Construction and Building Materials 191 (2018) 853–865

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Construction and Building Materials

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Porous arrangement and transport properties of geopolymers

Quang Hung Nguyen a,b, Sylvie Lorente a, Anne Duhart-Barone b, Hervé Lamotte b
a
LMDC, INSA/UPS Génie Civil, 135 Avenue de Rangueil, 31077 Toulouse cedex 04, France
b
DEN/DSN/SEEC/LECD, Bât. 326, CEA Cadarache, 13108 Saint Paul Lez Durance, France

h i g h l i g h t s

A new protocol and interpretation of the thermoporometry were proposed.

Geopolymers have a multi-scale porosity.

The effective diffusion coefficient is one order of magnitude smaller than the bulk coefficient diffusion.

Geopolymers behavior as ink-bottled materials with mesopores connected to macropores in the core of the material.

a r t i c l e i n f o a b s t r a c t

Article history: This paper documents the results of a study on the relationship of the pore structure and the transport
Received 30 March 2018 properties of potassium- and sodium-based geopolymers. The pore structure was investigated by water
Received in revised form 28 September porosity, mercury intrusion porosimetry and thermoporometry. The geopolymers transport properties
2018
were determined using a set of experiments, including natural diffusion of tritiated water and two elec-
Accepted 4 October 2018
trical methods (direct current and Electrochemical Impedance Spectrometry). The geopolymers
microstructure corresponds to materials with a pore structure made of poor access dimensions around
7 nm (potassium-based geopolymers), and 20 nm (sodium-based geopolymers) connected to larger pores
Keywords:
Porous network
not detected by MIP but revealed by thermoporometry. As a result, the transport properties appear to be
Geopolymer higher than expected.
Tritium diffusion Ó 2018 Elsevier Ltd. All rights reserved.
Direct current
EIS
MIP
Thermoporometry

1. Introduction cement production) geopolymer shifted to be used in the construc-

The term ‘‘geopolymer” was firstly introduced by Davidovits [1],
who developed a binder obtained from the polycondensation of
metakaolin in an alkali medium at the temperature of 100–
150 °C. As the raw material is mainly of geological origin (clay, kao-
lin), Davidovits termed geopolymer as a mineral polymer obtained
by chemical processes of geosynthesis [2]. According to Provis and
Deventer [3], geopolymers are framework structures produced by
the condensation of tetrahedral aluminosilicate units, with alkali
metal ions balancing the charge associated with tetrahedral Al.
The alumino-silicate source, which has a low content of calcium,
can be fly-ash class F (FA), natural pozzolan or metakaolin (MK)
as mentioned in Fig. 1.
In the beginning, geopolymer was developed as a heat-resistant
material after some catastrophic fires in Europe but later, thanks to
its eco-friendly properties (low CO2 emission in comparison to the
tion sector [4]. Geopolymers show advantages in immobilizing
low- and intermediate-level nuclear waste [5,6]. Moreover, they
also possess a compressive strength similar to that of cement-
based materials, which explains the primary application of
geopolymers as an alternative material to ordinary Portland
cement [7].
Several properties of geopolymers have been investigated in the
literature: chemical durability (acid attack, sulfate attack, alkali sil-
ica reaction, carbonation. . ..) [7–11], fire-resistance [12,13] and
electrical properties [7,14–17]. The durability of geopolymers, as
well as porous materials in general, depends on the ability to with-
stand the intrusion of aggressive agents. The transport properties
of a porous materials are influenced by the pore structure charac-
teristics [18,19]. The formation factor, defined as the ratio between
the electrical conductivity of the bulk solution and the one of the
material saturated by the same solution [20,21] can be related to

https://doi.org/10.1016/j.conbuildmat.2018.10.028
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
854 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865

