Construction and Building Materials 52 (2014) 473–481

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Construction and Building Materials

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Synthesis of geopolymer from large amounts of treated palm oil fuel ash:
Application of the Taguchi method in investigating the main parameters
affecting compressive strength
M.J.A. Mijarsh a,b, M.A. Megat Johari a,⇑, Z.A. Ahmad c
a
School of Civil Engineering, Universiti Sains Malaysia, Malaysia
b
Civil Engineering Department, Faculty of Engineering, Al-Merghab University, Al-Khums, Libya
c
School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Malaysia

h i g h l i g h t s

Geopolymer was synthesized from high content of treated palm oil fuel ash.
TPOFA-based geopolymer mortar gained compressive strength of 47 MPa at 7 days.
The optimized TPOFA-geopolymer mortar mixture was analysed using XRD and FTIR.
The main binding phases consist of N–A–S–H and C–S–H gels.

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

Article history: The aim of this study was to synthesize geopolymers using a large amount of treated palm oil fuel ash
Received 23 August 2013 (TPOFA). The efficiency of the TPOFA (as the source material) in producing geopolymer products was
Received in revised form 4 November 2013 enhanced via six factors which were optimized using the Taguchi method L25. The six factors were
Accepted 12 November 2013
divided into two different components: (i) additive materials i.e. Ca(OH)2, silica fume (SF), Al2(OH)3,
Available online 12 December 2013
and (ii) alkaline activators; i.e. NaOH concentration (moles), Na-silicate: NaOH ratio, and alkali-activa-
tor:solid-material ratio. Each of these factors was examined on five levels in order to obtain the optimum
Keywords:
mixture. A total of 25 mixtures were prepared in accordance to the L25 array proposed by the method.
Geopolymer
Palm oil fuel ash
The performance of the specimens was evaluated by compressive strength tests. The results show that
Compressive strength the optimum mixture consisted of 65 wt.% TPOFA and 35 wt.% additive materials which achieved a com-
Taguchi method pressive strength of 47.27 ± 5.0 MPa after 7 days of curing. The properties of the optimized mixture were
further analyzed via X-ray diffractography (XRD) and Fourier transform infrared spectroscopy (FTIR)
analyses. The results show that the main binding phases consist of aluminosilicate type gel ‘‘N–A–S–
H’’ (Na2O–Al2O3–SiO2–H2O) and calcium silicate hydrate (C–S–H) gels, formed simultaneously, within
the TPOFA-based geopolymer mortar.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction (CaO–Al2O3–SiO2–H2O) which is the main binding phase in the sys-

tem of alkali-activated aluminosilicate calcium-rich source mate-
A geopolymer is also known as an alkali-activated aluminosili- rial [3,4]. Therefore, geopolymer synthesis is dependent on the
cate material. A geopolymer binder has a three-dimensional amor- use of material rich in aluminum–silicate glass activated with alka-
phous structure of (N–A–S–H) type gel (Na2O–Al2O3–SiO2–H2O). line solutions [5]. The most commonly used material is calcined
The gel is formed by either the polymerization of individual kaolin or metakaolin (MK) [2,6]. However, industrial wastes such
[SiO4]4 and [AlO4]5 species as building blocks in the system as fly ash and ground granulated blast furnace slag (GGBFS) are
which are the main reaction product of alkali-activated aluminosil- also used due to their high silica and alumina content with little
icate (geopolymer) materials derived from low-calcium content and high CaO content, respectively [1,3]. In the major palm oil pro-
[1,2] or a calcium alumina silicate hydrate C–(A)–S–H type gel ducing countries, palm oil fuel ash (POFA) is another abundantly
available waste material which can be used for geopolymer syn-
theses. POFA [7] has high SiO2 (61.33) content, low Al2O3 (7.018)
⇑ Corresponding author. Tel.: +60 4 5996208; fax: +60 4 5941009. content, and high P2O5 (4.55) content compared to class C and class
E-mail addresses: [Link]@[Link] (M.J.A. Mijarsh), cemamj@ F fly ash, GGBFS, and MK or calcined kaolin [1–4,6]. It also has
[Link] (M.A. Megat Johari), zainal@[Link] (Z.A. Ahmad).

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
[Link]
474 M.J.A. Mijarsh et al. / Construction and Building Materials 52 (2014) 473–481

