Ceramics International 48 (2022) 36917–36924

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effect of amorphous silica fume as active filler for rapid densification of the
geopolymer products formed by warm pressing
Kosuke Nishikawa a, *, Keitaro Yamaguchi a, Tomotaka Suzuki a, Shinobu Hashimoto a,
Sylvie Rossignol b
a
Department of Life Science and Applied Chemistry, Division of Advanced Ceramics, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, 466-8555, Japan
b
IRCER (Institut de Recherche sur les Céramiques), University of Limoges, 12, Rue Atlantis, 87100, Limoges, France

A R T I C L E I N F O A B S T R A C T

Keywords: Geopolymers are attracting attention in the field of concrete building materials from the viewpoint of reducing
Geopolymer CO2 emissions. This study demonstrates the effects of the addition of silica fume in the warm press method on the
Warm press densification and mechanical properties of a geopolymer. First, geopolymer products hardened by conventional
Silica fume
slurry curing, using fly-ash and sodium hydroxide solution as starting materials, were prepared. The hardened
Filler
geopolymer products were then pulverized into small grains. Subsequently, various amounts of silica fume were
Densification
mixed into the fine geopolymer particles to form the starting powder mixtures. A series of these mixtures (10
mass% water added) were placed into a steel mold, which was then inserted into a warm press device. An
uniaxial pressure of 240 MPa was applied at room temperature and then the temperature was raised from 80 to
180 ◦ C. When the warm press temperature was set at 80 ◦ C, the compressive strength of the hardened bodies
increased in line with the amount of added silica fume. Particularly, in the case of a hardened body with 30 wt%
silica fume, the compressive strength reached 195 MPa, which was about three times that of a hardened body
with 0 wt% silica fume. The added silica fume was found to improve the fine stacking of starting geopolymer
particles in the early stages of warm pressing and help form objects with tightly packed voids between the
original geopolymer particles. In contrast, for heat treatment at a warm press temperature of 180 ◦ C, the
compressive strength of the hardened bodies with 30 wt% silica fume decreased compared to those for the
hardened bodies with 0, 10 and 20 wt% silica fume. From the results of nuclear magnetic resonance analysis, this
decrease in strength was considered to be due to an increase in the silica-rich phase.

1. Introduction geopolymers in a short time. In this approach, a ceramic starting powder

As a global sustainable development goal, it is becoming increasingly
important to reduce carbon dioxide (CO2) emissions. In particular, the
cement industry is estimated to account for about 7% of total CO2
emissions in the world [1–3]. Therefore, geopolymer-based concrete
materials that utilize industrial waste such as fly ash without the need
for cement are attracting attention as building materials [2–9]. How­
ever, geopolymer starting slurries consisting of alkali solutions and
aluminosilicates, such as fly-ash discharged from coal-power plants, are
not readily hardened at room temperature in timescales of a couple of
days [8–17]. Curing at high temperature can shorten the curing time,
but it is known that the strength decreases due to the occurrence of
cracks [18]. To overcome this issue, a warm press method is being
studied as a means for producing crack-free, dense, high-strength
with a certain amount of a solvent such as water is placed into a steel
mold and then the mold is warm pressed at 200–300 MPa and
200–300 ◦ C until the water is vaporized from the gaps among the steel
mold parts [19–23]. Water and/or hydroxyl ions (OH− ) plays an
important role in the densification and compaction of the starting
powder during the warm pressing process. As a specific example of
utilizing hydroxyl ions for warm pressing, a dense geopolymer body
could be fabricated using a pulverized geopolymer containing hydroxyl
ions obtained by pulverizing a geopolymer that was cured by a con­
ventional method [19]. These warm press methods may be regarded as
being almost equivalent to cold sintering, which has been a subject of
recent discussion by the scientific community [24–38], and have been
published as a kind of cold sintering technique in a cold sintering review
paper [39].

