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Cement Reaction and Resultant Physical Properties of Cement Paste

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DOI: 10.3151/jact.12.200

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Cement reaction and resultant physical properties of cement
paste
Ippei Maruyama , Go Igarashi
Journal of Advanced Concrete Technology, volume 12 ( 2014 ), pp. 200-213

Characterization and Modeling of Pores and Surfaces in Cement Paste: Correlations to Processing and
Properties
Hamlin Jennings, Jeffrey W. Bullard , Jeffrey J. Thomas, Jose E. Andrade-HIIUH\-&KHQ*HRUJH:6FKHUHU
Journal of Advanced Concrete Technology, volume 6 ( 2008 ), pp. 5-29

Mechanical, electrical and microstructural properties of cement-based materials in conditions of stray

current flow
Agus Susanto, Dessi A. Koleva , 2JX]KDQ Copuroglu, Kees van Beek.ODDVYDQ%UHXJHO
Journal of Advanced Concrete Technology, volume 11 ( 2013 ), pp. 119-134

Early age hydration, micro-structure and micro-mechanical properties of cement paste modified with
polymeric vesicles
Jie Hu, Dessi Koleva, Yuwei Ma , Erik Schlangen.ODDVYDQ%UHXJHO
Journal of Advanced Concrete Technology, volume 11 ( 2013 ), pp. 291-300
Journal of Advanced Concrete Technology Vol. 12, 200-213, June 2014 / Copyright © 2014 Japan Concrete Institute 200

Scientific paper

Cement Reaction and Resultant Physical Properties of Cement Paste

Ippei Maruyama1 and Go Igarashi2

Received 25 Janyuary 2014, accepted 20 May 2014 doi:10.3151/jact.12.200

Abstract
The body of data about the reaction kinetics of cement has greatly grown in recent years, and in terms of techniques for the
prediction of the resulting hydrate formation phases, databases contributing to thermodynamic equilibrium calculations
have been developed and are growing increasingly sophisticated. On the other hand, though many studies on cement aim
to contribute to concrete engineering and numerical model researchers have pointed out the necessity of shedding light on
the relationship between the microstructures generated by hydration and physical properties, such data remains scarce.
This study investigated Portland cements using two commonly used water-cement ratios and three types of mineral
compositions in the material age range of up to one year. The phase composition in relation to cement hydration was
determined by X-ray powder diffraction and Rietveld analysis. In terms of physical properties, compressive strength and
Young's modulus were measured through loading tests, and Young's modulus and Poisson's ratio were also obtained from
the ultrasonic pulse propagation velocity of longitudinal and transverse waves. Further, water vapor adsorption tests to
shed light on moisture behavior were conducted, yielding the BET specific surface area. Thermal conductivity, an im-
portant determinant of thermal behavior, was measured using the transient hot wire method. On the premise of the ap-
plication of these physical properties to numerical calculations, their correlation with the information obtained from the
phase composition was considered, leading to the proposal of simple and relatively high-accuracy empirical formulas.
Further, background information about raising the correlation of these empirical formulas was also discussed.