and results on the diffusion coefficient (effective diffusion coeffi-

Fig. 1. CaO-Al2O3-SiO2 ternary diagram of cementitious materials [68].
the material pore structure characteristic by using an expanded
version of Archie’s law [22]:
ro s2
Ff ¼ ¼ ð1Þ
rmat po T o
where Ff is the formation factor, ro is the electrical conductivity of
the bulk solution, rmat is the electrical conductivity of the saturated
material, s is the tortuosity, To is the constrictivity and po, the open
porosity.
The pore distribution of porous materials is often characterized
by mercury intrusion porosimetry (MIP) or nitrogen absorption
porosimetry (NAP). According to the literature, the pore size distri-
bution of geopolymers highlights a bell curve centered in a meso-
porous region [23–26]. For example, the potassium-based
geopolymer (GeoK) had a peak situated between the range of 8–
30 nm [26] and between 7 and 10 nm [24,25,27]. Concerning
sodium geopolymer (GeoNa), the peak was shifted toward higher
values, up to 30 nm [24,27]. In addition, while studying the nitro-
gen adsorption of potassium and sodium geopolymer, Steins et al.
[24] and Benavent et al. [28] claimed that these materials have a
type IV isotherms behavior, which is attributed to the ‘‘ink bottle”
effect. The potassium geopolymer exhibited a higher specific area
than sodium geopolymer. Several methods of measurement like
NAP, Small-angle neutron scattering (SANS) and Small-angle X-
ray scattering (SAXS) showed that the specific area of potassium
geopolymer was about 3 times higher than that of sodium geopoly-
mer [24,28].
To date, publications on the diffusivity of geopolymer are few in
number, regardless of the kind of geopolymer (metakaolin
geopolymer, Fly ash geopolymer, geopolymer mortar, geopolymer
concrete. . .). The following table summarize the relevant methods
cient – De or apparent diffusion coefficient – Da) of geopolymer
materials: (See Table 1).
As seen, the diffusion coefficient of geopolymer materials varies
in a large range, it is usually around 1011 m2/s essentially in the
case of sodium-based geopolymers.
Recent studies on transport properties at early age of
metakaolin-based geopolymer and cement paste indicate that the
geopolymer has a lower permeability than that of the cement paste
[36,37], despite a similar open porosity. However, other studies on
the permeability at the later ages of fly ash-based geopolymer
showed that the permeability of the latter is higher than that of
cement paste [38].
Here, we study the link between the porous arrangement of
sodium and potassium geopolymers and their transport properties,
at long term. Firstly, the porous structure of the porous samples
was characterized by water open porosity, MIP and thermoporom-
etry. Later, the transport properties were determined by a direct
current test, an electrochemical impedance spectrometry test
(EIS) and a natural diffusion of tritiated water test.
2. Materials and characterization methods
2.1. Geopolymers
GeoK and GeoNa were synthetized; the preparation of the activating solution
and the mixing process are detailed in [27]. The activating solution consisted of
an amorphous precipitated silica dissolved in alkali solution (soda and potash)
and stirred for 24 h. The silica powder was Tixosil 331Ò by Solvay, soda and potash
was supplied by VWR ProlaboÒ. Note that no sign of gelation was observed in the
activating solution. The median particle size of the silica powder was between
3 lm and 4 lm, the amount of amorphous silica (SiO2) was 95% and the sulfate
content was less than 4 wt% by relative weight of silica. Metakaolin (PieriÒ Premix
MK obtained from Grace Construction) was used as the aluminosilicate source. Its
chemical composition (in % mass) is given in Table 2.
The composition of the GeoK and GeoNa pastes is detailed in Table 3. Samples
were in cylindrical form, with a diameter of 50 mm and a length of 70 mm for direct
current and natural diffusion test, a diameter of 28 mm and a length of 50 mm for
EIS test. All specimens were endogenously cured (hermetically sealed) for
28 months in the room temperature: T = (20 ± 3) °C.
2.2. Water porosity
Water porosity was measured at the end of the curing period. The protocol used
was an adaptation of the AFPC-AFREM recommendations [39], as the saturation
time was 10 days instead of 24 h. The open porosity po of the samples was calcu-
lated by:
M sat  M dry
po ¼ q ð2Þ
M sat  M h water
where Msat is the mass of the saturated sample in the air, Mdry is the dry mass at
105 °C, Mh is the hydrostatic mass and qwater is the water density. The dry bulk den-
sity qa and wet bulk density qs were given by:
M dry
qa ¼ q ð3Þ
M sat  M h water

Table 1
Summary of the determination of the diffusion coefficient of geopolymer materials.

Author Materials Results Additional information

Lloyd et al. [29] FA geopolymer paste, sodium activator De = 0.67–7.3 1012 m2/s Porosity 30%
Jämstorp et al. [30] MK geopolymer paste, sodium activator De = 1.6–120 1012 m2/s NA
Asprogerakas et al. [31] FA geopolymer mortar, sodium activator Da = 3.7–7.1 1011 m2/s NA
Ismail et al. [32] FA geopolymer mortar, sodium activator Da > 8 1011 m2/s Porosity = 22%
Yang et al. [14] FA geopolymer concrete, sodium activator Da = 1.543 1011 m2/s Porosity 33% (MIP test), 28 days
Chindaprasirt et al. [33] FA geopolymer concrete, sodium activator Da = 2.9–6.2 1010 m2/s Porosity = NA
3 years exposure in marine environment
Law et al. [7] FA geopolymer concrete, sodium activator Da = 3.1–3.7 1011 m2/s NA
Ganesan et al. [15] FA geopolymer concrete, sodium activator Da = 1.24 1011 m2/s NA
Gunasekara et al. [34] FA geopolymer concrete, sodium activator Da = 7.9–9.9 1011 m2/s 1 year curing, Porosity = NA
Kupwade-Patil et al. [35] FA geopolymer concrete, sodium activator Da = 1.45–18.7 1012 m2/s 1 year exposed in salt water
 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865 855

Table 2
Chemical composition Properties PieriÒ Premix MK.

Chemical component CaO SiO2 Al2O3 Fe2O3 SO3 Na2O K2O Loss of ignition (LOI) Specific gravity g/cm3
Average value (% mass) 0.1 54.4 38.4 1.27 – less than 0.2 0.62 – 2.23

Table 3
Geopolymer composition (final molar ratio).

Molar ratio Activation solution Geopolymer paste

SiO2/M2O* H2O/M2O* SiO2/H2O M2O*/Al2O3 SiO2/Al2O3 H2O/M2O*
GeoK 1.4 12 0.117 1 3.8 12
GeoNa 1 12 0.083 1 3.4 12
*
M = K or Na.

