Deformation mechanism of hardened cement paste and effect of

water
Yuya Sakai, Toshiharu Kishi
Journal of Advanced Concrete Technology, volume 15 ( 2017 ), pp. 19-28

Multiscale model for creep of shotcrete- from logarithmic-type viscous behavior of CSH at the μm-scale
to macroscopic tunnel analysis
Christian Pichler, Roman Lackner, Herbert A. Mang
Journal of Advanced Concrete Technology, volume 6 ( 2008 ), pp. 91-110

Creep and Shrinkage of High Strength Self-Compacting Concrete: Experimental and Numerical Analysis
Farhad Aslani , Shami Nejadi
Journal of Advanced Concrete Technology, volume 11 ( 2013 ), pp. 251-265
Journal of Advanced Concrete Technology Vol. 15, 19-28, January 2017 / Copyright © 2017 Japan Concrete Institute 19

Scientific paper

Deformation Mechanism of Hardened Cement Paste and Effect of Water

Yuya Sakai1* and Toshiharu Kishi2

Received 20 April 2016, accepted 13 January 2017 doi:10.3151/jact.15.19

Abstract
Triaxial compressive tests were conducted at different confining pressures (Pc) and water contents to understand the
deformation mechanism of hardened cement paste (HCP). Results showed that the stress did not decrease up to 10% strain
and macroscopic damage was not observed when Pc was higher than a certain value. Pc required for this ductile behavior
differed depending on the HCP water content. Stepwise creep tests were also conducted. Most of the slopes of the ob-
tained differential stress–strain rate curves in the double logarithmic chart were approximately three, which indicates that
dislocation creep was the dominant deformation mechanism. The samples saturated with sucrose solution exhibited a
more brittle behavior after the peak stress than those saturated with tap water. The different behavior in the softening
region was attributed to calcium hydroxide precipitation because it was suppressed in the sucrose solution. These results
indicated that the HCP deformation may be affected by dislocation, mechanical twinning, and pressure solution.

1. Introduction The obtained differential stress–axial strain (SS) curves

Concrete is subjected to high pressure in various situa-
tions. Accordingly, concrete has been considered for
deep underground structures used for the disposal of
nuclear waste (Owada et al. 2008). Although still a topic
for discussion, building a city using concrete several
kilometers deep under the sea is also being considered
(McCurry 2014). Understanding the deformation
mechanism of concrete under high pressure is necessary
for a rational and safe design of these structures. Impact
load has also been reported to induce a triaxial stress of
more than 100 MPa (Gran and Frew 1997), followed by
extensive studies on concrete behavior under
high-pressure confinement. The effects of cement paste
volume (Vu et al. 2011), saturation degree (Vu et al.
2009), and loading rate (Zeng et al. 2013) have been
studied. Results show that concrete deformation changes
from brittle to ductile as the confining pressure (Pc) in-
creases. Moreover, the effects of cement paste volume
and saturation decrease and become prominent, respec-
tively. As previously mentioned, the macroscopic be-
havior of concrete subjected to triaxial stress under
various conditions has been studied. However, the type
of changes that occur in the cement paste matrix owing to
high pressure and how these changes affect the me-
chanical performance of concrete remain unclear. Un-
derstanding such changes in the cement paste is impor-
tant for estimating the long-term performance and mass
transfer resistance of concrete under confining pressure.
In a previous study, the authors (Sakai et al. 2016) con-
ducted a triaxial test on hardened cement paste (HCP).
1
Assistant Professor, Institute of Industrial Science, The
University of Tokyo, Tokyo, Japan. *Corresponding
author, E-mail: ysakai@iis.u-tokyo.ac.jp
2
Professor, Institute of Industrial Science, The University
of Tokyo, Tokyo, Japan.
were not dependent on Pc as seen in rocks under a high
pressure of several hundreds of MPa or high temperature
of several hundreds of °C. Moreover, the backscattered
electron images on the cutting surface of the HCP sam-
ples became darker after the test. These results show that
HCP probably plastically deformed, changing its struc-
ture at a molecular level under a Pc ≥ 30 MPa. However,
this conclusion is drawn from testing four samples only.
The condition under which such plastic deformation
occurs in HCP is unclear. Macroscopic observation was
not conducted on the HCP specimens in our previous
study.
This study aims to continue our understanding of the
deformation mechanism of cement paste under confining
pressure. Accordingly, we conducted a triaxial test on a
larger number of HCP samples. Water content was added
as an experimental factor. The samples were impregnated
in epoxy resin, cut, and polished after the triaxial tests.
These polished surfaces were observed by the naked eye
or under a microscope. The stepwise creep test was con-
ducted to study the slope of the strain rate–stress curves.
The deformation mechanism of cement paste was com-
pared mainly with limestone after the tests and observa-
tions. This is because limestone is more relatively similar
to cement paste than other rocks. Limestone is a raw
cement material composed mainly of calcium.
2. Experiment
2.1 Specimen preparation
2.1.1 Group 1
This study used HCP with a water-cement ratio of 0.4.
Table 1 shows the properties of ordinary Portland ce-
ment. The mixing procedure was based on JIS R 5201.
The mixed paste was cast in a 250 × 150 × 100 cm mold,
and sealed. The paste was demolded 24 h after casting,
and subsequently kept under water for 28 days. The
Y. Sakai and T. Kishi / Journal of Advanced Concrete Technology Vol. 15, 19-28, 2017 20

