Accepted Manuscript

Development of porous fly ash-based geopolymer with low thermal conductiv-

ity

Junjie Feng, Ruifang Zhang, Lunlun Gong, Ye Li, Wei Cao, Xudong Cheng

PII: S0261-3069(14)00714-6
DOI: http://dx.doi.org/10.1016/j.matdes.2014.09.024
Reference: JMAD 6795

To appear in: Materials and Design

Received Date: 16 July 2014

Accepted Date: 9 September 2014

Please cite this article as: Feng, J., Zhang, R., Gong, L., Li, Y., Cao, W., Cheng, X., Development of porous fly ash-
based geopolymer with low thermal conductivity, Materials and Design (2014), doi: http://dx.doi.org/10.1016/
j.matdes.2014.09.024

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 Development of porous fly ash-based geopolymer with low thermal

conductivity
Junjie Feng, Ruifang Zhang, Lunlun Gong, Ye Li, Wei Cao, Xudong Cheng∗
State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei,
Anhui 230027, PR China
Abstract
Porous fly ash-based geopolymer material was produced using fly ash and sodium
water glass as original material and H2O2 as foaming agent. The changes caused by
the geopolymerization and decomposition of H2O2 on the properties of the final
products were investigated by applying curing on geopolymer mortars with different
amounts of sodium water glass (60, 80 and 100 g) and H2O2 (4, 6 and 8 g) added at
various curing temperatures. The samples were cured at two different temperatures
(55 and 85 °C). Physical properties such as porosity, density and thermal conductivity
and mechanical property were determined from the completely dried samples. As a
result, this study confirmed that the amount of sodium water glass, H2O2 and curing
temperature had effects on properties of the samples. Given the compressive strength
obtained and the environmental and economic effect, the optimal thermal curing
temperature and the amount of sodium water glass and H2O2 were 55 °C, 80 g and 6 g,
respectively. Sample synthesized at this condition had porosity of 79.9%, thermal
conductivity of 0.0744 W/m·K and compressive strength of 0.82 MPa. Therefore, it
shows promise as thermal insulation material in some situations.
Keywords: fly ash, geopolymer, thermal conductivity, sodium water glass,
environmental contribution
1. Introduction
The name “geopolymer” was originally introduced by Davidovits [1] to describe
the inorganic aluminosilicate polymers produced by synthesizing natural materials
such as metakaolin [2] or industrial by-products such as fly ash [3-6] and blast furnace
slag [7] with highly alkaline activators. Geopolymers exhibit a wide variety of
properties and characteristics, including high compressive strength, low shrinkage,
high temperature resistance [8] and acid and fire resistance [9, 10], and seem to be a
desirable alternative to ordinary Portland cement and environmentally sustainable
characteristics [10, 11]. Besides, the CO2 emission due to production of fly ash-based
geopolymer is at least 80% less compared to manufacture of ordinary Portland cement
[11, 12].
Throughout the world, numbers of researches are being carried out on the use of
waste materials [13] in order to either avert an increasing threat to the environment or
to streamline current disposal techniques by making them more affordable and
environmentally friendly [14]. Fly ash is an industrial waste with pozzolanic
properties obtained from thermal power plants and a large portion of it is disposed in
∗
Corresponding author. Tel.: +86 55163606957. Fax: +86 55163606957.
E-mail address: chengxd@mail.ustc.edu.cn (X.D. CHENG).
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landfills or ash lagoons, which produces endangering consequences to the
environment and people’s health [15]. Containing high levels of amorphous silica and
alumina, fly ash, which has favorable size and shape, is recently often used as an
original material to produce geopolymer. The main factors affecting the properties of
fly ash-based geopolymers include the particle size of the utilized ash, curing
temperature, curing time and alkaline activating solution [16]. Results of previous
investigations [17, 18] showed that the finer the particle size, the better properties.
Furthermore, literature [16] has validated that curing time was not an important factor
to determine the compressive strength.
Up to present, scores of works [14, 19-22] have been conducted on fly ash based
geopolymers and have gained some achievements. However, almost all of these
literatures focused on the effects of some parameters on the compressive strength of
geopolymers and few researches have emphasized on adding foaming agent into the
polymer pastes to produce porous geopolymer materials and taken the thermal
conductivity of them into consideration. In this study, H2O2 was added to the polymer
pastes to make porous geopolymer materials through the decomposition of H2O2 at
alkaline environment before the pastes were concreted. Considering the fact that the
organic thermal insulation materials widely used today are flammable and the
inorganic thermal insulation materials need complex processing conditions and high
sintering temperature, which is a big component in manufacturing cost, the porous fly
ash-based geopolymer material synthesized in this study has good application
potential as thermal insulation material in some situations.
2. Materials and method
2.1 The characterization of the original materials
Coal fly ash (100 meshes), obtained from the coal fired power station at Hefei,
was used as the original material and the XRF result showed that SiO2 and Al2O3
account for over 75% (mass ratio, as shown in Table 1). Sodium silicate solution
(water glass) with SiO2:Na2O weight ratio of 3.55 was used as activator for the
activation of fly ash in the process of geopolymerization and for the decomposition of
H2O2 without following modification. The water used is the ordinary domestic water
to minimum the production cost.
2.2 Mixing procedure
The mass of fly ash and water used was constant as 80 g and 60 g, respectively.
Among the 60 g water, 10 g was used to dilute the H2O2 because in our previous study
we found that diluted H2O2 was more likely to synthesize specimens with
homogeneous pores. The weighed fly ash, water and water glass were mixed for 2
min to give complete homogenization. Afterwards, the diluted H2O2 was added to the
mixture and mixed for another 1 min. Then the pastes were poured into plastic
moulds.
2.3 Preparation of the porous geopolymer mortar
Different amounts of water glass were used to determine the effect of water glass
dosage on the porous geopolymer materials, so were the different additive amounts of
H2O2.
The pastes were shaped in 140mm×70mm×50mm plastic moulds. The mixtures
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were then placed at ambient temperature to precure for 24 h because this precuring
time has been proved to be beneficial to strength development [23]. And after this
precuring process, the mixtures were completely foamed and the specimens were
placed in a laboratory-type oven (DHG101-00) for 24 h to cure thermally. The
prepared samples are shown in Table 2. The samples cured at 55 °C were coded as A
and those cured at 85 °C were coded as B. When a prepared porous geopolymer
specimen was activated by 60 g water glass with 4 g H2O2 and cured at 55 °C, this set
of samples was coded as 60A-4. Other specimens were also encoded depending on the
dosage of water glass, additive amounts of H2O2 and curing temperature.
2.4 Physical and mechanical tests
The thermal conductivity was measured using a hot-disc thermal analyzer
(DRE-2c, Instrument and meter Co., Xiangtan, China) at room temperature, adopting
the transient plane source technique. To achieve a relatively precise result, we
measured each pair samples three times and got the average value.
The principles of Archimedes were used to determine the physical property of
apparent porosity using water as immersion medium.
Compressive strength was obtained by a universal testing machine (MST809,
USA) with a cross-head speed of 0.5mm/min, which required the specimens to be Φ

