Non-destructive evaluation of the adsorbed water content of

cement pastes during hydration

K. Klein
Assistant Professor, University of Toronto, Toronto, Canada

D. Simon
Former Ph.D. Student, University of Toronto, Toronto, Canada

M. Kwak
Former M.A.Sc. Student, University of Toronto, Toronto, Canada

ABSTRACT: Due to the ability of electromagnetic waves to excite different charges within a material depending
on the frequency of the applied electric field, the spectral response of the complex dielectric permittivity provides
information about particle-fluid interactions. This study utilizes electromagnetic waves to infer changes in the
adsorbed water content of cement pastes during cement hydration. An electromagnetic field at frequencies
between 100 MHz and 1.3 GHz is applied to selected cement pastes over a period of several days. An increase
in the relaxation of the real relative permittivity over this frequency range (i.e., dielectric decrement) with time
reflects an increase in the amount of adsorbed water in the pastes as cement hydration progresses. Unique
relationships between the real relative permittivity and the free water content, and the dielectric decrement and
the adsorbed water content were not found for the cement pastes tested in this study.

1 INTRODUCTION A cement paste initially contains a continuous pore

Small-strain electromagnetic perturbations render
valuable information about microscale particle-
particle and particle-fluid interactions in mixtures.
Additionally, small-strain electromagnetic waves are
a useful tool to monitor hydration in cement pastes,
since the water content, pore fluid chemistry, and
microstructure change during cement hydration
(Christensen et al., 1994; Perez-Pena et al., 1989;
McCarter and Afshar, 1984).
Upon mixing Portland cement (PC) and water, the
mixture transforms from a flowable paste to a solid due
to cement hydration. There are four hydration stages:
(i) early reactions period (020 minutes), when PC
grains begin to dissolve, releasing Ca, OH and alkali
ions into the pore solution, (ii) induction (dormant)
period (0.52 hours), when a protective barrier forms
around the PC grains, temporarily inhibiting further
dissolution of the grains, (iii) acceleration period (2
17 hours), when the protective barrier bursts causing
the accelerated dissolution of PC grains and formation
of hydration products, such as calcium silicate hydrates
(C-S-H), calcium hydroxide (CH) and ettringite (AFt ),
and (iv) deceleration period (after 17 hours), when
and an imaginary component
), electrical conduc-
hydration products form at a slow rate until all of the
cement and/or water are consumed.
measures the polarizability
network filled with water. During the early stages of
hydration (the first 2 hours after mixing cement and
water), the ions move freely through the cement paste.
As hydration proceeds, the water molecules and ions
become incorporated into the hydration products or
bond onto the surface of the hydrating cement or newly
formed hydration products, thus affecting the electri-
cal properties of cement paste (McCarter and Garvin,
1989).
The objective of this paper is to study changes in the
adsorbed water content in cement-based pastes dur-
ing hydration using non-destructive electromagnetic
wave-based measurements. The effect of the initial
water-to-cement ratio on hydration is also addressed.
2 ELECTROMAGNETIC PARAMETERS AND
POLARIZATION MECHANISMS
Three parameters represent the interactions between
the electromagnetic waves and the material in an
applied electromagnetic field: complex relative dielec-
tric permittivity * (which consists of a real component
tivity , and complex magnetic permeability *. The
real relative permittivity