M sat Thermoporometry experiments on geopolymers were performed with a Calvet-

qsat ¼ q ð4Þ
M sat  M h water
2.3. Mercury intrusion porosimetry (MIP)
The mercury intrusion porosimetry (MIP) was performed by an Autopore III
9420, commercialized by Micromeritics. The maximal hydraulic pressure of the
apparatus was 414 MPa, the contact angle was 130° and the surface tension was
0.485 N/m. The samples were oven-dried at 80 °C, until the variation of the mass
of the sample at two successive weighing was less than 0.1%. The equilibration rate
for low pressure and high pressure is 0.03 lL/g. An alternative drying method,
based on a lyophilization procedure was also performed but not retained, as dis-
cussed in the following sections. For each geopolymer, 3 samples of about 6 g were
tested. The pore size distribution shown here is the average of 3 tests. As MIP is a
classical technique, we do not enter into details here.
2.4. Thermoporometry
During the cooling process of a porous material saturated with a pure liquid
(water for example), the crystallization temperature (T) of the liquid phase confined
in the pore is lower than the normal temperature of the triphasic equilibrium (To).
The relation between the freezing temperature depression DT = T  To and the pore
radius was derived by Kubelka [40]. Based on thermodynamic considerations which
include Laplace equation and Gibbs-Duhem equation, fully developed later by Brun
et al. [41,42], the equation proposed by Kubelka has the following form:
DT 2000rls
¼ ð5Þ
To r q l Dh
where ql is the density of the liquid (kg/m3), rls is the liquid–solid surface tension (N/
m), r is pore radius assumed spherical (m), and Dh is the specific enthalpy of crystal-
lization (J/g).
The standard enthalpy of fusion of water in a bulk medium is DhStd = 334.1 [43],
but in the case of a confined medium, this value depends on the temperature. We
summarize in the following table the empirical formulae from the literature esti-
mating the enthalpy change, with the general form Dh = a(DT)2 + bDT + c:
If the liquid is water, Brun et al. [42] proposed a semi-empirical equation to
determine the radius of the pore. This equation accounts for the thickness of the
nonfreezable layer water, which they estimated at 0.8 nm.
During the cooling process, considering spherical pore shapes:
type low-temperature calorimeter (BT 2.15) from Setaram Instrumentation (Fig. 2),
using the scanning mode (constant gradient of temperature). The cooling device
uses a supply system with ethanol instead of liquid nitrogen. Due to the limitation
of the latter, the apparatus can detect the presence of pore size above 4 nm. GeoK (3
samples) and GeoNa (2 samples) were analyzed. The samples were crushed into
smaller pieces of about 2 g before being vacuum saturated in water. The water vol-
ume is much greater than that of the samples and the saturation period was long
enough to ensure that water would replace the original pore solution in the sample.
Moreover, we will see in the following section, that the high value of the effective
diffusion coefficient (De  71010 m2/s) of geopolymer samples can explain a
quasi-substitution of the interstitial pore solution by water. In addition, an evacu-
ation/renewal of the water in the desiccator to accelerate the substitution process
was also performed. No nucleation agent was added to the saturated sample.
Two thermal cycles made of a total of four consecutive sequences of cooling/
heating were applied to the samples, as shown in Fig. 3.
In the 1st thermal cycle, the 1st cooling sequence started at ambient tempera-
ture (20 °C) then went down to 50 °C. It was followed by a 1st heating sequence to
0.5 °C. During the 2nd thermal cycle, the temperature was lowered again to
50 °C (2nd cooling sequence) and finally the temperature was increased to the
ambient temperature (2nd heating sequence). The cooling rate was 0.07 °C/min
and the heating rate was 0.10 °C/min. The total time for such an experiment was
about 60 h. At the end of the test, the samples were removed from the calorimeter
and oven-dried at 80 °C to determine the oven-dried mass (movd) and the quantity
of water held inside the porous material (mw). The mass of ice that froze during the
1st cooling sequence and the one melted in the 2nd heating sequence are supposed
to be close to the total amount of water present in the porous sample (mw). 80 °C
was chosen rather than 105 °C in order to preserve the non-freezable layer of water,
which is not detectable by TMP.
The objective of the 1st heating sequence was to prevent the supercooling effect
occurring during the 1st cooling sequence [47]. Supercooling accounts for the fact
that water remains in liquid state when the temperature is below 0 °C in the pores,
as crystallization is a process based on nucleation and crystal growth. While heating
up to 0.5 °C, the ice in the pores below 130 nm of diameter melts, and water in the
pores of diameter above 130 nm remains as ice, according to Brun’s second equa-
tion (Eq. (7)). Therefore in the 2nd cooling sequence, water in the pore range of
(4–130) nm refreezes and the heat flux is the contribution of this pore range. The
mass ratio of ice frozen between the 2nd cooling sequence and the 1st cooling
sequence, Pf, and the mass ratio of ice melted between the 1st heating sequence
and the 2nd heating sequence, Pm, were calculated as follows:

64:67 mc2
r¼ þ 0:57 ð6Þ Pf ¼ ice
 100 ð8Þ
DT mc1
ice

and the heating process, considering cylindrical pore shapes: and:

32:33 mh1
r¼ þ 0:68 ð7Þ Pm ¼ ice
 100 ð9Þ
DT mh2
ice

Table 4
Literature value of enthalpy of crystallization/fusion.

Notation Enthalpy (J/g) a b c

Crystallization Fusion
Fagerlund [44] DhFag x 0 2.19 333.7
Brun et al. [42] DhBru x 5.56102 7.43 332
x 0.155 11.39 332
Ishikiriyama et al. [45] DhIsh x 7.83103 2.119 334.1
Matala [46] DhMat x 1.25102 4.83 334
856 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865

Fig. 2. Cross-section of the BT 2.15 low-temperature calorimeter (by courtesy of Setaram Instrumentation).

Both values are expected to be in the same range. 4. Calculation of the increment of volume of ice frozen/melted: DVi = Dmi t,
The thermogram (heat flux as a function of the temperature) provides informa- where t is the specific volume of ice, t = 1.000132(1 + 9.1 105T + 1.035 10
5 2
tion on the porous system, such as the pore size distribution and the porosity. To T ) [42].
this end, a baseline must be obtained before any further step. The baseline of a 5. Calculation of the pore size with Eqs. (6) and (7), for negative temperature val-
calorimeter is the recording of its signal as a function of time in the absence of ues only.
the phenomenon intended to be measured [48]. We chose 2 methods of baseline
construction from Hemminger’s paper [49]: the straight line method and the degree Next, we calculated the total amount of ice frozen/melted in the 4 sequences by
P
of conversion method [50]. The degree of conversion method is recommended but summing the increment Dmi: mice ¼ i Dmi . Among the 4 values obtained, those
only can be applied to the 1st cooling sequence and 2nd heating sequence. Hence, from the 1st cooling sequence and 2nd heating sequence were compared to the
the straight line method was used in the 1st heating sequence and 2nd cooling mass of water held inside the material (mw), to verify the accuracy of the calcula-
sequence. tion. The porosity can be estimated by:
Considering an increment of time Dt = ti+1  ti, which corresponds to a variation
X Dmi q
of temperature DT = Ti+1  Ti, we followed the calculation procedure in accordance po ¼ sat
ð10Þ
with the method proposed by Brun et al. [42,51]: i
M sat qwater

