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Yuyun Tajunnisa Masaaki Sugimoto Tetsuya Sato Januarti Jaya Mitsuhiro Shigeishi
Graduate School of Dept. of Civil and Technical Ekaputri Graduate School of
Science and Environmental Division, Faculty Dept. of Civil Science and
Technology, Engineering, of Engineering, Engineering, Technology,
Kumamoto Kumamoto Kumamoto Institut Kumamoto
University, University, University, Teknologi University,
Kurokami 2-39-1, Kurokami 2-39-1, Kurokami 2-39-1, Sepuluh Kurokami 2-39-1,
Chuo-ku, Chuo-ku, Chuo-ku, Nopember, Chuo-ku,
Kumamoto 860- Kumamoto 860- Kumamoto, Surabaya, Kumamoto 860-
8555, Japan. 8555, Japan. Japan. Indonesia. 8555, Japan.

KEYWORDS: Fly ash, microstructure, geopolymer, morphology, characterization.

Fly ash is a hazardous waste generated by coal combustion. Various factors influence the characteristics
of ash. This paper presents effects of ash properties on the setting time and compressive strength of ash-
based geopolymer. Samples of ash were collected from two coal-powered facilities, an Indonesian
fertilizer plant and a Japanese power plant. Both ash samples were classified as low calcium fly ash
(ASTM Class F or JIS Type II). The geopolymer consolidated using the Indonesian ash with Si/Al ratios
of 1.5, 2 and 2.5 required respectively around 1.5, 1 and 2 days for setting time at 27 °C, while the
Japanese under identical Si/Al ratios required respectively 4.5, 4, and 7 days. Experiments with activator
ratios of 1.5 and 2.5 resulted in setting time for the Indonesian sample of 12.9 and 7.3h, against that for
the Japanese of 23 and 27 h. High strength of 57.5 MPa was produced by the Indonesian sample with an
activator ratio of 1.5 compared to a strength of 50.9 MPa produced by the Japanese sample with an
activator ratio of 2.5. Several micro analyses were conducted using SEM, XRD, XRF, EPMA, and by
reactivity. This study found that factors affecting from ash include reactivity, morphology, lime content;
and from mixtures, Si/Al ratio, NaOH molarity, and ash to activators ratio.

Geopolymer-based materials are environmentally friendly paste as they provide building materials from
waste rich in Si and Al; as such, their utilization contributes to a sustainable future. Moreover, these paste
offer superior performance compared to that of ordinary Portland cement paste including their high
resistance to deleterious chemical agents, high strength values, and impressive durability. Geopolymer-
based materials are also suitable for application in noise abatement, toxicity immobilization, and fire and
thermal resistance [1−2]

Due to its SiO2 and Al2O3 content encourages fly ash use as a material source for geopolymer cement,
particularly because geopolymer technology is based on alkaline activation of materials containing mostly
Si and Al in amorphous form [3]. The geopolymerization implicates a chemical reaction between
alkaline and Si-Al minerals which then form three-dimensional polymeric structures consisting of Si-O-
Al-O bonds [4]

According Hardjito’s paper [5], aspects both from internal factors - physical and chemical composition -
and from external - material composition, initial and curing temperature and mixture volume - effect
setting time of geopolymer paste. Other aspects such as low CaO content may prolong setting time.
However, high ash CaO content enables high compressive strength [6] due to polymerization and
hydration reactions [7]. Hardjito also showed [8] that low-calcium fly ash-based geopolymers have a
setting time of about 2 hours.

Fly ash, a base material of geopolymer [7,9−10], is a heterogeneous waste of coal combustion [11] whose
composition varies depending on coal and boiler types, operation conditions, post-combustion
parameters, and power plant technologies [12]. ASTM classifies fly ash into two classes based on
chemical content: class F and C. Class F (low calcium) ash contains less than 10 percent lime but a large
amount of silica, alumina and iron (more than 70 percent). Conversely, class C fly ash generally contains
greater than 10 percent lime [13].

Fly ash is comprised of most amorphous (glass) rather than crystalline elements. Characterization of ash
as amorphous material has been complicated [14]. Several parameters which have not been distinguished,
both favor and hinder geopolymerization. High amorphous content is expected to enhance compressive
strength of paste. Conversely, some disruptions impede reaction, such as high Fe2O3 content, which
occurs in such crystalline minerals as magnetite and hematite, sulphides, and unburned carbon [15].