1. Introduction 1982; Beaudoin 1994; Shimomura and Maekawa 1997).

A discussion of the structural performance of reinforced
concrete structures and its time dependence requires
consideration of the time dependence of the properties of
concrete, taking into account the concreting and curing
processes, with the hydration of cement from the time of
water supply as the starting point (Sato et al. 2008).
Cement hydration kinetics models have been proposed
for a long time (Taplin 1959; Kondo and Ueda 1968;
Tomosawa 1974; Jennings and Johnson 1986), and in
recent years many studies have been proposed as the
scale and speed of numerical calculations have increased
(Thomas et al. 2011). For the phase composition result-
ing from the hydration reaction, an experiment-based
hydration reaction formula was proposed quite some
time ago (Osbaeck 1992), and more recently, the de-
velopment of data for thermodynamic equilibrium cal-
culations has been progressing, leading to more sophis-
ticated prediction methods (Lothenbach and Winnefeld
2006; Blanc et al. 2010; Nonat 2004). With regard to the
pore structure in cement paste, although a sufficient
scientific foundation is not yet in place due to the com-
plexity of C-S-H behavior, various engineering models
have been proposed, and there are many methods to
predict properties based thereon (Jons and Osbaeck
1
Assoc. Professor, Graduate School of Environmental
Studies, Nagoya University, Nagoya, Japan.
E-mail: ippei@dali.nuac.nagoya-u.ac.jp
2
Graduate School of Environmental Studies, Nagoya
University, Nagoya, Japan.
Extensive research has been conducted by Powers and
Brownyard in terms of the microstructure and properties
of cement paste (Powers and Brownyard 1947; Powers
1958). A gel-space ratio theory allowing quantitative
prediction of the compressive strength of mortar from the
microstructure has been proposed (Powers 1958). Based
on the study of water vapor adsorption behavior, a high
correlation between the water vapor adsorption BET
specific surface area and chemically bound water has
been pointed out (Powers 1946).
Subsequently, as various numerical models were
proposed reflecting the increasing availability of nu-
merical calculation power, experimental studies to asso-
ciate physical properties and hydrated (cured) cement
information have been conducted (Powers and Brown-
yard 1947; Osbaeck 1992, Boumiz 1996; Haecker 2005).
As analytical techniques have improved and thermo-
dynamic equilibrium calculation databases are now
available in the field of cement chemistry, further de-
velopment of fundamental data for the quantitative
evaluation of the physical properties of hardened cement
paste generated as the result of hydration is essential
from the perspective of concrete engineering.
From this perspective, this study consolidates data
about the hydration reaction and resultant physical
properties, using two different water-cement ratios and
three different Portland cement pastes. Further, it selects
among the indices indicating the microstructure of ce-
ment paste those with the highest correlation and pro-
poses engineering formulas for predicting physical
properties.
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014
It is noteworthy that there are companion papers
showing the physical data of cement paste made with the
same Portland cement. Drying shrinkage (Maruyama
2010) as well as the development of autogenous
shrinkage and linear expansion coefficient (Maruyama et
al. 2013) for the cements used in this study have been
reported elsewhere. The results for ordinary Portland
cement subjected to initial high temperature curing
simulating mass concrete temperature history were also
reported (Maruyama and Igarashi 2010).
2. Experimental methodology
2.1 Preparation of test specimens
The cements used in the experiments in this study con-
sisted of ordinary Portland cement (symbol N), moderate
heat Portland cement (symbol M), and low heat Portland
cement (symbol L). The test results of chemical analysis
according to JIS R 5202 and JIS R 5204 are given in
Table 1, and the mineral composition obtained through
X-ray powder diffraction (XRD) and Rietveld analysis
are given in Table 2. The specimens were fabricated
using cement paste with water-binder ratios of 0.55 and
0.40 (symbols 55 and 40, respectively). Hereinafter,
specimens will be designated with a symbol-based nota-
tion such as N55, indicating the binder type and the wa-
ter-binder ratio. The OM30-SA omni mixer (Chiyoda
Machinery, 30 liter capacity, hydraulic motor drive) was
used for mixing. After three minutes mixing followed by
scraping, mixing was done for an additional three min-
utes. The mixing volume was 25 L. After remixing for 4
to 6 hours until bleeding stopped, the cement was poured
to a thickness of 5 mm in aluminum foil bags the inner
surfaces of which were covered by a polyester film for
the purpose of hydration reaction analysis. The alumi-
num bags were then sealed with aluminum adhesive tape.
For compression loading test, specimens were fabri-
cated using lightweight molds of φ50 × 100mm.
For ultrasonic wave propagation measurement,
specimens of 40 × 40 × 160 mm were fabricated. At the
age of 0.5 days, the specimens were demolded and im-
Table 1 Properties of used cements.
Blaine
Density
Type value
3
(g/cm ) (cm2/g) LOI
Ordinary Portland cement (N) 3.16 3110 0.64
Moderate heat Portland
3.20 3210 0.80
cement (M)
Low heat Portland cement (L) 3.22 3400 0.70
Table 2 Mineral composition of used cements.
Mineral composition (mass%)
Type
C3S C2S C3A
N 62.2±1.0 18.3±0.8 5.6±0.5
M 41.6±1.0 38.6±1.4 3.7±0.3 12.7±0.3
L 24.5±0.6 61.3±1.6 2.2±0.3
where C:CaO, S:SiO2, A:Al2O3, F:Fe2O3, M:MgO, s:SO3, H:H2O.
201
mediately sealed with aluminum adhesive tape.
For thermal conductivity measurement, cement was
poured in disposable trays made of polypropylene and
measuring 100 × 150 × 20 mm. Immediately after
pouring, the specimens were sealed by wrapping them in
plastic film made of polyvinylidene chloride (PVC), then
covering them with adhesive aluminum tape, and further
sealing them in a zippered aluminum bag.
All the samples were allowed to stand in a 20±1°C
constant temperature chamber.
2.2 Cement hydration evaluation
Samples whose hydration was stopped at the designated
ages (0.5, 0.75, 1, 3, 7, 14, 28, 91, 182, and 364 days)
were used. The samples of each material age were
crushed into pieces of 20 mm or less with a hammer, and
then finely ground using a high speed vibrating sample
crusher. The milled sample powder was immediately
immersed for about 30 minutes in acetone, after which
the powder sample and acetone were separated by suc-
tion filtration. Then, the powder sample was again im-
mersed in acetone for an additional six hours, after which
the acetone was again separated. After the hydration
reaction was stopped by acetone, the samples were dried
for two weeks in a desiccator using circulated air
scrubbed using carbon dioxide absorbent and a saturated
lithium chloride aqueous solution at the constant tem-
perature of 20°C. After drying, the samples were graded
with a 150 μm sieve, and only the powder under the sieve
was used for the various measurements.
Measurement of powder X-ray diffraction was con-
ducted using a D8 ADVANCE X-ray diffractometer
(Bruker AXS) under the following conditions:
Cu-KαX-ray source, 40 kV tube voltage, 40 mA tube
current, 2θ =5~65° scanning range, 0.02° step width, and
0.5°/min scanning speed. The samples used for meas-
urement consisted of powder samples whose hydration
was stopped and which underwent humidity conditioning
to which corundum (α-Al2O3) was admixed at the rate of
10 wt% in terms of inner percentage as an internal
standard. Rietveld analysis was done for the entire chart
Composition (mass%)
SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O Cl－ Total
21.8 4.49 2.90 63.9 1.84 2.26 0.20 0.38 0.007 98.4
23.3 3.80 3.90 63.3 0.90 2.40 0.30 0.35 0.000 99.1
26.3 2.80 3.20 62.9 0.70 2.40 0.15 0.41 0.005 99.6
C4AF M CsH0.5 CsH2 Total
9.8±0.9 1.3±0.2 1.2±0.2 1.5±0.1 100±1.7
0.8±0.2 2.4±0.3 0.2±0.1 100±1.8
8.3±0.3 0.7±0.2 2.4±0.3 0.6±0.1 100±1.8
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014 202