* Corresponding author.
E-mail address: k.nishikawa.034@stn.nitech.ac.jp (K. Nishikawa).

https://doi.org/10.1016/j.ceramint.2022.08.258
Received 17 May 2022; Received in revised form 16 August 2022; Accepted 24 August 2022
Available online 31 August 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
K. Nishikawa et al.
Table 1
Chemical composition and description of glass phase of fly ash.
Fig. 1. Compressive strength and bulk density for hardened bodies for 0–30 wt
% SF and heat treatment up to 180 ◦ C for up to 40 min.
Fig. 2. Bulk density of hardened bodies with 0–30 wt% SF for different heating
times and temperatures.
Traditionally, amorphous silica is mixed with ordinary Portland
Cement products, given that it is possible to reduce the amount of water
added due to the ball bearing effect of the starting powder particles [40,
41]. For geopolymer products, amorphous silica has also been added as
an active filler material, and it increases the mechanical strength of the
final products [42–46]. It has been reported that geopolymerization
between amorphous silica and aluminum ions during processing leads to
the formation of strong interconnections between the starting particles,
resulting in an increase in the mechanical strength of the hardened body
[43]. Moreover, there is a further strengthening mechanism with the
addition of silica fume, namely, the amorphous silica fills the gaps be­
tween the geopolymer starting particles in such a way that the micro­
filler effect confers a more dense microstructure, leading to
strengthening of the hardened body [46]. However, to date, the effect of
amorphous silica on the densification and mechanical properties of
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Ceramics International 48 (2022) 36917–36924
Figure 3. Schematic of fine packing of geopolymer particles with co-existing SF
under uniaxial pressure.
geopolymer products fabricated by the warm press method has not been
reported in detail.
In this study, various amounts of amorphous silica were added to
ball-milled geopolymer powder fabricated by a conventional slurry
route for use as a starting powder mixture for the warm press method.
Fresh water was added to the starting powder mixture to accelerate the
reaction, and then the powder mixture was place in the warm press
device for heat treatment and simultaneous pressing. The changes in the
compressive strength and the dimensions were documented, and the
bulk density of the compacted hardened body with heat treatment up to
180 ◦ C was examined. The changes in compressive strength and bulk
density of the compacted hardened bodies as a function of the maximum
temperature were also investigated. Microstructural studies and
elemental analysis of the hardened body during warm pressing were
performed. Finally, to clarify the nature of the chemical bonding in the
hardened body, Fourier transform infra-red (FT-IR) spectroscopic anal­
ysis, mercury injection capillary pressure (MICP) measurements and 29Si
solid-state nuclear magnetic resonance spectroscopy (29Si-NMR) were
performed.
K. Nishikawa et al. Ceramics International 48 (2022) 36917–36924

Fig. 4. SEM images of hardened bodies with 0 and 20 wt% SF after warm pressing for 10, 20 and 40 min at maximum temperature of 180 ◦ C.

Fig. 5. FT-IR spectra of hardened bodies with 0 and 20 wt% SF for different heating times and temperatures.

2. Experimental procedures
2.1. Preparation of hardened bodies
The fly ash used was discharged from a power plant of the Chubu
Electric Power Co., Ltd (Japan). Details of the chemical composition and
the glass phase of the fly ash are shown in Table 1. Reagent grade sodium
hydroxide (Kishida Chemical Co., Ltd) was dissolved in distilled water to
give a concentration of 0.1 mol/L. As an amorphous silica phase, silica
fume SF98 (average diameter: 0.3 μm, purity: 98.5%, Al2O3: 0.2%,
Fe2O3: 0.2%, Na2O + K2O: 0.2%, H2O: 0.1%; manufactured by Shanghai
Topken Silica Fume Co., Ltd, China) was used. The loss on ignition of the
fly ash after heat treatment at 750 ◦ C for 1 h was 2.3 wt%.
First, the fly ash and the sodium hydroxide solution were mixed at a
ratio of 100:39 (mass%) to prepare a slurry. The slurry was transferred
to a plastic cup and cured at 80 ◦ C for 24 h in an electric oven without
lapping to form a hardened body. The hardened body was pulverized
manually using a mortar and pestle for a few minutes, and then the
particles were ball-milled in a wet ethanol media for 3 h. After drying the
wet-milled powder (110 ◦ C for 16 h), the powder was dry-milled for 6 h
with alumina balls to form fine particles with an average diameter of 6
μm. Subsequently, 0–30 wt% amorphous silica (silica fume, SF; average
diameter 0.3 μm) was mixed with the dry-milled powder to form fine
geopolymer particles that served as the starting powder mixtures. Each
of the starting powders (10 mass% distilled water added) was placed in a
steel mold, which was then inserted into a warm press device. The
uniaxial pressure during warm pressing was constant at 240 MPa. In
order to understand the initial behavior of the sample during warm
pressing, it was removed during the temperature rise to 180 ◦ C and the
characteristics of the hardened body after cooling to room temperature
were investigated. The rate of temperature rise was 9 ◦ C/min. The
removal times of the hardened body from the device were 5, 10, 20 and
40 min after the start of the temperature rise. Since in each case it took
20 min for the temperature to increase to 180 ◦ C, the time of 40 min
listed above means that the hardened body was removed 20 min after a
temperature of 180 ◦ C was reached. In order to understand the effect of
the warm pressing temperature, a test was also conducted in which this
temperature was changed to 25, 80, 120 and 180 ◦ C. The holding time at