Most coal minerals are classified as alumino-silicates, carbonates, sulphides, and silica [16]. Some
minerals may alter during combustion, while others such as quartz do not [17]. Wide variation in mineral
proportions [18] requires characterization of fly ash [19]. Thus, several micro-analysis methods were used
here to investigate the ash [3,6,20]: scanning electron microscopy (SEM), X-ray Diffraction (XRD), and
X-ray Fluorescense (XRF).

X-ray analyses have shown that major crystalline elements in fly ash are quartz (SiO 2), mullite
(3Al2O3.2SiO2), hematite (Fe2O3), magnetite (Fe3O4), lime (CaO), and gypsum (CaSO4.2H2O) [21].
Crystalline quartz amount is dependent on cooling rates [22]. Quartz and iron mineral proportions are
related to the various mineral quantities in the coal. Moreover, glass fraction composition, indicated by a
hump in XRD patterns [17], also varies by ash property [18]. Microstructural observations using SEM fit
well with phase transformations investigated by XRD [23].Ash can be assessed using SEM techniques [3]
but are limited to morphology [24] and ash surface composition [19]. The morphology of a particle of ash
depends on coal mineral matter, combustion conditions and post-combustion cooling [12].

Ash properties thus clearly influence geopolymer properties [9,25]. Several studies have investigated ash
reactivity [6,26], conducted according to ASTM C 311 [27] to determine ash activity [28]. The purpose of
this study is to investigate mechanical properties - setting time and compressive strength - of class F/ type
II/ low calcium-fly ash-based geopolymer paste and to conduct micro analyses through scanning electron
microscopy (SEM), X-ray Diffraction (XRD), X-ray Fluorescense (XRF), Electron Probe Micro-Analysis
(EPMA), and by reactivity assessment.


The Indonesian and Japanese ash used in this study are classified as type II according to the Japanese
Industrial Standard (JIS) [29], equivalent to class F based on the American standard (ASTM) [13]. The
type of activators used for geopolymerization were alkaline activators consisting of sodium hydroxide
(NaOH) and sodium silicate (Na2SiO3). NaOH was in pellet form with minimum purity of 98%. One day
before paste mixing, NaOH solution was prepared by mixing sodium hydroxide pellets and distilled water
with a specific concentration. Na2SiO3 consisted of maximum 0.02% Fe, 17-19% Na2O, 35-38% SiO2 and
46% H2O. The activators were from Kanto chemical Co., Inc., Tokyo, Japan.
Mix Design
Mix design for paste setting time test. Three experiments consisting of several paste compositions were
conducted to investigate setting times of low-calcium fly ash-based geopolymer. They are described as

1. The 1st setting time experiment varied activator ratio. Indonesian and Japanese fly ash: fly ash to
activator ratio: 65: 35; NaOH solution molarity: 8 M; variation of alkaline activator (Na2SiO3/ NaOH
solution) ratio for Indonesian ash: 1.5, 2, 2.5 and for Japanese: 1.5, 2.5.
2. The 2nd setting time experiment varied ash to activator ratio. Japanese and Indonesian fly ash: fly ash
to activator ratio: 1.86, 1.5, 1.22; NaOH solution molarity: 8 M; activator (Na2SiO3/ NaOH solution)
ratio: 1.5.
3. The 3rd setting time experiment varied Si/Al ratio in mixtures. Japanese and Indonesian fly ash: Si/Al
ratio in mixtures: 1.5, 2 and 2.5. These mixtures were determined by varying Si/Al ratio. As [30]
notes, the atomic ratio Si/Al in the structure of polysialate establishes the application; however, a low
ratio of Si/Al (1, 2, 3) commences a 3D-Network which is very rigid. In this experiment, each fly ash
sample was composed of 3 variations of chemical compounds. The paste compositions based on
molar ratios are shown in Table 1.

Table 1. Molar ratio of paste mix proportion in the 3rd setting time experiment
Fly ash Mix. Si/Al Na2O/SiO2 Na2O/Al2O3 H2O/SiO2 H2O/Na2O Water/solid
Indonesian 1 1.5 0.3 0.9 3.0 10.6 0.31
Indonesian 2 2 0.3 1.3 2.8 9 0.35
Indonesian 3 2.5 0.38 1.9 3.5 9 0.45
Japanese 1 1.5 0.3 0.9 3.0 9.6 0.36
Japanese 2 2 0.3 1.3 3.0 9.6 0.38
Japanese 3 2.5 0.3 1.5 2.9 9.2 0.39

Mix design for paste compressive strength test. The experiment utilized the following compositions for
cylindrical specimens of 50 mm in diameter and 100 mm in height. Both Indonesian and Japanese fly ash
types were used with ratio of fly ash to activators of 65:35; molarity of NaOH solution, 8 M; and activator
ratios, 1.5 and 2.5. Compressive strength was measured at 3, 7, 14, 21 and 28 days.