Table 1 Chemical composition of cement.

Chemical property (%)
Ig. Loss Insol. SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O
2.84 0.27 19.83 4.56 2.95 61.28 3.78 2.83 0.35 0.57

temperature of the room and water was 24°C. After
curing, the φ11.5 × 25.0 mm cylinders were cored from
the bulk HCP. Only the part deeper than 2 cm from the
surface was used to avoid the bleeding effect. Both cyl-
inder ends were polished to achieve flat surfaces. The
shaped cylinders were kept in a desiccator under a tem-
perature of 24°C with a relative humidity (RH) of 40%
for 24 h. The cylinders were then immersed in acetone
for 24 h to stop the hydration reaction and reduce capil-
lary suction in the subsequent drying period. After im-
mersion, the cylinders were dried in a desiccator under
24°C and 20% RH until the weight change over 24 h
because of moisture loss was less than 1% of the speci-
men weight. Saturated and oven-dried samples were also
prepared. These samples were immersed in tap water or
oven-dried under vacuum (95°C and 600 hPa absolute
pressure) after drying at 24°C and 20% RH until the
weight change over 24 h was less than 0.2% of the
specimen weight. Assuming that the moisture contents in
the saturated and oven-dried samples were 100% and 0%,
respectively, the calculated moisture content of a sample
dried at 24°C and 20% RH was 67%. The average car-
bonation depth of an intact sample measured after all
experiments was 0.2 mm.
2.1.2 Group 2
Group 2 HCP samples were prepared following the same
procedure used in Group 1. The differences were that the
cylinders were cored after being immersed in water for
two months and sized to φ10 × 24 mm. The cored cyl-
Table 2 Physical properties of cement.
Density Specific surface area
g/cm3 cm2/g
3.12 4110
inders were dried in a desiccator under 24°C and 20%
RH until the weight change over 24 h due to the moisture
loss was less than 1% of the specimen weight. Some
specimens were then saturated with tap water or sucrose
solution (0.1 M) until the weight change over 24 h due to
absorption was less than 0.2% of the specimen weight.
The Ca(OH)2 precipitation was reduced in the sucrose
solution (Banfill 1986). Group 2 samples were used to
observe how the HCP behavior changes with the liquid
type in the pores, and for the stepwise creep test.
2.2 Triaxial test
2.2.1 Test apparatus and sample assembly
The triaxial test apparatus used in this study used argon
gas as a pressure medium to introduce confining pressure
on the sample. A sample was put between alumina and
zirconia pistons enclosed with a heat-shrinkable tube
(Polyolefin) that sealed the sample from the confining
medium. The tube was heated up from the outside with a
heat gun for shrinkage. A saturated sample was wrapped
with a plastic film before being covered with a
heat-shrinkable tube. Steel anvils were then attached to
the top and bottom of the zirconia pistons and fixed with
steel wires over the heat-shrinkable tube. The prepared
sample assembly was inserted into the pressure vessel of

Pressure vessel

Anvil

Zirconia piston

Almina piston

Specimen

Transducer

Anvil

Internal load cell

External load cell

Fig. 1 Sample assembly and schematic diagram of the testing apparatus.

