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Microstructure Studies on the Effect of the Alkaline Activators of Fly Ash-

Based Geopolymer at Elevated Heat Treatment Temperature

Article  in  Applied Mechanics and Materials · September 2013

DOI: 10.4028/www.scientific.net/AMM.421.342

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Applied Mechanics and Materials Vol. 421 (2013) pp 342-348
© (2013) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMM.421.342

Microstructure Studies on the Effect of the Alkaline Activators of Fly

Ash-Based Geopolymer at Elevated Heat Treatment Temperature
A. M. Mustafa Al Bakri1,a, O. A. Abdulkareem1,b, H. Kamarudin1,c,
I. Khairul Nizar2,d, A. R. Rafiza1,e, Y. Zarina1,f, A. Alida1,g
1
Centre of Excellence Geopolymer & Green Technology (CEGeoGTech), School of Materials
Engineering, Universiti Malaysia Perlis (UniMAP), 01000, P.O. Box, D/A Pejabat Pos Besar, Kangar,
Perlis, Malaysia
2
School of Environmental Engineering, Universiti Malaysia Perlis (UniMAP), 02600 Jejawi, Perlis,
Malaysia
a
mustafa_albakri@unimap.edu.my, beng.omar83@yahoo.com, cvc@unimap.edu.my,
d
nizar@unimap.edu.my, erafizarazak@unimap.edu.my, fzarinayahya@unimap.edu.my,
g
alida@unimap.edu.my,

Keywords: Alkaline activator; Geopolymerization; Compressive strength; SEM analysis;

Geopolymer.

Abstract. Fly ash-based geopolymers are new binding materials produced to replace the ordinary
Portland cement (OPC) used in concrete. In this research, the effect of alkaline activators on the
compressive strength and the microstructure of low-calcium (Class F) fly ash-based geopolymers
were studied. Fly ash and the alkaline activator were mixed with alkaline activator to fly ash ratios
of 0.30, 0.35, and 0.40 at a constant ratio of water glass (sodium silicate) to sodium hydroxide
(NaOH). The alkaline activator solution was prepared by mixing water glass with a 15 M NaOH
solution. The samples were cured at a temperature 70 °C for 24 hr and maintained at room
temperature until the testing was conducted. The test results indicated that the compressive strength
increased when the ratio of alkaline activator to fly ash was increased at 7 days. The ratio of 0.4
produced the maximum compressive strength, which was 8.61 MPa. This was due to high reaction
rate between the fly ash and the alkaline activator solution. Morphology studies, conducted by SEM
analysis of the geopolymer samples, indicated that geopolymers synthesized at a ratio of 0.4 also
had the most homogeneous and less porous microstructures, which was attributed to the high
dissolution of the fly ash particles in the alkaline activator solution. The microstructure appearance
of geopolymers treated heat temperature of 400, 600 and 800°C, shows a sintering process takes
place for unreacted fly ash microspheres. It was observed as an overall, the visible microcracks
formed on the surface of the highest compressive strength geopolymers only, was due to loss of
water during heating.

Introduction
Over the last 20 years, geopolymers, which are also known as mineral polymers or inorganic
polymer glasses, have received much attention as a promising new form of inorganic polymer
material that could be used as a substitute for conventional or ordinary Portland cement, plastics,
and many other mineral-based products. However, to date, the exact mechanisms that govern
geopolymerization still are not fully understood [1].
Geopolymers are members of the family of inorganic polymers in which the chemical
compositions of the geopolymer materials are similar to natural zeolitic materials, but the
microstructure is amorphous. The composition of zeolites is based on an aluminosilicate framework
and a three-dimensional network of inorganic polymers made of SiO4 and AlO4 tetrahedra that are
linked by shared oxygen atoms into rings and cages. The polymerization process
(geopolymerization) involves a substantially fast chemical reaction under alkaline conditions with
Si and Al minerals that results in a three-dimensional polymeric chain and ring structure consisting
of Si-O-Al-O bonds [2].