Mix design for reactivity test of fly ash. The specimens were all mortars as specified by ASTM C 311
[27]. Three cylinder specimens of 50 mm in diameter and 100 mm in height were prepared for each
mixture, with proportion of hydrated lime Ca(OH)2 of 4%, fly ash or OPC 24%, and sand 72%. All
materials were in saturated dry condition.


Mixing and setting time of paste test.
NaOH pellets were dissolved with distilled water to make 1 liter of NaOH solution with 8 molar
concentration 24 hours prior to mixing. An activator consisting of Na2SiO3 gel and the NaOH solution
was then mixed. This activator mixing produced heat, requiring a wait for the temperature to drop to
around 27° C. Fly ash was then added and mixed. The paste was cast into molds, covered with plastic,
and stored at room temperature of 27˚C. The setting time test was conducted by measuring the penetration
of a needle into the paste according to [31]. As a standard, resistance of paste to penetration by standard
needles are measured at regular time intervals. Times of initial and final setting are determined from plots
of penetration versus elapsed time. Initial setting times are reached when the penetration shows 25 mm,
and final when penetration shows 0 mm.

Compressive strength paste test.

After mixing, the paste was cast to a cylinder of 50×100mm. Plastic sheet was wrapped to avoid
evaporation. Curing and demolding were conducted at a temperature of 27°C until completion of one of
the five paste aging durations: 3, 7, 14, 21 and 28 days.

Reactivity Test of Fly Ash

Mortar specimens were mixed and cured by steam curing machine at 38 ± 2˚ C for 7 days, then
submerged in water for 4 hours, dried for 1 hour, and subjected to the compressive strength test based on


X-Ray Fluorescense (XRF)
XRF was employed to trace elements in fly ash. As shown in Table 2, similarities in chemical compounds
can be recognized in both Japanese and Indonesian ash. For both ash types, the compound cumulative of
SiO2, Fe2O3 and Al2O3 exceeded 70% with CaO less than 10%, thus classifying the ash as class F
according to [13]. Fly ash for JIS type II classification [29] requires SiO2 percentage exceeding 45; XRF
results indicated SiO2 percentage of 55.19% in Japanese and 48.47% in Indonesian fly ash. Therefore,
both ash types were assumed to have similarity in reactivity, setting time, or compressive strength.
Chemical compositions of each ash precursor are listed in Table 2. From XRF, percentage of disruptor
species such as Fe2O3 in the Indonesia ash was higher than that of the Japanese. Contrarily, S content
existed in the Japanese. Both Fe2O3 and S may inhibit geopolymerization [15].

Table 2. XRF Test Results of the fly ash

SiO2 +
Oxide (%) Al2O3 SiO2 a S K2O CaO b TiO2 Fe2O3 Na2O K2O MgO Mn2O3 Al2O3 +
Fe2O3 c
Japanese 25.35 55.19 0.98 1.09 4.06 1.98 7.57 - - - - 88.11
Indonesian 26.05 48.47 - 1.66 5.18 0.92 12.54 0.47 1.66 2.77 0.19 87.06
As JIS A6201-2008, type II/ class F of fly ash contains SiO2 ≥ 45 %; b, c as ASTM C618, class F of fly ash contains CaO ≤ 10
% and total of SiO2+Al2O3+Fe2O3 ≥ 70%

X-Ray Diffraction (XRD)

XRD tests were conducted to identify crystalline material in the ash. XRD patterns for both ash types are
shown in Fig. 1. Results reveal that a large part of the ash was amorphous, consistent with the study in
[20]. However, results also showed that both ash types contained small parts of crystalline phase, i.e.,
quartz (SiO2), hematite (Fe2O3), and mullite (3Al2O3.2SiO2). In addition, the Indonesian also contained
srebrodolskite (Ca2Fe2O5), magnetite (Fe3O4), anhydrite (CaSO4) and lime (CaO). The Japanese ash
diffraction pattern shows a background hump at 2θ of 18 to 27 degree, while the Indonesian lacked such a
hump. At 2θ of 27 degree, XRD results of both ash types exhibited the highest intensity peak of quartz.
Indonesian ash had a higher peak than the Japanese. XRD results showed that the Indonesian ash
contained both disruptor species magnetite and hematite, while the Japanese contained only hematite.
Both species may inhibit geopolymerization. Conversely, higher lime content in the Indonesian ash may
favor reaction, thus shortening setting time and increasing paste strength [15].

