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Procedia Environmental Sciences 18 (2013) 722 – 730

2013 International Symposium on Environmental Science and Technology (2013 ISEST)

Synthesis and characterization of coal fly ash-based foamed


geopolymer
Sammy M. Nyale* , Omotola O. Babajide , Grant D. Birch, Nuran Böke,
Leslie F. Petrik
Environmental and Nano-Sciences Research Group, Department of Chemistry, University of the Western Cape, Bellville 7535,
South Africa

Abstract

Fly ash, a residue arising from the combustion of pulverized coal, is one of the major wastes generated in coal-fired
power stations. Several utilization options of fly ash are currently being practised in many countries in an effort to
minimize waste and protect the environment. This paper studied the potential use of fly ash from South African
power utilities in the production of foamed geopolymeric materials which may be suitable for various applications
including the building industry. The foamed geopolymers were synthesized through alkali activation of the fly ash
and subsequent hydrothermal treatment procedure. This was done by mixing fly ash (FA) with sodium hydroxide
(NaOH) and ultrapure water to form a paste, before introducing sodium hypochlorite solution (NaOCl, foaming agent)
into the existing paste. The resulting mixture was then placed in the oven to produce the foamed geopolymer. The
mixing was done using FA: NaOH: NaOCl: H2O mass ratio of 3.03: 1.00: 1.14: 1.00. The chemical composition,
mineralogy, morphology and molecular structure of the starting material (fly ash) and the synthesized product
(foamed geopolymer) were analyzed using XRF, XRD, SEM and FTIR respectively. The porosity and the bulk
density of the foamed geopolymer was also determined using mercury porosimetry.

© 2013 The
© 2013 The Authors.
Authors. Published
Publishedby
byElsevier
ElsevierB.V.
B.V.Open access under CC BY-NC-ND license.
Selection and/or
Selection and peer-review
peer-review under
under responsibility
responsibility of Beijing
of Beijing Institute
Institute of Technology.
of Technology.

Keywords: Fly ash; Geopolymer; Alkaline activation; Foaming agent; Porosity

1. Introduction

Fly ash is a fine grey powder and is the principal by-product generated during coal combustion
process[1]. Fly ash consists of particles arising from the combustion of pulverized coal at high
temperatures ranging from about 1400 °C to 1700 °C [2]. Wide scale coal firing for power generation
began in the 1920s [3] and since then millions of tons of fly ash waste have been generated around the

* Corresponding author. Tel.: +27-021-959-3878; fax: +27-021-959-3878.


E-mail address: 3004992@uwc.ac.za

1878-0296 © 2013 The Authors. Published by Elsevier B.V. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of Beijing Institute of Technology.
doi:10.1016/j.proenv.2013.04.098
Sammy M. Nyale et al. / Procedia Environmental Sciences 18 (2013) 722 – 730 723