obtained using the TOPAS ver. 4.2 software (Bruker
AXS). Alite (C3S), belite (C2S), aluminate phase (C3A),
ferrite phase (C4AF), periclase (MgO (M)), lime
(Free-CaO), calcite (CaCO3 (CĈ)), gypsum (CaSO4 ·
2H2O (CŜH2)), bassanite (CaSO4 · 0.5H2O (CŜH0.5)),
portlandite (Ca(OH)2 (CH)), ettringite (C3A · 3CaSO4 ·
32H2O (Ett)), monosulfate (C3A · CaSO4 · 12H2O (Ms)),
and hydrogarnet (C3AH6 (Hg)), as minerals and cement
hydration products, and α-Al2O3 (10wt%) admixed to the
analysis sample as the internal standard, were chosen to
be quantified. As the parameters related to the crystal
structure of the C3S, C2S, C3A, and C4AF crystalline
phases of the minerals for quantification, those in the
NIST Technical Report (Stutzman and Leigh 2002) were
used, and as the parameters for M, CŜH2, CŜH0.5, Cc, CH,
Ett，Ms, Hg, α-Al2O3, those in the ICSD Database (ICSD
2006) were used. The mass of amorphous materials was
calculated according to Equation (1) based on the
quantitative value of internal standard α-Al2O3 (Bish and
Howard 1988).
A={100×SR-S)}/SR×(100-S)/100} (1)
where A = amorphous material mass, S = mixing ratio
(%) of α-Al2O3, and SR = quantitative value (%) of
α-Al2O3. The maximum error in XRD/Rietveld analysis
was calculated from the analytical error in pattern fitting
of Rietveld analysis and the measurement error of the
quantitative values obtained from three measurements.
The standard deviation of quantitative values for the
cement materials in unhydrated cement was ±1.0 mass%
for C3S, ±1.6 mass% for C2S, ±0.5 mass% for C3A, and
±0.9 mass% for C4AF.
In assessing the reaction rates of the minerals in the
various cements and the phase composition including the
solid phase as affected by humidity conditioning, the
H2O/CaO ratio under different drying states was
considered, and the hydration rate was assessed by
converting all components into anhydrous matter by
using the chemical composition shown in Table 3 and the
chemically bound water values. Here, the humidity after

Table 3 Chemical composition of cement hydrates under different drying conditions.