Electron Probe Micro-Analysis (EPMA)

EPMA was used as a qualitative method of non-destructive elemental analysis of micron-sized volumes at
the ash surface, with high sensitivity. EPMA detected elements of the Japanese ash to be O, Na, Mg, Al,
Si, P, S, K, Ca, Ti, Fe, and those of the Indonesian to be the same except for the absence of P. The
Japanese ash had normal count intensities of Fe and Ca compared to the Indonesian ash, which was rich
in Fe and Ca, as shown in Fig. 2. EPMA results fit well with XRF results, showing a larger percentage of
Fe2O3 and CaO in Indonesian ash than in Japanese: the former contained 12.54% of Fe2O3 and 5.18% of
CaO, while the latter contained 7.57% and 5.18%, respectively. Element of Ca may influence mechanical
properties of the paste such as setting time and compressive strength.

2000 Indonesian FA Japanese FA

1800 Quartz, SiO2
Hematite, Fe2O3
Mullite, 3Al2O3.2SiO2

Srebrodolskite, Ca2Fe2O5
1000 Magnetite, Fe3O4
800 Anhydrite,CaSO4
Lime, CaO
0 10 20 30 40 50 60 70 80 90 100
2-θ (deg)

Fig. 1. XRD Pattern of The Japanese and Indonesian Fly ash.

(a). EPMA of the Indonesian fly ash (b). EPMA of the Japanese fly ash
Fig. 2. EPMA both of the fly ash
Scanning Electron Microscopy (SEM)
SEM analysis was used to characterize fly ash morphology. The ash microstructure appearance,
containing mostly glassy, spherical particle called cenospheres, is in agreement with Davidovits [15].
Various features of size, shape, and surface exist in the ash. SEM result revealed that the majority of the
Japanese ash particles consisted of solid spheres as illustrated in Fig. 4, while the Indonesian ash
consisted of irregular shaped particles as shown in Fig. 3. This may be due to the low temperature of
combustion and rapid cooling of Indonesian coal in comparison with Japanese power plant system. The
irregular shapes of Indonesian ash require more water compared to Japanese ash for the ash to be utilized
as paste mixture.

Fig. 3. SEM result of the Indonesian fly ash at magnification x500 and x3000

Fig. 4. SEM result of the Japanese fly ash at magnification x500 and x3000
Setting Time
Three setting time experiments were conducted using various compositions to investigate effects of fly
ash and mixtures on setting time. Both initial and final were measured. Setting time is defined as that
required for the paste to change from a fluid to a solid. Two setting times are generally used: initial and
final. Initial setting time is that which elapses from the time activators are added to fly ash to the time the
paste loses its plasticity, while final setting time is reached when the polymer has attained sufficient
hardness to certain resistance.
14 12.9 Initial Setting Time
12 10.9 Final Setting Time

Time (Hour)
7.4 7.3
1.5 2 2.5
Alkaline Activator Ratio (Na2SiO3/NaOH) Mass Ratio
Fig. 5. Relationship of setting time of Indonesian ash with alkaline activators ratio (The 1st experiment)
Alkaline activators mass ratio: sodium silicate (Na2SiO3) gel to sodium hydroxide (NaOH) solution ratio.
Fig. 5 shows decreases in both initial and final setting times for Indonesian ash with a ratio increase of
sodium silicate gel to sodium hydroxide solution (Na2SiO3/NaOH). The molarity of NaOH solution used
was 8 M. These results show an increased ratio of activators result in a faster setting time, indicating that
the reaction rate of geopolymer was faster at higher activator ratios. The final setting time of Indonesian
paste with activators ratios of 1.5, 2 and 2.5 were 12.9 h, 10.9 h, and 7.3 h.

