Electrochimica Acta 51 (2006) 18311841

Impedance spectroscopy to characterize the pore structure during the

hardening process of Portland cement paste
M. Cabeza a , M. Keddam b , X.R. Novoa a,,1 , I. Sanchez a , H. Takenouti b
a Universidade de Vigo, E.T.S.E.I., Campus Universitario, 36310 Vigo, Spain
b UPR15 CNRS, L.I.S.E., Universite Pierre et Marie Curie, 75252 Paris Cedex 05, France

Received 23 June 2004; received in revised form 16 November 2004; accepted 8 February 2005
Available online 25 August 2005

Abstract

The relationship between the pore structure and the dielectric properties of cement paste is studied in this work. Dielectric properties
clearly reflect the pore structure development and the degree of pore occupancy by electrolyte. Impedance spectroscopy (IS) measurements
in the high frequency range (10 kHz15 MHz) have been performed in samples with varying pore occupancy. For cement pastes with a
fully developed pore structure (curing time >28 days), when all pore families are filled with electrolyte, the main characteristic factor is the
asymmetry observed in ColeCole plots, whereas as these samples are dried off or the pore structure is not fully developed (curing time <15
days), the asymmetrical dispersion decreases and the symmetrical dispersion becomes more important. The relationship between ColeCole
plots dispersions and pore size distribution in samples is shown by performing bi-dimensional simulations.
2005 Elsevier Ltd. All rights reserved.

Keywords: Cement paste; Impedance spectroscopy; Electrical properties; Microstructure; Time constant dispersion

1. Introduction The model proposed in a previous work [6] for the

Impedance spectroscopy measurements performed on
concrete are of great importance due to the possibility of
correlating the dielectric properties and the microstructure of
the system [1,2].
In a first stage of these studies, the presence of only one
time constant in the high frequency loop was put forward,
and the high values obtained for the dielectric constant were
explained in terms of the dielectric amplification factor [3].
Some recent works on this field have demonstrated the
existence of two time constants in the high frequency domain
(10 kHz15 MHz) [47]. The capacitance associated to one
of these time constants correlates well with the fraction of
solid phase in the cement paste [68], while the other one has
been associated to some contribution of the electrolyte filling
the pores [5,9].
Corresponding author. Tel.: +34 986 81 22 13; fax: +34 986 81 22 01.
E-mail address: rnovoa@uvigo.es (X.R. Novoa).
1 ISE member.
interpretation of the impedance spectra obtained in a
blocking configuration corresponds to the Debye type
depicted in Fig. 1. The capacitance C1 accounts for the
solid phase contribution while C2 and the resistance
R2 are parameters associated to the liquid phase filling
pores.
While the relationship between C1 and the fraction of solid
phase is clear [6,8], the meaning of C2 and R2 , and the dis-
persion in the corresponding time constant, is not so clear at
present.
The parameters R2 and C2 have both a strong dependence
on the amount of water in the sample as well as on pore
structure. This aspect is illustrated in Fig. 2 (taken from Ref.
[6]) where it can be seen that the shape of the ColeCole
plot changes from symmetrical dispersion (ColeCole type,
Fig. 2A) to asymmetrical dispersion (ColeDavidson type,
Fig. 2B) as the pore structure develops.
The present paper explores the effect of the pore occu-
pancy and the pore size and dispersion in the impedance
of the system. Those effects are evaluated in terms of