20mm×20mm.
Pore morphology of samples was carried out using SAMSUNG ST200F on
fractures of samples to observe the effects of parameters on pore morphology.
3. Results and discussion
3.1 Density, Porosity and Thermal conductivity
Fig. 1-Fig. 3 represent the density, porosity and thermal conductivity of samples
cured at different temperatures. At the same curing temperature, when adding same
amount of sodium water glass, increases in H2O2 amount lead to a reduction in
density and thermal conductivity and increase in apparent porosity. H2O2 can be
easily decomposed in alkaline environment. However, if the basicity is too strong,
H2O2 will be decomposed in a shorter time even before the suspensions begin to
solidify. Similarly, the decomposition of H2O2 can not be finished while the
suspensions start to solidify if the basicity of suspensions is not enough. This can
explain why the properties of samples with 80g sodium water glass added are more
desirable than samples with 60g and 100g sodium water glass added. For instance,
porosities of samples 60A-4, 80-4 and 100A-4 are 78.5%, 79.1% and 76.3%,
respectively. And the corresponding thermal conductivities are 0.0886, 0.0816 and
0.0902 W/m·K, respectively.
In addition, with the increase of H2O2 amount, numbers of voids inside the
material with air contained could be generated, thus resulting in the reduction of
density and thermal conductivity and increase in apparent porosity. Density and
apparent porosity are generally correlated with thermal conductivity. For one thing,
some references has confirmed the opposite relationship between density and thermal
conductivity [24]. Meanwhile, the higher the porosity, the lower is the thermal