Conversely, the Japanese ash did not conform to this trend. With the same molarity of NaOH, 8 M, the
Japanese paste required a longer setting time with an increase in activator ratios (1.5 and 2.5): 23.3h and
26.9 h, respectively, as shown in Fig. 6. This differed from the Japanese ash with 14 molarity of NaOH:
contrary to the tendency of the Indonesian ash, Fig. 6 shows an increase in activator ratio decreases
setting times, which were 46.8 h and 28.7 h respectively. The discrepancy of these results may be due to
differences in the fly ash types; these would result in different chemical compounds of the material
precursor and influence different chemical compositions in the mixture, thus causing different
geopolymerisation reactions, and finally resulting in different setting time behaviors. These results show
that the first experiment was unable to compare different fly ash types.

Sodium hydroxide (NaOH) molarity. The concentration of sodium hydroxide solution reacting with fly
ash impacts geopolymer paste setting time. Fig. 6 shows initial and final setting time of the Japanese ash
under two activator ratios (1.5 and 2.5) and NaOH molarities (8 and 14 M). While higher NaOH
molarities resulted in longer paste setting times under both activator ratios, the activator ratio of 1.5
resulted in a far more significant difference between final setting times depending on molarity (23.3 vs
46.8 hours) compared with the activator ratio of 2.5 (26.9 vs 28.7 hours). Due to the certain alkaline
activators ratio, the higher molarity of NaOH made mixture become denser. If the mixture is more
concentrated, there is no enough space for geopolimerization process since the reaction requires more
water. This condition causes longer setting time.

Fly ash to alkaline activator ratio. Fig. 7 shows that a decrease in fly ash to activator (FA/AA) mass ratio
results in longer setting times. This is because an increase in the FA/AA mass ratio increases the amount
of fly ash absorbing the activator, thus making the mixture stiffer or less liquid and decreasing the setting
50 46.8
Initial Setting Time
40 Final Setting Time

Time (Hour)
26.9 26.7 28.7
10.0 11.7
10 6.7

1,5 2,5 1,5 2,5
8M 14 M
Alkaline Activator Ratio (Na2SiO3/NaOH) Ratio
Fig. 6. Relationship of setting time of Japanese ash with molarity of NaOH and alkaline activators mass
ratio (The 2nd experiment)

Initial Setting Time 100.5 98.9
100 Final Setting Time
Time (Hour)

80 73.9
60 47.8 46.2
36.6 33.1
20 8.3
1.86 1.50 1.22 1.86 1.50 1.22
Indonesian FA Japanese FA
Fly ash and Alkaline Activator Ratio (FA/AA) Ratio
Fig. 7. Relationship of setting time with fly ash to alkaline activator mass ratio (The 2nd experiment)

Water / Solid Ratio

0.31 0.35 0.45 0.36 0.38 0.39
150 Initial Setting Time 163.9
Final Setting Time
125 108.4
Time (Hour)

98.0 95.6
48.0 48.4 45.0 49.4
50 34.1
25 13.2 13.9
1.5 2.0 2.5 1.5 2.0 2.5
Indonesian FA Japanese FA
Molar Mass Ratio (Si/Al) Ratio
Fig. 8. Relationship of setting time with Si/Al and water/solid ratio (The 3rd experiment)
Si to Al ratio. On the microstructural and mechanical development of cementitious materials, soluble
silica is a significant factor as a result of fly ash-based geopolymer [14]. Furthermore, the setting time is
also influenced by Al2O3 [33]. In our third experiment, setting time test was conducted with three
mixtures of each ash. Each mixture consisted of a set ratio of the following materials: Na2O/SiO2 (0.3),
H2O/SiO2 (2.8 to 3.5), H2O/ Na2O (9 to 10.6), and water to solid (0.31 to 0.45). Varied materials were
Si/Al and Na2O/Al2O3, with Si/Al ratios of 1.5, 2.0 and 2.5, and Na2O/Al2O3 ratios of 0.9, 1.3, 1.9 for the
Indonesian ash and 0.9, 1.3, 1.5 for the Japanese. Fig. 8 illustrates that variation of Si to Al molar ratios in
the mixtures affects setting time. Both fly ash-based geopolymer paste, Japanese and Indonesian,
followed the same trend in setting time, which tended to decrease under Si/Al ratios of 1.5 to 2.0 and
increase under 2.0 to 2.5. The final setting times for Indonesian paste with Si/Al ratios of 1.5, 2 and 2.5
were, respectively, 34.1 h (1.5 days), 26.1 h (1 day), and 48.4 (2 days), while those for the Japanese were
longer at about 108.4 h (4.5 days), 98.0 h (4 days), and 163.9 h (7 days). These results agreed with the
theory of Davidovits that the polymerization process in geopolymer occurs between the alkaline mineral
Si-Al to produce three-dimensional polymeric chains and bonding structures of Si-O-Al-O. Therefore, a
certain ratio of Si to Al is required to form chain and ring polymers with Si 4+ and Al3+ in 4 fold
coordination with oxygen [15]. Fig. 8 indicates that both too little and too much Si/Al resulted in longer
setting times. For example, a Si/Al ratio of 1.5 required a longer time to the develop polymer, as did a
Si/Al ratio of 2.5. However, a Si/Al ratio of 2 resulted in a short setting time as a sufficient amount of Si
formed more oligomers, shortening the time required to develop polymers, while an excessive amount of
Si in solution hindered the dissolution process by silica species concentration.

