International Journal of Minerals, Metallurgy and Materials

Volume 21, Number 1, January 2014, Page 89

DOI: 10.1007/s12613-014-0870-4

Fabrication and properties of foam geopolymer using circulating fluidized bed

combustion fly ash
Ze Liu, Ning-ning Shao, Dong-min Wang, Jun-feng Qin, Tian-yong Huang, Wei Song, Mu-xi Lin,
Jin-sha Yuan, and Zhen Wang
School of Chemical and Environmental Engineering, China University of Mining & Technology, Beijing 100083, China
(Received: 26 June 2013; revised: 11 August 2013; accepted: 22 August 2013)

Abstract: In recent years, circulating fluidized bed combustion fly ash (CFA) is used as a raw material for geopolymer synthesis. Hydrogen
peroxide was employed as a foaming agent to prepare CFA-based foam geopolymer. The particle distribution, mineral composition, and
chemical composition of CFA were examined firstly. Geopolymerization products were characterized by mechanical testing, scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray fluorescence (XRF). The CFA-based foam geopolymer was successfully fabricated with different contents of hydrogen peroxide and exhibited uncompleted alkali reaction and reasonable strength with relative low
atomic ratios of Si/Al and Si/Na. Type-C CFA in this research could be recycled as an alternative source material for geopolymer production.
Keywords: fly ash; geopolymers; foamed products; microstructure; hydrogen peroxide

1. Introduction
Geopolymers are new materials for coatings and adhesives, new binders for fiber composites, waste encapsulation,
and new cement for concrete [1-2]. They possess excellent
mechanical properties, fire resistance, and chemical resistance [3-4]. The condensation polymers based on dissolved
aluminium and silicon entities are sourced from materials
containing high concentrations of amorphous aluminosilicates, such as metakaolin or fly ash [2,5-9]. Fly ash is an
important industrial by-product, in terms of its production
quantity and its influence on environment [3]. Fly ash has
been found a suitable raw material for geopolymers, with or
without the addition of some other minerals or industrial
by-products, and under the activation of alkali and alkali-silicate solution [10-13]. Fly-ash-based geopolymers
have also exhibited great fire resistance and thermal insulation for refractory-type applications [14-15].
Geopolymers with different densities can be applied in
different areas. Porous structured materials with low density
are normally used in fire-proofing application for their insulating ability during high-temperature exposure [16]. Porous
Corresponding author: Ze Liu

foam geopolymers can be prepared, inducing foaming

agents before gel hardening, such as aluminium and zinc
with alkali metal hydroxides and hydrogen peroxide [17-18].
Some researchers have done much research on the topic of
fly-ash-based geopolymers, but there are still many outstanding issues to be solved, including the geopolymerization and foaming mechanisms of the fly-ash-based system,
water-to-fly ash ratio, curing conditions, and the role, types,
and contents of fly ash, alkali, alkali-silicate, and foam agent
[6,15,19-22].
In this paper, circulating fluidized bed combustion fly ash
(CFA) was employed as a raw material for its great properties of geopolymer fabrication [23-24]. The physical properties and microstructure of fly-ash-based foam geopolymers,
which are influenced by curing temperature and the concentration of foaming agent (hydrogen peroxide), were reported.

2. Experimental
2.1. Raw materials
The aluminosilicate source used in this study was CFA
from China Coal Group Corp. (Shuozhou, China). The CFA

E-mail: lzk1227@sina.com

University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg 2014

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Int. J. Miner. Metall. Mater., Vol. 21, No. 1, Jan. 2014

was ground in a laboratory ball mill and separated in grade

prior to geopolymerization. Particle size distributions of the
CFA was determined by an LS-C(IIA) laser analyzer
(OMEC, China), and the results are shown in Fig. 1. The
average particle size of the CFA is about 13.33 m, and the
surface area is about 503 m2/kg. The chemical composition
of the CFA and geopolymer, determined by an AXIOS
X-ray fluorescence spectrometer (XRF, PANalytical, Netherlands), is presented in Table 1. The fly ash mainly contains silica (SiO2), alumina (Al2O3), and iron oxides (Fe2O3)
with varying amounts of calcium, magnesium, and sulfur,
which belongs to type C fly ash. An industrial grade sodium
silicate solution (SiO2/Na2O = 3.25 (mole ratio); density:
1.38 g/cm3; Na2O: 8.89wt%; SiO2: 27.81wt%; water:
63.3wt%) was supplied by Hongxing Ltd. Co., Beijing,
China, while 96% pure sodium hydroxide (A.R.) was sup-

plied by Beijing Chemical Works, China. Sodium hydroxide

and sodium silicate solutions were used for fly ash activation.