Y. Sakai and T. Kishi / Journal of Advanced Concrete Technology Vol. 15, 19-28, 2017
the test apparatus. Load was applied by moving the lower
piston upward. Figure 1 shows the photo of a sample
assembly and the schematic diagram of the test apparatus.
The stress was calculated by dividing the load measured
with the internal load cell by a sample's cross-sectional
area. The internal load cell did not include the confining
pressure effect. Therefore, the calculated stress corre-
sponded to the differential stress. The axial strain was
calculated by dividing the measured displacement with
the transducer below the sample assembly by the sam-
ple's initial length. The load, displacement, and confining
pressure were measured at intervals of 1 s, unless oth-
erwise noted. For some instances, more than one sample
was tested under the same condition to check repro-
ducibility. The number of samples for each case is pro-
vided later.
2.2.2 Monotonic loading test
Monotonic loading tests were conducted to obtain the
HCP SS curves by applying a constant displacement at
0.2 mm/min. The tests were stopped when the axial
strain reached 10%, except for tests without confining
pressure, which were stopped when the stress drop
stagnated. Some of the samples in Group 2 were satu-
rated with tap water or sucrose solution, and tested at a
constant displacement rate of 36 μm/h. The load, dis-
placement, and confining pressure were measured at
intervals of 2 s in these slow-loading cases.
2.2.3 Stepwise creep test
Stepwise creep test was conducted on some of the sam-
ples in Group 2 to obtain strain rate–differential stress
curves. The applied load in this test was increased step-
wise from 30% to 95% of the maximum stress obtained
in the monotonic loading test. The differential
stress–time relationship was analyzed in real time to
calculate the fitted line of data for the latest 20 min. The
condition was regarded to be in a steady state when the
determination coefficient of the fitted line was more than
0.99. The load was also increased. The steady state cor-
responded to the second stage when a creep deformation
was divided into three phases (JIS Z 2271 2010) (Fig. 2).
Primary
creep Secondary creep
Creep strain
Tertiary
creep
Time
Fig. 2 Schematic diagram of the creep phases.
21
The curve slope became constant in the second stage.
The judging time of the steady state was set to 20 min
herein because if it was too long, the shifting of failure to
the third creep stage, or a hydration reaction could pro-
ceed, causing property change of the sample. The aver-
age interval before the load increase was 30 min. The
interval of a few tens of minutes for the load increment
was obtained from similar experiments on rocks (Brantut
et al. 2013).
2.3 Observation of a sample's cross-section
surface
The sample covered with a heat-shrinkable tube was cut
out from the assembly and impregnated into a
two-component epoxy resin (room-temperature curing)
after the triaxial monotonic loading tests. The sample
was then cut parallel to the long axis when the epoxy
resin hardened. The cutting surface was polished with
alumina powder (55 and 15 μm in average diameter).
This surface was observed by the naked eye or under a
microscope.
3. Results
3.1 Monotonic loading test
Figure 3(a) shows the SS curves of the samples dried at
20% RH. The results of the samples at Pc = 30 MPa will
be shown later. The samples tested at Pc = 0–20 MPa
exhibited a similar behavior up to their maximum stress.
100MPa
Differential stress (MPa)
50MPa
20MPa
10MPa
0MPa
Axial strain (%)
(a) Pc = 0, 10, 20, 50, 100 MPa
Differential stress (MPa)
Axial strain (%)
(b) Pc = 30 MPa
Fig. 3 Triaxial test results of the specimens dried at 20%
RH.
Y. Sakai and T. Kishi / Journal of Advanced Concrete Technology Vol. 15, 19-28, 2017
Their maximum stress increased, and stress drop became
smaller with an increase in Pc. The stress did not decrease
up to 10% strain when Pc was larger than 50 MPa. The
sample under higher Pc showed lower stress in the 1–3%
strain range. Two samples were tested at each Pc, except
for Pc = 20 MPa (Fig. 3(a)). The gap of the maximum
stress between the two results were 6% and 7% at Pc = 0
and 10 MPa, respectively. The maximum stress deviation
of the two results at the same strain were 15% and 8%
under Pc = 50 and 100 MPa, respectively. Three samples
were tested at Pc = 30 MPa, and significantly different
results were obtained (Fig. 3(b)). Figures 4 and 5 show
the results of the saturated and oven-dried samples. The
saturated specimens showed a more ductile behavior than
the samples dried at 20% RH under the same Pc (Fig.
3(a)). The saturated sample tested at Pc = 10 MPa
showed slight softening. The stress did not decrease
when Pc was equal to or more than 20 MPa. The SS curve
change caused by Pc is small under Pc = 10–30 MPa. The
oven-dried samples exhibited softening even under Pc =
100 MPa. The samples tested under Pc = 30 and 100 MPa
show a similar slope up to a strain of 1.6%. However, the
sample under Pc = 100 MPa was derived from the other
curves after the strain reached 0.3%. Figure 6 shows the
results of Group 2 samples saturated with tap water or
sucrose solution at Pc = 0 and 20 MPa at displacement
rates of 36 μm/h and 0.2 mm/min. Each measured point
is shown with markers only in Fig. 6. The sample satu-
rated with the sucrose solution shows a higher maximum
stress and steeper stress softening curve at Pc = 0 with a
Differential stress (MPa)
20MPa
30MPa
Axial strain (%)
Fig. 4 Triaxial test results of the specimens saturated with
tap water.
30MPa
Differential stress (MPa)
300MPa
100MPa
Axial strain (%)
Fig. 5 Triaxial test results of the oven-dried specimens.
22
displacement rate of 36 μm/h than that saturated with tap
water (Fig. 6(a)). A similar difference is seen in Fig. 6(b),
where Pc = 20, and the displacement rate is 36 μm/h. The
sample saturated with the sucrose solution shows a
steeper slope even at the displacement rate of 0.2
mm/min (Fig. 6(c)). Five data were measured in the
sample saturated with tap water from the maximum
stress to the stagnation of the stress drop. However, no
data were measured in the sample saturated with the
sucrose solution. The decrease in the number of meas-
ured data is also seen in Fig. 6(a).
3.2 Stepwise creep test
Figure 7 shows an example of a measured strain–time
relationship. The dashed lines and σ in the figure indicate
the fitted lines at the steady state and applied differential
stress, respectively. The slope of the fitted lines increases
Differential stress (MPa)
Tap water
Sucrose solution
Axial strain (%)
(a) Loading at 36 μm/h under Pc = 0 MPa
Tap water
Differential stress (MPa)
Sucrose solution
10MPa
Axial strain (%)
(b) Loading at 0.2 mm/min under Pc = 20 MPa
Differential stress (MPa)
Sucrose solution
Tap water
Axial strain (%)
(c) Loading at 0.2 mm/min under Pc = 0 MPa
Fig. 6 Uniaxial test on the samples saturated with differ-
ent liquids.
Y. Sakai and T. Kishi / Journal of Advanced Concrete Technology Vol. 15, 19-28, 2017 23