world each year. Fly ash accounts for approximately 75 - 80 % of the total ash produced from the
combustion of pulverized coal in thermal power plants [4]. In the year 2000 approximately 349 Mt of coal
ash was produced worldwide [5]. As of 2010, the estimated amount of coal ash produced worldwide was
600 million tons, out of which 500 million tons was fly ash [4]. China and India produce approximately
160 and 118 million tons [6] of coal fly ash annually respectively while over 100 million tons [7] of coal
fly ash is produced annually in the USA and EU. In South Africa, Eskom which is the leading electricity
generating company produces approximately 22.5 million tons of coal fly ash per annum [8]. Other
leading countries in fly ash production include Australia (13 million tons p.a.), Greece (10 million tons
p.a.), Japan (9 million tons p.a.) and Italy (1 million tons p.a.) [6].
Fly ash is made up of inorganic matter, previously present in the feed coal, which is left behind after
the coal burning process with a small amount of carbon that remains from incomplete combustion [2, 9].
Fly ash is a ferro aluminosilicate material. The most common elements found in fly ash include Si, Al, Fe,
Ca, Mg, K and Na [1, 10]. Fly ash may also contain trace elements such as As, Zn, Pb and Se; base metals
such as Ga and Ge; and rare earth elements[11]. Fly ash contains elements and minerals in various
quantities. Approximately 188 minerals or mineral groups have been identified in coal fly ashes [12]. The
common minerals in coal fly ash are quartz (SiO2), mullite (Al6Si2O13), hematite (Fe2O3) and magnetite
(Fe3O4) [13]. Several studies on the morphology of coal fly ash have been done over the years. It has been
found that coal fly ash is mainly composed of fine spherical particles of aluminosilicate glass, some solid
and others hollow. However, the carbonaceous fraction in the fly ash consists of angular particles [4, 14].
The hollow spheres found in fly ash, commonly known as “cenospheres”, vary in size ranging between 45
μm and 150 μm [15]. Fly ash particles have a smooth outer surface which is due to the presence of the
aluminosilicate glass phase [16].
The disposal of fly ash often requires large land areas to be used as dump sites which may lead to
encroachment on agricultural land. Other challenges related to fly ash disposal include high disposal costs
and potential leaching of toxic elements from the dumped fly ash into surrounding soil or ground
water[17, 18]. It is of great importance to invest more in beneficiation techniques of fly ash in order to
optimize its utilization and increase its value and subsequently minimize environmental challenges
associated with its disposal [17]. The utilization of fly ash varies with different countries ranging from a
minimum of 3 % to a maximum of 57 %, however the world average figure comes to only about 16 % of
the 500 million tons of fly ash produced per annum globally being utilized [4] while the bulk of it is
disposed. It is necessary to focus more on utilization options of fly ash rather than on better ways of
disposing it. Understanding the mineralogy and chemical properties of fly ash from a particular source is
crucial in considering possible applications of fly ash, such as in the construction industry, as well as
environmental impact evaluation [19].
Fly ash can be utilized as starting material for geopolymer production with different synthesis methods
reported in literature [20-23]. The term ‘geopolymer’ was first used by Davidovits referring to a class of
three dimensional aluminosilicate materials [24]. Geopolymers are mineral polymers resulting from
geochemistry or geosynthesis [25]. According to Davidovits, geosynthesis is the science of manufacturing
artificial rock at a temperature below 100 °C in order to obtain natural characteristics such as hardness,
longevity and heat stability [26]. The exact mechanism of the geopolymerisation process is not fully
understood. However it is thought to be a two-step process involving firstly the dissolution of silicon and
aluminium species from the surfaces of the starting materials as well as the surface hydration of
undissolved particles of the starting materials, followed secondly by the polymerisation of active surface
groups and soluble species to form a gel and subsequently a hardened geopolymer structure. An alkali
metal salt and/or hydroxide component is needed for the dissolution of the silicon and aluminium
species[27, 28]. Geopolymeric materials, due to their fire resistance, durability and excellent mechanical
properties, can be utilized in various fields including ceramics, cements, matrices for hazardous waste
stabilization, fire-resistant materials, asbestos-free materials and high-tech materials [29].
724 Sammy M. Nyale et al. / Procedia Environmental Sciences 18 (2013) 722 – 730

2. Materials and methods

2.1. Sampling

The fly ash samples used in this study were obtained directly from the hoppers in the ash collection
system at a power station situated in Mpumalanga Province, South Africa.

2.2. Characterization of the ash samples

The raw fly ash samples were analysed for chemical composition, mineralogy, morphology and
molecular structure using XRF (Philips 1404 Wavelength Dispersive spectrometer), XRD (Philips
PANalytical pw3830 X-ray generator), SEM (LEO SEM 1450) and FTIR (Perkin Elmer spectrum 100)
respectively.

2.3. Synthesis

The foamed geopolymers were synthesized through alkali activation of the fly ash and subsequent
hydrothermal treatment procedure. This was done by mixing class F fly ash with sodium hydroxide
(NaOH) and ultrapure water to form a paste, before introducing sodium hypochlorite solution (NaOCl,
foaming agent) into the existing paste. The mixing was done using FA: NaOH: NaOCl: H2O mass ratio of
3.03: 1.00: 1.14: 1.00. The resulting mixture was poured into a mould and left at room temperature (1
hour for G1 and 24 hours for G2) then placed in an oven at 80 °C for 24 hours while completely sealed.
The resulting foamed geopolymer block was then unsealed and oven dried at 80 °C for another 24 hours
in order to expel excess moisture. Two foamed geopolymer blocks G1 and G2 were produced for
comparison purposes.

2.4. Characterization of the foamed geopolymer

The synthesized foamed geopolymers were analysed for mineralogy, morphology and molecular
structure using XRD, SEM and FTIR respectively. The porosity, density, pore area and pore diameter of
the synthesized foamed geopolymers was also determined using mercury porosimetry (AutoPore II 9220
V3.03).