1. Construction of the baseline and determination of the heat flux Q. The contribution of the mesoporous region, which is situated between 2 nm and
R tiþ1 50 nm, in each characterization method was determined by the following equation:
2. Determination of the heat released/absorbed by the sample DEi ¼ ti
dQ by
using a numerical integration, based on the trapezoidal method. pmeso
Bmeso ¼  100 ð11Þ
3. Determination of the incremental amount of ice frozen/melted, Dmi = DEi/Dhi, po
where Dhi is the enthalpy of crystallization/fusion. To the authors’ knowledge,
only Brun [42] gave the formulations of enthalpy during crystallization and where pmeso is the porosity of the mesopore region and po is the open porosity mea-
fusion, cf. Table 4. We considered that the other formulations in Table 4 were sured in each method.
applicable for both the crystallization and fusion processes. The temperature Finally, the pore size distribution of geopolymer samples is plotted, from the data
was calculated at (Ti + Ti+1)/2. of the 1st cooling sequence and 2nd cooling sequence. Note that the supercooling
 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865
Fig. 3. Sequence for the thermoporometry.
effect occurs in the 1st cooling sequence. Moreover, data extracted from 2nd cooling
sequence were used to determine the pore size distribution between 4 and 130 nm.
3. Transport properties
Diffusion and direct current tests were communally developed
in our laboratories. We used natural diffusion test to calculate
the effective diffusion coefficient of geopolymer pastes, at the same
time, electrokinetic tests (direct current + EIS) were performed to
determine the formation factor of geopolymer samples. The forma-
tion factor was not used to calculate the effective diffusion coeffi-
cient. We have recently reported that the analogy between the
formation factor and the diffusivity is not applicable in the meso-
pore range [52]. Note that diffusion and direct current tests were
used so far for mortar and concrete samples [53,54] but an adapta-
tion of the test was necessary to avoid damaging the geopolymer
pastes. A 70 mm diameter cylinder was extracted concentrically
from a PVC cylinder (diameter 120 mm, height 100 mm). The
geopolymer sample was then placed into the resulting hole and
secured to the PVC cylinder thanks to resin epoxy. The whole sys-
tem was then sawed into thin slices of 8 mm thick by a precision
diamond wire (Fig. 4). The top and the bottom of the cylinders
were not used in order to ensure the homogeneity of the sample
properties. The composition of the artificial solution used to satu-
rate the samples was based on the internal pore solution of the
geopolymers which was extracted following the protocol described
in [53]. The pH of the pore solution was measured immediately
after the pore solution extraction test by a standard pH meter
(HACH 31) and gave a value of 13 for GeoK and GeoNa. A simplified
saturation solution, close to the pH value of the pore solution was
chosen (100 mol/m3 of NaOH for GeoNa samples, 100 mol/m3 of
KOH for GeoK samples). All the samples were saturated following
the AFPC-AFREM protocol [39] and the saturation was extended
to 2 weeks.
3.1. Direct current test
The direct current test is based on the application of a constant
electric field through the sample [53,55–58]. Each sample was
placed between two compartments named anodic and cathodic
depending on the electrical current direction. Both compartments
of equal volume (1.7 L) were filled with the same solution as the
samples saturation solution to avoid any concentration gradient.
A constant and uniform electric field of 400 V/m was applied
between the two parallel faces of the sample, using two electrodes
made of a stainless steel grid placed between the sample faces. The
value of the electric field is typically used in the literature [53,58].
857
Fig. 4. Sketch of the migration cell and tested sample [54].
The resulting current was monitored during the experiment. The
details of the experimental test are given in [54] and shown in
Fig. 4.
The duration of the test was short enough to avoid any signifi-
cant changes of the electrolytic solution in both compartments and
any electro-osmotic flow between the 2 compartments [58]. The
waterproofing of the system (PVC-resin-geopolymer) was carefully
checked. A blank test was previously conducted using only the
epoxy resin and showed no current through the system. We calcu-
lated the electrical conductivity of the saturated material (rmat)
from Ohm’s law:
I L
rmat ¼ ð12Þ
DU A
where DU is the voltage applied to the sample (V), L is its thickness
(m), A is the sample cross-section (m2), and I is the measured cur-
rent (A).
The bulk conductivity was calculated from [59]:
F2 X 2
ro ¼ z D cbulk
i i o;i i
ð13Þ
RT
where F is the Faraday constant, R is the gas constant (J/K mol), T is
the temperature (K), z is the charge number and cbulk is the concen-
tration of the ionic species in the bulk solution (mol/m3).
3.2. Electrical impedance spectroscopy (EIS)
EIS tests were made following the protocol developed by Mer-
cado et al. [53]: a sinusoidal voltage of small amplitude (200 mV)
