Construction and Building Materials 94 (2015) 2834

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Construction and Building Materials

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A study on pozzolanic reaction of y ash cement paste activated

by an injection of alkali solution
Phuong Trinh Bui, Yuko Ogawa, Kenichiro Nakarai, Kenji Kawai
Department of Civil and Environmental Engineering, Hiroshima University, 1-4-1, Kagamiyama, Higashi-Hiroshima, 739-8527 Japan

h i g h l i g h t s
 We investigate the pozzolanic reaction of y ash activated by alkali injection.
 Alkali injection increases the CH consumption by pozzolanic reaction.
 Alkali activation for 1 month decreases the volume fraction of 20330 nm pores.
 Alkali activation for 1 month increases the volume fraction of 320 nm pores.
 Alkali injection accelerates the pozzolanic reaction of the y ash cement paste.

a r t i c l e

i n f o

Article history:
Received 24 February 2015
Received in revised form 15 June 2015
Accepted 22 June 2015
Available online 1 July 2015
Keywords:
Alkali activation
Pozzolanic reaction
Fly ash cement paste
Ca(OH)2 content
Ca(OH)2 consumption
Porosity

a b s t r a c t
The purpose of this study is to investigate the pozzolanic reaction of the y ash cement paste by an injection of an alkali solution after hardening. Cement pastes with 0%, 20%, and 40% of y ash replacement
ratios were used. An NaOH or saturated Ca(OH)2 solution was injected into the paste through a syringe
1 month after casting at normal temperature. In addition to the reduction of the Ca(OH)2 content, the
consumptions of Ca(OH)2 in the paste with 40% replacement of y ash activated by NaOH and Ca(OH)2
solution were observed to be 2.6 and 4.5 times as large as that with 20% replacement of y ash. It indicates the alkali solution accelerates the pozzolanic reaction, together with the promotion of cement
hydration. The results of pore structure analysis also conrmed this activation. As a result, it can be
concluded that the 1-month alkali solution injection was effective in accelerating the pozzolanic reaction
of the cement paste with 40% replacement of y ash.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Fly ash concrete has been applied extensively in the building
construction because of taking the advantage of the enhanced
durability, cost saving, and environmental protection [1,2].
However, it was reported that the early age strength of the y
ash concrete is one of its disadvantages due to the high replacement of cement with y ash [3]. In addition, the slow pozzolanic
reaction of y ash is considered as one of factors which result in
the low early age strength of the y ash concrete [36].
Many researchers have focused on investigating the mechanism
of the pozzolanic reaction and exploring the reasons of this slow
reaction [711]. It is known that the pozzolanic reaction of the
y ash cement paste is the chemical reaction between reactive
Corresponding author.
E-mail addresses: d123252@hiroshima-u.ac.jp (P.T. Bui), ogaway@hiroshima-u.
ac.jp (Y. Ogawa), nakarai@hiroshima-u.ac.jp (K. Nakarai), kkawai@hiroshima-u.ac.jp
(K. Kawai).
http://dx.doi.org/10.1016/j.conbuildmat.2015.06.046
0950-0618/ 2015 Elsevier Ltd. All rights reserved.

silica or alumina in the y ash particles and calcium hydroxide

(Ca(OH)2CH) formed from cement hydration in the presence of
water at normal temperature [7]. Therefore, the cross-linked
silica-tetrahedra (or cross-linked alumina-tetrahedra) in y ash
have to be broken so that the silica or alumina become reactive
[9,10]. It was found that the disruption of these links occurs at a
pH of 12.5 of pore solution in the paste at the room temperature
[9] and more than 13 at 20 C in NaOH solution [10]. This results
in considering the addition of an alkali solution in order to increase
the alkalinity of pore solution in the y ash cement paste which
owns the less alkalinity [10].
Hence, many methods of alkali activation have been investigated for accelerating the pozzolanic reaction of the y ash cement
paste [1115]. However, this alkali activation in almost of these
researches has been mainly carried out by adding an alkali solution
or mixture of many alkali solutions in the water mixing of the y
ash cement paste which is cured at high temperature.
The aim of this paper is to investigate an inuence of activation
on the pozzolanic reaction of the y ash cement paste at normal