higher Fe2O3 (5.11) content compared to GGBFS, and MK or cal- Ca(OH)2 wt.%, SF wt.%, Al(OH)3 wt.%, NaOH concentration (mole),
cined kolin [2,3,6], and higher MgO (4.69) and CaO (8.20) content Na2SiO3/NaOH (weight ratio), and alkali-activator/solid materials
compared to class F fly ash and MK [1,2]. Theoretically, there (weight ratio). A total of 25 experiments were conducted according
should be a direct correlation between the geopolymerization re- to L25 array proposed by the Taguchi method. The efficiency of the
sults and the total silica content of the source materials. Increasing TPOFA was enhanced by investigating the effects of the abovemen-
the amount of silica causes the number of Si–O–Si bonds which are tioned parameters on the mechanical properties of the product in
stronger than Si–O–Al and Al–O–Al bonds [8], to increase; this im- order to obtain the optimum mixture. This mixture was then
plies that the strength of geopolymers would also increase with the examined using X-ray diffraction (XRD) and Fourier transform
Si/Al ratio because the density of the Si–O–Si bonds increases with infrared spectroscopy (FTIR).
the increase in Si/Al ratio [9,10]. Hence, the high silica content of
the POFA reflects its feasibility as source material for geopolymer
2. Materials and methods
synthesis.
Untreated POFA has been used in combination with pulverized 2.1. Materials
fuel ash (PFA) at a ratio of 30:70, and activated with an alkaline
activator to produce geopolymer with a compressive strength of Four basic raw materials were used to produce the geopolymer mortar. Raw
POFA was collected from a nearby palm oil mill in Nibong Tebal, Penang, Malaysia.
30 MPa after 28 days of curing [11]. This rather limited strength
The incompletely combusted fibers and kernel shells were separated using a
potential of the resulting geopolymer could be attributed to the 300 lm sieve. The POFA was then ground in a ball mill to obtain particle sizes of
high content of unburned carbon in POFA, as unburned carbon of about 10 lm. To remove the unburned carbon, POFA was heated at 500 °C for 1 h
base material has been found to affect compressive strength of in a gas furnace and then the POFA was subjected to second stage grinding to form
geopolymer [12]. Therefore, POFA has to be treated to reduce the the TPOFA. The chemical and physical properties of the TPOFA in this study are pro-
vided in Table 1. Based on ASTM C618 [25], the treated POFA could be classified as a
carbon content in order to promote the geopolymerization process.
class F mineral admixture. The same approach has recently been used and was re-
The potential of POFA, especially treated POFA (TPOFA) [7], as a ported to be effective in increasing the efficiency of TPOFA for use in high-strength
source material for geopolymer synthesis has not been adequately green concrete [7] and engineered cementitious composites [26]. The TPOFA is the
explored as in the case of class C and class F fly ashes, GGBFS, and major source material in this research. The alkaline activators used were solutions
combining NaOH and Na2SiO3. The analytical grade NaOH was in pellet form with
MK or calcined kaolin [1–4,6]. Nonetheless, this is changing as
98% purity and the commercial Na2SiO3 was in liquid form with a specific gravity
great interest in POFA has sparked among researchers, especially of 1.53 g/cm3 at 20 °C and a silica modulus (Ms, where Ms = SiO2/Na2O) of 2;
those from palm oil producing countries. 14.7% Na2O, 29.4% SiO2, and 55.9% H2O were combined. The additives used were
To the authors’ best knowledge, no geopolymerization of TPOFA Ca(OH)2, Al(OH)3, and SF. The surface area of Ca(OH)2, Al(OH)3 and SF were
has ever been reported, possibly due to its efficiency as it contains 0.6214 m2/g, 0.3298 m2/g, and 0.1364 m2/g, respectively. Clean river sand passing
a 1.18 mm sieve and retained on a 150 lm sieve, with a fineness modulus of 2.8
a high amount of silica, but a low amount of alumina, as well as
and specific gravity of 2.65, was used.
calcium which need to be initially enhanced. Recent research
works have shown that the inclusion of specific amounts of cal-
cium hydroxide (Ca(OH)2) [13], aluminum hydroxide (Al(OH)3) 2.2. Design of the mixtures

[14], and silica fume (SF) [15] can enhance the geopolymerization
In this study, the Taguchi method was used to design the mixtures and to obtain
processes. In all cases, they were done individually in different the optimum mixture design by considering the effects of the parameters on their
aluminosilicate source materials. A significant amount of these mechanical properties. Six primary factors were examined followed by a statistical
materials showed considerable impact on the geopolymerization study of the Ca(OH)2 wt.% (designated as A); the SF wt.% ‘‘B’’; the Al(OH)3 wt.% ‘‘C’’;
the NaOH concentration (moles) ‘‘D’’; the Na2SiO3 to NaOH weight ratio ‘‘E’’; and the
processes. Therefore, it is important to introduce TPOFAs contain-
liquid alkaline to solid material weight ratio ‘‘F’’. Each factor was examined at the
ing different amounts of these materials in order to investigate five levels as described in Table 2. The level of each factor and the values of the
the enhancement of TPOFA for efficient geopolymer synthesis. tested factors were chosen based on previous researches [14,27–29]. The amount
Another crucial parameter that affects the TPOFA geopolymer of water added to each mixture was calculated based on the percentage of geopoly-
synthesis is alkali activator types (combination and concentration). mer paste at 5% by weight ratio [30]. All of the geopolymer mortars were made with
sand to solid material weight ratios of 1.5 which is similar to that used in previous
Several works have been carried out on geopolymers, yet no clear
researches [31,32]. This is the optimum ratio for the binder (solid material) and
explanation has been provided on the effects of various factors for sand; anything beyond this ratio will cause the compressive strength to be dramat-
upsetting source materials, such as how the strength increased ically reduced [33]. The design suggested by the Taguchi method for six factors at
with high NaOH concentrations [16,17]. However, some other five levels is the L25 array, as shown in Table 3, while Table 4 shows the values
and trial mixture proportions used in the series of 25 mixtures. The compressive
researchers [18,19] found that high concentrations of NaOH have
a negative effect on strength. Moreover, previous research has con-
cluded that the use of Na2SiO3/NaOH in a weight ratio of 1.0 gives Table 1
strength of up to 70 MPa [20]. The highest compressive strength Chemical compositions using XRF technique and physical properties of TPOFA.
value of 71 MPa was observed at 2.5 Na2SiO3/NaOH weight ratio
Chemical Component (%)
[21].
Investigating all of these parameters (Ca(OH)2 wt.%, SF wt.%, SiO2 61.33
Al2O3 7.018
Al(OH)3 wt.%, NaOH concentration (mole), Na2SiO3/NaOH (weight Fe2O3 5.11
ratio), and alkali-activator/solid materials (weight ratio)) in a sin- CaO 8.20
gle work may not be possible. However, with a suitable design MgO 4.69
method, one may consider some of the factors affecting these prop- P2O5 4.55
K2O 6.50
erties. The Taguchi experimental design is one of the most famous
SO3 0.27
methods used to design the parameters of specific problems. The TiO2 0.25
application of the Taguchi method in geopolymers by past MnO 0.097
researchers for similar purposes [22–24], but with different source Na2O 0.123
materials, has been successful. C 1