0013-4686/$ see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2005.02.125
1832 M. Cabeza et al. / Electrochimica Acta 51 (2006) 18311841
Fig. 1. Schematic representation of the equivalent circuit model employed
for fitting high frequency impedance data corresponding to cement paste.
C1 represents the solid phase contribution, and R2 and C2 , are attributed to
the electrolyte filling the pores.
Fig. 2. (A) ColeCole plot corresponding to a Portland cement paste spec-
imen (water/cement = 0.5, sample thickness = 0.71 cm) at 5 days hardening.
(B) The same specimen at 16 days hardening. Data from Ref. [6].
the symmetrical and asymmetrical dispersion coefficients
associated to ColeCole plots.
2. Experimental
2.1. Sample preparation
Cement paste samples were prepared using Portland
cement CEM I 52.5R according to the Spanish/EU standard.
In order to obtain different porosities and pore structures,
three different water-to-cement (w:c) ratios were employed:
0.45, 0.55 and 0.65. After mixing carefully, the mixtures were
cast into cylindrical moulds of 5.9 cm in diameter and 20 cm
height, and cured at 100% RH for 28 days. After this curing
period, slices of different thickness, from 3 to 8 mm, were cut
from these cylinders.
2.2. Mercury intrusion porosimetry
Mercury intrusion porosimetry (MIP) has been employed
for microstructure characterisation. Although the limitations
of this technique are significant [10,11], it enables us to
obtain valuable information on pore structure. MIP is based
on Washburn law (Eq. (1)) that gives a relationship between
the size of a cylindrical pore and the pressure necessary to
introduce a non-wetting fluid in it:
4 cos
D= (1)
P
where D is the pore diameter, P the applied pressure to fill up
the pore with mercury (the fluid in this case), the surface
tension of the fluid and is the contact angle between the fluid
and the pore mouth. Mercury has a very high surface tension,
so it gives high resolution in the small pores zone. The surface
tension for mercury at room temperature is 0.485 N m1 and
the contact angle employed was 130 .
The porosimeter employed was an AUTOPORE IV 9500
from Micromeritics that, according to Eq. (1), enables the
measurement of pore diameters from 0.9 mm down to 5 nm
because the maximum yield pressure is 227 MPa. As mercury
is not able to access occluded pores, samples of irregular and
random shapes were cut form the original cylinders in order
to make the measuring sample representative of the real pore
structure.
Porosity determinations begin with a stage of air evac-
uation (down to 50 mHg) from the recipient holding the
sample. This high vacuum ensures that there is no air or
moisture in the pores, so the mercury will have free access to
all open pores. In the next step, the recipient is filled up with
mercury; and finally, in the intrusion stage a prefixed table of
pressures, depending on the required resolution, is applied
to the sample. The volume of mercury, having penetrated
the sample at every applied pressure, gives the total volume
of pores which have a larger diameter or one equal to
the corresponding applied pressure, and is called accu-
mulated intrusion volume; while the volume of mercury
intruded between two consecutive applied pressures, called
incremental volume, gives the volume of pores which
have a diameter in the range defined by the two pressures
[12].
2.3. Impedance spectroscopy (IS)
The impedance spectroscopy measurements, from
15 MHz down to 10 kHz, were performed using an
HP4194A impedance gain/phase analyser. This apparatus
enables capacitance measurements to be performed in the
 M. Cabeza et al. / Electrochimica Acta 51 (2006) 18311841
Fig. 3. Flat cell employed for impedance measurements (schematic). Elec-
trodes are circular, = 40 mm.
range of 1014 to 0.1 F with a maximum resolution of
1016 F.
The method employed for measurements, has been pre-
sented elsewhere [4], and minimises the possible contribu-
tions of the sample-electrode interface. It consists of placing
a polyester sheet (100 m thick) between the sample and the
electrode. The electrodes employed were high density sheets
of graphite, circular cut to an electrode surface of 15.9 cm2 .
The experimental setup used is shown in Fig. 3.
The impedance of the polyester sheets is subtracted from
the overall impedance after measurement, so that the remain-
ing part corresponds to the impedance of the sample.
As it can be seen in Fig. 4A, the impedance of the sam-
ples is capacitive, so the ColeCole transformation (Eq. (2))
is used to obtain accurate representations, which have well
defined high and low frequency limits. C() is the complex
capacitance and Z() the impedance of the sample at angular
frequency .
1
C() =
jZ()
The ColeCole transformation of data presented in Fig. 4A
is depicted in Fig. 4B. The capacitance C1 obtained from
this plot, 1.23 pF cm2 , enables us to obtain the apparent
dielectric constant of the material [6], which results in = 9.4.
This value lies in the range of the main components of the
clinker: CaO (67%, = 11.8) and SiO2 (22%, = 3.9).
3. Results and discussion
3.1. Mercury intrusion porosimetry (MIP)
MIP was performed for the three w:c ratios studied in this
work at different curing times. Fig. 5A and B correspond
1833
Fig. 4. (A) Nyquist plot corresponding to the impedance data obtained for
a sample w:c = 0.45 after 90 days ageing. Sample thickness = 0.68 cm. (B)
ColeCole plot corresponding to impedance data given in Fig. 4A (according
to Eq. (2)). The experimental data correspond to the circle-shaped symbols
and the triangles correspond to the data fitted using Eq. (3) (this equation
corresponds to the equivalent circuit given in Fig. 1. The best fitting param-
eters are: C1 , 1.23 pF cm2 ; R2 , 1.88 k cm2 ; C2 , 34.47 pF cm2 ; , 0.89;
, 0.63.
(2) to the initial curing period (28 days) where the main
structural changes occur. As can be seen in Fig. 5A, the
intruded volume at 7 days is lower than at 18 days, so the
porosity decreases as curing progresses. Moreover, Fig. 5B
clearly shows that the pore structure evolves with the curing
time towards the formation of pore families distributed in
broader pore diameter range. The fraction of small pores
increases with time and the diameter of large pores increases
too.
The comparative results of the final structure at 90 days
ageing are given in Fig. 5C and Table 1. For each w:c ratio,
three pore families are observed, as can be seen in Fig. 5C
the total porosity increases as the w:c ratio does (see data
in Table 1). The experimental results are presented in pore
size logarithmic scale. The fitting of these three peaks to
three gaussian distributions is also presented. The best
1834 M. Cabeza et al. / Electrochimica Acta 51 (2006) 18311841