as applied stress increases. Figure 8 shows the rela- not observed on the saturated specimen tested at Pc = 20
tionships between the differential stress and strain rate MPa. A clear shear plane was formed even at Pc = 100
calculated from the curve slopes at the steady state. The MPa on the oven-dried sample. The oven-dried sample
results of the sample saturated with tap water and tested did not show macroscopic damage at Pc = 300 MPa.
at Pc = 50 MPa were fitted with two lines (exponential
approximation). Their slopes (multiplier of stress when
exponentially approximated) were 0.39 and 9.86 in the
double logarithmic chart. Each of the other results was
fitted with one line. Their slopes are 2.90–3.46.

3.3 Sample observation

Figures 9–11 show the cut and polished surfaces of the
samples after the triaxial tests. The images in Figs. 12
and 13 were observed under an optical microscope. The
black lines in the samples denote the epoxy resin that
penetrated through the cracks. A shear plane was formed
only in the samples that showed a sudden stress drop
regardless of Pc and water content. A discontinuous shear (a) 0 Mpa (b) 10 MPa (c) 20 MPa
plane was observed in the sample dried at 20% RH and
tested at Pc = 30 MPa (Figs. 9(d) and 12(a)). The three
samples showed significantly different behaviors under
this condition (Fig. 3(b)). The specimens with shear
plane had circular voids on their cutting surface. The
other specimens had ellipsoidal voids with a short axis in
the loading direction (Fig. 13). Macroscopic damage was

σ = 129 MPa

(d) 30 MPa (e) 50 MPa (f) 100 MPa

σ = 118 MPa
Axial strain (%)

Fig. 9 Cross-section of the specimens dried at 20% RH.

