Materials and Design 74 (2015) 125137

Contents lists available at ScienceDirect

Materials and Design

journal homepage: www.elsevier.com/locate/matdes

An investigation of the microstructure and durability of a uidized bed

y ashmetakaolin geopolymer after heat and acid exposure
Ping Duan a,b,c,, Chunjie Yan a,b,c, Wei Zhou a,b, Wenjun Luo a,b, Chunhua Shen d
a

Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430074, China
Engineering Research Center of Nano-Geomaterials of Ministry of Education, China University of Geosciences, Wuhan 430074, China
c
Zhejiang Research Institute, China University of Geosciences, Hangzhou 311305, China
d
Center of Materials Research and Analysis, Wuhan University of Technology, Wuhan 430070, China
b

a r t i c l e

i n f o

Article history:
Received 28 November 2014
Revised 5 March 2015
Accepted 7 March 2015
Available online 9 March 2015
Keywords:
Geopolymer
Fly ash
Metakaolin
Durability
OPC

a b s t r a c t
This study aims to investigate durability and microstructure of uidized bed y ash and metakaolin based
geopolymer exposed to elevated temperatures and acid attack. Geopolymer specimens were prepared by
combination of y ash and metakaolin activated by sodium silicate and sodium hydroxide solutions and
were cured in microwave radiation environment plus a heat curing period. Compressive strength and
several key durability parameters for geopolymer and ordinary Portland cement (OPC) were assessed
and compared. Microstructure formation and development was characterized in terms of morphology
and pore structure as well as simulation.
The experimental results reveal a dense microstructure of geopolymer compared to OPC. In terms of
resistance to the acidic solution and elevated temperatures, geopolymer is superior to OPC as indicated
by the relatively lower strength loss and lower mass change. Compressive strength shows a dramatic
drop in OPC while geopolymer shows a strength increase after 400 C. The mass loss curves of geopolymer are similar to OPC, but it shows relatively lower mass loss compared to OPC. The result of saturated
water absorption after 28 days curing indicates less water absorption in geopolymer before and after
thermal and acid exposure. Durability of geopolymer is demonstrated by monitoring the pore structure.
Crown Copyright 2015 Published by Elsevier Ltd. All rights reserved.

1. Introduction
Cement production is associated with the emission of considerable amount of greenhouse gas [1]. The amount of carbon dioxide
released in the manufacture of cement is about one ton for one ton
cement clinker. Therefore, it is considered vital to search for alternative low CO2 emission binders for concrete in order to reduce its
carbon footprint and the development of alternative binders utilizing industrial by-products is one of existing strategies.
Geopolymer is such an emerging alternative binder, which is
prepared using by-product materials such as y ash (by-product
of coal combustion in thermal power plants with an average size
of less than 20 lm and low bulk density (0.540.86 g/cm3), high
surface area (300500 m2/kg) and light texture with spherical in
shape and consist of solid spheres, cenospheres, irregular-shaped
debris and porous unburnt carbon), blast furnace slag (produced
when iron ore is reduced by coke at about 13501550 C in a blast
Corresponding author at: Faculty of Materials Science and Chemistry, China
University of Geosciences, Wuhan 430074, China.
E-mail address: dp19851128@sina.com (P. Duan).
http://dx.doi.org/10.1016/j.matdes.2015.03.009
0261-3069/Crown Copyright 2015 Published by Elsevier Ltd. All rights reserved.

furnace. It normally contains more than 95% of glass. Generally,

they are ground to ne powder, called ground granulated blast
furnace slag), metakaolin (produced by calcining kaolin at
650800 C. The main components are amorphous Al2O3 and
SiO2 with high pozzolanic activity. Besides the lling effect, metakaolin reacts with calcium hydroxide, which is one of the hydration
products of Portland cement, to form calcium silicate hydrate gels)
or a combination of them instead of cement and results in less CO2
emission to reduce the environmental impact of the cement
production.
During the last decade, increased research efforts [29] have
been directed to this area due to the wide range of potential applications of these by-product materials, which has gained increasing
attention due to the energy conservation, economic and environmental considerations.
By-products of industry are some of the most complex and
abundant of anthropogenic materials. They cause water and soil
pollution, disrupt ecological cycles and environmental hazards
[10]. The current worldwide annual production of y ash, one of
such by-products, is estimated around 750 million tones [11]. At
present, only a minor part of this material is utilized (2030%) on