was applied between 2 electrodes and the frequency varied in
the range of 40 Hz to 110 106 Hz. The saturated samples were
placed between copper electrodes specifically designed for the
EIS experiments as shown in Fig. 5.
The sample diameter was 28 mm and the sample thickness was
19 mm for GeoK, 18.5 mm for GeoNa. The amplitude, the phase
angle and the complex impedance were registered by an HP Agi-
lent 4294A.
The impedance Z(x) of the saturated sample was estimated by
the impedance of an electrical equivalent model:
Z ðxÞ ¼ Z real ðxÞ þ iZ im ðxÞ ð14Þ
This latter is represented in a complex plane plot (Nyquist plot),
where the real part is plotted on the X-axis and the imaginary part
is plotted on the ordinate axis. The value of the resistance (Rmat) of
the saturated material is correlated to the minimum value of the
imaginary part of the Nyquist plot [53]. This model is valid only
when the material is totally saturated. When the material is par-
tially saturated, a complex model was developed in [60]. The satu-
rated material electrical conductivity in this test is then calculated
as follows:
L
rmat ¼ ð15Þ
ARmat
858 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865
Fig. 5. Configuration of the sample for EIS measurements [53].
The formation factor was calculated as above (Eq. (1)), while ro
was measured directly by means of a conductimeter.
3.3. Diffusion test
After performing the direct current test, the tested sample was
placed in a diffusion cell. The sample was sandwiched between
two compartments containing the same saturated solution as the
material sample (Fig. 6).
The system was tested previously to guarantee no leakage
through the epoxy resin. Tritiated water (HTO), with specific activ-
ity Co = 3.71010 Bq/m3, was added to the upstream compartment
[61]. Due to the concentration gradient, HTO diffuses toward the
downstream compartment by molecular diffusion following Fick’s
first law of diffusion. The activity of tritiated water in both com-
partments was regularly measured using a liquid scintillator coun-
ter. The HTO upstream concentration was maintained constant by
adjusting it after each scintillation measurement, whereas the HTO
downstream concentration was maintained close to null in order
to have a constant concentration gradient between the 2 faces of
the sample.
The effective diffusion coefficient was calculated in steady state
by measuring the slope of the curve plotted [62] as:
L aL2
nðt Þ ¼ De t 
AC o 6 Material
where n(t) is the cumulative quantity of HTO (Bq) in the down-
stream compartment at time t, and a is defined analytically by:
a ¼ po þ ð1  po Þqs K D
Fig. 6. Representative sketch of a diffusion cell [61].
where KD is the distribution ratio (cm3/g) and qs is the density of the
solid phase of the material (g/cm3) [62]. More details on the exper-
imental set-up can be found in [61].
4. Results and discussion
We present in the following table the characteristic properties
for both geopolymers, obtained from water porosity and MIP tests
(see Table 5):
The open porosity of the geopolymers is higher than cement-
based materials that generally is found in a range of (23–35)% for
blended cement pastes [63]. This open porosity is in the same
range as values in the literature; for example in the case of GeoNa,
50–61% [64], 49–52% [27]. The open porosity for GeoK was 48% in
[27]. The specific area of GeoK is about 2.5 times higher than that
of GeoNa, in agreement with the results in [24,28]. The pore size
distribution curves obtained by MIP are given in Fig. 7.
As seen, the geopolymers have a monomodal distribution with
one peak centered on 7 nm for GeoK and 20 nm for GeoNa. These
results matched well the literature review, mentioned in the previ-
ous section. A complementary MIP test using a freeze drying pro-
cedure was also conducted on GeoK sample. We obtained a
similar pore size distribution curve, with one peak situated in the
vicinity of 7 nm. These values correspond to the range of meso-
pores, according to the IUPAC classification [65]. The presence of
macropores was not noticed, as reported in previous studies on
geopolymers [23,25,27].
The pore size distribution and the porosity were also examined
by thermoporometry in order to get more information on the
microstructure of the materials. The thermogram of GeoK and
GeoNa are shown in Figs. 8 and 9.
A steep increase in heat flux was observed during the first cool-
ing sequence (Figs. 8a and 9a). It was in the vicinity of 10 °C for
the GeoK samples, and 7 °C for the GeoNa materials. Such peak
is due to supercooling, which contains information on the pore size
range. No other peak was found when the temperature continued
to decrease. The second cooling sequence exhibits 2 peaks, much
smaller than the one observed in the first sequence (Figs. 8b and
Table 5
Characteristic properties of the two geopolymers.
ð16Þ
Open porosity (%) Dry bulk density Specific area
(g/cm3) (m2/g)
Water MIP Water porosity MIP
porosity
ð17Þ GeoK 56.8 50.8 1.09 113.5
GeoNa 55.5 42.0 1.12 44.6
Fig. 7. Pore size-distribution of geopolymers by MIP.
 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865 859