Water/ solid (w/s) ratio. Fig. 8 shows both low and high water/solid (w/s) ratios resulted in longer setting
times, while middling ratios tended to decrease setting time. This is due to the Si/Al ratio. Interestingly,
Japanese ash required longer setting times than Indonesian even when the w/s ratio used in the Indonesian
ash was more than that in the Japanese. A w/s ratio of 0.45 in the Indonesian ash required a setting time of
only around 48.4 h, compared to Japanese ash with w/s of 0.39, which required about 163.9 h.

Compressive Strength

49.0 50.9
Compressive Strength

40 45.8

27.1 26.9

20 13.7
10 Paste 8M; 1.5
0.5 Paste 8M; 2.5
0 3 7 14 21 28
Age (days)
Fig. 9. Compressive Strength Japanese FA paste
Compressive strength development of Japanese ash-based geopolymer paste is presented in
49.0 50.9
Compressive Strength 48.3
40 45.8

27.1 26.9

20 13.7
10 Paste 8M; 1.5
0.5 Paste 8M; 2.5
0 3 7 14 21 28
Age (days)
Fig. 9. Lower strengths occurred from the lower ratio of alkaline activators (AA). The trend of increment
was not same for each ratio of AA used. At an AA ratio of 2.5, strength increased rapidly from 0 to 14
days, then slowed between 14 and 28 days. Conversely, at a ratio of 1.5, strength increased rapidly from 0
to 21 days, then slowed from 21 to 28 days.

Fig. 10 shows that a high paste strength of 57.5 MPa was produced by Indonesian ash with an AA ratio of
1.5, while the Japanese reached up to 47.7 MPa. Conversely, a higher strength was achieved by the
Japanese ash at an AA ratio of 2.5, while the strength of the Indonesian ash fell. The chemical content of
the Indonesian ash, rich in CaO and Fe2O3, influenced geopolymer paste strength. In particular, the high
levels of CaO in the fly ash led to mutual reaction of polymerization and hydration, as was noted by
Hardjito [7,8].

75 Japanese FA Indonesian FA
Compressive Strength

60 47.7 50.9 50.5

1.5 2.5
Alkaline Activator Ratio (Na2SiO3/NaOH) Ratio
Fig. 10. Compressive Strength paste on 28th days
Reactivity Test
This method was conducted according to ASTM C 311 [27]. The mixture standard is given with ordinary
Portland cement which has highest reactivity with quick lime as the activator. Compressive strength
profiles are shown in Fig. 11. It can be seen that Indonesian mixture had higher compressive strength than
the Japanese. Reactivities of Indonesian and Japanese mortars are respectively 14% and 5%. The
reactivity test shows the ability of ash to start both geopolymerization reaction and hydration at the same

Compressive Strength


5 2.11
Portland Cement Indonesian FA Japanese FA

Fig. 11. Compressive strength of specimens on 7th days

Based on this results of this experimental and subsequent discussion, the following conclusions can be