126

P. Duan et al. / Materials and Design 74 (2015) 125137

worldwide basis, while the rest is still disposed of in landlls, thus

contributing to the pollution of soil, water and air.
The environmental impact of coal y ash is well known for its
massive generation, large usage of land for disposal and short
and long term impact on surrounding areas. The principal environmental concern stems from the possible leaching of heavy metals
and organic compounds and their migration into ground water or
nearby surface water. In addition, y ash could also affect human
health through direct inhalation or ingestion of airborne or settled
ash. The unproductive use of land and its maintenance results in
long-term nancial burden [12].
Aggressive efforts have been undertaken recently to recycle y
ash [1317] in concrete production as mineral admixture, soil
amendment, zeolite synthesis, and as ller in polymers. However,
these applications are not sufcient for complete utilization of y
ash, thereby it is imperative to develop new recycling techniques
for y ash.
The concept of sustainable solutions for y ash is closely linked
with technologies with aligned vision for environment, economy
and societal goals. Fly ash was widely used as the source material
to manufacture geopolymer products owing to its aluminosilicate
composition, ne size, signicant amount of glassy content and
availability across the world [14,1820]. This is one of the existing
important strategies and it is believed to be the sustainable solution for utilization of y ash. It will consume large part of y ash
and relieve the pollution of soil, water and air.
The term geopolymer was introduced in 1970 by Davidovits,
who made a signicant breakthrough in understanding and
development of binders from metakaolin and alkaline metal
solutions. Geopolymer was originally applied to three-dimensional
aluminosilicate materials formed by condensation of a solid aluminosilicate source such as dehydroxylated kaolinite (metakaolin)
with an alkali silicate solution under highly alkaline conditions [21].
This new material was likely to have enormous potential to
become an alternative to Portland cement and it is receiving
increased attention due to the need of new binders with enhanced
durability performance [2228].
Although different source materials can be used to prepare
geopolymer binders, y ash, which provides the greatest opportunity for commercial utilization and has the potential to reduce the
carbon footprint, has been extensively used and found to be the
most practical source material suitable for concrete applications
due to the plentiful worldwide raw material supply, which is
derived from coal-red electricity generation [29].
Excellent properties of y ash-based geopolymer concrete have
been reported in the last decades [3038]. Fly ash-based geopolymer concrete has properties favourable for its potential use as a
cementitious material due to excellent durability aspects. Some
authors [3943] have reported good engineering properties of
geopolymer concrete that were favourable for its use as a construction material.
Geopolymer can be composed from metakaolin or wastes, such
as y ash, slag, and tailing [4448]. Geopolymer can be used as
building materials and llers due to their ameproof characteristics [4951]. In addition, geopolymer has several other advantages
such as high strength, acid/alkaline resistance and heat resistance
[44].
Having more outstanding mechanical properties and environmental friendliness, geopolymer, is considered to be a new
cementing material with widely potential application value in construction. With the aim of reducing consumption of non-renewable
raw materials whilst increasing the use of industrial by-products
(residue), research has recently focused on the alkali activation of
metakaolin and y ash.
Some authors [5257] explored some basic aspects of metakaolin or y ash-based geopolymer activated using sodium alkali for