Fig. 8. Thermogram of GeoK: (a) 1st thermal cycle (b): 2nd thermal cycle (c): 2 thermal cycles together.

Fig. 9. Thermogram of GeoNa: (a) 1st thermal cycle (b): 2nd thermal cycle (c): 2 thermal cycles together.

9b). The additional peak was detected at a temperature higher than
the one during the first cooling sequence, in the vicinity of 3 °C to
2 °C.
Using the methodology described in Section 2.4, the pore size
distribution of the geopolymers could be obtained. Results from
the 1st and 2nd cooling sequences are given in Figs. 10 and 11
for GeoK and GeoNa respectively. Note that these figures were
obtained by using only Brun’s enthalpy, and that they are the
results from several samples of geopolymers in each case. Full
details of Figs. 10 and 11, with the specific enthalpies given in
Table 4 were presented in the Appendix 3 and 4 (Figs. 15 and 16).
The impact of supercooling can be easily observed in both cases
(Figs. 10a and 11a). Remember that the first thermal cycle (from
ambient temperature to 50 °C, then up to 0.5 °C, cf. Fig. 3)
was implemented with the objective of decreasing the supercool-
ing effect. The pore size distribution plotted from the 2nd cooling
sequence shows that the intensity of the peak was decreased
(Figs. 10b and 11b). That peak corresponds to 15 nm for GeoK,
860 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865
Fig. 10. Pore size distribution of GeoK from thermoporometry (Brun’s enthalpy): (a)
from the 1st cooling sequence (b): from the 2nd cooling sequence.
Fig. 11. Pore size distribution of GeoNa from thermoporometry (Brun’s enthalpy):
(a) from the 1st cooling sequence (b): from the 2nd cooling sequence.
and 20 nm for GeoNa. The presence of a second peak can be
noticed. It is in the vicinity of 35 nm in the case of GeoK and
70 nm for GeoNa. Therefore, unlike the MIP results which indicate
only one pore mode (7 nm for GeoK), Fig. 10b shows that the
potassium-based geopolymer has 2 pore sizes in the mesopores
domain. Similar behavior is noticed in the case of sodium-based
geopolymers with again 2 pore families instead of 1 detected by
MIP (20 nm for GeoNa), Fig. 11b. In addition to the mesopore range,
the presence of macropores (> 50 nm) is clearly highlighted. Com-
paring pore size values is not relevant here as MIP is based on the
assumption of cylindrical pores, while the cooling sequences in
thermoporometry consider spherical pores (Eq. (6)). Important is
the occurrence of a pore family of larger dimension which could
not be detected by MIP. At present the explanation we can propose
is based on the ink-bottle effect, a well-known and long recognized
bias of the MIP technique. The measured pressure is the mercury
pressure necessary to access the pore entrance. What happens
behind the pore neck is unknown. As the pressure needed to push
mercury into the pore network is inversely proportional to the pore
size, pores with larger dimensions than the pore entrance cannot
be detected.
We present in Table 6 the calculations of the mass of water that
froze or melted during the 1st and 2nd cooling sequences of the
thermal process for the GeoK. The average values were obtained
using the standard specific enthalpies of crystallization/fusion,
DhStd, and the ones provided in Table 4. Full details of the calcula-
tions of 4 sequences for each sample are given in the Table 10
(Appendix 1). The values were obtained using the standard specific
enthalpies of crystallization/fusion, DhStd, and the ones provided in
Table 4. Given also in the second column of the table is the total
mass of water per mass of material, measured after the oven-
drying at 80 °C, as mentioned earlier. The specific latent heat pro-
vided by Brun et al. [42] is the one giving the closest results to mw.
Taking the example of the first sample in Table 10, the calculations
using DhBru, show that the sample contains 0.41 g of water per
mass of material during the 1st cooling sequence (from 20 °C to
50 °C). Then, the 1st heating sequence (from 50 °C to 0.5 °C)
allowed to melt the ice in the pore range of (4 –130) nm. The mass
of ice melted in this sequence is mh1 ice ¼ 0:25 g. The remaining mass,
mc1
ice  m h1
ice ¼ 0:15 g per mass is the mass in the largest pores
(> 130 nm). Next, during the 2nd cooling sequence from 0.5 °C
to 50 °C, liquid water in the range of (4 –130) nm freezes again
and mc2 ice ¼ 0:31 g per mass of material. This value is close enough
to mh1ice to be considered acceptable. Finally, the entire volume of
water melts during the 4th sequence which allows to the reach
the ambient temperature of 20 °C. The difference between Pf and
Pm is minimized for the Brun’s enthalpy formulation. The porosity
acquired from the specific enthalpy DhBru is of 46.5% for the
potassium-based geopolymer, which is lower than the open poros-
ity obtained from water porosity test (56.8%).
In the case of the sodium-based geopolymer, the crystalliza-
tion/fusion specific enthalpy given by Brun et al [42] provides
the closest result to the mass of water mw. The average results of
the 1st and 2nd cooling sequences are given in Table 7, the details
of the calculations are also given in the Table 11 (Appendix 2).
Results from Thermoporometry (TMP) are highly different from
that of MIP, particularly in the mesoporous region. Using Eq. (11),
we present in the following table the proportion of mesopores
obtained in each methods (see Table 8).
MIP shows that most of the pores of geopolymer samples
(97%) are centered in the mesoporous region, whereas TMP high-
lights a lower proportion of mesopores, particularly in the case of
GeoNa (11%). TMP also quantifies a large amount of the macrop-
ores, questioning the type of pore arrangement of all families
inside the geopolymers.
Now we will expose the results from the transport tests, in
order to correlate to the previous characterization results. Fig. 12
presents the voltage applied between the 2 parallel faces of the
samples, together with the electric current as a function of time.
Here, we show the case of GeoNa, yet the other geopolymer exhib-
ited similar behavior. The reproducibility was checked by testing 3
samples of each geopolymer; repeatability was also insured by
testing each sample 3 times. The drop in voltage (and therefore
in direct current) measured at the very start of the test is due to
 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865 861

Table 6
Mass of frozen/melted water per mass of material, and porosity. Case of GeoK.

mw/movd (g/g) Crystallization/fusion specific enthalpy 1st cooling sequence 2nd heating sequence Pf Pm
(20 °C ? 50 °C) (50 °C ? 20 °C)
(J/g) mc1
ice (g/g)
Porosity (%) mh2
ice (g/g)
Porosity (%) (%) (%)

0.45 ± 0.01 DhStd 0.30 ± 0.005 35.1 ± 0.4 0.31 ± 0.005 36.1 ± 0.4 79.8 ± 0.8 62.6 ± 5.0
DhFag 0.33 ± 0.008 38.2 ± 0.5 0.32 ± 0.005 37.3 ± 0.4 78.9 ± 0.8 63.4 ± 4.9
DhBru 0.41 ± 0.008 47.3 ± 0.6 0.35 ± 0.005 40.7 ± 0.4 77.1 ± 0.8 65.5 ± 4.8
DhIsi 0.33 ± 0.008 38.2 ± 0.5 0.32 ± 0.005 37.2 ± 0.5 79.0 ± 0.8 63.4 ± 4.9
DMat 0.37 ± 0.008 42.5 ± 0.5 0.33 ± 0.005 38.8 ± 0.5 77.9 ± 0.8 64.4 ± 4.8

Table 7
Mass of frozen/melted water per mass of material, and porosity. Case of GeoNa.

mw/movd (g/g) Crystallization/fusion specific enthalpy 1st cooling sequence 2nd heating sequence Pf Pm
(20 °C ? 50 °C) (50 °C ? 20 °C)
(J/g) mc1
ice (g/g)
Porosity (%) mh2
ice (g/g)
Porosity (%) (%) (%)