Fig. 1. Particle size distribution of the CFA.

Table 1. Chemical compositions of CFA and geopolymer

Sample
CFA
GEO

SiO2
41.98
48.47

Al2O3
34.20
20.71

CaO
10.98
7.76

Fe2O3
2.84
1.94

MgO
1.44
1.10

Na2O
0.088
15.24

K2O
0.31
0.24

TiO2
1.37
1.34

P2O5
0.34
0.21

SO3
6.07
2.64

LOI
5.60
-

Note: LOIloss on ignition (960C).

2.2. Geopolymer synthesis

The alkali activator (AA, SiO2/Na2O = 1.0 (mole ratio),
67.5wt% of water) was prepared by adding NaOH pellets in
sodium silicate solution. Different amounts of foam stabilizers (1.0wt% sodium dodecyl benzene sulfonate and
0.8wt% triethanolamine, the weight of foam stabilizers were
equal to that of foaming agent) were added into the alkali
activator solution. The mass ratio of CFA/AA was 0.86, and
that of water/binder was 0.76. The CFA was mixed with
composite alkali activator solution and stirred for 10 min.
After adding different amounts of foaming agent H2O2 (0,
0.83wt%, 1.67wt%, 3.33wt%, and 5wt% of CFA) and stirring for 5 min, the reactive mixture was placed in triplet
steel molds (40 mm 40 mm 160 mm for each cuboid)
covered with polyethylene films and vibrated for 30 s to
make the slurry homogeneously. Then, the molds were
sealed with polyethylene films and set into a standard curing
box. After initial curing at 70C for 24 h, the samples were
demolded and subjected to further curing at room temperature. The molds were only half filled to allow the slurry to
expand unrestricted. All the experiments were performed
using the same batches of raw materials and chemicals, and
deionized water was used throughout.
2.3. Characterization
The density of the samples after 28 d was measured by

the simple method of dividing the mass by volume. Cuboid

samples (4 cm 4 cm 16 cm) were used for density
measurements. All the reported density results are the average of measurements from three samples. The porosities of
the cured samples after 28 d were measured using the Archimedes method. The microstructural characteristics of the
samples (e.g., pore size, pore wall thickness, their distributions, and geopolymerization morphology) were determined
using a scanning electron microscope (JEOL JSM-7001F).
Moreover, XRD patterns were recorded by an XTRA
high-performance powder X-ray diffractometer (ARL,
Switzerland) with Cu K radiation generated at 40 mA and
40 kV. Compressive strength and flexural strength tests
were performed immediately after the curing of 1, 3, 7, and
28 d had finished, using a TYE-300D compressive strength
testing apparatus (Wuxi Jianyi, China).

3. Results and discussion

Geopolymerization is a complex multiphase process that
involves a series of dissolution, reorientation, and
solidification reactions [1,25]. Fig. 2 shows the XRD patterns of the raw CFA and geopolymer. The patterns exhibit
a generally amorphous feature of the FA with some crystalline phases of quartz. A large amount of quartz in the raw
CFA has reacted with the alkali activator and has been converted into sodium aluminosilicate after fusion treatment.

Z. Liu et al., Fabrication and properties of foam geopolymer using circulating fluidized bed combustion fly ash

Therefore, it is reasonable to expect that the formation of

zeolite and mullite leads to enhanced dissolution of Si and
Al species from the fused CFA in aqueous solutions.

91

duced steam pores under high-temperature steam curing.

The pore structures of CFA-based foam geopolymers with
different foaming agent contents are shown in Fig. 4. It can
be seen that relative smaller pores in the matrix decrease and
relative larger pores in the matrix increase with increasing
foaming agent (H2O2) content. On the other hand, with the
increase in content of the foam stabilizer, macro-pores distribute more uniformly by interface modification. The
macro-pore sizes of the matrix is about 200-600 m, and the
pore wall thickness is about 100-200 m.

Fig. 2. X-ray diffraction patterns of CFA before and after

geopolymerization.