This study is an investigation on the synthesis and characteriza- Physical properties

tion of geopolymers produced using TPOFA as the source material. Specific surface area (m2/g) 1.775
Loss on ignition (%) 2.53
Six design factors were examined at five levels by the Taguchi Median particle size d50 (lm) 2.06
method to obtain the optimum mixture. The six factors are
M.J.A. Mijarsh et al. / Construction and Building Materials 52 (2014) 473–481 475

Table 2 Table 4
The introduced levels for each factor in Taguchi experimental design. Mix proportions of geopolymer used for Taguchi optimization.

Factor Unit Level Level Level Level Level Mix POFA Ca(OH)2 Silica Al(OH)3 Sand Na2SiO3 NaOH Added
1 2 3 4 5 fume water
(g) (g) (g) (g) (g) (g) (g) (g)
A: Ca(OH)2 wt.% 15 17.5 20 22.5 25
B: Silica fume wt.% 2.5 3.75 5 6.25 7.5 T1 500 120 20 40 1030 240 120 100
C: Al(OH)3 wt.% 5 6.25 7.5 8.75 10 T2 490 100 40 60 1040 230 120 100
D: NaOH concentration Mole 10 12 14 16 24 T3 470 140 50 40 1080 130 200 100
E: Na2SiO3-to-NaOH wt. 0.67 1 1.5 2 2.5 T4 540 100 20 30 1050 150 220 100
ratio T5 480 140 40 30 1040 250 100 100
F: Alkali-activator-to- wt. 0.46 0.47 0.48 0.49 0.50 T6 480 160 40 40 1060 170 170 100
solid material ratio T7 500 120 30 50 1050 240 100 100
T8 470 140 30 60 1050 200 140 100
T9 490 120 40 60 1070 140 200 100
T10 490 140 20 50 1050 170 170 100
Table 3 T11 490 120 50 30 1050 210 140 100
Taguchi method of orthogonal arrays [L25 (5 * 6)] of the experimental design. T12 470 160 40 40 1070 190 130 100
T13 450 180 40 40 1060 230 90 100
Trial Factor A Factor B Factor C Factor D Factor E Factor F
T14 470 100 50 70 1050 240 100 100
T1 2 1 2 3 4 5 T15 430 180 60 60 1100 150 150 100
T2 1 4 4 4 4 4 T16 450 180 20 70 1080 190 120 100
T3 3 5 2 4 1 3 T17 500 100 30 50 1040 210 140 100
T4 1 1 1 1 1 1 T18 470 180 30 40 1060 220 110 100
T5 3 4 1 3 5 2 T19 520 100 30 40 1040 180 180 100
T6 4 3 1 4 2 5 T20 470 160 20 60 1060 230 90 100
T7 2 2 3 4 5 1 T21 450 160 50 50 1080 210 100 100
T8 3 2 4 1 3 5 T22 440 180 50 50 1090 130 190 100
T9 2 3 4 5 1 2 T23 470 120 40 70 1070 170 170 100
T10 3 1 3 5 2 4 T24 460 140 40 70 1070 210 110 100
T11 2 5 1 2 3 4 T25 460 160 30 70 1080 130 200 100
T12 4 4 2 5 3 1
T13 5 3 2 1 5 4
T14 1 5 5 5 5 5
T15 5 5 4 3 2 1 Table 5
T16 5 1 5 4 3 2 Changes of compressive strength of trial mixes.
T17 1 3 3 3 3 3
Trial mix Combination Compressive strength (MPa)
T18 5 2 1 5 4 3
T19 1 2 2 2 2 2 Response 1 Response 2 Response 3
T20 4 1 4 2 5 3
1 day 3 days 7 days
T21 4 5 3 1 4 2
T22 5 4 3 2 1 5 T1 A2B1C2D3E4F5 20.65 21.98 23.07
T23 2 4 5 1 2 3 T2 A1B4C4D4E4F4 18.6 19.8 20.855
T24 3 3 5 2 4 1 T3 A3B5C2D4E1F3 15.67 16.69 18.42
T25 4 2 5 3 1 4 T4 A1B1V1D1E1F1 18.59 19.79 22.79
T5 A3B4C1D3E5F2 30.39 31.31 33.63
T6 A4B3C1D4E2F5 27.74 29.33 30.52
strength values of the trial mixtures results were evaluated by calculating a re- T7 A2B2C3D4E5F1 30.65 32.71 33.454
sponse index for each factor based on signal-to-noise ratio (S/N) principles [34], T8 A3B2C4D1E3F5 27.94 30.19 31.19
i.e. a higher S/N provides a ‘better’ response index. T9 A2B3C4D5E1F2 24.66 25.1 26.25
T10 A3B1C3D5E2F4 17.81 18.97 20.185
2.3. Geopolymer synthesis T11 A2B5C1D2E3F4 18.69 19.9 20.185
T12 A4B4C2D5E3F1 32.73 33.72 35.855