0.37 ± 0.005 DhStd 0.24 ± 0.010 30.0 ± 1.1 0.26 ± 0.01 31.5 ± 0.9 47.5 ± 2.0 33.5 ± 3.5
DhFag 0.26 ± 0.005 31.5 ± 1.1 0.26 ± 0.01 31.6 ± 0.9 46.1 ± 1.6 33.7 ± 3.5
DhBru 0.29 ± 0.010 35.9 ± 1.4 0.26 ± 0.01 31.9 ± 0.9 42.8 ± 1.1 34.3 ± 3.5
DhIsi 0.26 ± 0.005 31.5 ± 1.2 0.26 ± 0.01 31.6 ± 0.9 46.1 ± 1.6 33.6 ± 3.5
DMat 0.28 ± 0.005 33.5 ± 1.3 0.26 ± 0.01 31.7 ± 1.0 44.4 ± 1.3 33.9 ± 3.5

Table 8
Proportion of the mesopore region (percentage) in each characterization method.

MIP TMP
GeoK 97.8 57.3
GeoNa 97.1 11.2

Fig. 13. Nyquist plot for the GeoNa sample.

rent tests. Presented in Fig. 13 is the example of one test for GeoNa.
Here, Rmat = 383 X, corresponding to 0.82 MHz. Eq. (15) allows to
calculate the material conductivity and Eq. (1) gives the formation
factor. The electrical conductivity of the bulk solution of NaOH
Fig. 12. Voltage and current in the direct current test of GeoNa. 0.1 M or KOH 0.1 M was respectively 22.3 mS/cm and 24.3 mS/
cm. These results match well to the ones estimated by Eq. (13).
As shown in Table 9, the material conductivities are similar what-
the time needed to obtain the targeted voltage. The material ever the electrical method, direct current or EIS. The electrical con-
conductivity and the corresponding formation factor were then ductivity of the saturated material rmat is one order of magnitude
calculated by means of Eqs. (12) and (1) (cf. Table 9). smaller than the bulk conductivity.
Electrical Impedance Spectroscopy tests were also performed In comparison with results on cement-based materials using
on the GeoK and GeoNa geopolymers. Reproducibility and repeata- the previous electrical methods, the formation factor obtained for
bility were again checked in the same manner as for the direct cur- a saturated blended cement paste (type V cement) with an EIS test
(Ff  300) [66] was found one order of magnitude higher than the
geopolymers tested in this work (Table 9). In Mercado et al. [66],
Table 9 the blended cement paste had an open porosity of 37% and MIP
Electrical conductivities and formation factors of the geopolymers. tests showed that most of the pore sizes were below 30 nm. The
Material Direct current EIS open porosity of geopolymers is about 1.5 times higher than the
rmat (mS/cm) Ff rmat (mS/cm) Ff
one of cement paste (55% vs 37%). The formation factor of cement
paste is about 300, compared to 20 for GeoNa, as to say 15 times
GeoK 2.15 ± 0.40 12 ± 2 1.88 ± 0.14 14 ± 1
GeoNa 1.12 ± 0.02 19 ± 1 1.04 ± 0.09 22 ± 2
higher. The difference in open porosity cannot explain such a
discrepancy.
862 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865

mono-modal materials but rather an example of ink-bottled

model when fully cured.

5. Conclusion

In this work, we characterized sodium- and potassium-based

geopolymers through their microstructure and transport proper-
ties. The main conclusions can be highlighted as follows:

– Mercury Intrusion Porometry tests indicate that the pore size is

Fig. 14. Results of a diffusion test, case of GeoNa.
Fig. 14 represents the cumulative quantity of molecular HTO in
the downstream compartment over time. When the steady-state is
reached, the slope of this curve is constant, the effective diffusion
coefficient of the material can then be calculated. Again, the test
was repeated to check the validity of the results. A simple
modelling using the data of the characterization tests from GeoNa
sample (De,HTO = 7 1010 m2/s, po = 0.555, L = 8.1 mm, Diame-
ter = 50.1 mm, Co = 3.99 1010 Bq/m3) was ran. The steady-state in
the theoretical case is reached within 8 h, as shown in Fig. 14. Note
how fast steady state is obtained. Such a fast transfer challenged
the applicability of Eq. (16) which assumes constant boundary con-
ditions in concentration on the two faces of the sample. The natural
diffusion tests were stopped after a few days, and the correspond-
ing effective diffusion coefficient has to be considered in an order
of magnitude sense, with respect to the bulk diffusion coefficient
of tritiated water (2.44 109 m2/s [67]). In the case of GeoNa, we
obtained De,HTO  7 1010 m2/s. The GeoK was not tested.
In summary, the measurements, whether based on an electri-
cal driving force – direct current and EIS, or a concentration dif-
ference – natural diffusion, indicate that the obtained transport
properties are much higher than expected. Such results corre-
spond to a pore network that cannot be made only of mesopores
as predicted by Mercury Intrusion Porometry experiments. The
second family of pores detected by thermoporometry may explain
the high values of the effective diffusion coefficients obtained.
The existence of large pores in numbers is the reason why the
formation factor is much smaller than the one of a blended
cement paste. The conclusion may be that geopolymers are not
centered around 20 nm for sodium-based geopolymers, and
around 7 nm for potassium-based geopolymers. Thermoporom-
etry results indicate that a second pore family exists: it is cen-
tered around 70 nm for sodium-based geopolymers, and
around 35 nm for potassium-based geopolymers. Larger pores
(above 130 nm) were also detected but not quantified.
– The pore structure determined by MIP does not allow alone to
understand the results provided by transport properties exper-
iments (direct current and diffusion) as those properties are
much higher than expected. Indeed the tritium diffusion coeffi-
cient is within the range 1010 m2/s, only one order of magni-
tude smaller than its value in infinitely diluted solution.
– Thermoporometry combined with MIP provides a better view of
not only the pore size distribution but also the pore arrange-
ments. Geopolymers seem to behave as ink-bottled materials
with pore necks dominated by mesopores connected to macro-
pores in the core of the material. The transport properties
appear clearly controlled by this pore family.
Conflict of interest
The authors declared that there is no conflict of interest.
Acknowledgments
The authors would like to acknowledge the French National
Radioactive Waste Management Agency, Andra for supporting this
work and contributing to the funding of this research and the
French Atomic Energy and Alternative Energies Commission at
Marcoule (DEED/SEAD/LCBC) for the help they have brought to
our research.
Appendix 1. Full details of the sequences of Table 6
See Table 10.