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K. Nishikawa et al.
Fig. 6. FT-IR spectra of hardened bodies with 30 wt% SF after 5 and 40 min at
180 ◦ C; starting materials: geopolymer fine powder and SF.
Fig. 7. Compressive strength of hardened bodies with 0–30 wt% SF for heating
at 25–180 ◦ C for 40 min under uniaxial pressure of 240 MPa.
each temperature was 20 min. During the heating cycle and with
simultaneous application of a uniaxial pressing load, the change in the
height of the compacted powder inside the steel mold as a function of
time was recorded by measuring the width between the punches. From
the diameter of the steel mold, the bulk density of the hardened body
during warm pressing was calculated. After warm pressing, the hard­
ened bodies were removed from the mold and dried at 110 ◦ C for 12 h in
an electric oven. The water content of the hardened body immediately
after warm pressing was calculated using the weight difference before
and after the drying treatment. The final bulk density was calculated
based on the weight and dimensions of the cylindrical hardened body
(diameter 15 mm).
2.2. Evaluation of hardened bodies
The bulk density of the hardened bodies was calculated by measuring
the volume based on the outer dimensions and the weight of the body.
The compressive strength of the hardened body (cylindrical shape,
length 15 mm, diameter 15 mm) after warm pressing was examined
using a universal test machine (Instron 5582, Instron Corporation, USA).
The crosshead speed of the test machine with respect to the compressive
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Ceramics International 48 (2022) 36917–36924
Figure 8. MICP pore-size distribution for hardened bodies with 0 and 30 wt%
SF at 80, 120, and 180 ◦ C: (a) 0 wt% SF; (b) 30 wt% SF.
Figure 9. 29Si NMR spectra of hardened bodies with 0, 30 wt% SF before warm
pressing, and after warm pressing at 120 and 180 ◦ C.
strength was 0.5 mm/min. The number of test pieces required for the
compressive strength measurements was at least 3 for each experimental
condition, and the average value was used as a measure of the
compressive strength. To evaluate the geopolymerization of the hard­
ened bodies with amorphous silica added to the starting fine geopolymer
particles, FT-IR spectroscopy (JASCO FT/IR-4700, Japan) was con­
ducted. For sample preparation, KBr was mixed with the pulverized
hardened body and pressed to form sample discs. The microstructure of
the hardened body after cold sintering warm pressing was studied by
scanning electron microscopy (SEM; JSM-6010LA: JEOL, Japan) and the
element distribution was obtained using the attached energy dispersive
X-ray spectrometer. The pore-size distribution for some hardened bodies
was evaluated by MICP. The mercury porosimeter (Micromeritics 9620
AutoPore V, USA) can generate a maximum pressure of 414 MPa and can
evaluate a theoretical pore diameter of 0.003 μm. To analyze the fine
K. Nishikawa et al.
Figure 10. Schematic of effect of SF addition on warm pressing of geopolymer products.
local structure of the geopolymer, 29Si NMR spectra (JEOL RESO­
NANCE, ECA600II, Japan) of some hardened bodies after pulverization
were recorded at 3 kHz.
3. Results and discussion
3.1. Densification and compressive strength
The changes in the compressive strength and bulk density of the
hardened bodies (0–30 wt% SF) heated at a maximum temperature of
180 ◦ C for up to 40 min are shown in Fig. 1. The error bars represent the
maximum and minimum measured values. Thereafter, a uniaxial pres­
sure of 240 MPa was applied at room temperature. As can be seen, the
compressive strength increased with time. As shown in Fig. 2, after 10
min, the temperature of the steel mold reached 120 ◦ C. After 10 min, the
compressive strength tended to increase with increasing SF content. The
average compressive strength of the hardened bodies with 30 wt% SF
was 210 MPa, despite the average compressive strength without SF
being approximately 120 MPa. The bulk density also increased with
increasing SF content. In contrast, after 20 min at 180 ◦ C, the difference
in the compressive strength with and without SF was not so clear. In
addition, it was found that the amount of SF added did not have a large
effect on the compressive strength. The average compressive strength