The synthesis of geopolymer mortar from TPOFA was carried out using mixtures T13 A5B3C2D1E5F4 37.77 39.97 42.15
of solid materials and an alkaline activator. The solid materials were TPOFA, the T14 A1B5C5D5E5F5 18.91 19.8 20.915
source material, which was substituted with various ratios of Ca(OH) 2, SF, and T15 A5B5C4D3E2F1 27.71 29.2 31.94
Al(OH)3. The alkaline activator was made from Na2SiO3 and NaOH solutions. The T16 A5B1C5D4E3F2 36.95 38.26 39.77
NaOH pellets were poured into the beaker with distilled water to obtain concentra- T17 A1B3C3D3E3F3 26.02 28.27 29.55
tions of 10, 12, 14, 16, and 24 M. The solution was stirred until the NaOH pellets dis- T18 A5B2C1D5E4F3 30.65 31.98 34.91
solved and the solution became clear. During this process, a significant amount of T19 A1B2C2D2E2F2 19.09 20.85 23.43
heat can be released. To ensure that the heat did not interfere with the geopolymer T20 A4B1C4D2E5F3 30.21 33.01 35.02
reaction, the solution was covered and sealed for at least 3 h which allowed the T21 A4B5C3D1E4F2 31.08 33.57 35.63
solution to cool down to ambient temperature (28 ± 2 °C, 70% RH). The Na2SiO3 T22 A5B4C3D2E1F5 24.38 26.29 28.06
solution was used without further preparation and poured into the beaker with T23 A2B4C5D1E2F3 26.65 27.77 30.55
the aforementioned NaOH solution and mixed for 2 min. Water was added to the T24 A3B3C5D2E4F1 41.82 42.62 44.74
solid material and alkaline activator prior to the slow addition of sand, as seen in T25 A4B2C5D3E1F4 27.26 28.7 31.445
Table 4. Immediately after mixing, the geopolymer mortar was cast into 50 50
50 mm steel molds in two layers so that it becomes compact, as described in
the ASTMC109M [35]. This was followed by an additional vibration of 15 s using
a vibrating table. The specimens were wrapped with cling film to avoid moisture infrared spectroscopy (FTIR). XRD was used to determine the phases present in
evaporation, left in the laboratory for 1 h and then cured at 75 °C for 48 h to activate the specimens and FTIR was used to identify the different types of chemical bonds
the geopolymerization [36,37]. The specimens were left in the laboratory to cool present in the materials on a molecular level. Analysis was carried out using an XRD
down. After that, the specimens were demoulded and kept under ambient temper- machine (Bruker D8 Advance) with Cu Ka radiation (1.5406 Å) from 10 to 90 of 2h°.
ature (28 ± 2 °C, 70% RH) for 1, 3, and 7 days of curing time. Diffraction patterns were then analyzed using Expert HighScorePlus software. For
FTIR, the equipment used was Perkin–Elmer Spectrum One. Approximately 5 mg
2.4. Specimen analysis of powdered specimen was mixed with 95 mg of potassium bromide (KBr) and
ground using an agate mortar and pestle. The powder was pressed for 2 min under
The specimens were tested for compressive strength according to ASTM C109M 2.758 MPa using hydraulic pressing to prepare the translucent pellets which were
[35]. The test was performed on three specimens from each mixture. The optimum then inserted into the infrared spectrometer. The infrared spectra were recorded
mixture was also analyzed by X-ray diffraction (XRD) and Fourier transforms in the range of 400–4000 cm1 wavelength.
476 M.J.A. Mijarsh et al. / Construction and Building Materials 52 (2014) 473–481