high-temperature applications. They estimated that the structure

was stable enough to resist to high temperatures.
On balance, ash-based geopolymer was prepared based on a
precursor derived from y ash, generally consisting of spherical
particles, glassy or amorphous as well as crystalline phases.
Recently, increased utilization of uidized bed technology led to
the production of a great amount of uidized bed y ash including
little glassy spherical particles, which forms by burning coal
gangue in a low temperature. Circulation uidized bed combustion
is an advanced, clean and reliable coal ring technology for power
generation. There are many unreacted CaO, desulphurized products CaSO4 and a little CaCO3 remaining in the uidized bed y ash.
Coal y ash is typically found in the form of coarse bottom ash
and ne y ash, which represent 515 and 8595 wt% of the total
ash, respectively. Bottom ash refers to the ash that falls down
through the airow to the bottom of the boiler and is mechanically
removed. The term coal y ash is often used to refer to ne y ash,
particles of which are captured from ue gas and collected by electrostatic or mechanical precipitation.
Bottom ash is a coarse, granular, incombustible by-product that
is collected from the bottom of furnaces that burn coal for the generation of steam, the production of electric power, or both. Bottom
ash is coarser than y ash, with grain sizes spanning from ne sand
to ne gravel.
In general, uidized bed y ash differs from coal y ash in terms
of particle shape, chemical composition and amorphous phase content. Fluidized bed y ash particles are approximately 1300 lm in
size, with irregular shape, while coal y ash particles are normally
slightly ner at approximately 1200 lm in size and the content of
amorphous phase is usually higher than that of uidized bed y
ash. Coal y ash is widely used as pozzolanic material for partial
replacement of Portland cement due to its spherical shape and high
reactivity. Comparing with coal y ash, uidized bed y ash has
higher contents of lime (CaO), gypsum (CaSO4) and crystalline
phase thus its usage as pozzolanic material is limited. The unique
thermal history, featuring low combustion temperatures of
800950 C, makes uidized bed y ash differ greatly in physical
and chemical characteristics from coal y ash, whose typical ring
temperatures are 12001400 C.
It is well acknowledged that compositions and structure of
precursors have signicant effects on performance of geopolymer.
Previous research efforts about the relevant topic mainly focused
on cement paste [5870], or preparation and properties of geopolymer but below 1000 C, and acid attack was not mentioned
[7176]. Existing references on the utilization of uidized bed y
ash to prepare geopolymer and the durability aspects investigation
are scant, and the ash used belonged to high calcium y ash, there
have been very few published references on uidized bed y ash
based geopolymer exposed to elevated temperature at 1000 C
from ambient temperature and acid attack.
In the present study, geopolymer specimens were prepared by
combination of uidized bed y ash and metakaolin activated by
alkaline activator and were cured in microwave radiation environment. Compressive strength was investigated and several key
durability parameters for geopolymer and ordinary Portland
cement (OPC) were assessed and compared. Microstructure formation and development was characterized in terms of morphology,
pore structure and simulation.
2. Experimental
2.1. Materials
Fluidized bed y ash was provided by Shenhua Junggar Energy
Corporation in Junggar, Inner Mongolia, China. Metakaolin was
obtained from Yunnan, China. The chemical analysis of those raw

127

P. Duan et al. / Materials and Design 74 (2015) 125137

Table 1
Chemical compositions of raw materials by XRF analysis (mass, %).

Cement
Fly ash
Metakaolin
a

SiO2

Al2O3

Fe2O3

MgO

CaO

Na2O

K2O

MnO

TiO2

LOIa

21.35
29.47
53.32

7.67
51.72
42.09

3.31
2.25
2.33

3.08
0.15
0.21

62.60
5.21
0.09

0.35
0.05
0.49

0.39
0.35
0.64

0.05
0.03
0.02

0.25
1.83
0.63

0.95
8.58
0.08

LOI: mass loss of dried sample after calcined between 1000 and 1100 C.

Fig. 1. The micrographs (SEM) of uidized bed y ash.

materials mentioned above was listed in Table 1 and their micrographs were shown in Figs. 1 and 2, respectively. Alkali activator
was a combination of sodium silicate and sodium hydroxide
(99.2% NaOH) in analytical reagent degree. The liquid portions in
the mixture were 10 M sodium hydroxide (NaOH) and sodium
silicate (Na2SiO3) with 14.51% Na2O, 33.39% SiO2, and 48.53% H2O.
Portland cement (CEM I 42.5) (relative density 3100 kg/m3,
specic surface area 369.6 m2/kg) was used as binder and was
compared to geopolymer. The properties of cement were shown
in Table 2.
2.2. Test procedure
Geopolymer specimens were synthesized by alkaline-activation
of combination of uidized bed y ash and metakaolin with mass
ratios of 1.0 in alkali silicate solutions (MR = 1.6, MR means
modulus of alkaline activator). The liquid/solid (L/S) mass ratio
was kept constant and equaled to 0.4 (the liquid consists of water
in alkaline solutions and the extra water, the solid materials consists
of y ash, metakaolin or a combination of them), which depended
on an acceptable workability for each paste sample. Fresh geopolymer pastes and cement paste were cast in triplet steel cubes molds
with size of 40  40  40 mm3 and 20  20  20 mm3, respectively,
and vibrated to remove entrained air bubbles. The molds were then
sealed with polyethylene lm and set into a standard curing box in
microwave radiation environment for 5 min. After initial curing at
40 C for 1 day, the samples were released from the molds and were
subjected to further curing at 40 C for acquired ages.