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Copyright 2005 Taylor & Francis Group plc, London, UK
of a material in response to an applied electromagnetic
field, the imaginary relative permittivity
measures dielectric coaxial termination probe. The dielectric
losses, and the electrical conductivity measures ion
mobility. The complex magnetic permeability * mea-
sures the magnetizability of a material (i.e., the ability
of magnetic dipoles in a material to orient themselves
towards the applied magnetic field). The Portland
cement used in this study is a non-ferromagnetic
material, and the complex magnetic permeability is
* = o , where o is the permeability of vacuum.
The charges that are excited due to an applied elec-
tric field depend on the frequency of the field and the
composition of the material under test. The polariza-
tion mechanisms include electronic polarization: the
displacement of electron(s) with respect to the atoms
core; ionic polarization: the displacement of atoms in
a molecule; molecular or orientational polarization:
the displacement of dipolar molecules, such as water
molecules; interfacial or Maxwell-Wagner polariza-
tion: the accumulation of charges at a solid-fluid
interface, caused by the differences in the electri-
cal properties of the mixtures components; adsorbed
water polarization: the hindered orientation of water
molecules that are adsorbed onto the surface of a par-
ticle; and double layer polarization: the displacement
of the charges in the double layer. Additional informa-
tion about these polarization mechanisms is presented
in Santamarina et al. (2001).
Due to the high polarizability of free water
molecules (free 78), the real relative permittivity is a
good indicator of the free water content in solid-water
mixtures. Topp et al. (1980) developed an empirical
relationship between the real relative permittivity at
approximately 1 GHz and the volumetric free water
content for soil-water mixtures using time-domain
reflectometry measurements. The polarizability of the
water molecules decreases if the water is adsorbed onto
a solid surface (i.e., bound 20; deLoor, 1968).
3 EXPERIMENTAL PROCEDURE
The specimens tested in this study consist of CSA
Type 10 Portland cement (Lafarge, Inc.) and deionized
water, mixed at three different water-to-cement ratios
(w:c = mass of water/mass of Portland cement): 0.3,
0.4 and 0.5. The Portland cement and deionized water
were mixed for two minutes using an electric house-
hold mixer. The time when the Portland cement was
added to the water was taken to be the start of the test.
The paste was then poured into a hollow Lucite cylin-
der (height = 50 mm, diameter = 50 mm) and tapped
with a rod to ensure that there were no large air voids
in the specimen.
The complex dielectric permittivity measurements
at frequencies between 100 MHz and 1.3 GHz were
and the conductivity for the 0.4 w:c paste after 7 minutes
conducted using an Agilent 8712ET RF network
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Copyright 2005 Taylor & Francis Group plc, London, UK
analyzer in conjunction with an Agilent 85070C
probe was placed in contact with the specimen, and
the specimen was paraffin-sealed to prevent water
evaporation. The readings were taken at approximately
logarithmic time intervals from 1 minute to more than
10,000 minutes (approximately 7 days).
Separate samples of the paste were placed in small
containers and sealed. The gravimetric evaporable
(free) water content of these samples was determined
at selected times by placing the sample in an oven at
100 C for 24 hours. The volumetric evaporable (free)
water content wv was calculated as:
where wgr is the gravimetric water content of the speci-
men, tot is the total bulk density of the specimen, and
w is the bulk density of water. The adsorbed water
content was calculated as the difference between the
initial water content and the evaporable water content.
4 RESULTS
The spectral response of the 0.4 w:c paste is pre-
sented in Figure 1. Similar trends were found for the
0.3 and 0.5 w:c pastes. The polarization mechanisms
that develop within the measured frequency range
(100 MHz to 1.3 GHz) are adsorbed water polariza-
tion and free water polarization. An increase in the
real relative permittivity with decreasing frequency
at megahertz frequencies suggests adsorbed water
polarization, while the increase in conductivity with
increasing frequency is due to free water polarization.
The temporal response of the conductivity is shown
in Figure 2. These data reflect the various cement
hydration stages. All of the specimens exhibit an initial
increase in the effective conductivity, which reflects
the increase in the pore fluid concentration caused by
cement dissolution during the initial reactions period
(stage 1) and induction period (stage 2). The abrupt
55 2.5
adsorbed water ' (7 min) ' (300 min)
50
45 (7 min) (300 min) 2
[S/m]
40
1.5
'
35
30 1
25 free water
20
100 300 500 700 900 1001
0.5
1300
frequency [MHz]
Figure 1. Spectral response of the real relative permittivity
and 300 minutes of hydration.
decrease in conductivity is caused by precipitation
of the dissolved ions and formation of the hydration
products during the acceleration period (stage 3). The
effective conductivity continues to decrease at a slow
rate, reflecting the formation of the hydration prod-
ucts at a reduced rate (i.e., deceleration period or
stage 4). The data show that as the water-to-cement
with hydration time
ratio increases, the abrupt decrease in the effective
conductivity shifts to later times, indicating a delay
in the onset of the acceleration period in the higher
water-to-cement ratio specimens.
decreases as the evaporable water
1.4
1.2 1 2
1 3
, which is the difference between the
[S/m]
The evolution of the real relative permittivity at
1 GHz for the three pastes is presented in Figure 3.
At early times, the real relative permittivity is high-
est for the paste with the highest initial water content
because the real relative permittivity at this frequency
reflects the free water content. All of the specimens
exhibit an abrupt decrease in
during the acceleration stage; however, the time when
this occurs increases as the water-to-cement ratio of
the specimen increases. The relationship between the
real relative permittivity at 1 GHz and the volumetric
evaporable water content is presented in Figure 4. In
all of the pastes,
content decreases.
Figure 5 presents the evolution of the dielectric
0.5 w:c
0.4 w:c decrement 