3. Results and discussion

3.1. Bulk chemical analysis using XRF

The distribution of the major and trace elements present in the fly ash is shown in Table 1. It is evident
that the fly ash is predominantly composed of SiO2 and Al2O3 which together account for 82.06 % by
mass of the total ash content, although fair amounts of iron oxide and calcium oxide are also present. The
SiO2 and Al2O3 contained in the ash provide a rich source of Si and Al atoms necessary for geopolymer
formation. The fly ash used in this study can be classified as Class F as per ASTM standards as the
combined amount of the oxides of silicon, aluminium, and iron by mass is greater than 70 % and calcium
oxide is less than 10 % [30]. The loss on ignition (LOI) is a measure of unburnt carbon in the fly ash
(6.27 % by mass) and can be used as an indicator for the efficiency of the combustion chamber at a power
station.
Sammy M. Nyale et al. / Procedia Environmental Sciences 18 (2013) 722 – 730 725

Table 1. Chemical composition of the fresh fly ash (n=3)

Element (mass %) A1 A2 A3 Mean mass (%) Std Dev


SiO2 55.65 55.03 54.96 55.21 0.38
Al2O3 27.04 26.78 26.73 26.85 0.17
CaO 5.48 5.56 5.56 5.53 0.05
Fe2O3 6.21 6.19 6.19 6.20 0.01
Na2O 0.19 0.05 0.06 0.10 0.08
MgO 1.53 1.58 1.56 1.56 0.03
TiO2 1.56 1.67 1.68 1.64 0.07
K2O 0.59 0.58 0.57 0.58 0.01
P2O5 0.38 0.38 0.38 0.38 0.00
MnO 0.05 0.05 0.05 0.05 0.00
Cr2O3 0.03 0.03 0.03 0.03 0.00
LOI 6.27 6.27 6.27 6.27 0.00

3.2. Morphological analysis using SEM

Fig1 shows the surface morphologies of the fly ash in comparison with the synthesized foamed
geopolymer blocks. It can be seen that the fly ash mainly consists of spherical particles with smooth outer
surfaces. The smooth aluminosilicate spherical particles, also known as cenospheres, are formed as a
result of thermochemical transformations of mineral particles during coal combustion process, where the
minerals melt to form small droplets, which upon sudden cooling and action of surface tension forces
adopt the spherical shape [31]. The morphology of the synthesized foamed geopolymer G1 consists of
agglomerated particles and partially broken cenospheres while G2 features irregular particles and
complete disappearance of the cenospheres. These morphological changes observed in the geopolymer
blocks are due to the dissolution of SiO2 and Al2O3 (contained in the cenospheres) in alkaline solution
leading to the formation of aluminosilicate gel [32] which then acts as a precursor to geopolymer
formation.
726 Sammy M. Nyale et al. / Procedia Environmental Sciences 18 (2013) 722 – 730

FA G1

G2

Fig. 1. SEM micrographs of the foamed geopolymer blocks vs. fly ash (FA: Fly ash, G1: 1 hour, G2: 24 hours).

G1 G2

Fig. 2. SEM micrographs of the foamed geopolymer blocks (G1: 1 hour, G2: 24 hours).
Sammy M. Nyale et al. / Procedia Environmental Sciences 18 (2013) 722 – 730 727

The absence of cenospheres in G2 as seen in Figure 1 clearly shows that the dissolution of SiO2 and
Al2O3 appears to increase with an increase in the fly ash/NaOH contact time, since G2 was left to stand
for 24 hours before being placed in the oven while G1 was left to stand for 1 hour. In Figure 2, it is
evident that G1 has larger and more spherical pores than G2 meaning that the amount of foam trapped in
the slurry is affected by the length of time the mixture is left in slurry form before being placed in the
oven to harden.

3.3. Mineralogical analysis using XRD

The XRD spectra of the fly ash in comparison with the synthesized foamed geopolymer blocks G1 and
G2 are presented in Figure 3. Four crystalline mineral phases were present in the fly ash namely quartz
(SiO2), mullite (3Al2O32SiO2), magnetite (Fe3O4) and lime (CaO). There is the appearance of sodalite
(Na4Al3Si3O12Cl), halite (NaCl) and tobermorite (Ca5Si6O16(OH)2·4H2O) mineral phases in G1 and G2
which were not present in the fly ash. However, quartz and mullite were also still present in G1 and G2.
Magnetite and lime were present only in the fly ash but not in G1 or G2. The foaming agent (sodium
hypochlorite solution, NaOCl) used in the geopolymer synthesis process may have played a role in the
formation of sodalite and halite phases seen in G1 and G2, while the lime present in the fly ash may have
been involved in the formation of tobermorite phase present in G1 and G2. The presence of quartz and
mullite in G1 and G2 indicates that not all SiO2 and Al2O3 originally in the fly ash was fully utilized
towards geopolymer formation.