All samples were calcined from ambient temperature to 1000 C

in an electric mufe furnace with a heating rate of 2 C/min and
then cooled to room temperature. Sample characterization was
conducted on geopolymer and OPC specimens to evaluate the
effects of the elevated temperature exposure on properties of
them.
2.2.1. Compressive strength
After casting, the molds containing the specimens were covered
with a plastic sheet and stored in the laboratory environment
(20 C and 90% RH) for 24 h. The paste specimens with size of
40 mm  40 mm  40 mm were then removed from the molds.
The compressive strength was determined using a universal
testing device with a loading capacity of 3000 kN. The loading rates
applied during the compression tests was 0.6 MPa/s. For each
mixture, the compressive strength was measured at the age of
acquired days.
2.2.2. Drying shrinkage
Paste specimens of the size 20  20  200 mm3 were prepared
for the drying shrinkage test. The specimens were removed from
the molds after being cured for 24 h. The prism specimens were
installed onto the setup for the length change tests and cured in
a room with constant temperature and relative humidity
(20 3 C, RH = 90 5%). Length changes of the prism before and
after high temperature exposure were recorded by reading the dial
gauge regularly [77].

128

P. Duan et al. / Materials and Design 74 (2015) 125137

Fig. 2. The micrographs (SEM) of metakaolin.

Table 2
The properties of cement.
Compressive
strength (MPa)

Flexural
strength (MPa)

3 days

28 days

3 days

28 days

27.3

47.5

6.3

8.7

Initial setting time

(min)

Final
setting
time (min)

132

187

2.2.6. Micrographs test

The morphological changes that occurred during thermal exposure were obtained by means of JSM-5610LV scanning electronic
microscopy (SEM). The specimens for morphology observation
were cut into prisms of about 8  8  2 mm3.
3. Results and discussion

2.2.3. Acid attack

Cement and geopolymer pastes were placed in a cylinder mold
with size of 100 mm  50 mm. Test pieces were kept in a moist
room. After 24 2 h curing, the test pieces were removed from the
molds. The test pieces were immerged in the sulfuric acid (2%) plus
hydrochloric acid (2%) solutions for 28 days. After the immersion
test, compressive strength loss compared to the original strength
was measured and appearance of the exposure surfaces was
observed to evaluate the resistance to acid attack.
2.2.4. Water sorptivity
Water sorptivity test was carried out on specimens with size of
100 mm  50 mm for both cement and geopolymer paste. The
specimens were oven dried for 3 days at 50 C followed by 28 days
sealed storage. After this curing stage, the specimens were
immerged into deionized water for several days and the mass
changes before and after immerged into water were measured to
evaluate the resistance to water permeability.
2.2.5. Mercury intrusion porosimetry
The porosity and pore size distribution of paste were measured
by mercury intrusion porosimetry (MIP, AutoPore IV 9500 type)
with a maximum pressure of 207 MPa. The contact angle was
140 and the measurable pore size ranged from about 6 nm to
360 lm. The samples in the shape of pellets of 5  5  5 mm3 in
size for pore structure testing were separated from the crushed
specimens. The samples were immerged in ethanol to avoid rehydration immediately after being crushed and dried at about 105 C
for 24 h before pore structure test.

3.1. Temperature prole

It is believed that geopolymer possesses good thermal stability
property due to re resistance stems from ceramic-like properties.
To evaluate thermal resistance of the investigated samples and the
inuence of high-temperatures on microstructure, dimension stability and mechanical properties, all samples were calcined from
room temperature to 1000 C in an electric furnace with a heating
rate of 2 C/min and then cooled naturally to room temperature.
Sample characterization was conducted on untreated and calcined
samples to evaluate the effects of the elevated temperature exposure on OPC and geopolymer with size of 40  40  40 mm3 and
20  20  20 mm3, respectively.
The temperature of the air inside the furnace was measured by
an in-built thermocouple. The temperature at the centre of the specimen was measured by a K-type thermocouple inserted in the
specimens during casting. The thermocouples were connected to
electronic data loggers that recorded the measured temperatures.
The result provided in Fig. 3 reveals the temperature evolution
at different distances from the heated surface of a cubic OPC and y
ashmetakaolin geopolymer to the center of paste specimens
during heating process. Maximum thermal gradient between the
exposure surface and center can be observed to occur between
180 and 270 min. This clearly shows that the distribution of temperature is not uniform and a thermal gradient exists. This thermal
gradient is likely to have adverse effects on the integrity of the OPC
and geopolymer paste at elevated temperatures.
Heat resistance is the ability of materials withstanding a high
temperature treatment while not destroying during the treatment.

P. Duan et al. / Materials and Design 74 (2015) 125137

Fig. 3. Temperature evolution of geopolymer and OPC at various distances to the

surface.