Molar mass Density
Hydrates Drying state H/C Composition formula Note
(g/mol) (g/cm3)
1000℃ 0 CxSH0 155 ―
1) 105℃ 0.88 CxSH1.5 182 2.60 2)
C-S-H
11%RH,20℃ 1.47 CxSH2.5 193 2.41 3)
Saturated 1.47 CxSH2.5 193 2.41 4)
1000℃ 0 C3A･3(CŜ)･H0 679 ―
105℃ 2.00 C3A･3(CŜ)･H12 895 2.38 5)
Ett
11%RH,20℃ 5.33 C3A･3(CŜ)･H32 1255 1.78 6)
Saturated 5.33 C3A･3(CŜ)･H32 1255 1.78
1000℃ 0 C3A･CŜ･H0 406 ―
105℃ 2.00 C3A･CŜ･H8 550 2.40
Ms
11%RH,20℃ 3.00 C3A･CŜ･H12 623 1.99
Saturated 3.00 C3A･CŜ･H12 623 1.99
1000℃ 0 C3AH0 270 ―
105℃ 0.88 C3AH6 378 2.52 7)
HG
11%RH,20℃ 0.88 C3AH6 378 2.52
Saturated 0.88 C3AH6 378 2.52 8)
1000℃ 0 C4AH0 326 ―
105℃ 1.75 C4AH7 452 2.52 7)
C-A-H
11%RH,20℃ 3.25 C4AH13 561 2.05
Saturated 3.25 C4AH13 561 2.05 8)
1000℃ 0 C4FH0 384 ―
105℃ 1.75 C4FH7 510 2.84 9)
C-F-H
11%RH,20℃ 3.25 C4FH13 618 2.16 10)
Saturated 3.25 C4FH13 618 2.16 8), 10)
1) The molecular weight of C-S-H when x is assumed to be 1.7 is listed.
2) References : Jennings (2000), Taylor (1986)
3) Reference : Feldman and Ramachandran (1982)
4) In the present study, the adsorbed water at the condition above 11% RH is assumed to behaves like a bulk water.
5) References : Zhou and Glasser (2001). Tennis and Jennings (2000)
6) References : Tennis and Jennings (2000), Poellmann et al. (1993)
7) References : Fischer and Kuzel (1982), Brouwers (2005)
8) This has been reported to become C4AH19 at relative humidity of 88% or higher, but it was decided to consider it to be stable
C4AH13 as a crystal in consideration of the easy dehydration condition.
9) Because of missing data, the density was calculated by assuming the same crystal structure as C4AH7.
10) It is generally accepted that Fe forms a liquid solution partly substituting with Al in C-A-H, while they are separated for con-
venience in this study.
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014
humidity conditioning is assumed to be 11%RH. Further,
in this study, in view of the changes in the Ca/Si atomic
ratio due to the hydration reaction, we identified the
phase composition through the following iterative
calculation process from the values obtained by Rietveld
analysis.
(1) Each phase in cement paste is converted into anhy-
dride. Then, the C-S-H amount value is assigned by
using a temporary Ca/Si atomic ratio of C-S-H, such
as 1.7.
(2) The hydration reaction rate of each anhydrous phase
is calculated.
(3) The amounts of Al2O3 and Fe2O3 in unhydrated ce-
ment minerals and crystalline hydrates are calculated
based on the Rietveld analysis results. The difference
in the amounts of Al2O3 and Fe2O3 between cement
minerals and hydrates is considered to have been
used in the formation of C-A-H or C-F-H in amor-
phous material (Collepardi et al. 1978).
(4) The amounts of CaO and SiO2 in unhydrated cement
minerals, crystalline hydrates, and C-A-H and
C-F-H are calculated based on the Rietveld analysis
results and the results of step 3) above. The differ-
ence in the amount of CaO and SiO2 between the
hydrated cement minerals and hydrates C-A-H and
C-F-H are considered to have been used in the for-
mation of C-S-H.
(5) The Ca/Si atomic ratio of C-S-H is calculated and all
amorphous material is converted into anhydride.
(6) The phase composition can be identified as the value
at convergence through repetition of the above cal-
culations.
Through the iterative calculation of 1) through 6),
convergence of the Ca/Si atomic ratio of C-S-H is
Calculate mass-ratio of each
phase in cement paste based on
XRD/Rietveld analysis.
(All amorphous is assumed to
be C-S-H.)
Convert each calculated phase
to anhydrates.
(Temporary C/S ratio is
applied.)
Calculate degree of hydration of
each cement mineral.
Fig. 1 Flowchart of convergence calculation for phase composition.
203
achieved and the calculation is completed. It should be
noted that in the scope of this study, differences in mo-
lecular weight due to differences in the Ca/Si atomic ratio
of C-S-H were taken into account, but owing to the lim-
ited amount of data available, it was assumed that there
are no changes in the H/Si ratio and density of C-S-H.
Figure 1 shows an overview of the above-described
iteration algorithm. The amount of matter of each phase
is identified through that calculation flow. Furthermore,
the phase composition in terms of equivalent volume was
obtained by using the amount of chemically bound water
and density of each hydration product in the sealed state
described in Table 3.
In this study, we measured the ignition loss for sam-
ples after humidity conditioning, for the purpose of
verifying the XRD/Rietveld method and examining the
possibility of developing a physical property assessment
index system. Measurements were performed using a
TG-DTA 2010 SA (Bruker AXS). Samples of mass 20±2
mg were subjected to thermogravimetric (TG) analysis in
the temperature range from room temperature to 1000°C
with a rate of temperature increase of 10 °C/min under an
N2 flow. The amount of chemically bound water was
calculated from ignition loss.
2.3 Compression loading test
The compressive strength and Young's modulus were
measured using φ50 × 100 mm specimens fabricated
from cement paste at the ages of 1, 3, 7, 14, 28, 91, 182,
and 364 days. The sealed samples were demolded im-
mediately prior to testing, and their loading face was
polished. The tests were conducted on three specimens
and the results were averaged. Young's modulus was
determined by measuring vertical strain with a com-
1) Calculate mass-balance of
Al2 O3 and Fe2 O3 between
reacted cement minerals and
hydrates.
2) Estimate amount of Al2 O3
and Fe2O3 in amorphous.
Calculate amount of C-A-H
Convergence of C/S ratio
and C-F-H in amorphous.
(C4AH13 and C4FH13 are
assumed.)
Calculate balance of CaO and
SiO2 between reacted cement
minerals and hydrates.
Renew C/S ratio of C-S-H
Re-convert amorphous phase to
anhydrates and re-calculate
degree of hydration of each
cement mineral.
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014
pressometer (50 mm rating interval, 1/1000 mm accu-
racy) at the lording one-third of the maximum, and then
using least squares approximation to calculate Young's
modulus as the ratio of compressive stress to vertical
strain. Because the compressive strength results varied
widely from the age of 91 days for L40 and M40, and at
the age of 364 days for L55 and M55, compressive
strength was not evaluated.
2.4 Ultrasonic wave velocity test
Prismatic specimens of 40 × 40 × 160 mm made of ce-
ment paste were demolded at the age of 0.5 days, the
ultrasonic wave arrival time was measured at the ages of
0.5, 0.75, 1, 1.5, 2, 3, 5, 7, 14, 28, 91, and 182 days, and
Poisson's ratio was calculated as an average of the values
obtained for three specimens. After demolding, the
specimens were sealed at all times with aluminum ad-
hesive tape except at the measurement points, and the
measurement points were also sealed when measurement
were not being performed to prevent as much as possible
the escape of moisture.
Measurement of the ultrasonic wave arrival time was
done using Panametrics-NDT™ ultrasonic transducers
(V103-RM, V153-RM), Panametrics-NDT™ pulser-
receiver 5077PR Olympus), and digital scope
oscilloscope TDS2012B (Tektronix). Using pulsed
voltage of -400 V, probe frequency of 1.0 MHz, and pulse
repetition frequency (PRF) of 100 Hz as the
measurement conditions, the longitudinal wave arrival
time and transverse wave arrival time were respectively
measured at the middle of each specimen by the
transmission method from the difference between the
reference waveform and the transmitted waveform. The
results were converted into longitudinal wave
propagation speed and transverse wave propagation
speed. Determination of the arrival time was done at the
maximum peak waveform by using the time showing the
maximum value. The thickness of the specimen s used
for this calculation was 40 mm throughout.
Poisson's ratio was calculated from these data with
Equation (2), based on elastic theory, using the speed
ratio of the longitudinal and transverse waves.
1 − 2 (Vs V p )
2
ν=
2 − 2 (Vs V p )
2
where ν = Poisson's ratio ( － ) ， V p = Longitudinal
wave propagation speed (km/s)， Vs = transverse wave
propagation speed (km/s).
Further, from Poisson's ratio and the apparent density,
Young's modulus (longitudinal elastic modulus) is ob-
tained by Equation (3).
(1 + ν )(1 − 2ν ) 2
E= Vp ρ
1 −ν 2
= 2(1 +ν )Vs ρ
where ρ = apparent density (g/cm3) ， E = Young's
204
modulus (GPa)， G = shear modulus (GPa)，and K =
bulk modulus (GPa).
Because no change in mass should occur in a sealed
condition, the apparent density of the hardened cement
paste was assumed to be a constant value from immedi-
ately after water supply, and was calculated from the
cement density indicated in Table 1 and the wa-
ter-cement ratio.
Equations (2) and (3) are based on the elasticity theory.
Data supporting their applicability to hardened cement
paste at an early material age when plastic deformation
due to fine cracks is most likely to occur is limited.
However, given the experimental confirmation of the
tendency of a value with no volume change such as water
(ν = 0.5 ) to change over time to a value that converges
closely toward Poisson's ratio for concrete, which is
generally known, as the result of curing, as predicted and
confirmed by previous studies (Kawasumi 1994; Abeele
et al. 2009), these equations were judged capable of
yielding the elastic Poisson's ratio of hardened cement
paste.
2.5 Water vapor adsorption test
Water vapor adsorption tests were carried out on samples
graded between 25 μm and 75 μm after humidity condi-
tioning. A Hydrosorb 1000 (Quantachrome) was used for
measurement based on the volume method. As a pre-
processing condition for the samples, the samples were
heated for one hour at 105°C using a mantle heater under
the condition of vacuum degassing by a rotary pump
(ultimate pressure performance: 6.7 × 10-2 Pa). During
measurement, a sample cell was placed in a controlled
temperature environment of 20±0.1°C using constant
temperature water tank control. Allowable pressure dif-
ferential of 0.05 mmHg and equilibrium time of 120 s
were adopted for measurement, and in terms of meas-
urement points, 5% increments from 5% RH to 95% RH
were used, with 98%RH as the final point. Based on the
results of the water vapor adsorption test, we calculated
the BET specific surface area using the data in the region
of 5%RH to 30%RH. At that time, we used the value of
0.114 nm2 as the area occupied by one water molecule
(Mikhail and Selim 1966).
(2) 2.6 Thermal conductivity measuring device
A Kemtherm QTM-D3 (Kyoto Electronics Manu-
facturing), a box-type probe meter using the transient hot
wire method was used for measurement. Thermal con-
ductivity was obtained by Equation (4).
I 2 ln (T2 T1 )
λ = K⋅ −H (4)
V2 − V1
where λ = thermal conductivity of the hardened cement
paste (W/(m･K)), K, H = constants determined by the
(3)
probe, V1, V2 = electromotive force of the thermocouples
at times T1 and T2, respectively (mV), and I = current
flowing through the heating wire (A). In this experiment,
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014 205