Table 10

mw/movd Crystallization/fusion 1st cooling sequence 1st heating sequence 2nd cooling sequence 2nd heating sequence Pf Pm
(g/g) specific enthalpy (20 °C ? 50 °C) (50 °C ? 0.5 °C) (0.5 °C ? 50 °C) (50 °C ? 20 °C)
(J/g) mc1
ice (g/g)
porosity (%) mh1
ice (g/g)
porosity (%) mc2
ice (g/g)
porosity (%) mh2
ice (g/g)
porosity (%) (%) (%)

1st sample 0.44 DhStd 0.30 34.6 0.21 24.9 0.23 27.2 0.31 35.7 78.7 69.6
DhFag 0.32 37.6 0.23 25.9 0.26 29.3 0.32 36.9 77.9 70.3
DhBru 0.40 46.5 0.25 29 0.31 35.4 0.35 40.3 76.1 72.1
DhIsi 0.32 37.6 0.23 25.9 0.26 29.3 0.32 36.9 77.9 70.2
DMat 0.36 41.8 0.23 27.3 0.28 32.2 0.33 38.4 76.9 71.1
2nd sample 0.45 DhStd 0.31 35.6 0.19 21.4 0.25 28.7 0.32 36.7 80.5 58.3
DhFag 0.34 38.7 0.19 22.4 0.27 30.8 0.33 37.9 79.7 59.1
DhBru 0.41 47.5 0.22 25.3 0.32 37.1 0.36 41.3 78.1 61.1
DhIsi 0.34 38.7 0.19 22.4 0.27 30.8 0.33 37.9 79.9 59.1
DhMat 0.37 42.8 0.21 23.7 0.29 33.8 0.34 39.5 78.8 60.1
 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865 863

Table 10 (continued)

mw/movd Crystallization/fusion 1st cooling sequence 1st heating sequence 2nd cooling sequence 2nd heating sequence Pf Pm
(g/g) specific enthalpy (20 °C ? 50 °C) (50 °C ? 0.5 °C) (0.5 °C ? 50 °C) (50 °C ? 20 °C)
(J/g) mc1
ice (g/g)
porosity (%) mh1
ice (g/g)
porosity (%) mc2
ice (g/g)
porosity (%) mh2
ice (g/g)
porosity (%) (%) (%)

3rd sample 0.46 DhStd 0.30 35.2 0.19 21.4 0.25 28.3 0.31 35.8 80.3 59.8
DhFag 0.33 38.4 0.20 22.5 0.26 30.5 0.32 37.0 79.2 60.8
DhBru 0.42 47.9 0.22 25.5 0.32 36.8 0.35 40.4 77.0 63.3
DhIsi 0.33 38.4 0.20 22.4 0.26 30.4 0.32 36.9 79.2 60.8
DhMat 0.38 42.9 0.21 23.9 0.29 33.5 0.33 38.5 78.0 62.0

Appendix 2. Full details of the sequences of Table 7

See Table 11.

Table 11

mw/movd Crystallization/fusion 1st cooling sequence 1st heating sequence 2nd cooling sequence 2nd heating sequence Pf Pm
(g/g) specific enthalpy (20 °C ? 50 °C) (50 °C ? 0.5 °C) (0.5 °C ? 50 °C) (50 °C ? 20 °C)
(J/g) mc1
ice (g/g)
porosity (%) mh1
ice (g/g)
porosity (%) mc2
ice (g/g)
porosity (%) mh2
ice (g/g)
porosity (%) (%) (%)

1st sample 0.37 DhStd 0.25 30.7 0.10 11.7 0.12 15.0 0.27 32.4 48.9 36.0
DhFag 0.26 32.3 0.10 11.7 0.13 15.3 0.27 32.5 47.2 36.2
DhBru 0.30 36.9 0.10 12.0 0.13 16.0 0.27 32.8 43.5 36.7
DhIsi 0.26 32.3 0.10 11.7 0.12 15.2 0.27 32.5 47.2 36.1
DMat 0.28 34.4 0.10 11.8 0.13 15.6 0.27 32.6 45.3 36.3
2nd sample 0.36 DhStd 0.23 29.2 0.08 9.5 0.11 13.5 0.25 30.6 46.1 31.0
DhFag 0.25 30.7 0.08 9.5 0.11 13.8 0.25 30.6 44.9 31.2
DhBru 0.28 34.9 0.08 9.8 0.12 14.7 0.25 30.9 42.0 31.8
DhIsi 0.25 30.6 0.08 9.5 0.11 13.8 0.25 30.6 44.9 31.1
DhMat 0.27 32.6 0.08 9.6 0.11 14.2 0.25 30.7 43.4 31.4

Appendix 3. Fig. 15 (Full details of Fig. 10)

Appendix 4. Fig. 16 (Full details of Fig. 11).
See Fig. 15.
See Fig. 16.

Fig. 16. Pore size distribution of GeoNa from thermoporometry, calculated from all
Fig. 15. Pore size distribution of GeoK from thermoporometry, calculated from all enthalpy values (a) from the 1st cooling sequence (b): from the 2nd cooling
enthalpy values: (a) from the 1st cooling sequence (b): from the 2nd cooling sequence. sequence.
864 Q.H. Nguyen et al. / Construction and Building Materials 191 (2018) 853–865

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