(b)
(a) 40

rength (MPa)
40
rength (MPa)

30
30

Compressive St
20
Compressive St

20

10
10

)
)
7 days

ay
ay
7 days

(d
(d
3 days

ge
ge
0 3 days 0

ga
ga
A5 B5
1 day

rin
1 day B4

rin
A4 B3
Calci A3

Cu
Cu
um H A2 Silica B2
ydrox A1 Fume B1
ide (w (wt.%
t.%) )

(c) (d)
rength (MPa) 35
40
rength (MPa)

30

25
30
20
Compressive St

20 15
Compressive St

10
10

)
ay
)

7 days
ay

7 days 5

(d
(d

3 days

ge
3 days
ge

0 0

ga
ga

C5 D5
1 day

rin
C4 1 day D4
rin

Alum C3 NaOH D3

Cu
inum C2 Conc D2
Cu

Hydr C1 entra D1
oxide tion (
(Wt.% Mole
) )

(f)
(e)
40
rength (MPa)

35
rength (MPa)

30
30
25
Compressive St

20 20
Compressive St

15

10 10
y)

7 days 7 days
a
)

5
ay

(d
(d

3 days
ge

3 days 0
0
ge

ga

E5 Alkal F5
ga

rin

E4 1 day i-Acti F4 1 day

Na S
rin

E3 vator F3
Cu

2 iO -to E2 -to-so F2
Cu

-NaO lid m
H (wt E1 F1
3
ateria
.ratio l (wt.r
) atio)

Fig. 1. Effect of (a) Ca(OH)2 wt.%, (b) SF wt.%, (c) Al(OH)3 wt.%, (d) NaOH concentration (in terms of molar), (e) Na2SiO3-to-NaOH weight ratio, (f) alkali-activator-to-solid
material weight ratio on each response of compressive strength at different curing ages.