σ = 108 MPa

σ = 97 MPa
RH20%，Pc = 50 MPa

Elapsed time (s)

Fig. 7 Axial strain–time relationship in the stepwise creep
test.

(a) 10 MPa (b) 20 MPa (c) 30 MPa

Saturated with tap water, Pc = 50 MPa RH 20%，Pc=50MPa
Fig. 10 Cross-section of the specimens saturated with
Saturated with tap water, Pc = 50 MPa RH 20%，Pc=0MPa
tap water.
Strain rate (sec-1)

Differential stress (MPa)

Fig. 8 Differential stress–strain rate relationship in the (a) 30 MPa (b) 100 MPa (c) 300 MPa
stepwise creep test. Fig. 11 Cross-section of the oven-dried specimens.
Y. Sakai and T. Kishi / Journal of Advanced Concrete Technology Vol. 15, 19-28, 2017
4. Discussion
4.1 Failure pattern
The HCP SS curves were changed in a complicated
manner at different Pc values, as seen in section 3.1. The
stress drop and shear plane were observed when Pc was
small, regardless of the water content. The stress did not
decrease up to 10% strain with an increase in Pc. More-
over, macroscopic damage was not observed. In rock
mechanics, the former pattern is considered brittle,
whereas the latter is ductile (Paterson and Wang 2005).
Following this classification, the HCP deformation
changed from brittle to ductile with an increase in Pc. The
specimens dried at 20% RH and tested at Pc = 30 MPa
showed a significantly different behavior (Fig. 3(b)),
which was probably because these specimens were in the
transition zone between brittle and ductile deformation.
Rocks have shown an unstable behavior in the transition
zone (Lubarda et al. 1996). Accordingly, the discon-
tinuous shear plane supports this understanding (Fig.
9(d)). The horizontal crack in Fig. 9(d) probably formed
during unloading. The clear shear plane was not ob-
served on the cutting surface of the saturated specimen
tested at Pc = 10 MPa (Fig. 12(b)), and the SS curve of
the oven-dried specimen tested at Pc = 100 MPa was
unstable. Therefore, these two specimens may also be in
the transition zone.
4.2 Comparison of the stress–strain relation-
ship with concrete
The stress is known to not decrease in concrete under a
certain Pc (Sfer et al. 2002). Accordingly, the stress did
not decrease up to 10% strain under certain Pc values, as
seen in section 3.1. However, the stress decreased in the
low strain region (i.e., less than 3% strain) in this study,
(a) Dried at 20% RH, Pc = 30 MPa (b) Saturated, Pc = 10MPa
Fig. 12 Discontinuous shear plane.
1mm 1mm
(a) Dried at 20% RH, Pc = 0 MPa (b) Dried at 20% RH, Pc = 50MPa
Fig. 13 Air voids on the cutting surfaces.
24
which has not been reported for concrete. It must be
noted that Sfer et al. showed a plot in axial stress, and not
in differential stress, including confining pressure. This
result may be attributable to the contact between the
aggregates during deformation. The aggregate was
mainly composed of silicate mineral. This rock required
high pressure and temperature to deform in a ductile
manner (Paterson and Wang 2005). Meanwhile, the
stress in porous rocks decreased because of the increase
in Pc (Lubarda et al. 1996; Gueguen and Bouteca 2004).
This decrease was attributed to the microcrack genera-
tion (Lubarda et al. 1996; Zheng et al. 1991). The mi-
1mm 1mm
crocrack density increased, but its length decreased with
an increase in Pc. Therefore, the stress decrease in HCP,
which was dried at 20% RH and tested at Pc ≥ 50 MPa,
was probably caused by the microcracks.
4.3 Comparison with the previous triaxial test
result on HCP
The SS curves in our previous triaxial test on HCP did
not depend on Pc (Sakai et al. 2016). Elastic deformation
generally took place first in the triaxial test on rocks.
Accordingly, the stress was proportional to the strain.
The SS curve slope decreased, shifting to ductile de-
formation, with a strain increase under a certain Pc. In our
previous study, the SS curve slopes decreased at 0.5%
strain, and the deformation that followed was regarded as
ductile deformation. In rocks (Paterson and Wang 2005)
and concrete (Sfer et al. 2002), the independent behavior
of Pc has generally been observed only during elastic
deformation at room temperature. The curves in section
3.1 are linear up to 1% strain, followed by a slope de-
crease. Therefore, the deformation after 1% strain was
ductile. The SS curves of the samples dried at 20% RH
and tested at 0–20 MPa show a similar behavior up to 2%
strain (Fig. 3). The saturated samples had little depend-
ence on Pc (Fig. 4). The oven-dried samples show a
similar behavior up to 1.5% strain at Pc = 30 and 100
MPa. In our previous study, the dependence on Pc was