0.8 0.3 w:c real relative permittivity at 160 MHz and the real
0.6 relative permittivity at 1 GHz. All of the specimens
0.4 4 show a fairly constant  during the initial reactions
0.2 and induction periods, followed by an abrupt increase
0 during the acceleration stage. This increase in  sug-
1 10 100 1000 10000 100000
time [minutes]
gests an increase in the amount of adsorbed water in the
pastes. The time of the abrupt increase in  increases
Figure 2. Temporal variation of the conductivity at as the water-to-cement ratio of the PC paste increases.
100 MHz. The hydration stages are shown: 1. initial period, Figure 6 presents the relationship between the dielec-
2. induction period, 3. acceleration period, and 4. deceleration tric decrement  and the adsorbed water content.
period. In general,  increases as the volumetric adsorbed
water content increases.

60
50 0.5 w:c 25
0.4 w:c 0.5 wc
40 0.3 w:c 20 0.4 wc
30 0.3 wc
'

15
'

20
10
10
0 5
1 10 100 1000 10000 100000
time [minutes] 0
1 10 100 1000 10000 100000
time [minutes]
Figure 3. Temporal variation of the real relative permittivity
at 1 GHz.
Figure 5. Variations in the dielectric decrement  with
time.
70
0.5 w:c
60 25
0.4 w:c
50 0.3 w:c 0.5 w:c
20 0.4 w:c
40 Topp's model
0.3 w:c
'

30 15
'

20 10
10
5
0
20 30 40 50 60 70 0
volumetric evaporable water content [%] 0 2 4 6 8 10 12 14 16 18
volumetric adsorbed water content [%]
Figure 4. The relationship between the real relative per-
mittivity at 1 GHz and the volumetric evaporable water Figure 6. The relationship between the dielectric decrement
content.  and the volumetric adsorbed water content.

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Copyright 2005 Taylor & Francis Group plc, London, UK
5 DISCUSSION
Adsorbed water polarization at megahertz frequencies
in cement pastes has been observed in previous studies
(Miura et al., 1998; Hu et al., 1999). However, some
researchers believe that adsorbed water polarization
is only evident during the later stages of hydration
(McCarter and Garvin, 1989; Olp et al., 1991).
The relationship between the real relative permit-
tivity of a soil-water mixture m and the free water
content wv proposed by Topp et al. (1980) is:
As shown in Figure 4, this relationship agrees with
the measured data for the 0.3 w:c paste at all water
contents, and agrees with the measured data for the
other two pastes at volumetric water contents greater
than about 50%. This relationship overestimates the
real relative permittivity for the 0.4 and 0.5 w:c pastes
at lower water contents.
The increase in the adsorbed water content during
the acceleration period, as inferred from the increase
in 
, may be attributed to the rapid formation of
hydration products during this stage, converting free
water into adsorbed water. The decrease in the dielec-
tric decrement during the deceleration stage (after 17
hours) may be due to the incorporation of the adsorbed
water into the structure of the hydration products,
reducing the amount of water molecules available to
respond to an applied electric field.
Determining the adsorbed water content as the
difference between the initial water content and the
measured evaporable water content cannot account
for the water that becomes structurally bound in the
cement paste. This limitation may explain the decrease
in 
with increasing adsorbed water content at
higher water contents (Figure 6).
The data suggest that as the initial water content of
the paste increases (i.e., higher w:c), the amount of
adsorbed water in the specimen increases and cement
hydration is delayed. This delay occurs because as the
water-to-cement ratio increases, the time to reach the
required saturation concentration of ions in order to
form hydration products increases.
6 CONCLUSIONS
The conductivity, real relative permittivity, and dielec-
tric decrement data indicate that hydration is delayed
in higher water content (i.e., higher water-to-cement
ratio) specimens.
Changes in the dielectric decrement as a function
of time, at the frequencies tested in this study, reflect
Copyright 2005 Taylor & Francis Group plc, London, UK
changes in the free and adsorbed water contents. The
data suggest that the amount of adsorbed water in the
pastes increases as the initial water-to-cement ratio
increases.
Unique relationships between the real relative per-
mittivity and the free volumetric water content, and
the dielectric decrement and the adsorbed volumetric
water content were not found for the cement pastes
tested in this study, although all of the pastes show
similar trends.
ACKNOWLEDGEMENTS
The authors would like to acknowledge R.D. Hooton
for providing the Portland cement used in this study.
Financial support for this study was provided in part
by NSERC.
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