Fig. 3. XRD data for the foamed geopolymer blocks vs. fly ash.

The lack of any Fe-containing mineral phase in G1 and G2 suggests that the magnetite in the fly ash
may have dissolved, but the resulting free Fe species did not participate in the formation of any crystalline
mineral phase during geopolymer formation, and could not be detected by the qualitative XRD technique
used in this study.
728 Sammy M. Nyale et al. / Procedia Environmental Sciences 18 (2013) 722 – 730

3.4. FTIR analysis

Fig. 4 shows the FTIR spectra of the fly ash in comparison with the synthesized foamed geopolymer
blocks G1 and G2. It can be seen that the fly ash exhibited a peak at 1070 cm-1 corresponding to a region
assigned for Si-O and Al-O asymmetric stretching vibrations [33, 34]. G1 had a peak at 965 cm-1 while
G2 had a peak at 957 cm-1, both regions assigned for Si-O and Al-O asymmetric stretching vibrations [33,
34]. The band shift observed can be attributed to the formation of the geopolymer structure which
typically shifts to lower wave numbers in comparison with fly ash as a result of Al atoms being
incorporated into the tetrahedral framework [21].

Fig. 4. FTIR spectra for the foamed geopolymer blocks vs. fly ash.

The further shift to lower wave numbers observed for G2 compared to G1 (Figure 4) shows a greater
extent of geopolymer formation with increase in the fly ash/NaOH contact time as G2 was left to stand
for 24 hours before being placed in the oven while G1 was left to stand for 1 hour. The peak at 822 cm-1
for the fly ash falls within the region assigned for Si-O and Al-O symmetric stretching vibrations [21].

3.5. Mercury intrusion porosimetry analysis

The mercury porosimetry data for the fly ash in comparison with the synthesized foamed geopolymer
blocks G1 and G2 are presented in Table 2.
Table 2. Mercury porosimetry data for the foamed geopolymer blocks

3 3 2
Sample ID Skeletal Density (g/cm ) Bulk Density (g/cm ) Total pore area (m /g) Average pore diameter (nm) Porosity (%)
G1 0.9500 0.6977 0.902 1688.6 26.56
G2 1.2714 1.0878 0.243 2187.1 14.44
Sammy M. Nyale et al. / Procedia Environmental Sciences 18 (2013) 722 – 730 729

G1 registered higher porosity and total pore area than G2 which corroborates with SEM analysis
showing G1 with larger pores than G2 (Figure 2). Due to higher porosity, G1 is less dense than G2 as
shown in Table 2. Therefore G1 has lower average pore diameter than G2.

4. Conclusions

The major chemical components in the fly ash were SiO2 and Al2O3, accounting for 82.06 % of the
total ash content, highlighting the aluminosilicate nature of the starting material and the availability of Si
and Al necessary for geopolymer formation. There is the appearance of mineral phases in the synthesized
foamed geopolymer which were not present in the fly ash e.g. sodalite, halite and tobermorite. Quartz and
mullite were present in the fly ash and the synthesized foamed geopolymer, however, magnetite and lime
were present only in the fly ash but not in the synthesized foamed geopolymer.
The fly ash consisted of smooth aluminosilicate spherical particles (cenospheres), while the
morphology of the synthesized foamed geopolymer featured agglomerated and irregular particles, thus
showing the extent to which the cenospheres were attacked by the hydroxide component. Furthermore,
the dissolution of SiO2 and Al2O3 appeared to increase with an increase in the fly ash/NaOH contact time.
Also, porosity of the foamed geopolymer was affected by the length of time the mixture was left in slurry
form before being placed in an oven to harden. Geopolymer formation was confirmed by FTIR bands at
965 cm-1 and 957 cm-1 corresponding to Si-O and Al-O stretching vibrations.

Acknowledgements
The authors would like to acknowledge the support of Environmental and Nano Sciences Research
Group, University of the Western Cape. The authors thank Remy Bucher, Adrian Josephs, Stephanie
Snoek and Cynthia Sanchez-Garrido for their assistance in analysis.

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