Fig.2 Degree of hydration of each cement minerals and their average.

I = 2.00 A, and the measurement time is 60 s.

The specimens described in section 2.1 were removed
from their tray at the time of measurement, covered with
a PVC film, turned upside down to make their bottom
side face up, and fitted with the probe used for meas-
urement. The film served to control moisture escape
caused by heating during measurement, and the fact that
it did not affect measurements was confirmed during
preliminary tests. The materials ages were 0.5, 0.75, 1,
1.5, 2, 3, 5, 7, 14, 21, 28, 91, and 182 days, and the
measurement value was the average for five specimens.

3. Experimental results and discussion

3.1 Hydration analysis Fig.3 Calculated phase compositions.
Figure 2 shows the relationship between the hydration
reaction rate of the cement minerals and the material age
of each cement paste. The error bars represent 1 standard
deviation of variability during measurement and ana-
lytical error during Rietveld analysis. Figure 3 shows the
development of phase composition, calculated from the
composition of the unhydrated cement, the reaction rate
in Fig. 2, and the analysis flow shown in Fig. 1. In order
to verify the validity of this development, the comparison
of chemically bound water measured by TG and the
chemically bound water calculated from the phase
composition is shown in Fig. 4. As shown in this figure,
there is a good correlation between the two, thus confer-
ring a certain degree of validity to the calculated phase
compositions. Fig. 4 Comparison of measured chemically bound water
and estimated chemically bound water from the phase
3.2 Strength, Young's modulus, and Poisson's compositions shown in Fig. 3.
ratio
Figures 5 to 8 show the development in compressive As shown in Fig. 5, development of compressive
strength (compression test), Young's modulus (compres- strength shows sign of almost completely leveling off at
sion test), Young's modulus (ultrasonic test), and the age of 1 year for N55. M and L show slow strength
Poisson's ratio (ultrasonic test), respectively. development, reflecting the hydration rate. Figures 6
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014 206

Fig.5 Development of compressive strength of cement Fig.8 Development of Poisson’s ratio of cement pastes
pastes. calculated by using the results of ultrasonic pulse velocity
measurements.