3. Results and discussion averaging the strengths at 1, 3, 7 days for each trial mixture
containing a particular factor. For example, the response index
Table 5 shows the results of the compressive strength tests for factor A1 was tested on trial mixtures marked with factor A1,
conducted on the 25 trial mixtures prepared as suggested by the as shown in Table 5 (i.e. T2, T4, T14, T17, and T19). Therefore,
Taguchi method. Based on these results, the evaluation of compres- the response index for factor A1 at 1 day after curing was the aver-
sive strength (response index) for each factor was calculated by age of the response index for trial mixtures of T2, T4, T14, T17, and
M.J.A. Mijarsh et al. / Construction and Building Materials 52 (2014) 473–481 477

Table 6 due to the finer sized particles of SF (Factor B) which hinders the
Optimization of the factors combination of TPOFA-based geopolymer mortar mixture process of geopolymerization [28]. Therefore, adding Factor B up
at different curing ages.
to B3 crammed the voids existing between the sand particles and
Optimum mixture Combination Compressive strength (MPa) contributed to the improvement of porosity, producing denser
1 day 3 days 7 days microstructure [15]. The decrease in response index with additions
1 A3B3C5D1E5 F1 42.64 45.55 47.27
beyond B3 is also linked to the amount of unreacted material in the
specimens [40].

3.1.3. Effect of Al(OH)3 content (Factor C)

T19. Similarly, the calculations were done for factors A1, A2, A3, A4,
The response index for Factor C is shown in Fig. 1c. The response
and A5 at 1, 3, and 7 days, respectively. The results have been plot-
index increased with the increase of Factor C up to C5. It was also
ted in Fig. 1a. The plot indicates that the Factor A5 gave the highest
found in the actual experiments that the specimens containing
response index; therefore, it is the optimum value for factor A.
Factor C close to C5 produced higher workability. The results indi-
Optimum values for factors B (Fig. 1b), C (Fig. 1c), D (Fig. 1d), E
cated that Factor C played an important role in gel structure devel-
(Fig. 1e) and F (Fig. 1f) were calculated in the same way. A detailed
opment in the early stages of the reaction during the initial
discussion is given in the following subsections.
strength development of the geopolymer by promoting the geo-
polymeric reaction and strengthening the matrix. These results
3.1. Effect of additive materials generally agree with the experimental results obtained in an ear-
lier study [14].
3.1.1. Effect of Ca(OH)2 content (Factor A)
The response index for Factor A is shown in Fig. 1a. The re- 3.2. Effects of alkaline activator combinations and concentrations
sponse index increased with the increase in Factor A amount. There
is an obvious positive influence on the response index when the 3.2.1. Effects of sodium hydroxide concentration (Factor D)
Factor A is above A3. However, in the actual experiment, specimens The response index for Factor D is shown in Fig. 1d. The re-
produced using A3 onwards exhibited very rapid setting (less than sponse index reduced with the increase of Factor D up to D5. In
3 min) and poor workability due to higher dissolution of Factor A. the actual experiment, specimens fabricated with more Factor D
Therefore, replacing TPOFA with Factor A above A3 in geopolymer had reduced workability and higher porosity. This result is attrib-
synthesis is not useful. uted to the high number of OH groups that inhibit the geopoly-
Factor A plays a significant role in improving the strength of the merization and C–S–H reaction which produces the gel binder
hardened geopolymer mortar due to the pozzolanic reaction. Posi- and increase the total porosity to directly influence the response
tive ions such as Ca2+ need to be present in the framework cavities index. In addition, Na+ changed the balance requirements within
to balance the negative charge of the aluminate group. However, it the structure by satisfying the sodium content, thus leading to
is still not clear why Ca(OH)2 plays such a significant role in the higher strengths. In contrast, with increased sodium content, so-
strength of alkali-activated binders [13,15]. In particular, the addi- dium carbonate starts to form. This carbonate compound will
tion of highly alkaline activating solutions into TPOFA containing compete with the geopolymerization process, producing poorer
Ca(OH)2 has the net effect of lowering the pH of the activating mechanical properties, thereby reducing the response index
solution. This is due to the removal of the OH ions which signifi- [18,19]. However, previous researchers found that, when using dif-
cantly affects the rate of further dissolution/precipitation processes ferent source materials, the increase of NaOH concentrations either
to form C–S–H and geopolymeric gel at low alkalinity [38]. Hence, increased [16,17] or reduced [18,19] the strength of the specimens.
the unreacted Ca(OH)2 is slowly recarbonated into calcite over The typical geopolymer composition is generally expressed as
time, while free OH hydroxyl ions that could be involved in the nM2OAl2O3xSiO2yH2O, where M is an alkali metal [32]. The most
carbonation of Ca(OH)2 into CaCO3 move in the other direction. widely adopted alkaline activators are MOH-type caustic alkalis
This carbonation principle contributes to the growth of geopoly- and R2O(n)SiO2 type silicates which are used individually or in
mer strength. It has been noted that the strength of geopolymers combination, as exhibited in previous researches [16–19]. Here,
that contain reasonable quantities of calcite had improved with M denotes the alkaline activator, which is generally NaOH, Na2-
time on account of the interaction between calcite and geopoly- SiO3, or Ca(OH)2 containing alkaline metal ions such as Na+ and
meric phase. In addition, it also functions as a physical filler/mi- alkaline earth metal such as Ca2+ serving as an accelerator of the
cro-aggregate [39]. Other researchers have found that loss of reaction speed by activating Al and Si through a reaction with
strength occurs when Ca(OH)2 is above 10% at 14 days of curing; the binder. In previous researches, the alkaline Na2SiO3 was used
however, the source material of the geopolymer was tungsten without specifying its Ms (silica modulus) SiO2/Na2O ratio in their
mine waste mud, not POFA or FA. This relates to the fact that the system [17,19], as shown in Eq. (1); however, the modulus was
C–S–H and geopolymeric reactions compete against each other specified in other system [16]. The SiO2/M2O ratio in an alkaline
for soluble silicates, resulting in a binder composed of two poor silicate solution affects the degree of polymerization of the dis-
phases that leads to loss of strength [27]. solved species [41]. This presents some difficulties when compar-
ing results and findings in previous researches. The SiO2/M2O
3.1.2. Effect of SF content (Factor B) molar ratio (M = Na+) of the activating solution (NaOH and Na2-
The response index for Factor B is shown in Fig. 1b. The re- SiO3) is the most critical factor for the synthesis of geopolymers
sponse index increased with the increase of Factor B up to B3 [42]. Previous researches used NaOH without Na2SiO3 or/and
and started to reduce once it was above B3. It was expected that Ca(OH)2 in their systems [18,43,44]. It is important to understand
adding Factor B to the TPOFA-based geopolymer mortar mixtures the roles of Ca(OH)2, NaOH, Na2SiO3 in optimizing the properties of
would increase the response index. However, this increase in re- user-friendly geopolymer systems.
sponse index is not more than the efficacy of TPOFA containing There should be strong correlation between the total solid SiO2/
61.33% SiO2 that would chemically react with Factor A to form Na2O ratio and water content H2O/Na2O ratio in alkaline activator
C–S–H or with Factor C and alkaline activation to form (N–A–S– and they must be taken into account [32]. In this research, the total
H) gels. Nevertheless, in actual experiments, the workability of water content H2O/Na2O resulted from the contribution of water
specimens fabricated with amounts above B3 started to reduce content from the alkaline activator (NaOH and Na2SiO3) as well
478 M.J.A. Mijarsh et al. / Construction and Building Materials 52 (2014) 473–481