not observed up to 2% strain. This result corresponds to
the range in which the effect of Pc was small in the results
of section 3.1. In other words, the independent behavior
of HCP on Pc is also obtained in this study. However, in
our previous study, the independence was seen under a
wide Pc range of 30–400 MPa. The results obtained in
this study show a narrower range. The widest inde-
pendent range is 30–100 MPa, which was seen in the
oven-dried samples. The differences in age, moisture
content, and constraint condition at the samples' ends
possibly caused the different range. The effect of these
factors needs to be systematically studied to quantita-
tively understand the HCP behavior under high pressure.
4.4 Moisture effect mechanism on deformation
behavior
A shear plane was not observed in the 20% RH-dried
samples tested at Pc = 50 and 100 MPa, the saturated
sample tested at Pc = 20 and 30 MPa, and the oven-dried
Y. Sakai and T. Kishi / Journal of Advanced Concrete Technology Vol. 15, 19-28, 2017
sample tested at Pc = 300 MPa. This result indicates that
the HCP deformation is significantly affected by both
confining pressure and water content. The effect of water
on deformation has been reported for concrete (Vu et al.
2009) and rocks (Krokosky and Husak 1968). The sur-
face energy change for concrete has been supported as a
moisture effect mechanism on strength (Hori 1962; Cook
and Haque 1974; Matsushita and Onoue 2006). This
mechanism indicates that the surface energy of a solid is
reduced by moisture adsorption, which consequently
reduces the energy required for crack propagation. In
rock mechanics, the suction (West 1994), stress corrosion
(Anderson and Grew 1977), and friction reduction be-
tween particles (Ogata et al. 2003) have been supported
to mainly cause the moisture effect on strength. The
stress corrosion in rocks composed of silicate mineral
was a phenomenon, where water molecular cuts siloxane
bond (Si-O-Si), which accelerates crack propagation.
The results in section 3.1 show that the higher moisture
content reduces the required Pc to avoid macroscopic
damage. The deformation mechanism without macro-
scopic damage at lower Pc should be explained to explain
these moisture-induced behavior changes, aside from the
decrease in strength. The moisture effect mechanisms
can explain the strength reduction, but not the deforma-
tion without macroscopic damage at lower Pc. Griggs
(1967) pointed out that water made dislocations glide
more easily on silicate minerals. In the present study, the
dislocation is a defect in the crystal. Its movement is one
of the main mechanisms of plastic deformation in rocks
and metals (Koehler 1941). Rutter (1972) studied lime-
stone and found that the grain boundary moisture affects
strength reduction and deformability improvement. The
effect of moisture is more prominent in rocks with larger
porosity and surface area. Referring to Boozer et al.
(1962) and Rehbinder and Lichtman (1957), Rutter
pointed out that the polarity of water molecules, as a
mechanism of moisture effect, reduces the surface energy
of the grain surface so that dislocation can appear on a
crystal surface. Dislocation can move easily under con-
fining pressure because of the energy produced by the
crystal structure deformation (Pluijm and Marshak 2004).
However, the dislocation should be removed to continue
plastic deformation; otherwise, the dislocation accumu-
lation causes strain hardening, which leads to brittle
failure (Biswas et al. 2015). Rutter concluded that water
accelerates the dislocation removal. The results of the
present study show that the samples with higher water
content deformed without macroscopic damage at lower
Pc. This finding indicates that the movement and removal
of dislocation, or a similar mechanism, occurred in HCP.
Dislocation can be formed in calcium hydroxide (Ha-
rutyunyan et al. 2003), which occupies approximately
25% of cement hydrates by volume, in concrete by the
stress induced by drying shrinkage. Each data set, except
for the saturated sample tested at Pc = 50 MPa, was fitted
with one line (exponential approximation), and their
slopes were approximately three (Fig. 8). The strain rate
25
of the rocks at the steady-state creep test has been ex-
pressed as follows (Bürgmann and Dresen 2008):
⎛ Q + pV ⎞
ε = Aσ n d − m f water
r
exp ⎜ ⎟, (1)
⎝ RT ⎠
where A, σ, n, d, m, fwater, r, R, T, Q, p, and V are the
coefficient that depend on rocks, stress, stress component,
grain size, grain size component, fugacity of water, fu-