Fig.6 Development of Young’s modulus of cement pastes

measured by loading test. Fig.9 Comparison of Young’s modulus obtained by load-
ing test with Young’s modulus obtained by ultrasonic
pulse velocity measurement.

this figure, while some variation can be seen, overall

there is good agreement. With regard to Poisson's ratio
shown in Fig. 8, it tends to converge around the age of 7
days toward the value of 0.26 regardless of the wa-
ter-cement ratio and cement mineral composition.
As described above, the physical properties show
some variation over time according to the water-cement
ratio and mineral composition, and in this study we at-
tempted to evaluate the various mechanical properties
with just one index encompassing these differences.
In this study, we calculated the gel-space ratio (g/s)
expressed by Equation (5) from the phase compositions
Fig.7 Development of Young’s modulus of cement pastes
in the sealed state shown in Fig. 3, and adopted the
calculated by using the results of ultrasonic pulse velocity
evaluation of strength based on the gel-space ratio the-
measurements.
ory of Powers expressed by Equation (6) (Powers
1958).
and 7 show the development of Young’s modulus, but
Vhyd
that behavior largely mirrors that of strength. For X= (5)
Young’s modulus, the data up to the age of 364 days is Vhyd + V pore
available. The correspondence between Young's
(6)
modulus obtained by loading test and Young's modulus σ = σ0 X N
obtained by ultrasonic pulse velocity measurement is
shown in Fig. 9 for verification purposes. As shown in where X = gel-space ratio (vol./vol.), V hyd = sum of
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014
amounts of various hydration products (cm3), V pore =
total void volume (cm3), σ = strength (MPa), σ 0 =
ultimate strength (MPa), and N = material constant.
The gel-space ratio is the ratio of the amount of hy-
dration product to the sum of the total void volume and
amount of hydration product. In the present study, the
skeleton of C-S-H in the saturated or sealed condition is
assumed to be the same as that dired dried under at 11%
RH, even though some additional adsorption in the in-
ter-layer is possible. This assumption is reflecteds by the
fact that the water above 11% RH is easily evaporate
under the drying process and can not be considered as a
part of C-S-H structure (Allen et al. 2010). Corre-
spondingly, the density of water in C-S-H above 11%
RH is considered as 1.0 g/cm3 by Young & Hansen
(1986) and Setzer & Liebrecht (2007). Based on these
resultsstudies, we take adopted such assumption. In ad-
dition, we will not show the impact of individual cement
hydrates and cement minerals on the physical properties,
because we can not draw the significant results from the
present data set. Nevertheless, the precise phase compo-
sition in cement paste is necessary to obtain the value of
volume of solids, water, and voids.
Under ideal conditions where all voids are filled by
gel (hydration product), σ becomes σ 0 , and the
strength becomes either the theoretical ultimate strength
or maximum ultimate strength. The N value represents
the dependence of strength on the gel-space ratio. In this
hypothesis, it is considered that unhydrated cement does
not contribute to strength, or alternatively, to collapse of
the paste. This is reflected by the fact that hydration
product has lower strength compared to unhydrated ce-
ment. This means that the collapse of cement paste is
initiated from the hydration products phase, namely, the
interfaces between cement hydrates, when as far as the
the system in the cement paste is assumed to be com-
posed of three phases, such as voids, hydration product
phase, and unhydrated cement mineral phase.
Figure 10 shows the results for compressive strength
as a function of the gel-space ratio. As shown in this
figure, the high correlation between g/s and strength Fp
is reproduced. With regard to the relationship between
g/s and strength, N is distributed in the value range of
Fig. 10 Compressive strength as a function of g/s.
207
2.0 to 3.0 in the studies of Powers (1960), Taylor (1997),
Osbaeck (1992), and Sakai (1998), but in this study, the
value of N is 3.9, which is higher than for any of the
above-mentioned studies. This is due to the fact that
because of differences in the preparation of the paste,
the loading conditions, and the values used in the phase
composition assessment, direct comparison of consis-
tency with the constants in this study is not possible.
But the assumption that the C-S-H in sealed condition is
the same as that dried under 11% RH affects the amount
of the solid volume and resultantly, may pose a large
impact on the N value.
Next, we examined Young's modulus. While a pri-
mary correlation between Young's modulus and g/s is
obtained for each mix proportion, there was no univer-
sal relationship with regard to W/C and cement type. By
considering the interior of hardened cement paste con-
sisting of unhydrated particles, hydrates, and voids, de-
formations in hardened cement paste are determined by
the volume of hydration products and voids. This is why
Young's modulus and g/s have linear correlation.
Generally, Young's modulus and density are related
by the equation of motion (Equation (7)).
∂ 2u ∂ 2u
ρ = E (7)
∂t 2 ∂x 2
Based on the fact that in a uniform body, Equation (7)
holds true at any time and at any coordinates, density
and Young's modulus have a linear correlation to each
other.
Thus, evaluation of Young's modulus by the index
consisting of density and g/s yielded the high correlation
shown in Fig. 11. As shown in that figure, the index
obtained by multiplying density by g/s can predict
Young's modulus as a straight line regardless of the wa-
ter-cement ratio, material age, and mineral composition
of the cement.
This straight line has an x-intercept and does not pass
through the origin. This is thought to be due to the fact
that even though hydration products are produced,
Young's modulus is not expressed without the formation
of a structure that serves as the stress transfer path. Re-
garding this point, it is believed that the validity of this
Fig.11 Young’s modulus as a function of (g/s･ρ).
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014
equation can be further boosted in the development
process of Young's modulus by accumulating data in the
vicinity of the intercept in the future.
Next, let us consider Poisson's ratio. Plotting Pois-
son's ratio against g/s showed that evaluation on the
same curve is possible, as shown in Fig. 12. The fact
that Poisson's ratio could be evaluated from the
gel-space ratio regardless of the water-cement ratio and
cement types is considered to be due to the significantly
higher rigidity of unhydrated cement particles than hy-
dration products and voids, resulting in a relatively
small amount of deformation that does not contribute to
Poisson's ratio of hardened cement paste.
Fig. 12 Poisson’s ratio as a function of g/s.
Fig. 13 Sorption properties of cement pastes.
(Note: pre-treatment of sample is vacuumed and heated at 105 ºC for 1 h.)
208
3.3 Water vapor adsorption test
Figure 13 shows the water vapor adsorption process data,
and Fig. 14 presents the development of BET specific
surface area of water vapor calculated from this data. The
relationship between chemically bound water and the
specific surface area was also examined in order to pre-
dict this trend from hydration. Figure 15 shows the data
verified with regard to the correlation of chemically
bound water at 11%RH and BET specific surface area of
water vapor adsorption SH2O. As shown in this figure, it
was reconfirmed that the relationship between the BET
specific surface area of water vapor and chemically
bound water amount is represented by a single curve,
irrespective of the cement type and water-binder ratio.
Moreover, from a different perspective, a bilinear trend
with 0.2 g/g of chemically bound water as the boundary
can be identified.
A discussion of the above follows. In this discussion,
based on the assumption that C-S-H of hardened cement
paste accounts for the greatest part of hydration products,
we will discuss the behavior of hardened cement paste
with a focus on C-S-H.
Based on the fact that the BET surface area of the
water vapor adsorption isotherms of C-S-H are higher
than that of nitrogen adsorption isotherms (Feldman and
Sereda 1968; Odler 2003), water vapor is considered to
be a highly hydrophilic chemical adsorption rather than
physical adsorption determined from the physical surface
structure of C-S-H (Feldman and Sereda 1968). On the
other hand, based on the fact that according to previously
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014 209