Table 1
Total porosity (volume %), central value of the pore diameter, xc , for each
pore family and pore familys contribution to the overall samples porosity,
%vol
Total porosity w:c = 0.45 w:c = 0.55 w:c = 0.65
27.7 30.9 32.1

xc , nm %vol xc , nm %vol xc , nm %vol

Macropores >105 4.27 >105 3.07 >105 3.55
Family 1 8558 0.53 7488 1.23 7189 0.35
Family 2 85.05 12.0 90.01 13.0 81.03 13.6
Family3 15.43 10.9 10.56 13.6 15.0 14.6
The pore families are identified in Fig. 5C. Samples aged for 90 days.

3.2. Impedance spectroscopy

The impedance of the samples was obtained using the

non-contacting method described in Section 2. Prior to
impedance testing, the samples were submerged in distilled
water and held for 48 h under 1 mmHg atmospheric pressure.
In these conditions, according to the ASTM Standard C 1202-
97 [13], the air occupying the pores is fully replaced with
water and the sample results fully water-saturated. So, it is
expected that in the water-filled pores ions will dissolve from
pore walls to give a saturated Ca(OH)2 solution filling all the
pores.
The samples initial impedance was measured at that point.
Furthermore, samples were left at laboratory atmosphere for
natural drying. Periodically, the weight loss and specimen
impedance were recorded. Once the steady state had been
achieved, the samples were dried in an oven at 75 C (this
temperature is low enough to avoid structural water evapora-
tion [14] and thus limits possible morphological changes). An
example of the ColeCole plots obtained for different weight
loss is given in Fig. 6.
These spectra were fitted to the Debye model previously
proposed [6], using a simplex method as optimisation proce-
dure. The equation representing the model is:

C2
Fig. 5. MIP results for a sample of w:c = 0.55. (A) Accumulated volume of C() = C1 + (3)
mercury intruded as a function of pore diameter at 7 and 18 days curing time. (1 + (jR2 C2 ) )
(B) Incremental volume of mercury intruded as a function of pore diameter
at 7 and 18 days curing time. (C) Incremental volume of mercury intruded
as a function of pore diameter after 90 days ageing. Experimental results are
depicted in open squares, and the fitting to three gaussians in a continuous
line. Each gaussian is represented with dashed lines, and the centre of every
family is also shown.

fitting parameters give the centre of the distribution and the

corresponding standard deviation.
Table 1 summarises the values obtained for the total poros-
ity for every w:c ratio, the centre of each distribution family,
and the volume for each family (area under the fitted curve).
It can be noticed from these values that the pore central sizes
do not vary significantly on w:c ratio. Increasing the w:c ratio Fig. 6. Evolution of the ColeCole plots for a sample w:c = 0.55 and 0.46 cm
just increases the number of pores (area under the curve) for thick, when dried from the saturated condition. Plots for 0.9, 5.8 and 10.2%
each family. weight loss.
 M. Cabeza et al. / Electrochimica Acta 51 (2006) 18311841 1835

that corresponds to the HavriliakNegami expression for

relaxation in polymers [15]. C1 is the high frequency limit of
the ColeCole plot and C2 the diameter of the corresponding
arc (see Fig. 2A) so that C1 + C2 is fixed by the low fre-
quency limit. The parameter holds for the symmetrical
dispersion of the R2 C2 time constant and represents the
asymmetrical dispersion.
In Fig. 7A, the evolution of the dielectric parameters C1 ,
C2 and R2 during the drying process is depicted. As expected,
C1 remains constant because during this process no changes
occur in the solid phase. However, a decreasing tendency can
be observed in C2 , while R2 increases exponentially as the
sample dries off. The weight loss corresponds to pore dry-
ing, so the number of free charge carriers decreases because
they are confined to pore walls, and the pore connectivity
decreases. All these factors lead to the measured resistance
increasing. Fig. 7B gives a closer view of the R2 variation with
weight loss. Three different intervals can be easily differenti-
ated for which the slope values obtained by linear fitting are
summarised in Table 2.
The presence of three slopes in Fig. 7B correlates well
with the three pore families detected by MIP. As, according
to the Kelvin law [16], large pores dry faster than small ones,
the initial weight loss will correspond to large pores drain.
The comparison of data given in Tables 1 and 2 shows that the
samples weight loss corresponding to the atmospheric steady
state achieved corresponds to the volume of large pores (fam-
ily 1 plus >105 nm, in Table 2). So, it can be said that those
pores are virtually dry in atmospheric exposure. Moreover,
their contribution to R2 is the smallest, according to the slope
values given in Table 2.
Pore families 2 and 3 (Fig. 5) represent fractional volumes
(see Table 1) higher than the weigh loss ranges given in
Table 2. The difference is significantly large for family
3. The smallest pores cannot be dried at 75 C and about
30% of pore volume from family 2 remains occupied.
So, the drying process in general and the oven drying in
particular represents a kind of pore occupation scanning
in which the fraction of small pores increases as drying
progresses.
Another interesting feature concerns the dependence of
segment slopes (Fig. 7B) on w:c ratio (and therefore, cement
paste total porosity). As shown in Table 2, when w:c increases Fig. 7. (A) Evolution of C1 , C2 and R2 during drying for a sample of 0.46 cm
the slope of all segment lines decreases. This can be explained thick and w:c = 0.55. The tendency lines for R2 (continuous) and C2 (dashed)
are also depicted. (B) Detail of the evolution of R2 vs. weight loss in a
taking into account the data of volume occupied by every logarithmic scale. Experimental data are fitted to three straight line segments
pore family given in Table 1. The pore volume increases as (indicated). The fitting parameters (slopes) are given in Table 2. The weight
the w:c does, so when one pore is dried in a sample with loss corresponding to the open atmosphere steady state is also indicated.
low porosity, its influence on the overall resistance is higher (C) Evolution of the ColeCole () and ColeDavidson () dispersions of
than for the same pore in a sample which has higher porosity the R2 C2 time constant for the same samples drying process. The tendency
lines are also depicted.
(more pores), because of the parallel contribution of every
pore to the measured R2 .
The two other parameters in Eq. (3) affected by the pore and the ColeCole dispersion increases (0) and the Cole-
saturation degree are and . In Fig. 7C, the variation of Davidson dispersion decreases ( 1).
both parameters is shown for one of the tested samples. As All these observations can be summarised in a physical
the sample is dried off, the pore occupancy is being scanned model of the cement paste porosity discussed in the next
from full occupancy down to mainly family 3 occupancy, section.
1836 M. Cabeza et al. / Electrochimica Acta 51 (2006) 18311841