P.T. Bui et al. / Construction and Building Materials 94 (2015) 2834

temperature by an injection of an alkali solution 1 month after

casting through a syringe. In order to evaluate this inuence, a
quantitative analysis of the Ca(OH)2 content and porosity of the
y ash cement paste was carried out by thermal gravimetric analysis and mercury intrusion porosimetry.
2. Experiments

29

temperature increase of TGA equipment was installed at

20 C/min up to 100 C and kept at 100 C for 30 min to remove
evaporable water completely, and then at 20 C/min up to
1000 C. The CH content was calculated based on the ignited mass
of the sample and the mass loss due to the dehydration of calcium
hydroxide. This mass loss was picked up from differential thermal
gravimetric (DTG) curves between the initial and nal temperatures of the corresponding DTG peaks [16].

2.1. Materials
2.5. Measurement of porosity
The cementitious materials selected in this study were
high-early-strength Portland cement, and low calcium y ash
which met the standard values of type II per JIS A 6201 (y ash
for concrete). The chemical composition and physical properties
of these materials are shown in Table 1.
2.2. Preparation of paste specimens
Fly ash was used to replace high-early-strength Portland
cement at ratios of 0%, 20% and 40% by mass (hereafter, abbreviated as FA0, FA20, and FA40, respectively). A water to binder ratio
of 0.30 was kept constant. The pastes were mixed in a mechanical
mixer and cast in 40 mm cube molds, and then sealed by
aluminum tape to prevent water loss as well as carbonation.
After that, a syringe with a capacity of 1 ml, of which the plunger
was disconnected, was inserted in the specimen center (as shown
in Fig. 1). All specimens were demolded 24 h after casting and
cured in sealed condition at 20 C.
2.3. Activation method
An activation was conducted by supplying an alkali solution
1 month after casting through a syringe, which was prepared in
the Section 2.2. Two alkali activators, which were an NaOH solution (pH = 13.0) and a saturated Ca(OH)2 solution (pH = 12.6), were
injected naturally through the permeability of the pastes by themselves. Additionally, water was also injected instead of an alkali
solution for the comparison.
2.4. Measurement of CH content
The CH content of the pastes at the age of 2 months was determined by thermal gravimetry analysis (TGA), using the half samples as shown in Fig. 1. The CH content of the sample was tested
by each 4 mm-section from the surface to the point of the needle
(as shown in Fig. 1). These samples were obtained in the form of
a powder by a driller. Then, they were soaked in ethanol for 24 h
to stop the further hydration, and dried in a vacuum desiccator
for 24 h before measuring the CH content. The rate of the

Table 1
Chemical composition and physical properties of cementitious materials.
Chemical composition and physical
properties

Cement

Low calcium y
ash

SiO2 (%)
Fe2O3 (%)
Al2O3 (%)
CaO (%)
MgO (%)
SO3 (%)
Na2O (%)
K2O (%)
Loss on ignition (%)
Density (g/cm3)
Blaine specic surface area (cm2/g)

20.30
2.71
4.96
65.49
1.21
2.98
0.22
0.35
1.19
3.14
4590

57.7
5.43
27.54
1.26
1.06
0.36
0.44
0.76
2.8
2.21
3290

The porosity of the pastes at the age of 2 months was measured

by mercury intrusion porosimeter (MIP). The samples for test ranging 2.55 mm in size were obtained by crushing and choosing the
area, which was around the position of the needle for the injection
(as shown in Fig. 1). After that, these samples were soaked in ethanol for 24 h to stop the further hydration and dried in a vacuum
desiccator for 24 h before MIP measurement. The MIP is built on
the mercury intruded into the cylindrical pores under the strictly
controlled pressure. The diameter of the cylindrical pore into
which the mercury has been intruded is calculated according to
the following Washburn equation [17].