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 Applied Mechanics and Materials Vol. 421 343

In addition, since the geopolymer synthesis technology is based on the alkaline activation of
source materials that contain mostly silicon (Si) and aluminum (Al) in amorphous form [3], the
similarity of some fly ashes to natural aluminosilicates (due to the presence of SiO2 and Al2O3 in the
ash) has encouraged the use of geopolymerization as a possible technology solution for making
cement with special properties [4-5]. The successful stabilization and immobilization of some toxic
heavy metals in geopolymeric material by Jaarsveld et al. [6] and Jaarsveld and Deventer [7], have
also encouraged the use of this fairly new technology.
Hos et al. [8] systematically analyzed the microstructure of an aluminosilicate inorganic polymer.
By using scanning electron microscopy (SEM), they observed that the polymer had a nonporous
microstructure. According to the authors, the structure is a result of the extensive dissolution of
aluminosilicate species that occurs before polycondensation begins, resulting in the consolidation of
the shapes of the specimen through a chaotic, three-dimensional network of polysodium
aluminosilicate. In addition, fly ash-based geopolymers also exhibit the extensive formation of
pores (or air bubbles). Palomo et al. [9] reported that fly ash-based geopolymer material is very
porous and that the microspheres (originating from fly ash grains) are surrounded by a curst of
reaction products. The adherence of the crust to the sphere does not appear to be very strong, and
the bonding between grains is produced through the necks of the reaction products, as indicated in
Fig. 1a. The development of cracks, which is likely to have been initiated from the pore, is evident
in the middle of the matrix (Fig. 1b).

a b

Fig. 1: Microstructure of the fly ash-based geopolymer (Palomo et al., 1999).

Materials and Experimental Details

Raw Materials. The raw materials used to prepare the samples were fly ash (class F) and alkaline
activator, which consisted of sodium silicate (water glass) mixed with a 15 M sodium hydroxide
(NaOH) solution. Solid NaOH pellets with 97% purity were obtained from Sigma-Aldrich Pty. Ltd.,
Germany, were used to prepare the 15 M NaOH solution. Technical grade sodium silicate liquid
(water glass) was supplied by South Pacific Chemical Industries Sdn Bhd (SPCI), Malaysia. The
chemical composition of the water glass solution was 9.4% Na2O, 30.1% SiO2, and 60.5% H2O,
with a weight ratio of SiO2:Na2O of 3.20-3.30), a specific gravity of 1.4 at 20 °C, and a viscosity of
400 cP at 20 °C. The fly ash was obtained from Sultan Abdul Aziz Power Station in Kapar, Selangor,
Malaysia, and it was equivalent to ASTM Class F. It was used as the base material for the
production of the geopolymers. The composition of the fly ash is given in Table 1.

Table 1: XRF analysis data of Fly ash composition

Compound Percentage in Fly ash (%)
SiO2 52.11
Al2O3 23.59
Fe2O3 7.39
TiO2 0.88
CaO 2.61
MgO 0.78
Na2O 0.42
K 2O 0.80
P 2O 5 1.31
SO3 0.49
MnO 0.03
344 Information Technology for Manufacturing Systems IV

Mix Proportion and Mixing Process. The geopolymers were synthesized by the activation of fly
ash with alkaline activator solution at alkaline activator to fly ash ratios of 0.30, 0.35, and 0.40 at a
constant ratio of water glass/NaOH solution. The alkaline activator, which consisted of a mixture
water glass and NaOH solution, was prepared and mixed at constant waterglass to NaOH solution
ratio of 1.0. The NaOH solution was prepared by dissolving sodium hydroxide pellets in deionized
water, and the concentration of the NaOH solution was kept constant at 15 M. It is preferable to mix
the water glass and the NaOH solution at least one day before adding the liquid to the solid
constituent. Geopolymer samples were synthesized by adding the alkaline activator gradually at the
different alkaline activator/fly ash ratios. Additional water, which amounted to a constant 17% of
the weight of the samples, was added to achieve suitable workability. The ratio of alkaline activator
to fly ash that was 0.25 was not used because it required the addition of water that would have
amounted to more than 17% of the weight of the sample. Table 2 shows the details of the mixing
proportions.
Table 2: Detailed of mix proportion

Water Activators (g)