Table 2
Weight loss ranges and slopes (log ((k cm2 )/% weight loss) obtained by fitting the results of R2 to three straight lines as shown in Fig. 7B
Segment w:c = 0.45 w:c = 0.55 w:c = 0.65

Weight loss range (%) Slope Weight loss range (%) Slope Weight loss range (%) Slope
1 04 0.12 06 0.08 08.5 0.05
2 412 0.34 616 0.15 8.519.3 0.07
3 1215 0.94 1621 0.45 19.324 0.4

3.3. Modelling to the phase height, and inversely proportional to its length
(L, the samples thickness).
In order to determine the physical origin in the cement Parallel to the capacitance Cs the pore network contribu-
paste microstructure of the ColeCole representation tion is considered. The elements considered are: CL1 , which
parameters C1 , C2 , R2 , and (Eq. (3)), some numerical represents the double layer capacitance between the solution
simulations were carried out. These simulations are based in pores and the gel layers in contact with the unreacted paste.
on the already proposed idea of obtaining the impedance of Some ionic exchange between the solution filling the pores
a composite material from the elements contribution [17]. and the mother unreacted paste is assumed and the resis-
A first approach to the problem was presented in the last tance Rt , parallel with CL1 , accounts for this ionic flux. Cd1
EIS meeting [18] and now a simple bi-dimensional model is and Cd2 have the same nature; both represent the capacitance
proposed, based on the cement paste structure. of the gel layers; the first one corresponds to the gel layers in
The different chemical and mineral phases, present in contact with the unreacted paste and the second one to the gel
the cement powder, hydrate at different rates, depending on layers located between pores. No ionic exchange is assumed
their size and composition, and interact with each another to between pores, so Cd2 shall be placed in series with CL2 and
form various reaction products. Some of those products are Rp , Rp being the electrolyte resistance for each pore and CL2
deposited on the remaining cement particle surfaces (surface the double layer capacitance (same nature as CL1 ). Hence, in
products) while others form crystals in the water-filled pore the model there is no resistance parallel with Cd2 and CL2 .
space between cement particles (pore products). From the Each individual pore is Lp length and a1 height, the thickness
structural point of view, cement paste can be considered as of pore walls being ep . The total length between electrodes is
consisting of four phases: unreacted cement, surface products L and the unreacted paste height is as . The ratio a1 /as defines
(like CSH gel), pore products (like calcium hydroxide), the samples porosity.
and capillary pore space. Surface products grow outward The distribution of all those electrical elements can be
from the unreacted cement particles and contain connected summarised in the transmission line depicted in Fig. 8C keep-
(percolated) gel pores, while pore products are generally ing the following equivalencies:
polycrystalline and completely dense, with no connected
1 1 1
pores. The capillary pores are the remaining water-filled Z1 = ; Z2 = Re + + ; (4)
space between solid phases, which are left over after a given jCd1 jCd2 jCL2
degree of hydration takes place. Capillary pores generally Rt
range from about 10 to 100 nm in size, in a well-hydrated Z3 = (5)
1 + jRt CL1
cement paste, although in early hydration they can range up
to a few micrometers in size. The nominal values for the model parameters (and hence
The model considers two parallel contributions: The unre- for Z1 , Z2 and Z3 ) are varied with pore size according to
acted cement paste (not porous) and a porous network made the scaling of resistances and capacitances with Lp and a1 .
of pore space, CSH gel layers and pore products. The The impedance Z in Fig. 8C corresponds to the termination
structure of the gel layers and the pores is shown schemat- impedance of the transmission line. The expression for the
ically in Fig. 8A [19]. Thus, the cement paste structure can impedance of that transmission line was originally developed
be described using the idealised 2D structure schematically to study magnetite layers growth over steel [20] and corre-
drawn in Fig. 8B, where two parallel paths for current flow sponds to Eq. (6):
between electrodes (the unreacted paste and the pore net-
Z1 Z2 2 Z1 Z2 + (Z12 + Z22 )C + Z22 S
work) are depicted. The structure presented in Fig. 8B repre- Z= L+
sents an elemental unit. It will be necessary to stack a number Z1 + Z 2 (Z1 + Z2 )( S + C)
of those units to reach the experimental probe height. No (6)
interconnection paths between elemental units are consid-
where C = cosh( L) and S = sinh( L). The values
ered at this stage. of and are given by the expressions:
The unreacted paste is assumed to be purely capacitive
(very high resistivity associated because it is not porous). The Z1 + Z2 Z1 + Z 2
= ;= (7)
associated dielectric capacitance, Cs , is directly proportional Z3 Z
 M. Cabeza et al. / Electrochimica Acta 51 (2006) 18311841 1837