was about 250–280 MPa.
After 40 min, the average compressive strength without SF increased
to approximately 350 MPa. The compressive strength gradually
decreased with increasing SF content up to 20 wt%. However, the
compressive strength with 30 wt% SF decreased remarkably to 210 MPa,
although the bulk density of samples did not show much difference for
samples with and without SF. The reason for the decrease in the
compressive strength will be discussed in section 3.4. In a previous study
[19], the strength of a hardened body formed by warm pressing was
about 120 MPa, whereas in this study, a value of 350 MPa was obtained
for a sample without SF. The reason for the discrepancy is that in the
previous study only hydroxyl ions (OH− ) in the ground geopolymer
served to provide the water content, whereas in this study a sufficient
amount of water (10 wt%) was added. The water content in the hard­
ened body after heat treatment for 40 min at 180 ◦ C was about 7%
without SF and about 5% with SF. This water content indicates that
water remains even after warm pressing. Thus, a sufficient amount of
water was found to increase the strength.
The changes in the bulk density of the hardened bodies for various SF
contents (0–30 wt%) as a function of time at a maximum temperature of
180 ◦ C are shown in Fig. 2. For the samples prepared with the addition of
SF, the bulk density was higher than that without SF for all conditions. In
particular, a large difference was observed in the bulk density imme­
diately after the start of the experiment. For example, for 20 and 30 wt%
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Ceramics International 48 (2022) 36917–36924
SF, when a uniaxial pressure of 240 MPa was applied, the bulk density
instantly increased. This behavior was thought to be caused by efficient
particle stacking due to the ball bearing effect of the SF [40]. Further,
the SF also functioned as a micro filler occupying the spaces between the
voids of adjacent geopolymer particles to form a denser body [43].
Consequently, after initial shrinkage, the bulk density increased as a
function of time, until complete shrinkage was achieved, with or
without SF addition. However, in the case of 30% SF, densification
stopped within 20 min. Therefore, the addition of SF had an important
effect on the fine filling of the geopolymer powder immediately after the
pressure was applied. A schematic of the fine packing of the geopolymer
particles together with the co-existence of the SF under uniaxial pressure
is presented in Fig. 3.
3.2. Microstructural evolution
SEM images of the fracture surface of hardened bodies with 0 and 20
wt% SF after warm pressing for 10, 20 and 40 min at a maximum
temperature of 180 ◦ C are presented in Fig. 4. For the unsintered sample
with 0 wt% SF just after application of a pressure of 240 MPa, the
compressive strength was not tested due to the low mechanical strength
of the prepared sample. However, after 10 min, the compressive strength
of the hardened bodies prepared with or without 20 wt% SF could be
evaluated. It was found that for 20 wt% SF, the fine geopolymer particles
started to merge with each other, and after 20 min at 180 ◦ C, a dense
microstructure was formed. Hence, the cross-sectional surface of this
sample was relatively flat, although individual particles were still
distinguishable for the case without SF addition. The hardened body
appeared to have undergone trans-granular fracture. In contrast, at 10
min, the hardened body without SF seemed to have undergone breakage
as a result of intergranular fracture among the grains, because fine
geopolymer particles could still be distinguished. Finally, after 40 min
under the maximum temperature of 180 ◦ C, the fracture surface of the
hardened body without SF was also flat and exhibited a dense micro­
structure. The microstructure of the hardened body with 20 wt% SF was
more dense.
The relationship between the bulk density and compressive strength
is next discussed. As seen in Fig. 1, after 40 min, the hardened body
without SF had a maximum compressive strength of 320 MPa. For 10
and 20 wt% SF, the compressive strength was 290 and 280 MPa,
respectively. Thus, the addition of SF caused a slight decrease in
compressive strength. In addition, although the microstructure for 30 wt