Fig. 14 Development of BET surface area of water vapor Fig. 15 SH2O as a function of chemically bound water.
adsorption (SH2O). (Note: sample is equilibrium to the saturated lithium
chloride solution at 20 ºC.)
proposed structural models of C-S-H, structural water
constituting the molecular structure of C-S-H occurs as hardened cement paste is considered to be affected not
hydroxy groups (e.g. Nonat 2004; Richardson 2004), only by the amount of C-S-H in the hardened cement
adsorption sites for water vapor are considered to be paste, but also by the Ca/Si atomic ratio of C-S-H. The
located on the hydroxy groups of C-S-H, and thus there is change over time of average Ca/Si atomic ratio calcu-
a high correlation between the BET specific surface area lated from the phase composition is shown in Fig. 16,
of water vapor and the amount of chemically bound where the Ca/Si atomic ratio shows a tendency to decline
water as hydroxy groups in C-S-H. with time in all cases. The relationship between the BET
Given the results of these tests in this respect, while specific surface area of water vapor and the amount of
the amount of adsorbed water is determined by the chemically bound water when the Ca/Si atomic ratio
H2O/Si ratio as a number of adsorption sites in a dry state drops below 0.3 is considered below. For the relationship
at 105°C, which is the pre-treatment condition for the between the Ca/Si atomic ratio of C-S-H and the water
water vapor adsorption test, the amount of chemically vapor adsorption specific surface area SH2O (m2/g), we
bound water obtained from thermal analysis is deter- used the following equation obtained from previously
mined by the H2O/Si ratio, which is a function of the published work (Igarashi and Maruyama 2012). The
amount of desorption of adsorbed water at 11%RH and relationship between the Ca/Si atomic ratio of C-S-H and
the amount of desorption of structural water caused by SH2O obtained with the same technique as that of present
the production of siloxane bonds by the hydroxy groups. study is shown in Fig. 17.
The BET specific surface area of water vapor and amount
of chemically bound water are both considered to be SH2O = 234-297･ln(Ca/Si) (8)
functions of the hydroxy groups.
The relationship between chemically bound water and
If the adsorption potential exerted on water molecules
SH2O at 11%RH or lower when the Ca/Si atomic ratio
from the hydroxy groups at the C-S-H surface is constant,
differs by 0.3 is shown in Fig. 18. As shown in this figure,
the amount of adsorbed water is determined solely by the
the relationship between the two properties shifts toward
amount of hydroxy groups, and the relationship between
the upper right when the Ca/Si atomic ratio decreases.
the BET specific surface area of water vapor and the
When the effect of the decline of the Ca/Si atomic ratio
amount of chemically bound water is considered to be
linear. However, since the relationship between the two is
curvilinear and not proportional, the fact that the ad-
sorption potential from the hydroxy groups varies cannot
be ignored. Considering that the initial hydration occurs
in the interlayer spaces of C-S-H, it can be surmised that
this variation is caused by the variation in overlapping
effects of bonding (or adsorption) potential from both
sides resulting from changes in interlayer spacing due to
changes in the Ca/Si atomic ratio (Diamond 1964). It is
generally known that the Ca/Si atomic ratio of C-S-H
generated from synthesized C3S, C2S, and various ce-
ments varies depending on the hydration reaction (Kan-
tro et al. 1962; Nishikawa and Suzuki 1994), and that the
BET specific surface area increases as the Ca/Si atomic
ratio of C-S-H decreases (Kantro et al. 1961; Bentur and
Berger 1979). Based on this, the specific surface area of Fig. 16 Calculated Ca/Si atomic ratio of C-S-H.
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014 210

Direction of Ca/Si decrease

Direction of
chemically bound water
increase

Fig. 18 Hypothetical study on the effect of Ca/Si change

in C-S-H over the relationship between chemically bound
Fig. 17 Relationship between Ca/Si atomic ratio of syn- water and SH2O .
thesized C-S-H and SH2O . (after Igarashi and Maruyama
2012) monic mean, the series-parallel model (hereinafter,
W&M model) (Woodside and Messmer 1961), and the
and the tendency for the specific surface area to increase geometric mean model (Deguchi model) (Deguchi et al.
due to hydration overlap, the slope becomes similar to 1995). The equations of each model are shown below
that seen when the amount of bound water is 0.2 g/g or (Eqs. (9) to 12)).
higher. Thus, it is considered possible to evaluate the
relationship between chemically bound water and SH2O λ = Vs λs + Vl λl + Vg λg (9)
on the same curve.
1
λ= (10)
3.4 Thermal conductivity
(V + V )
2