D 4c cos h=P

where D: the diameter of pores (lm), c: the surface tension of mercury (assuming a value of 480 mN/m), h: the contact angle of mercury on the paste (taken as 140), P: the pressure at which mercury
is intruded into the pore (mN/m2).
The MIP equipment used in this study has the maximum pressure of 414  106 N/m2. The porosity of the pastes at the age of
2 months was measured at a diameter range of 3 nm300 lm.
3. Results and discussions
3.1. Effect of y ash
3.1.1. CH content
The CH content of the control samples, which were the samples
without the injection of water or alkali solution, at each
4 mm-section of the samples is shown in Fig. 2. It can be seen that
the higher the replacement ratio of cement with y ash, the less
the CH content. This can be attributed to the high cement replacement with y ash [3] and the consumption of CH by the pozzolanic
reaction [6].
The consumption of CH by the pozzolanic reaction was calculated according to the following equation [18]:

CHcons: CHPC c=c f  CHFC ;

where CHcons. is the consumption of CH by the pozzolanic reaction

(%), CHPC is the CH content in the plain cement paste FA0 (%), CHFC
is the CH content in the y ash cement paste FA20 or FA40 (%),
(c/(c + f)) is the mass ratio of cement in the mixture of cement
and y ash.
The consumption of CH by the pozzolanic reaction at each
4 mm-section of the samples is shown in Fig. 3 left. It shows the
consumption of CH was increased signicantly with the increase
in the y ash content (40% replacement of y ash). This phenomenon was considered to be the result of the large quantity of
y ash used to replace the cement, resulting in the consumption
of CH by the pozzolanic reaction. Comparing the consumption of
CH between FA20 and FA40, the normalization is also shown in
Fig. 3 right. It can be seen that the consumption of CH for FA40,
which had 2 times as high the y ash content as FA20, was less
than 2 times of that for FA20. This may be due to the fact that
the smaller Ca(OH)2 content in FA40 than that in FA20 (as shown

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P.T. Bui et al. / Construction and Building Materials 94 (2015) 2834

Fig. 1. Activation method and preparation of the samples for analyzing the Ca(OH)2 content.

Fig. 2. The CH content of the control samples (FA0, FA20, and FA40) at each 4 mmsection of the samples at the age of 2 months.

in Fig. 2) is attributed to the pozzolanic reaction of y ash partially.

It also results in a lot of unreacted y ash particles in FA40 remaining, and playing mainly as the space ller at the age of 2 months
[5,6]. Therefore, the injection of the alkali solution at the early
age would be effective in accelerating the pozzolanic reaction of
the y ash cement paste.
3.1.2. Porosity
The total pore volumes and the volumes of pores ranging 20
330 nm and 320 nm in diameter of the control samples are shown
in Fig. 4. It is known that the porosity of the y ash cement paste is
coarser at the early ages than that of the cement paste [10]. Similar

Fig. 4. The porosity of the control samples (FA0, FA20, and FA40) at the age of
2 months.

tendency was also observed in the case of FA40. However, the total
pore volume of FA20 was smaller than that of FA0. It can be
explained by the fact that the use of 20% replacement of y ash
at the same water to binder ratio increased the water to cement
ratio; resulting in promoting the hydration extent of cement and
y ash which forms more hydration products lling up the pores
of the paste [5,13]. Furthermore, the decreasing and increasing tendency of the volume ratio of pores ranging 20330 nm and 3
20 nm in diameter relative to the total pores respectively are also
reported when the pozzolanic reaction of y ash occurs [19].
These tendencies are also observed in the cases of FA20 and
FA40 when compared with FA0.

Fig. 3. The consumption of CH by pozzolanic reaction (left) and its normalization (right) of the control samples at each 4 mm-section of the samples at the age of 2 months.

P.T. Bui et al. / Construction and Building Materials 94 (2015) 2834

31

3.2. Effect of water injection

Fig. 5. The CH content of the control and 1-month-water-injected samples without

y ash FA0 at each 4 mm-section of the samples at the age of 2 months.

Fig. 6. The CH content of the control and 1-month-water-injected samples with

20% replacement of y ash FA20 (top) and 40% replacement of y ash FA40
(bottom) at each 4 mm-section of the samples at the age of 2 months.