% SF was essentially the same as that for 20 wt% SF, as shown in Fig. 4,
the compressive strength of the former sample was only 220 MPa. The
reason for this will be discussed in section 3.4.
K. Nishikawa et al.
3.3. Spectroscopic analysis
In an attempt to clarify the reason for the decrease in compressive
strength of the hardened body with SF, despite an increase in the bulk
density, an FT-IR spectroscopic analysis was performed after warm
pressing. The changes in the FT-IR spectra for 0 and 20 wt% SF as a
function of time under the maximum treatment temperature of 180 ◦ C
are shown in Fig. 5. For 0 wt% SF, a broad peak centered at around 1000
cm− 1 is observed, which corresponds to vibrations of Si–O–Al, which is
thought to be the basic geopolymer structural unit. Moreover, it was
found that this basic structure did not change with treatment time
during warm pressing. In the case of 20 wt% SF, up to 10 min after the
start of the experiment, a peak at around 1100 cm− 1, corresponding to
vibrations of Si–O–Si in the SF was detected. However, this peak was
almost undetectable after 20 min, and only the broad peak at around
1000 cm− 1 corresponding to Si–O–Al vibrations was detected. Conse­
quently, it is considered that most of the SF was incorporated into the
elemental network chain of the geopolymer at this stage of heat treat­
ment. This reaction seemed to be accelerated by the warm pressing
process. However, the compressive strength in the case of 20 wt% SF
decreased slightly compared to that for 0 wt% SF, and the compressive
strength for 30 wt% SF decreased to 60% of that for 0 wt% SF after 40
min. To clarify the reason for the large decrease for the latter sample, a
FT-IR spectroscopic analysis was performed. FT-IR spectra of hardened
bodies with 30 wt% SF after heat treatment at 180 ◦ C for 5 and 40 min
are shown in Fig. 6. It is surmised that the SF was incorporated into the
local structure of the geopolymer after 40 min, given that the peak
around 1100 cm− 1 corresponding to the SF was not detected and there
was a shift of the broad peak at around 1000 cm− 1. These results suggest
that excessive incorporation of Si4+ into the geopolymer matrix lowers
the mechanical strength and/or toughness of the geopolymer itself. This
will be discussed again with the results of NMR in section 3.4 below.
3.4. Effect of silica fume on warm pressing of geopolymer powder
The relationship between the rapid densification and strengthening
of the geopolymer products with SF after warm pressing, in the context
of microstructural considerations, is next discussed. So far, only the in­
crease in the bulk density and compressive strength of the hardened
bodies of the geopolymer powder with SF for warm pressing at 180 ◦ C
has been discussed. However, the hardening and mechanical strength
for lower warm pressing temperatures has not been described. The
compressive strength of hardened bodies prepared with 0–30 wt% SF
following heating for 40 min at 25–180 ◦ C under a uniaxial pressure of
240 MPa is shown in Fig. 7. The error bars represent the maximum and
minimum values of the measurements. Up to 120 ◦ C, the compressive
strength increases with increasing heating temperature and SF content.
In particular, at 25 and 80 ◦ C, the compressive strength with 30 wt% SF
is 2.5–3 times that for 0 wt% SF. It is considered that this densification
and increase in compressive strength are due to fine packing of the
original geopolymer particles by the ball bearing effect arising from the
added SF, and from the microfiller effect whereby the gaps between the
geopolymer particles were filled with the SF. However, at 120 ◦ C,
although there is a slight increase in compressive strength with
increasing SF content, the difference is not significant compared to the
case without SF. In contrast, at a temperature of 180 ◦ C, the compressive
strength with 10 and 20 wt% SF decreases slightly compared to that
without SF. For 30 wt% SF, the compressive strength is dramatically
reduced compared to the case without SF.
The results of an MICP analysis of hardened bodies with 0 and 30 wt
% SF at 80, 120 and 180 ◦ C are presented in Fig. 8. At 80 ◦ C, the pore
diameter is slightly smaller for 30 wt% SF than for 0 wt% SF. The pore
diameter decreases as the temperature increases, but at 120 and 180 ◦ C,