gacity index, gas constant, absolute temperature, activa-
tion energy, pressure, and activation volume, respectively.
The slope in Fig. 8 corresponds to a stress component n.
The creep mechanism is classified by n. A case n = 1 is
the diffusion creep, while n = 3 is the dislocation creep
(Mei and Kohlstedt 2000). The former is the creep
mechanism governed by atom diffusion, while the latter
is the dislocation movement. Burgmann and Dresen
(2008) classified n = 3–6 as a creep governed by the
dislocation climb (removal). A similar equation to Eq. (1)
and a similar classification are applied to metals (Sato et
al. 2005) and ice (Goldsby and Kohlstedt 1995). There-
fore, the slope of three in Fig. 8 is classified as a creep
governed by dislocation (climb), which supports the
effect of dislocations in the HCP deformation. However,
the saturated sample tested at Pc = 50 MPa has slopes of
0.39 and 9.86. The creep mechanism in rocks, metals,
and ice generally changes from a diffusion creep to a
dislocation creep with increasing differential stress.
Therefore, having two slopes is not a special behavior.
However, the 0.39 slope is small for a diffusion creep,
while 9.86 is large for a dislocation creep. The strain rate
in the amorphous metal is expressed as follows (Schuh et
al. 2007):
⎛ Q⎞ ⎛ σV ⎞
ε = α 0ν 0 γ 0 exp ⎜ − ⎟ sinh ⎜ ⎟, (2)
⎝ kT ⎠ ⎝ 3kT ⎠
where α0, ν0, γ0, and k are the constant, attempt frequency,
characteristic shear transformation zone volume, and
Boltzmann constant, respectively. The slope can be very
large when the strain rate and stress relationship ac-
cording to Eq. (2) are plotted on a double logarithmic
scale. Therefore, the behavior is more like the amorphous
material than the crystalline material in the saturated
sample tested at Pc = 50 MPa. Moreover, twinning (i.e.,
symmetrical deformation of crystalline lattice) is de-
veloped in limestone at a low stress (i.e., 2–12 MPa) and
at room temperature (Passchier and Trouw 2005). Re-
garding dislocation, twinning can cause ductile defor-
mation. However, other mechanisms, such as diffusion in
grain or pressure solution, need to occur in parallel to
continue deformation by twinning (Passchier and Trouw
2005). The pressure solution herein is a phenomenon, in
which dissolution occurs at the compressed part of a
grain, while precipitation occurs at the part with rela-
tively lower stress. In the presence of water, the pressure
solution can be a governing deformation mechanism
even at low temperature and low Pc. The specimen
saturated with the sucrose solution shows a higher
Y. Sakai and T. Kishi / Journal of Advanced Concrete Technology Vol. 15, 19-28, 2017
maximum stress and steeper stress softening curve than
the specimen saturated with tap water under a displace-
ment rate of 36 μm/h. The difference in the slopes after
the maximum stresses is small when the displacement
rate is 0.2 mm/min. However, the number of the data
measured every second after the peak stress is less in the
sample saturated with the sucrose solution than that
saturated with tap water. This result indicates a sudden
stress drop. The suppressed calcium hydroxide precipi-
tation in the sucrose solution may have caused this brittle
behavior. Pachon–Rodrigueza et al. (2014) studied the
pressure solution in gypsum and noted that this pressure
solution can occur in HCP. The results in Fig. 6 support
their prediction. The difference in the SS curves is only
seen around and after the maximum stress, which is
probably because the resistance to deformation, caused
by the precipitated calcium hydroxide, is small compared
to that of the other hydrates. This resistance becomes
dominant after the other hydrates are damaged. In this
study, displacement is given at a rate of 5 × 10−7 ε/s.
However, the pressure solution is dominant in the lime-
stone deformation slower than 1 × 10−7 ε/s (Passchier and
Trouw 2005). Slower loading may more clearly show the
difference between the samples saturated with tap water
and sucrose solution. The obtained results indicate that
dislocation and/or twinning occurs in HCP as with rocks.
Moisture prevents strain hardening by accelerating the
dislocation climb and pressure solution to continue plas-
tic deformation. As mentioned in the introduction, the
triaxial test results and SEM observation on HCP in our
previous study (Sakai et al. 2016) support the crystal
plasticity being caused by dislocation and twinning.
These results correspond to the results obtained in this