1. Although fly ash types were categorized as the same class, they could not guarantee identical
mechanical properties. Properties such as setting time and compressive strength can be influenced by
various factors including fly ash and its mixtures in paste.
2. Several microanalysis studies conducted. format the XRD pattern, show that peak intensity of the
Indonesian ash are higher than that of the Japanese; however, both ash types contain crystalline
minerals but most consist of amorphous materials. EPMA test detected similar elements in both ash
types (O, Na, Mg, Al, Si, S, K, Ca, Ti, Fe), except the P element was found only in the Japanese. The
Japanese ash displayed count intensities of Fe and Ca in normal amounts, while the Indonesian had
large numbers. EPMA results were consistent with XRF, which determined that a rich percentage of
Fe2O3 and CaO existed in the Indonesian ash. The existence of CaO led to higher strengths and faster
setting times of the Indonesian paste. SEM observation established that the majority of the Japanese
ash particles consisted of solid spheres, while those of the Indonesian had irregularly shaped
particles. These irregular shapes resulted in a need for more water for workability to utilize as
geopolymer paste.
3. Setting time experiment results under 8 M of NaOH showed an increase in setting times for the
Indonesian mixture with increasing of alkaline activators ratio, while that of Japan did not meet with
this trend. Conversely, under 14 M of NaOH, Japanese mixture did display the same tendency. This
discrepancy indicates the difficulty faced by the experiment grouping mixtures based on activator
ratios and NaOH molarity to fly ash ratio in comparing mechanical properties of paste made from
different fly ash. However, the use of atomic ratio (molar ratio) in the mixtures could be generally
applied. The variation of Si to Al molar mass ratio in the mixtures influenced the setting time, which
tended to decrease for Si/Al of 1.5 to 2.0 and increase for Si/Al of 2.0 to 2.5. Both fly ash types
followed the same trend.
4. The reactivity of the Japanese mix was 5% compared to that of the Indonesian, which achieved 14%.
This may also be evidence that the higher reactivity of Indonesian ash compared with Japanese
influenced the setting times and compressive strengths of ash based geopolymer paste. The highest
paste compressive strength, 57.5 MPa, was produced by Indonesian ash with an activator ratio of 1.5;
this compares with the highest of the Japanese, which was 50.9 MPa under an activator ratio of 2.5.

[1] K. Okada, A. Ooyama, T. Isobe, Y. Kameshima, A. Nakajima and K. J. D. Makenzie, "Water