Figure 19 shows the development of thermal conduc- Vs l g

+
tivity of the hardened cement pastes. As shown in this λs (V λ + V λ )
l l g g
figure, the thermal conductivity of hardened cement
paste shows a tendency to slow down after increasing up
to around the age of 7 days for all parameters. Further,
⎧
⎪⎪λ =
a
+ bλs + c ⋅
(Vl λl + Vg λg )
after peaking around the age of 28 days, thermal con- ⎨
d 1− d
+ (Vl + Vg ) (11)
ductivity tends to decline for some of the parameters. ⎪ λs λl
Focusing on differences in water-cement ratio, the ⎩⎪a + b + c = 1, ad + b = Vs , b  0, d = 0.97
thermal conductivity of hardened cement paste was
Vg
confirmed to tend to be higher for W/C=0.40 compared
⎛ 1 ⎞Vg +Vl
with W/C=0.55. Moreover, looking at differences in ⋅ ⎡⎣Vs λs + (1 − Vs ) λl ⎤⎦ ⋅ λlVl ⋅ λg g
Vs
λ =⎜ ⎟
V
(12)
cement type, the thermal conductivity of hardened ce- V
⎝ s⎠
ment paste was found to be almost the same for N and M,
and tended to be lower for L. The possibility of evalu- where Vs = volume ratio of solid phase (vol./vol.), Vl =
ating the development of thermal conductivity of hard- volume ratio of liquid phase (vol./vol.), Vg = volume ratio
ened cement paste through previously proposed rules of of gas phase (vol./vol.), λs = thermal conductivity of
mixture was examined. Four rules of mixture were con- solid phase (W/(m ･ K)), λl = thermal conductivity of
sidered, namely the parallel model, which uses the liquid phase (=0.6W/(m･K)), λg = thermal conductivity
arithmetic mean, the series model, which uses the har- of gas phase (= 0.026W/(m･K)), and a to d = constants.
Rule of mixture evaluation using each of the
above-mentioned models for the solid, liquid, and gas
phases was attempted.
The evaluation procedure consisted in subtracting the
contributions of the liquid phase and the gas phase from
the experimental values of thermal conductivity of
hardened cement paste. With regard to the contribution to
thermal conductivity of the solid phase thus obtained, the
average of all the plots was used as the solid phase
thermal conductivity. Using the identified solid phase
thermal conductivity and the thermal conductivities of
the liquid phase and gas phase, the thermal conductivity
of hardened cement pastes was estimated and the results
were compared with the experimental values. Table 4
Fig. 19 Thermal conductivity of cement pastes. lists the estimated solid phase thermal conductivity val-
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014
Fig. 20 Comparison of predicted thermal conductivity evaluated by different models with experimental results.
Table 4 Estimated thermal conductivity of solid phase in
cement past.
Thermal conductivity λs
Model
(W/(m･K))
Parallel model 1.54
Series model 5.81
W&Mmodel 1.58
Deguchi model 3.04
ues for each rule of mixture, and Figure 20 shows a
comparison of the predicted thermal conductivity of
hardened cement paste using the obtained solid phase
thermal conductivity results with the experimental values.
As shown in Fig. 20, the parallel model and W&M
model are found to be well suited as mixture models
owing to their high coefficient of determination.
These results are thought to be attributable to the fact
that the thermal conductivity of hardened cement paste
occurs mostly as parallel conductivity of the solid phase
and liquid phase (parallel model), and conductivity in
series of the solid phase and liquid phase (series model)
does not occur to any great extent. Given that the struc-
ture of hardened cement paste is formed by the solid
phase, this can be said to be reasonable. For the purpose
of simple evaluation, the parallel model appears to be a
sufficiently useful evaluation method.
4. Conclusion
As a basic research for predicting the properties of con-
crete, this study experimentally obtained the changes in
phase composition for the hydration process in two wa-
ter-cement ratios and three types of Portland cement and
211
the resultant physical properties, i.e. compressive
strength, Young's modulus, Poisson's ratio, water vapor
adsorption specific surface area, and thermal conductiv-
ity. Further, beneficial empirical formulas correlating
phase compositions with physical properties of hardened
cement paste at sealed condition were proposed, and the
backgrounds of these empirical formulas were discussed.
Followings are the summary of the obtained experi-
mental results:
− Compressive strength of hardened cement paste can be
evaluated as a function of gel to space ratio, which is
originally proposed by Powers.
− Young’s modulus of hardened cement paste was a
function of the product of density and gel to space ra-
tio.
− Poisson’s ratio of hardened cement paste was also a
function of gel to space ratio.
− Water vapor BET surface area of hardened cement
dried at the saturation to the equilibrium with saturated
LiCl solution for 2 weeks resulted in a function of
chemically bound water.
− Thermal conductivity of hardened cement paste at
sealed condition is well-predicted by the parallel
model considering the volume fraction of solid, void,
and liquid.
Acknowledgements
This research was partially supported by Japan Society
for the Promotion of Science (Project Number: 21686052)
and the framework of “Japan Ageing Management Pro-
gram on System Safety” project sponsored by the Nu-
clear and Industrial Safety Agency, Japan (NISA) and
Nuclear Regulation Authority (NRA), Japan.
I. Maruyama and G. Igarashi / Journal of Advanced Concrete Technology Vol. 12, 200-213, 2014
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