Water accumulated inside the geopolymer structure is the main

contributor to re resistance and it would release during the
heating process to reduce the heat temperature and also to form
a porous microstructure. Therefore, geopolymer shows lower temperature at the same distance to the surface compared to OPC.
3.2. Compressive strength at elevated temperatures
The compressive strength of OPC and geopolymer paste specimens at 28 days of curing were tested and compared before and
after elevated temperatures exposure and the results has been
summarized in Fig. 4.
The results provided in Fig. 4 show that the OPC suffers strength
loss after high temperature exposure. However, the y ash
metakaolin geopolymer gains strength after the same high temperature exposure around 400 C. Compressive strength development
indicates a dramatic drop of nearly 100% in OPC paste specimen
while y ashmetakaolin geopolymer shows a strength increase
of about 3% after 400 C, attaining a peak strength of 72 MPa at
400 C. Subsequently, this strength can be observed to deteriorate
gradually. However, a nal strength of 46 MPa is recorded after
the 1000 C temperature exposure, which is about a 25% decrease
over the strength of the reference specimen at ambient temperature.

129

On the other hand, the compressive strength of OPC specimens

drops considerably between temperatures of 400 C and 600 C.
This strength deterioration of OPC is attributed to the Ca(OH)2
decomposition that occurs at about 400 C. In geopolymer, aluminosilicate gel is the major binding phase that provides interparticle
bonding, which in turn enhances the macroscopic strength [7880]
and takes over the strength gain behavior of geopolymer paste.
The compressive strength of geopolymer changes dramatically
at early ages. The compressive strength of OPC and geopolymer
paste specimens at 3 days of curing were also tested and compared
before and after elevated temperatures exposure and the results
has been summarized in Fig. 5.
The results provided in Fig. 5 reveal that the OPC suffers strength
loss after high temperature exposure, however, the y ash
metakaolin geopolymer gains strength around 400 C. Compressive
strength development shows a dramatic drop of nearly 100% in
OPC paste specimen after 600 C, and a nal strength of 25 MPa
for geopolymer can be observed after the 1000 C temperature
exposure.
As mentioned above, water accumulated inside the geopolymer
structure is the main contributor to heat resistance and it would
release during the heating to reduce the heat temperature and also
to form a porous microstructure. The water releases during
geopolymer formation is expelled from the geopolymer matrix
during heating process, causing discontinuous nano pores throughout the matrix, which improves the strength of the geopolymer
[81] before 400 C. On the other hand, the generation of bubble
and foam-like structure subjects to high temperature makes the
geopolymeric system porous and it reduces the density, which
shows a negative effect on the compressive strength after 400 C.
3.3. Thermal stability
Thermal stability of the selected geopolymer specimens was
also investigated in terms of dimension evolution after exposed
to elevated temperature (1000 C) for 2 h. Fig. 6 presents the photographs of geopolymer before and after the thermal exposures. It
can be observed that geopolymer gets a certain degree of volume
shrinkage after the thermal exposures.
Actually, OPC exhibits a higher rate of shrinkage compared to
geopolymer [8284], which can cause severe defects when it is
practically applied.
The increase in strength with increasing temperature up to
400 C may also be attributed to the hardening of geopolymer

80

Compressive strength (MPa)

70
60
50
40
30
Portland cement

20
Geopolymer

10
0
20

100

200

300

400

500

600

700

800

900 1000

Temperature (C)
Fig. 4. Compressive strength of geopolymer and OPC pastes at 28 days of curing at
various temperatures.

Fig. 5. Compressive strength of geopolymer and OPC pastes at 3 days of curing at

various temperatures.

130

P. Duan et al. / Materials and Design 74 (2015) 125137

OPC

OPC

Geo

Geo

OPC

OPC

Geo

Geo

Fig. 6. Dimension evolution of OPC and geopolymer after the thermal exposure.