3.2.1. CH content
The CH contents of the pastes, into which water were injected
1 month after casting, and their comparisons with the control samples at each 4 mm-section of the samples are shown in Figs. 5 and
6. In general, it can be found that the injection of water increased
the CH content in some positions of the samples. It is evident that
the water injection promoted the cement hydration of the paste
with and without the y ash replacement.
The consumption of CH by the pozzolanic reaction of the
water-injected samples at the point of the needle was only considered for the comparison with that of the control sample. It was also
calculated according to the Eq. (2). The consumption of CH by the
pozzolanic reaction of the control and water-injected samples at
this position is shown in Fig. 7 left. In the case of the
water-injected sample with 20% replacement of y ash, the consumption of CH was smaller than that of the control sample. This
may be explained by the fact that water promoted the cement
hydration more in FA20. This is also compatible with the larger
CH content of the water-injected sample with 20% replacement
of y ash than that of the control sample (Fig. 6 top). Thus, these
additional hydration products covered the surfaces of the y ash
particles with more extent, resulting in the postpone of the pozzolanic reaction of y ash particles in FA20 [20].
In the case of the water-injected sample with 40% replacement
of y ash, the consumption of CH for the water injection was larger
than that for the control sample. It indicates the pozzolanic reaction of FA40 was accelerated by the addition of water.
Comparing the consumption of CH between FA20 and FA40, the
normalization is also shown in Fig. 7 right. It can be found that
the consumption of CH for FA40, which had 2 times as high the
y ash content as FA20, was 1.9 times as much as that for FA20
in the case of the water injection, and were more than that of
the control sample. It indicates the water injection was effective
in accelerating the pozzolanic reaction in the case of FA40.
3.2.2. Porosity
The total pore volumes and the volumes of pores ranging 20
330 nm and 320 nm in diameter of the 1-month-water-injected
samples and their comparison with the control samples are shown
in Fig. 8. The total pore volume of the 1-month-water-injected
samples was smaller than that of the control samples in the cases
of FA0 and FA40, except for FA20. It indicates the water injection
was effective in improving the porosity of the paste by promoting
the cement hydration more.
In the case of FA20 into which water was injected, the less
decreasing and increasing tendencies of the volume ratio of pores

Fig. 7. The consumption of CH by pozzolanic reaction (left) and its normalization (right) of the control samples and 1-month-water-injected samples at the point of the
needle at the age of 2 months.

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P.T. Bui et al. / Construction and Building Materials 94 (2015) 2834

Fig. 8. The porosity of the control and 1-month-water-injected samples at the age of 2 months.

Fig. 9. The CH content of the control and 1-month-NaOH-activated samples (top)

and -saturated-Ca(OH)2-activated samples (bottom) without y ash FA0 at each
4 mm-section of the samples at the age of 2 months.

ranging 20330 nm and 320 nm respectively than that in the control sample also conrms the delay of the pozzolanic reaction.
Therefore, the total pore volume of the water-injected sample
was larger than that of the control sample.
3.3. Effect of alkali activation
3.3.1. CH content
The CH contents of the plain cement pastes into which the alkaline solutions were injected 1 month after casting and their comparisons with the control samples are shown in Fig. 9. It can be

Fig. 10. The CH content of the control and 1-month-NaOH-activated samples (top)
and -saturated-Ca(OH)2-activated samples (bottom) with 20% replacement of y
ash FA20 at each 4 mm-section of the samples at the age of 2 months.

said that the presence of NaOH solution (pH = 13.0) or saturated

Ca(OH)2 solution (pH = 12.6) caused the CH content to decrease
slightly 1 month after the injection. It indicates the alkali solution
injection for the sample without y ash played a negative role
toward the production of CH. This may be explained by the fact
that it was difcult for the cement paste to release Ca2+ ion to
the outside due to the high alkali concentration of pore solution
supplied from the injected alkali solution, resulting in limiting
the production of CH in the case of the plain cement paste. Thus,
the CH content of the activated samples was smaller than that of
control samples.

P.T. Bui et al. / Construction and Building Materials 94 (2015) 2834

33

alkali-activated sample was smaller than that for the control

sample, whereas in the case of FA40, it was larger. This tendency
was similar to that in the case of the water-injected sample as
shown in Section 3.2.1.
In the case where the alkali solution was injected into FA40,
however, the consumption of CH for the NaOH activation was
slightly smaller than that for control sample. Comparing the consumption of CH between FA20 and FA40, the normalization is also
shown in Fig. 12 right. It can be found that the consumption of CH
for FA40, which had 2 times as high the y ash content as FA20,
was 2.6 and 4.5 times as much as that for FA20 in the case of the
NaOH activation and saturated Ca(OH)2 activation respectively,
and these consumptions were more than that of the control sample
and water-injected sample with the values of 1.6 and 1.9 times
respectively (as shown in Fig. 7 right). It indicates the alkali activation was more effective in accelerating the pozzolanic reaction
than the water injection in the case of FA40.