as free water from the decomposition of (Al(OH)3, Ca(OH)2, and experimental study produced a similar observation. The workabil-
NaOH) as shown in Eqs. (2)-(4) and the amount of added water. ity started to increase with the increase in Factor F; however, even
The effects of alkaline activator to solid weight ratio is explained at very low amounts of Factor F, the mixture still had moderate
in the following subsection. workability. This may have occurred because increasing the activa-
tor content in the mixture led to an increase in water content. Geo-
Na2 O nSiO2 ðaqÞ ! Na2 O þ nSiO2 þ H2 O ð1Þ
polymer reactions are dependent mainly on polymerization and
condensation reactions. The reasons for the increase in water con-
2AlðOHÞ3 ! Al2 O3 þ 3H2 O ð2Þ
tent are less obvious, although it is clearly necessary to provide
sufficient water to facilitate mixing and to provide a mechanism
CaðOHÞ2 ! CaO þ H2 O ð3Þ
for ionic transport. The effect of excess water may be to dilute
the reaction or leach the more soluble components and transport
2NaOH ! Na2 O þ H2 O ð4Þ
them away from the reaction zone [47].
Nevertheless, the formation of gel is dependent on the concen-
tration of alkaline OH group to initiate the dissolution of amor- 3.3. Optimum level of key components of treated POFA-based
phous phases (e.g. aluminosilicate source) at the initial stage of geopolymer mortar
the geopolymerization reaction [45]. The dissolution process in
alkaline medium with the inclusion of Al(OH)3 and Ca(OH)2 formed Finally, the statistical analysis of the Taguchi method can deter-
more OH than NaOH alone. The OH attacks the covalent bond mine the ideal combination of the optimum levels of all factors
(oxygen) of source materials, implying that Si–O–Si, Al–O–Al and while simultaneously meeting the highest response index for TPO-
Si–O–Al bonds are broken, yielding Al–OH and Si–OH groups [46]. FA-geopolymer mortar mixture. The compressive strength obtained
As discussed in the previous section, the influence of Ca(OH)2 as from the various trial mixtures (Table 5) ranged from 15.67 to
an activator increases the response index while NaOH reduces it. 44.74 MPa at 1, 3, and 7 days. Optimum levels achieved for the
This observation could be correlated to previous work which con- effective performance of each response are shown in Table 6. How-
cluded that when NaOH concentration is 10 M or above, dissolu- ever, the results can be verified by fabricating new mixtures and
tion of Ca(OH)2 is very difficult due to the presence of hydroxide producing nine specimens according to the optimum levels of all
[43,44]. This means that there will not be enough for the formation factors and testing them at 1, 3, and 7 days. The compressive
of C–S–H gel. Instead, sodium-based aluminosilicate is formed, strength obtained ranged between 42.64 and 47.27 ± 5.0 MPa at 1,
attracting OH to its structure, lowering the total amount of 3, and 7 days. This is higher compared to that of the 25th mixtures,
hydroxide groups and allowing the formation of C–S–H gel as a as shown in Table 5. Thus, the Taguchi method can be effectively
secondary reaction product [13]. Previous work [22] indicates that applied to optimize the compressive strength of TPOFA-geopoly-
NaOH concentrations may depend on the aluminosilicate source; mer mortar. The detailed analysis for this mixture is given in the
this has been verified by the findings of the present work. There- next section.
fore, one may conclude that for geopolymers with TPOFA as the
alumino silicate source, NaOH with a concentration of 10 M best 4. Characterization of the TPOFA-based geopolymer mortar mix
increases the strength.
4.1. Mineralogical analysis
3.2.2. Effects of Na2SiO3 to NaOH weight ratio (Factor E)
The response index for Factor E is shown in Fig. 1e. The response Fig. 2 shows the XRD diffractograms for TPOFA, TPOFA
index increased with the increase of Factor E up to E5. Nonetheless, containing the optimum amount of Factors A, B, & C, and the final
in the actual experiment, the workability of specimens fabricated optimized TPOFA geopolymer mortar. The phases found in raw
with amounts above E1 started to decrease due to higher viscosity TPOFA are similar to the XRD pattern observed by previous
of Factor E. The increased response index contributes to higher researchers [7,26,48]. It contains quartz (SiO2), cristobalite (SiO2)
[SiO4]4 concentrations which in turn increases the reaction rate and potassium aluminum phosphate (K3Al2(PO4)3), as shown in
(a higher concentration of reactants results in a higher reaction
rate).
The analysis of the response index which increased with the in-
crease in amorphous silica content testified to the insufficient reac-
A-Albite, C-Calcite, Cr-Cristobalite, G-Gibbsite, H-Hillebrandite, J-Jadeite,
tion of the amorphous silica introduced in the form of Factor B K-[ K3Al2(PO4)3], P- Portlandite, Q-Quartaz Low.
‘‘SF’’, as indicated in (Fig. 1b). This phenomenon can be compared
to that introduced in the form of Factor E ‘‘soluble sodium silicate Q
(water glass)’’, as indicated in (Fig. 1e). This difference was attrib-
uted to the rate of influence on the response index by the forma-
tion of C–S–H and geopolymer (N–A–S–H) gels with an increase
in the amorphous silica content. In general, the trends observed Q C
were in agreement with those from a previous investigation [29] G J G J Q
(c) J H H Q QC Q H Q Q
which showed that Factor E at E5 leads to the highest compressive
P
strength. The addition of Factor E into the activating solutions also (b) Q A G G
GA G PA Q P QP P P
A QG
enhances the polymerization process of the ionic species present in Q
the system, thus leading to higher response index. On the other (a) Cr k Cr k k Cr Q Q Q Q Q Q
hand, the decreased silica concentration in these solutions leads
to a less-polymerized distribution of silicon species, thereby reduc-
ing the compressive strength.
10 20 30 40 50 60