Retention Properties of Porous Geopolymers for Use in Cooling Applications," Journal of the
Australian Ceramic Society, vol. 29, pp. 1917-1923, 2009.
[2] E. Obonyo, E. Kamseu, U. C. Melo and C. Leonelli, "Advancing the Use of Secondary Inputs o
Geopolymer Paste for Sustainable Cementitious Composites: A Review," Sustainability, vol. 3, pp.
410-423, 2011.
[3] A. M. M. Al Bakri, H. Kamarudin, M. N. Norazian, C. M. Ruzaidi, Y. Zarina and A. R. Rafiza,
"Microstructure Studies on the Effect of the Alkaline Activators Ratio in Preparation of Fly Ash-
Based Geopolymer," International Conference on Chemistry and Chemical Process (IPCBEE), vol.
10, 2011.
[4] J. Davidovits, "Global Warming Impact on the Cement and Aggregates Industries," World Resource
Review, vol. 6, no. 2, pp. 263-278, 1994.
[5] A. S. W. Wijaya and D. Hardjito, "Factors Affecting the Setting Time of Fly Ash-Based
Geopolymer," Materials Science Forum, vol. 841, pp. 90-97, 2016.
[6] J. J. Ekaputri, M. B. Ulum, T. R. Bayuaji, T. E. Susanto and A. M. M. Al Bakri, "A Comprehensive
Characterization and Determination of Fly Ashes In Indonesia using Different Methods," Applied
Mechanics and Materials, Vols. 754-755, pp. 320-325, 2015.
[7] D. Hardjito, "Studies on Fly Ash-Based Geopolymer Concrete," Curtin University of Technology,
[8] D. Hardjito, C. C. Cheak and C. H. L. Ing, "Strength and Setting Times of Low Calcium Fly Ash-
based Geopolymer Mortar," Modern Applied Science, vol. 2, no. 4, 2008.
[9] J. S. van Jaarsveld, J. S. J. van Deventer and G. C. Lukey, "The characterisation of source materials
in fly ash-based geopolymers," Materials Letters, vol. 57, p. 1272–1280, 2003.
[10] J. L. Provis, P. Duxson, R. M. Harrex, C. Z. Yong and J. S. J. van Deventer, "Valorisation of Fly
Ashes by Geopolymerisation," Global Nest, vol. 11, no. 2, pp. 147-154, 2009.
[11] B. Valentim, A. Guedes, D. Flores and C. Ward, "Variations in fly ash composition with sampling
location: Case study from a Portuguese power plant," Coal Combustion and Gasification Products,
vol. 1, pp. 14-24, 2009.
[12] B. G. Kutchko and A. G. Kim, "Fly ash characterization by SEM–EDS," Fuel, vol. 85, p. 2537–
2544, 2006.
[13] ASTM C 618, "Standard Specification for Coal Fly Ash and Raw or Calcined Natural Pozzolan for
Use in Concrete," - 03.
[14] M. Criado, A. F. Jimenez, A. G. d. l. Torre, M. A. G. Aranda and A. Palomo, "An XRD Study of the
Effect of the SiO2/Na2O ratio on the Alkali Activation of Fly ash," Cement and Concrete Research,
vol. 37, pp. 671-679, 2007.
[15] J. Davidovits, Geopolymer Chemistry and Applications, Third ed., Saint-Quentin: Institut
Géopolymère, 2011.
[16] H. J. Gluskoter, "Mineral Matter and Trace Elements in Coal," in Trace Elements in Fuel,
Washington DC, American Chemical Society, 1975, pp. 1-22.
[17] S. C. White and E. D. Case, "Characterization of fly ash from coal-fired power plants," Journal of
Materials Science, vol. 25, p. 5215 5219 , 1990.
[18] C. R. Ward and D. French, "Relation between Coal and Fly Ash Mineralogy, Based on Quantitative
X-Ray Diffraction Methods," World of Coal Ash (WOCA), 2005.
[19] F. D. Riley and C. R. Ward, "Characterisation, classification and properties of coal combustion
products," in Coal Combustion Products Hand-book, Brisbane, Co-operative Research Centre for
coal in Sustainable Development, 2007, pp. 37-100.
[20] S. Kramar and V. Ducman, "Mechanical and Microstructural Characterization of Geopolymer
Synthesized from Low Calcium Fly ash," Chemical Industry and Chemical Engineering Quarterly,
vol. 21, no. 1, pp. 13-22, 2015.
[21] G. C. Fisher and D. F. S. Natusch, "Analytical Methods for Coal and Coal Products," in Size
Dependence of the Physical and Chemical Properties of Coal Fly Ash, vol. III, 1979, p. 489.
[22] W. D. Kingery and D. R. Uhlmann, in Introduction to Ceramics, 2 ed., New York, John Wiley and
Son, 1976.
[23] P. D. Silva and K. S. Crenstil, "The Role of Al2O3, SiO2 and Na2O On the Amorphorus Cristalline
Phase Transformation in Geopolymer Systems," Journal of the Australian Ceramic Society, vol. 45,
no. 1, pp. 63-71, 2009.
[24] R. P. Williams and A. van Riessen, "Determination of the reactive component of fly ashes for
geopolymer production using XRF and XRD," Fuel, vol. 89, p. 3683–3692, 2010.
[25] E. I. Diaz, E. N. Allouche and S. Eklund, "Factors affecting the suitability of fly ash as source
material for geopolymers," Fuel, vol. 89, p. 992–996, 2010.
[26] J. J. Ekaputri, T. K. A. Priadana, T. E. Susanto and S. Junaedi, "Physico-Chemical Characterization
of Fly Ash," Advanced in Structural Engineering and Mechanics (ASEM), vol. 13, 2013.
[27] ASTM C 311, "Standard Test Methods for Sampling and Testing Fly Ash or Natural Pozzolans for
Use in Portland-Cement Concrete," - 02.
[28] R. Nurwidayati, M. B. Ulum, J. J. Ekaputri, T. and P. Suprobo, "Characterization of Fly Ash on
Geopolymer Paste," Materials Science Forum, vol. 841, pp. 118-125, 2016.
[29] JIS A6201, "Fly Ash for Use in Concrete," - 2008.
[30] A. M. M. Al Bakri, H. Kamarudin, M. Bnhussain, I. K. Nizar and W. I. W. Mastura, "Mechanism
and Chemical Reaction of Fly Ash Geopolymer Cement of Fly Ash Geopolymer Cement: A
Review," Journal of Asian Scientific Research, vol. 1, no. 5, pp. 247-253, 2011.
[31] ASTM C 403/ C 403 M, "Standard Test Method for Time of Setting of Concrete Mixtures by
Penetration Resistance," - 99.
[32] ASTM C 39/C 39M, "Standard Test Method for Compressive Strength of Cylindrical Concrete
Specimens," - 03.
[33] P. D. Silva and K. S. Crenstil, "The Effect of Al2O3 and SiO2 On Setting and Hardening of Na2O-
Al2O3-SiO2- H2O Geopolymer Systems," Journal of the Australian Ceramic Society, vol. 44, pp.
39-46, 2008.