Fig. 8. (A) FeldmanSereda model of the structure of the CSH gel of Portland cement paste (from Ref. [19]). (B) Schematic model for the elemental unit
used in the numerical calculations. The unreacted paste, gel layers and pores are shown. Lp is the pore length and ep corresponds to the thickness of the wall
between pores. L is the sample thickness. as is the height of the unreacted paste portion and a1 corresponds to the height of the pores and reacted paste. (C)
Electrical transmission line equivalent (see text for equivalences).

The physical meaning of is related to the penetration
depth, , of the electric signal. This relationship can be written
as = 1/2 .
Because the method employed for measurements avoids
any direct contact between the electrode and sample, the value
of Z is infinite, and so Eq. (6) becomes [21]:
Z1 Z2 2Z1 Z2 + (Z12 + Z22 ) cosh( L)
Z= L+
Z1 + Z 2 (Z1 + Z2 ) sinh( L)
Several simulations have been done using MATLAB
to obtain the impedance spectra, and the correspond-
ing ColeCole transformation. In these numerical calcula-
tions the sample is divided in a number of elements, ny ,
(ny = 2 106 ) every element has the same structure as the
one shown in Fig. 8B. Because the ny elements are placed in
parallel, the overall admittance is directly the addition of the
individual admittances.
In a first stage, simulations have been preformed using
single pore size of 13 nm, and porosity of 30% (v/v) (values in
the experimental range obtained by MIP). The corresponding
ColeCole plot obtained for this simulation is depicted in
(8)
Fig. 9A.
The correlation between the model parameters and the
high and low frequency limits of the ColeCole plots as well
as the frequency at the plot apex is explored in Fig. 9BD.
Fig. 9B shows that the high frequency limit of the ColeCole
plot corresponds to Cs , and Fig. 9C reveals that the diameter
1838 M. Cabeza et al. / Electrochimica Acta 51 (2006) 18311841