Fig. 11. The CH content of the control and 1-month-NaOH-activated samples (top)
and -saturated-Ca(OH)2-activated samples (bottom) with 40% replacement of y
ash FA40 at each 4 mm-section of the samples at the age of 2 months.

The CH contents of the y ash cement pastes into which the

alkaline solutions were injected 1 month after casting and their
comparisons with the control samples are shown in Figs. 10 and
11. It is noticed that the CH contents of the activated samples were
larger than that of the control samples in both of FA20 and FA40. In
the case of FA40, however, the CH content of the NaOH-activated
sample was approximately equal to and that of the
saturated-Ca(OH)2-activated sample was smaller than that of the
control sample at the point of the needle (as shown in Fig. 11). It
indicates that the alkali solutions were actually effective on the
acceleration of the pozzolanic reaction after the activation for
1 month in FA40.
Similar to the water injection, the consumption of CH of the
alkali-activated samples at the point of the needle was also considered for the comparison with that of the control sample. It was also
calculated according to the Eq. (2). The consumption of CH of the
control and alkali-activated samples at this position is shown in
Fig. 12 left. In the case of FA20, the consumption of CH for the

3.3.2. Porosity
The total pore volumes and the volumes of pores ranging
20330 nm and 320 nm in diameter of the saturated-Ca
(OH)2-activated samples and their comparison with the control
samples are shown in Fig. 13. In the case of FA0, the total pore
volume of the saturated-Ca(OH)2-activated samples was smaller
than that of control samples because the cement hydration was
promoted by water supplied from the alkali solution. In the
cases of FA20 and FA40, the total pore volume of the
saturated-Ca(OH)2-activated samples was almost the same as that
of the control samples. Compared with the control sample, however, the decreasing and increasing tendency of the volume ratio
of pores ranging 20330 nm and 320 nm in diameter relative to
the total pores respectively were observed in the case of FA40 into
which the saturated Ca(OH)2 solution was injected. It demonstrates that the saturated Ca(OH)2 activation was effective in accelerating the pozzolanic reaction in FA40. This is also compatible
with the decrease of the CH content in the case of the
saturated-Ca(OH)2-activated paste with 40% replacement of y
ash at the point of the needle (as shown in Fig. 11 bottom).
4. Conclusions
An activation by the injection of an alkali solution was investigated on the y ash cement paste 1 month after casting at normal
temperature. In addition, water was injected into the paste instead
of an alkali solution for the reference. A quantitative analysis of the
Ca(OH)2 content and porosity were examined in order to evaluate
its effect on the pozzolanic reaction of y ash. The following conclusions can be drawn:

Fig. 12. The consumption of CH by pozzolanic reaction (left) and its normalization (right) of the control samples and 1-month-alkali-activated samples at the point of the
needle at the age of 2 months.

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P.T. Bui et al. / Construction and Building Materials 94 (2015) 2834

Fig. 13. The porosity of the control and 1-month-saturated-Ca(OH)2-activated samples at the age of 2 months.

1. The 1-month water injection was effective in promoting the

cement hydration of the paste with or without y ash.
2. The 1-month water or alkali injection improved the porosity of
the plain cement paste by promoting the cement hydration,
resulting in reducing the total pore volume.
3. In the case of the cement paste without y ash, the presence of
NaOH or Ca(OH)2 solution caused the Ca(OH)2 content in the
cement paste to decrease slightly. It indicates the negative role
of the alkali injection for the production of Ca(OH)2 at the early
age.
4. In the case of the cement paste with 40% replacement of y ash,
the 1-month alkali activation not only decreased the Ca(OH)2
content but also increased the consumption of Ca(OH)2 by the
pozzolanic reaction. In addition, the volume ratio of pores ranging 20330 nm in diameter relative to the total pores of the
paste was decreased, while the volume ratio of pores ranging
320 nm in diameter relative to the total pores of the paste
was increased. It demonstrates that the 1-month alkali solution
injection was effective in accelerating the pozzolanic reaction of
the high volume y ash cement paste.

Acknowledgement
The authors would like to thank Mr. Yuhei Ito, a master student,
for his help in carrying out some of the experiments.
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