AA/FA glass/NaOH FA (g) NaOH H2O in NaOH Water H 2O (g)
solid solution glass
0.30 1.00 450.00 25.312 42.188 67.50 102.45
0.35 1.00 450.00 29.531 49.219 78.75 103.27
0.40 1.00 450.00 33.750 56.250 90.00 107.10
*AA – Alkaline Activator, FA – Fly Ash
Molding, Curing and Compressive Strength Test. After 15 minutes of mechanical mixing, the
fresh, homogeneous, geopolymer paste was poured into standard steel molds that measured 50 x 50
x 50 mm. The samples were compacted with two layer placing, as described in ASTM C109. The
samples were maintained at room temperature for 24 hr prior to being cured in an electrical, low-
temperature furnace (L T Furnace, L6-1200) for 24 hr at 70 °C. The evaporation of water was
prevented by sealing the top of the molds with a thin plastic layer during storage as well as during
the curing stage. When curing was completed, the samples were removed from the furnace and left
at room temperature for seven days. The samples were sealed and not exposed to ambient air during
the aging period. In accordance with ASTM C109, after seven days of aging, the samples were
tested using an Instron mechanical testing machine (Instron 5569, USA). Three compression
strength tests were conducted for samples prepared with each ratio, and the values reported were the
averages of the three compressions strength values. The study on effect of compressive strength at
evaluated temperatures (400, 600, and 800°C respectively) also has been tested in this study.
Microstructure Analysis. Scanning electron microscopy (SEM) was performed using the SEM
JSM-6460 LA, Jeol, Japan, located in School of Material Engineering, Universiti Malaysia Perlis
(UniMAP), to analyze the microstructure of the fly ash and the geopolymer samples. The tests were
conducted using secondary as well as backscattered electron detectors. The samples were cut into
0.5-mm-thick slices and then ground into the powder form needed for the SEM analysis and also
study on optimum compressive strength fly ash-based geopolymer at evaluated temperatures (400,
600, and 800°C respectively).

Result and Discussion

Fig. 2 shows the effect of increasing the alkaline activator/fly ash ratio on the compressive strength
of the fly ash-based geopolymer. A rapid increase in the compressive strength from 3.695 to 8.325
MPa was observed as the alkaline activator/fly ash ratio was increased from 0.30 to 0.35. When the
ratio was increased from 0.35 to 0.40, the compressive strength increased from 8.325 to 8.610 Mpa.
This result was obtained due to the change in the alkaline activator content, which affected the
contents of Si species, base water, and Na+ ions. All of these factors have a major effect on the
 Applied Mechanics and Materials Vol. 421 345

geopolymerization process and on the strength of the resulting geopolymer. An increase in the
alkaline activator content (alkaline activator/fly ash ratio) increased the content of Si species
because the alkaline activator contained sodium water glass (more Si species), increased the
SiO2/Al2O3 ratio, and also increased the geopolymer strength since the increased the SiO2/Al2O3
ratio resulted in more Si-O-Si bonds, which are stronger than Si-O-Al bonds.

Compressive strength at 10
8.61
8 8.325
7 days (MPa)

4 3.695

0
0.25 0.3 0.35 0.4 0.45
Alkaline activator/Fly ash ratio

Fig. 2: Effect of alkaline activator/fly ash ratio on the compressive strength of fly ash-based
geopolymer.
Fig. 3 shows the SEM-determined microstructure of the original fly ash used in preparation of
the fly ash-based geopolymer. The fly ash consisted mostly of glassy, hollow, spherical particles,
which were cenospheres (thin-walled, hollow spheres); the appearance of the microstructure of the
original fly ash agreed well with that reported by Davidovits [10]. Although the fly ash particles
were essentially the same, variations in shape did occur (rounded to angular) with some crystals of
mullite and iron [11]. Furthermore, the surface texture appeared to be smooth and dense to highly
porous, and the surfaces sometimes had coatings, such as magnetite.

Fig. 3: SEM analysis of fly ash

Fig. 4 illustrates the SEM-determined microstructure characteristics of the original fly ash and
the prepared fly ash-based geopolymers synthesized at alkaline activator/fly ash ratios of 0.30, 0.35,
and 0.40 with a water glass/NaOH mass ratio of 1.0. The micrograph of the geopolymer synthesized
with an alkaline activator/fly ash ratio of 0.30 showed the typical microstructure associated with a
low geopolymerization rate, i.e., a porous, heterogeneous matrix with a high content of unreacted
fly ash microspheres, which gives low compressive strength (3.695 MPa). However, the
geopolymers synthesized with alkaline activator/fly ash ratio of 0.35 and 0.40 had microstructure
appearances that showed the formation of continuous, less porous, homogenous matrices that had
microcracks that resulted when water evaporated during the curing and aging processes. The
samples prepared using an alkaline activator/fly ash ratio of 0.40 also contained unreacted fly ash.
The higher dissolution rates associated with samples synthesized with alkaline activator/fly ash
ratios of 0.35 and 0.40 resulted in high geopolymerization rates, more homogeneous matrices, and
the highest compressive strength.
346 Information Technology for Manufacturing Systems IV