the decrease in pore diameter tends to be suppressed for 30 wt% SF
compared to 0 wt% SF. In the early stage of warm pressing, the bearing
effect of SF promotes densification, but in the final stage, SF is
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Ceramics International 48 (2022) 36917–36924
considered to hinder densification. The reason for this behavior will be
considered based on the changes in the microstructure determined by
NMR analysis.
In order to analyze the microstructure of the geopolymer in the final
stage of warm pressing, 29Si-NMR analysis of the hardened bodies with
0 and 30 wt% SF hardened at 120 and 180 ◦ C are shown in Fig. 9. For
comparison, an NMR analysis of the starting material before warm
pressing with 0 and 30 wt% SF mixed into the pulverized geopolymer
was also performed. According to the literature [47], the peaks
appearing at − 87, − 92, − 96, − 103, − 108 and − 111 ppm are attributed
to Q4(4Al), Q4(3Al), Q4(2Al), Q4(1Al) and quartz, respectively. From the
NMR spectrum in Fig. 9, the sample with 30 wt% SF has more Si-rich
structures such as Q4(1Al), Q4(0Al), and quartz than the sample with
0 wt% SF. The increase in the quartz spectrum with increasing tem­
perature is considered to be due to the formation of quartz crystal nuclei
during warm pressing. As shown in Figs. 2 and 7, the compressive
strength of the hardened body warm pressed at 180 ◦ C for 40 min
decreased. This is considered to be due to the non-uniformity of the
structure resulting from the formation of quartz crystal nuclei by warm
pressing.
Fig. 10 shows a schematic illustration of the effect of SF addition on
densification of the geopolymer by warm pressing. In the initial stage of
warm pressing, the SF produced a ball-bearing effect, and together with
the microfiller effect, produced a matrix structure consisting of finely
packed geopolymer particles. In the intermediate stage (10 min from the
start of heating), the SF reverted to a fluid glass phase, leading to
additional close packing of the geopolymer particles. This caused the
formation of a densified body with a high compressive strength. In the
final stage (40 min from the start of heating), the glass phase of the SF
reacted with the original geopolymer particles to form new crystal
nuclei of quartz. In general, the mechanical properties of geopolymers
tend to improve as the Si/Al ratio increases [43]. On the other hand, it
has also been reported that when the silica content is increased too
much, the compressive strength drops sharply [48]. Consequently, the
addition of SF can provide high mechanical strength to the cured
product in the early stage of curing when the reaction between the SF
and the geopolymer has not progressed, but as this reaction progresses,
the formation of a silica-rich phase between the original geopolymer
particles can cause a decrease in strength.
4. Summary
The effect of amorphous SF on the density and compressive strength
of geopolymer hardened bodies during warm pressing was studied.
During the initial stage of warm pressing, the SF was considered to
behave like ball bearings, permitting fine stacking of the original geo­
polymer particles and acting as a microfilling agent that filled the voids
between adjacent geopolymer particles to form a dense body. In the
intermediate stage, the SF reverted to a glass phase and exhibited the
properties of a liquid before forming a dense body. The final product
following heating at 120 ◦ C was a hardened body with a high
compressive strength of 240 MPa. In contrast, after heat treatment at
180 ◦ C, the compressive strength of the hardened body decreased as the
SF content increased, despite the increase in density. The compressive
strength for 30 wt% SF was 40% lower than that for 0 wt% SF (350
MPa). This was due to the fact that the silica fume reacted with the
original geopolymer particles to form a novel silica-rich geopolymer
phase with poor mechanical properties.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
K. Nishikawa et al.
Acknowledgement
We would like to express our gratitude to Dr. Seizo Obata, Gifu
Prefectural Ceramics Research Institute, for providing the mercury
porosimeter in order to measure the pore-size distribution of the
geopolymer.
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