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conductivity. This is because higher porosity means more voids and the thermal
conductivity of air within the voids is much lower than that of solid substance, thus
leading to a comparatively lower thermal conductivity of the whole material [25].
Take 80A-4, 80A-6 and 80A-8 for example, thermal conductivity of them are 0.0816,
0.0744 and 0.0721 W/m·K, respectively. And the relevant density and apparent
porosity are 335, 260 and 239 kg/m3 and 79.1%, 79.9% and 81.2%, respectively.
Comparing the thermal conductivity of this porous fly ash-based geopolymer
material with other thermal insulation materials, it can be seen that the thermal
conductivity of this material is bigger than those of expanded perlite and kenaf
insulation board [26, 27], but close to that of cotton stalk insulation board [25] and
even smaller than that of lightweight aggregate [28]. Meanwhile, considering its
noninflammability, simple technology, cost saving and environmental contribution,
the material synthesized in present work shows potential for building thermal
insulation application.
Moreover, comparing the properties of samples cured at different temperatures,
we can figure out that increasing the curing temperature contributes to changing the
samples to dense. As for the thermal conductivity, the increase of curing temperature
magnifies it except for the samples with 100g sodium water glass added. This should
be attributed to the rapid decomposition of H2O2 which weakens the effect of curing
temperature.
3.2 Compressive strength
The compressive strength of porous fly ash based geopolymer samples were
measured using mechanical testing with a universal testing machine (MST809, USA).
The strength of samples was tested after the samples were completely dried. Fig. 4
represents the compressive strength of samples cured at different temperatures with
various dosages of H2O2 and sodium water glass added. The increase of H2O2 amount
declines the compressive strength when adding the same amount of water glass. For
example, compressive strength of samples 80A-4, 80A-6 and 80A-8 is 0.96, 0.82 and
0.67 MPa, respectively. This should be attributed to the increased porosity of samples
due to the increment of H2O2. Meanwhile, with the same additive dosage of H2O2,
increasing the quantity of water glass facilitates the compressive strength. Because the
increase of sodium water glass increases the Si species content, water content and
SiO2/Al2O3 ratio and the increased SiO2/Al2O3 ratio resulted in more Si-O-Si bonds,
which are stronger in comparison with Si-O-Al [29, 30]. Moreover, water content is
considered the most important factor in the geopolymerization process [31], thus the
increased sodium water glass favors the compressive. In addition, comparing the
compressive strength of samples cured at different temperatures, it can seen that the
compressive strength of samples cured at 85 °C is slightly higher than those cured at
55 °C.
3.3 Pore morphology
Fig. 5 represents the photographs of fracture surfaces of samples cured at various
temperatures with different amounts of sodium water glass and H2O2 added. It can be
figured out clearly that the increase of sodium water glass amount enlarges the pore
size of the samples. In addition, when adding superfluous water glass, the

4
decomposition of H2O2 is violent and some macropores are left inside the sample,
which is unfavorable. Comparing photographs of (d), (e) and (f), it is easy to reach a
decision that increasing the dosage of H2O2 can also magnify the pore size because of
the continuous decomposition of H2O2. Moreover, by the contrast of images (b) and
(e), conclusion can be made that curing temperature has little influence on the pore
morphol
4. Conclusions
In present work, porous fly ash-based geopolymer materials with low thermal
conductivity (as low as 0.0721 W/m·K) were prepared using fly ash and water glass as
original materials. The additive amount of sodium water glass and H2O2 were the
major parameters controlling porosity, density, thermal conductivity and pore
morphology. Too much or too little water glass, namely too strong or too weak
basicity of suspensions, was not appropriate for the decomposition and synthesis of
samples. Meanwhile, with the same amount of water glass added, higher dosage of
H2O2 meant higher porosity, lower compressive strength and thermal conductivity and
irregularity of pore morphology. Effects of curing temperature on pore morphology
were not so obvious. However, increase in curing temperature led to the densification
of samples, increase of thermal conductivity (samples except 100B-6 and 100B-8) and
gain in compressive strength. Given the compressive strength obtained and the
economic effect, the optimal thermal curing temperature and the amount of sodium
water glass and H2O2 were 55 °C, 80g and 6g, respectively. Samples synthesized at
this condition had porosity of 79.9%, thermal conductivity of 0.0744 W/m·K and
compressive strength of 0.82 MPa. The samples obtained in present work shows
promise in application of wall insulation materials.
Acknowdgements
The authors gratefully acknowledge the financial support from Basic Research
Program of China (973 Program) (Grant No.2012CB719701) and National Key
Technology R&D Program of China (2013BAJ01B05).
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Figure captions
Fig. 1 Density of the porous fly ash based geopolymer material
Fig. 2 Apparent porosity of the fly ash based geopolymer material
Fig. 3 Thermal conductivity of the porous fly ash based geopolymer material
Fig. 4 Compressive strength of the porous fly ash based geopolymer material
Fig. 5 Photographs of fracture surfaces of samples (a) 60A-6 (b) 80A-6 (c)
100A-6 (d) 80B-4 (e) 80B-6 (f) 80B-8

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 Oxides Fe2O3 SiO2 K2 O CaO Al2O3 TiO2 Na2O MgO SO3
Contents
6.68 46.77 1.48 11.15 25.22 1.58 1.57 1.37 3.0
（%）

Table 1 Chemical composition of FA

Porous geopolymer Dosage of water glass Curing temperature Dosage of H2O2

(g) (°C) (g)
60A-4 60 55 4
60A-6 60 55 4
60A-8 60 55 4
80A-4 80 55 6
80A-6 80 55 6
80A-8 80 55 6
100A-4 100 55 8
100A-6 100 55 8
100A-8 100 55 8
60B-4 60 85 4
60B-6 60 85 4
60B-8 60 85 4
80B-4 80 85 6
80B-6 80 85 6
80B-8 80 85 6
100B-4 100 85 8
100B-6 100 85 8
100B-8 100 85 8

Table 2 Prepared samples and curing temperature

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Highlights

 Using industrial waste fly ash as main material to reduce its environmental
endanger.
 Its synthetic process is simple and environmently friendly and needs no sintering.
 Its thermal conductivity is as low as 0.0721 W/m·K.
 It can be used as lowcost insulation materialin some conditions.
 The properties of samples made at various experimental conditions were
discussed.

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