Fig. 4: SEM micrographs of the original fly ash and the synthesized geopolymers at activator/fly
ash ratios of 0.30, 0.35, and 0.40 and a water glass/NaOH solution ratio of 1.0
SEM Study of the Optimum Compressive Strength Fly Ash-Based Geopolymer at Evaluated
Heat Treatment Temperatures. The fly ash-based geopolymer samples attaining highest (optimum)
compressive strength (after 7days of aging) were conducted SEM study on their performance at
high temperatures of 400, 600 and 800°C. The prepared geopolymer samples as mentioned before
with optimum compressive strength (8.61MPa) obtained at Activator/Fly ash ratio of 0.4, at
waterglass/NaOH ratio of 1.00, were heat treated at 400, 600, and 800°C, with the same heating rate
(4.4°C/min) and same heating period of 1hour. Fig. 5, show fly ash based geopolymer samples after
heat treatment at 400, 600, and 800°C respectively.

Fig. 5: The optimum Fly ash-based geopolymers with optimum compressive strength of 8.61 MPa,
Activator/Fly ash ratio= 0.4 and waterglass/NaOH ratio = 1.00, after heat treatment at 400, 600, and
800°C
It was observed in Fig. 5, the heat treated geopolymer at temperature of 400°C shows noticeable
macrocracks of 0.1 to 0.2mm width appearing on the surface of sample as a result of temperature
exposure due to the evaporation of water, without any change in sample color. The microstructure
appearance of geopolymers treated heat temperature of 600°C and 800°C, shows a sintering process
takes place for unreacted fly ash microspheres. It was observed the sintering was resulted more at
higher temperature of 800°C than 600°C. The microstructure appearance at these temperatures were
rough heterogeneous with large proportion of micropores.
 Applied Mechanics and Materials Vol. 421 347

Furthermore, lighter gray of color was noticed in the geopolymer sample heat treated at
temperature of 600°C, and wider macrocracks were appeared than the geopolymer sample treated at
400°C. Whereas, at 800°C the geopolymer sample significantly formed relatively wide visible
cracks on the outer surface, due to the high rate of water evaporation from the sample at this
temperature, although higher sintering resulted in microstructure. The geopolymer destruction was
not only the visible gained property after the current treatment, but the significant color changing to
slightly red was also noticed. Moreover, other researcher reported that the deterioration in the
structure of the high temperatures treated geopolymers was occurred due to the evaporation of the
free water molecules as well as for chemically bonded water [12].
However, the SEM micrographs of the heat treated fly ash-based geopolymers at 400, 600, and
800°C indicated the degree of deterioration in the microstructure comparing with untreated
geopolymer show at Fig. 6. It was observed the initial matrix formed at 70°C, was start deteriorated
after heat treating at temperature of 400°C. The deterioration was due to the evaporation of water
from the surface, caused the formation micropores and extremely subverted and ruptured the
homogenous formed matrix at low temperature. It was observed as an overall, the visible
microcracks formed on the surface of the highest compressive strength geopolymers only, was due
to loss of water during heating. But sintering process occurred at high temperature more
significantly at 600 and 800 °C.
Before At 400°C

Micropores

Matrix Matrix

At 600°C At 800°C

Sintered fly ash Sintered fly ash

microspheres microspheres

Fig. 6: SEM micrographs of fly ash-based geopolymers (Activator/Fly ash ratio= 0.4,
waterglass/NaOH ratio = 1.00), before heat treatment and after heat treatment at 400, 600, and
800 °C

Conclusion
An increasing ratio of alkaline activator/fly ash resulted in increasing compressive strength of the
samples. The highest compressive strength (8.61 MPa) was obtained at an alkaline activator/fly ash
ratio of 0.40:1.0. The SEM study indicated that significant changes occurred in the microstructure
of original fly ash when it was mixed with the alkaline activator due to the formation of a matrix
during the geopolymerization reaction. The microstructure of the optimum strength geopolymer
appeared to be homogenous and contained the minimum proportion of unreacted fly ash
 348 Information Technology for Manufacturing Systems IV

microspheres. The microstructure appearance of geopolymers treated heat temperature of 600°C

and 800°C, shows a sintering process takes place for unreacted fly ash microspheres. The SEM
micrographs of the heat treated fly ash-based geopolymers at 400, 600, and 800°C indicated the
degree of deterioration in the microstructure comparing with untreated geopolymer.

Acknowledgement
This study was funded by King Abdul Aziz City Science and Technology (KACST). We would like
to extend our appreciation to the Green Concrete @UniMAP and the School of Material
Engineering, Universiti Malaysia Perlis (UniMAP).

References
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[3] D. Hardjito, S. Wallah, B. V. Rangan. Properties of Geopolymer Concrete with Fly Ash as
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