Fig. 9. (A) ColeCole plot for a sample (L = 0.5 cm thick) with a single pore size (Lp = 13 nm) and 30% of volume occupied by pores (a1 /(a1 + as ) = 0.3). The total
sample height is 4 cm divided between ny = 2 106 elements. Cs = 4.5 1019 , Cd1 = 2 1019 , Rt = 4000, CL1 = 80 1015 , Rp = 7 109 , CL2 = 15 1018 ,
Cd2 = 17 1019 , ep = 5 nm. (B) ColeCole plot for the sample described in Fig. 9A but the Cs value has been duplicated. (C) ColeCole plot for the sample
described in Fig. 9A but the CL1 value has been increased 100%. (D) ColeCole plot for the sample described in Fig. 9A but the Re value has been increased
100%.

of the arc is directly linked to the double layer capacitance Maximum and minimum values for the pore sizes included
CL1 , which in turn depends either on the nominal value of in each family have also been imposed.
the pore length. The effect of the pore electrolyte resistance An example of the pore size distribution obtained for dif-
appears in Fig. 9D: the Rp increase makes the plot to rotate ferent values can be seen in Fig. 11A. Each pore family
towards the high frequency extremity. has the same central value, xc = 13 nm. The sample is divided
So, a first approach to the physical meaning of the param- in ny = 2 106 parts, as in the case of one pore size. Every
eters in Eq. (3) can be advanced: C1 corresponds to the one of these ny parts consists of a transmission line of pores
dielectric capacitance of the unreacted solid phase, C2 to with size x (Eq. (9)), in parallel with the corresponding solid
double layer capacitance CL1 and R2 to the resistance of the
electrolyte filling the pores.
The perfect semicircle shape depicted in Fig. 9 (no dis-
persion is present) can be understood in terms of penetration
depth of the electric signal. Fig. 10 represents the value of
L/|| for the case of Fig. 9A (Lp = 13 nm). It is clear that the
penetration length, , is three orders of magnitude greater
than the pore length all over the measured frequency range,
so, the flat electrode behaviour is observed in Fig. 9A.
The effect of distribution in pore size has been analysed
using a lognormal distribution (gaussian distribution in a log-
arithmic scale, as employed for the fitting of MIP data). The
mathematical expression for this distribution is given in Eq.
(9) where f(x) correspond to the number of elements with a
pore size x, xc is the central value of the pore family and
the standard deviation:


(ln(x/xc ))2
f (x) = exp (9) Fig. 10. Sample thickness/penetration depth ratio vs. frequency for
2 2 Lp = 0.5 cm, case of Fig. 9A.
 M. Cabeza et al. / Electrochimica Acta 51 (2006) 18311841
Fig. 11. Influence of the standard dispersion in pore size in the symmetrical
dispersion ( in Eq. (3)) of the R2 C2 time constant. (A) Different pore size
distributions, centred at xc = 13 nm and obtained using Eq. (9), for different
standard deviations ( = 0.25, 0.3, 0.45 and 1.0). The limits imposed on
the pore size are also shown. The term number of elements refers to the
elemental units, defined in Fig. 8B placed in parallel to obtain the electrode
impedance (see text). (B) ColeCole plots obtained for distributions having
single pore size (circles, = 0), and two different values of standard deviation
(square, = 0.25; triangle, = 0.7). (C) Evolution of with the standard
deviation in the pore size distribution considered for the calculation. Data
fitted to Eq. (3).
phase (unreacted
 paste). The distribution in pore sizes has to
be such that f (x) = ny and the volume fraction occupied
by pores is constant.
The ColeCole plots obtained for different pore size dis-
tributions (different ) are depicted in Fig. 11B. The plots
show symmetrical dispersion and the relationship between
the coefficient (Eq. (3)) and the standard deviation of the
1839
Fig. 12. (A) Pore size distribution including two pore families calculated
using the log-normal distribution (Eq. (9)). The term number of elements
refers to the elemental units, defined in Fig. 8B placed in parallel to obtain
the electrode impedance (see text). (B) ColeCole plot calculated using the
pore size distribution shown in Fig. 12A and result of the fitting to Eq. (3).
The values of the dispersion factors are = 0.89 and = 0.76.
pores size distribution is given in Fig. 11C. It can be seen
that the value of decreases (dispersion degree increases) as
the standard deviation increases. The degree of dependence
(slope of the plot) between and decreases when the pore
size distributions reach the imposed limits for the bigger and
smaller pore size in the pores family (26 and 5 nm, respec-
tively).
So, from this result it is possible to conclude that, for a
single pore family, the standard deviation of the correspond-
ing pore size is responsible of the symmetrical dispersion
observed in the ColeCole plots.
Finally, the effect of having different pore families in the
same system has been explored considering two lognormal
pore size distributions, similar to those observed in Fig. 5.
The pore size distribution used is shown in Fig. 12A, and the
ColeCole plot obtained using this distribution is depicted in
Fig. 12B. In this figure, the fitting to Eq. (3) is also depicted.
The values for the symmetrical and asymmetrical dispersion
factors result 0.89 and 0.76, respectively. The value obtained
for is concordant with the presence of pore size distributions
around central sizes, as obtained for the previous simulations.
The presence of ColeDavidson dispersion ( < 1) shall be
associated to the occurrence of different pore families in the
same system.
With all these results, and those obtained from mercury
intrusion porosimetry, it is easy to give an interpretation of
1840 M. Cabeza et al. / Electrochimica Acta 51 (2006) 18311841
Fig. 13. Dependence of C1 and C2 parameters on sample thickness (from
Ref. [9]).
the evolution of and shown in Fig. 7C. In the first stages
(05% of weight loss) all pores are filled with electrolyte,
and have their contribution in the impedance of the system
ColeDavidson type dispersion. By the end of drying (>15%
weight loss) only one pore family remains occupied, and in
consequence, the symmetrical dispersion in the time constant
dominates. By the middle region of the experiment (515%
of weight lost) two pore families (not very different in central
size, see Fig. 5C) contribute to the impedance of the sample,
so both symmetrical and asymmetrical dispersion in the time
constant appear.
The same argument allows explaining the change observed
at about 15 days hardening (see Fig. 2): Fig. 5A and B show
that the development of the pore structure corresponds to
the shift of pore families central diameters towards lower
and higher values. This resolution of pore families makes
the initial ColeCole dispersion (Fig. 2A) to evolve towards
ColeDavidson type (Fig. 2B).
The proposed model explains also the dependence of the
high and low frequency limits of the complex capacitance
plots. Fig. 13 shows that C1 (the high frequency limit) scales
inversely with sample thickness (as it corresponds to a dielec-
tric capacitance). Nevertheless, C2 (the difference between
low and high frequency limits) increases with film thickness.
This can be understood according to the proposed model
because C2 is related to the double layer capacitance CL1 ,
and this overall capacitance is proportional to the samples
thickness, L.
4. Conclusions
The above presented results show that impedance mea-
surements in the frequency range 0.01100 MHz can supply
information on pore network development as well as on
pore occupancy. The ColeCole representation (complex
capacitance plot) is the simplest way of studying the
dielectric behaviour of cement paste. The phenomeno-
logical parameters associated to that representation (C1 ,
C2 , R2 , and ) have been associated to various physical
properties of the system using a physical model based on
MIP results. The high frequency limit of the ColeCole
plot, C1 , is defined by the dielectric capacitance of the
solids. It decreases either as sample thickness or porosity
increases. The capacitance C2 defines the low frequency
limit of the complex capacitance plot (C1 + C2 ), and it is
directly linked to the double layer capacitance formed at the
CSH gel layers limiting occupied pores. This capacitance
increases with pore occupancy and with sample thickness.
The symmetrical (ColeCole) dispersion parameter, ,
has been shown to be directly related to the distribution
of pore sizes around a central value (pores family). The
asymmetrical (ColeDavidson) dispersion parameter, , is
linked to the presence of several pore families in the same
system.
Acknowledgement
The authors are grateful to the Spanish Ministry of Science
and Education for founding this research under Project No.
MAT2004-06435-C02-01.
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