study. The surface energy reduction in the oven-dried
sample is small because of the small amount of water.
Therefore, a higher Pc might be necessary to produce
high strain energy or to squeeze water from hydrates to
show ductile deformation. Assuming that the above-
mentioned mechanism is correct, the deformation of all
samples in this study, and concrete structures in general,
may be affected by dislocation and twinning. This is
because Pc and water only work to continue plastic de-
formation because of dislocation and twinning. The
sample tested at Pc = 0 in Fig. 8 actually shows a slope of
approximately three, which indicates a dislocation creep.
As mentioned, dislocation can be introduced in calcium
hydroxide in concrete only by stress caused by drying
shrinkage. The results in Fig. 6 support the effect of the
calcium hydroxide precipitation on the mechanical per-
formance under no confinement conditions. More direct
and clear pieces of evidence regarding forming and re-
moval of dislocation, development of twinning, and
pressure solution are necessary to conclude the defor-
mation mechanism of HCP.
4.5 Deformation mechanism of C–S–H
The behavior change in HCP caused by Pc and the
moisture content obtained in this study are similar to that
26
of limestone. This result shows the ductile deformation
by dislocation and twinning at room temperature. The
dislocation is observed in calcium hydroxide in concrete
(Harutyunyan et al. 2003). However, a large part of HCP
is composed of C–S–H, which is generally regarded as a
gel. In the field of amorphous material, some researchers
tried to describe the deformation mechanism using dis-
location theory (Gilman 1973). The ideas of shear
transformation zone (STZ) these days are supported by
more researchers (Schuh et al. 2007). The STZ is the
inelastic shear distortion of local clusters composed of
several tens of atoms. Using the STZ concept, the rela-
tionship of strain rate to stress is described by Eq. (2).
The saturated sample tested at Pc = 50 MPa has a large
slope (i.e., 9.86). The slope can also be described by Eq.
(2). Therefore, the deformation of calcium hydroxide,
which is a crystalline material, is possibly governing the
HCP deformation rate when the sample is not saturated,
or Pc is low. The slope is approximately three, which
indicates a dislocation creep. On the contrary, calcium
hydroxide flows and the deformation of the surrounding
amorphous material (C–S–H gel) becomes dominant
when the sample is saturated, and high Pc is given. Its
deformation is expressed by Eq. (1). The structural
change in C–S–H due to RH and moisture content has
been studied experimentally and numerically. Cong and
Kirkpatrick (1995) analyzed the structural changes of
C–S–H cured at different RHs and reported that the po-
lymerization of C–S–H did not change but the local
structure became more disordered with decreasing RH.
Hou et al. (2014) analyzed the structure of C–S–H using
molecular dynamics and reported that the increasing
water content transformed the C–S–H from an amor-
phous into a layered structure. Further study is necessary
to conclude the slope change mechanism.
5. Conclusions
The following general conclusions can be drawn from
this study:
– HCP deforms without stress drop and macroscopic
damage up to 10% strain under a certain confining
pressure.
– The confining pressure, at which stress drop and shear
plane do not occur, differs depending on the moisture
content.
– The differential stress–strain rate relationships ob-
tained in the stepwise creep test have a slope of ap-
proximately three on the double logarithm chart. Stud-
ies in the rock and metal field state that this slope in-
dicates a deformation caused by the dislocation creep.
– The sample saturated with sucrose solution shows a
more brittle behavior than that saturated with tap water
after the peak stress. The pressure solution of calcium
hydroxide possibly affects the behavior because the
calcium hydroxide precipitation is suppressed in the
sucrose solution.
– The HCP does not show stress drop and macroscopic
Y. Sakai and T. Kishi / Journal of Advanced Concrete Technology Vol. 15, 19-28, 2017
damage with confining pressure and water content
increase. These results can be explained by assuming
dislocation, twinning, and pressure solution in the
HCP.
Acknowledgment
This study was supported by the Kajima Foundation’s
Assistance for Exchange of Researcher and the Steel
Foundation for Environmental Protection Technology.
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