As shown in Fig. 3, when the foaming agent (H2O2) content increasing from 0 to 5wt%, the density of the foaming
agent decreases from 1593.7 to 276.6 kg/m3, and the
macro-porosity increases from 11.2% to 63.0%. The sample
without the addition of the foaming agent (H2O2) also exhibits some degree of macro-porosity due to the residue
pores of alkali-activated reaction in the mixture and the in-

Fig. 3. Density and porosity of CFA-based foam geopolymers

with different foaming agent contents.

Fig. 4. Pore distribution of CFA-based foam geopolymers with different foaming agent contents: (a) 0; (b) 0.83wt%; (c) 1.67wt%;
(d) 3.33wt%; (e) 5wt%.

According to van Jaarsveld et al.s study [26], alkali

metal cations control and affect almost all the stages of
geopolymerization and, in particular, during gel hardening

and crystal formation. Geopolymers with the atomic ratios

of Si/Al in the range of 3.16-3.46 have a higher compressive
strength [27]. The atomic ratio of Si/Na in an alkali solution

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affects the polymerization degree of the dissolved species.

Based on XRF data, the reacted products with the atomic ratios of Si/Al and Si/Na of 1.99 and 1.64 identified that the
reaction was uncompleted and formed N-A-S-H gel. It is
believed that the unreacted material in specimens with a
higher silica content acts as the defect site and has a negative effect on strength [28]. It can be seen in Fig. 5(a) that

the residual pores of 20-50 m are distributed among the

large pores after reaction, and it is noted that there is still
aluminosilicate gel mixed with the reacted product of
N-A-S-H gel, as shown in Fig. 5(b). Figs. 5(c) and 5(d)
show the evidence of a certain amount of tabular sodium
crystals due to the insufficient dissolution of sodium crystals.

Fig. 5. Geopolymerization micromorphologies of the CFA-based foam geopolymer.

The strength of the foam geopolymer is directly affected

by the foaming agent content. As shown in Fig. 6, the compressive strength decreases gradually with the increase in
foaming agent (H2O2) content. Due to the low atomic ratio
of Si/Al, the 1-d compressive strength of the geopolymer
without foaming agent is about 30.27 MPa. The development of compressive strength mainly occurs in 1-d steam
curing. The strengths do not increase obviously in the next
27 d because there is little foaming agent participated in
geopolymerization. With the decrease of density, the growth
rate of compressive strength increases gradually. For the
geopolymer containing 5wt% foaming agent (H2O2) with
the density of 276.7 kg/m3, the compressive strength increases from 0.35 to 0.65 MPa in the range of 1 to 28 d. The
flexural strength of the CFA-based foam geopolymer decreases with the increase in H2O2 content, and it can be improved by changing the atomic ratio of Si/Al and toughening fibers, as shown in Fig. 7.

Fig. 6. Compressive strength versus the content of foaming

agent (H2O2) in the CFA-based foam geopolymer.

4. Conclusions
(1) The particle sizes of CFA mainly distribute from 5 to
40 m, and the average particle size of CFA is about 13.33

Z. Liu et al., Fabrication and properties of foam geopolymer using circulating fluidized bed combustion fly ash

[5]

[6]

[7]
[8]
Fig. 7. Flexural strength versus foaming agent (H2O2) content
in the CFA-based foam geopolymer.

m. XRD patterns exhibit a generally amorphous feature of

the FA with some crystalline phases of quartz.
(2) With the increase in foaming agent (H2O2) content
from 0 to 5wt%, the density of the foaming agent decreases
from 1593.7 to 276.6 kg/m3, and the macro-porosity increases from 11.2% to 63.0%. Based on SEM observations,
the macro-pore sizes of the matrix are about 200-600 m,
and the pore wall thickness is about 100-200 m.
(3) According to XRF data, the foam geopolymer with
the atomic ratios of Si/Al and Si/Na of 1.99 and 1.64, respectively, identified that the reaction was uncompleted and
formed N-A-S-H gel. It exhibited some aluminosilicate gel
and tabular sodium crystals at partial places and relative low
strength at 1 to 28 d.

Acknowledgements
This work was financially supported by the National
Natural Science Foundation of China (No. 50872151),
the National Key Technology Support Project (No.
2009BAB48B02), the Fundamental Research Funds for
Central Universities (Nos. 2009KH09 and 2009QH02), and
the Specialized Research Fund for Doctoral Program of
Higher Education of China (No. 20120023110011).

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