3.2.3. Effects of alkaline activator to solid weight ratio

The response index for Factor F is shown in Fig. 1f. The response Fig. 2. X-ray diffractograms of (a) TPOFA, (b) TPOFA substituted with optimum
index decreased with the increase in Factor F up to F5. The actual amount of (Ca(OH)2, Al(OH)3 and SF) and (c) TPOFA-based geopolymer mortar.
M.J.A. Mijarsh et al. / Construction and Building Materials 52 (2014) 473–481 479

Fig. 2a. However, for the TPOFA containing the optimum amounts spectra can be easily distinguished. TPOFA exhibiting a broad band
of Ca(OH)2, Al(OH)3 and SF, the XRD pattern shows the presence of around 1103 cm1 is associated with the asymmetric stretching
various new compounds, as shown in Fig. 2b. The main constitu- of Si–O–Si bonds of SiO2, along with a vibration mode at
ents are quartz low (SiO2) (ICSD No. 98-007-9362), portlandite 474 cm1 attributed to the symmetric stretching of Si–O–Si
(Ca(OH)2) (ICSD No. 98-003-5165), gibbsite (ICSD No. 98-011- bonds of SiO4 [53]. A band at 693 and 713 cm1 is associated with
2963), and albite Na(AlSi3O8) (ICSD No. 98-005-2543). This clearly the asymmetric vibration mode of the quartz double band [54],
indicates that various active reactions occurred between TPOFA that at 795 cm1 is attributed to the bending vibration mode of
and the additives. the Si–O–Si bonds [55], that at 875 cm1 is associated with the
XRD diffractograms of the TPOFA-based geopolymer mortar, as asymmetric vibration mode of the Al–O–H [56], that at
shown in Fig. 2c, indicate the formation of different phases dur- 1445 cm1 is associated with the asymmetric vibration mode of
ing geopolymer synthesis. The peaks correspond to hillebrandite the O–C–O bonds in carbonates, and that at 3600–2200 cm1 is
(ICSD No. 98-003-7574), quartz low (ICSD No. 98-005-6888), attributed to the stretching vibration mode of the (–OH, HOH)
jadeite (ICSD No. 98-011-0201), calcite (ICSD No. 98-000-5340), [57]. The FTIR spectrum of the TPOFA with additive material spec-
and gibbsite (ICSD No. 98-011-2963). The presence of the two imen showed certain differences when compared to the spectrum
significant phases, i.e. jadeite and hillebrandite indicate the for- of the starting TPOFA (source materials). The band at 3600–
mation of high quality geopolymer binders [49]. Jadeite (NaAlSi2- 2200 cm1 disappeared and the new band at the 3640 cm1 re-
O6) belongs to the family of aluminosilicates and its crystal gion is attributed to the stretching vibration mode of the Ca(OH)2
structure contains Si which are tetrahedrally coordinated in sin- [58]. A band indicated at source material TPOFA around
gle chains, with Al and Na in octahedral coordination [50]. Hille- 1103 cm1 which shifted to higher frequency at 1112 cm1 was
brandite, Ca2Si03(OH)2, is a natural member of the CaO–SiO2–H2O similarly associated with the asymmetric stretching of Si–O–Si
ternary system which includes numerous natural and synthetic bonds of silicon dioxide tetrahedra due to an increase in silica
calcium silicate hydrate (C–S–H) phases that result in an count derived from SF [53]. A new vibration band was also indi-
improvement in strength. Hillebrandite is composed of a three- cated at the 950 cm1 region and was associated with the asym-
dimensional network of Ca–O polyhedra that accommodate wol- metric stretching of Al–O–Si bonds due to increased number of
lastonite-type Si–O tetrahedral chains which resemble those octahedral aluminum atoms derived from Al(OH)3 [55].
reported for many calcium silicate hydrate (C–S–H) phases The differences between the FTIR absorption frequencies for the
[49,51]. The calcite (CaCO3) phase resulting from the carbonation source materials TPOFA (with and without additive) and geopoly-
of Ca(OH)2 or C–S–H with carbon dioxide to form calcium car- mer products could provide evidence of effective geopolymeriza-
bonate which presents itself between 20 and 30 (2h) [52]. There tion in this study. Bands indicated at source material TPOFA
was a small peak near 20° (2h), which was attributed to gibbsite, (with and without additive) around 3640 cm1, 950 cm1, and
Al(OH)3. It should be noted that preparation was not performed 875 cm1 disappear and the main characteristics bands of the
in an inert atmosphere. The presence of gibbsite likely resulted vibration spectra signaled at regions of 1103–1112 cm1 at TPO-
from unreacted material or the carbonation of excess Al(OH)4 FA (with and without additive) shifted to lower frequencies at
species. In the presence of excess sodium, this reaction can also wave number region 990–1015 cm1, indicating stretching vibra-
lead to the formation of sodium carbonate, though none was tion of Si–O–Al or Si–O–Si chains. This was correlated to the de-
detected by the XRD. crease in the number of Si–O–Al bonds (N–A–S–H gel) and the
increase in the number of Si–O–Si bonds (C–A–S–H gel) due to
4.2. Chemical bond development analysis using FTIR more cross-linked (N–A–S–H) and (C–S–H) binder gels which
caused the compressive strength to increase [8–10]. Theoretically,
Fig. 3 exhibits the FTIR analysis for the TPOFA (source material there should be a direct correlation between the mechanical
without additives, Fig. 3a), TPOFA (substituted with the optimum strength and silica content because increasing the amount of silica
amount of Ca(OH)2, SF, and Al(OH)3 (Fig. 3b), and alkali-activated increases the number of the Si–O–Si bonds which are stronger than
TPOFA (with additives, Fig. 3c) specimens. The three different Si–O–Al and Al–O–Al bonds. In agreement with alkali-activated
materials only based on slag or fly ash, this vibration band is usu-
ally identified between 950–1100 cm1, and is typically associated
with the binding gels (C–(A)–S–H for slag and N–A–S–H for fly ash)
(a)
[11]. On the other hand, TPOFA (with and without additive) vibra-
tions bands at 795 cm1 disappeared and double bands (693 and
3406

713 cm1) shifted to higher frequency at 779 cm1 and 796 cm1
3589

which is associated with the asymmetric vibration mode of the

693 and 713
875
795

(b) quartz double band [54], and vibrations band at 474 cm1 shifted
to lower frequency 451 cm1 region due to the bending of Si–
O–Si and O–Si–O bonds of SiO4 [53]. New vibrations band at
669 cm1 is attributed to the bending vibration mode of the O–
950

(c)
Si–O bending [54]. The common atmospheric carbonation of the
geopolymer was revealed by the band centered at 1500–
1112

1400 cm1, which indicated the appearance of O–C–O stretching

1650

669
1420

vibrations. Another interesting finding related to geopolymeriza-

3467

451

1015-990 tion includes the significant bands located at approximately

3467 cm1 and 1650 cm1 for the O–H, H–O–H stretches and H–
O–H bending, respectively [57].
4000 3500 3000 2500 2000 1500 1000 500
The observation from both XRD and FTIR is well-correlated and
Wavenumber (cm-1) explains the formation of the gel binder (C–S–H and N–A–S–H) in
Fig. 3. FTIR spectra of (a) TPOFA, (b) TPOFA with additive (substituted with
the geopolymer. This gel binder is responsible for the high com-
optimum amount of Ca(OH)2, Al(OH)3 and SF) and (c) TPOFA-based geopolymer pressive strength which has been proven by the experimental
mortar. works.
480 M.J.A. Mijarsh et al. / Construction and Building Materials 52 (2014) 473–481

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