, experimentally measured
strengths are approximately recovered for both
C-S-HHD and C-S-HLD. Also, the results from
molecular dynamics are consistent.
• Preliminary findings show that microcracks or
internal defects as long as 100 μm exist and they
control strength of cement pastes. The origin of
those defects, their formation and description
need further research.
ACKNOWLEDGEMENT
Financial support of the Czech Science Founda-
tion’s project 17-18652S is gratefully acknowledged.
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