paste caused by drying and further hydration, as indicated by Xu

et al. [85], who observed an increase in strength when exposure
temperature increased to 250 C. In our study, the increase in the
strength was recorded up to a temperature of 400 C.
In the beginning of hydration from the rst watercement (or
y ash and metakaolin) contact to the initial setting, the capillary
stress can be negligible, and the autogenous shrinkage is mainly
related to the Le Chateliers contraction and is thus identical to
the chemical shrinkage [86]. Considering the aforementioned
results, it can be stated that the autogenous shrinkage of geopolymer may be due to self-desiccation in the hardened state rather
than volume contraction by chemical shrinkage in fresh state.
3.4. Thermal shrinkage
Thermal shrinkage results for the OPC and geopolymer samples
have been illustrated in Fig. 7. All samples were tested after
pre-drying at 105 C for 24 h to remove free water and to avoid
excessive shrinkage in the initial stage of the measurement.
As is shown in Fig. 7, all samples exhibit shrinkage up to 1000 C
due to dehydroxylation of chemically bound water. The shrinkage
is particularly evident for cement sample where dehydration of the
CASH phase and CSH phase is believed to dominate the
dilatometry prole, resulting in loss of contact with the pushrod
at about 1000 C. The shrinkage for geopolymer may be due to
sintering and further geopolymerization above 600 C.
Polynomial trend lines can be used to show the trend of
shrinkage evolution in geopolymer specimens with increasing
temperature. A polynomial relationship also exists between
shrinkage evolution and the elevated temperature for cement
specimens. The tting coefcients (R2) are all excess 0.99 for
geopolymer and OPC paste. Obviously, cement exhibits evident
and higher shrinkage values compared to geopolymer pastes.

According to previous published paper [87], the drying shrinkage of cement paste may be due to a higher volume of mesopores,
which causes a higher capillary stress by the water meniscus
developed in the capillary pores of the paste, resulting in a higher
level of drying shrinkage [88].
3.5. Mass loss at elevated temperatures
The mass losses of the OPC and geopolymer samples due to
elevated temperature were determined from the mass change
before and after heat exposure. The average values of mass loss
after exposure to different temperatures have been plotted in
Fig. 8. An increasing trend of the mass loss in OPC up to 600 C
can be observed. However, the exact values of the mass loss in
the OPC could not be determined after 600 C because of spalling
attributed to the Ca(OH)2 decomposition that occurs at this temperature. The geopolymer specimen shows similar mass loss curves
as OPC before 500 C but with relatively lower mass loss. It can be
seen from Fig. 8 that most of the mass loss takes place at around
500 C for geopolymer. The rate of mass loss reduces and become
stable in geopolymer after this temperature while OPC continues
at a similar rate until 600 C. The mass loss of the geopolymer specimens at 1000 C is 3.39% in total compared to that at ambient
temperature.
3.6. Electron microscopy after thermal exposure
The morphological changes of OPC and geopolymer during the
thermal exposure were illustrated in the micrographs of Fig. 9.

5.0
4.5
4.0

Mass loss (%)

3.5
3.0
2.5
2.0
1.5
Portland cement

1.0

Geopolymer

0.5
0.0
0

200

400

600

800

1000

Temperature (C)
Fig. 7. Thermal shrinkage of Portland cement and geopolymer paste with elevated
temperatures.

Fig. 8. Changes in mass loss of the OPC and geopolymer at elevated temperatures.

P. Duan et al. / Materials and Design 74 (2015) 125137

OPC 20C

OPC 100C

OPC 200 C

OPC 400 C

GEO 20 C

GEO 100 C

GEO 200 C

GEO 400 C

OPC 600 C

GEO 600 C

131

Fig. 9. The morphological changes of geopolymer and OPC at various temperatures.

The geopolymer microstructures become denser with the

increase of temperature up to 400 C. This change has occurred in
the microstructure because of sintering and further geopolymerization of y ash and metakaolin with the increasing temperature.
As mentioned above, an increasing trend of the mass loss in the
OPC up to 600 C can be observed because of spalling, and the

corresponding microstructure at 600 C becomes looser with

microcracking. However, the microstructure of geopolymer
remains to be stable after exposure to high temperatures and the
rate of mass loss reduces and becomes stable nally.
Geopolymer possesses notable denser microstructure than OPC.
The Si/Na atomic ratio in an alkaline silicate solution affects the

132

P. Duan et al. / Materials and Design 74 (2015) 125137

polymerization degree of the dissolved species [8990]. The

alkaline aluminosilicate system is symbolized by NASH.
The formation process of these systems is a polycondensation. The
amorphous NASH gel in geopolymer becomes more compact.
3.7. Resistance to acid attack
Geopolymer and OPC specimens were immerged in the sulfuric
acid (2%) plus hydrochloric acid (2%) for 28 days to assess the resistance to acid attack. Fig. 10 shows the photographs of geopolymer
before and after the acid exposure.
Geopolymer specimens show very small change in appearance
after 28 days of immersion in the acidic solutions. Some softening
of the surface cover and insignicant change of the color can be
noticed in the geopolymer specimens after exposure to the acid solution, and there is only 0.7% mass change in geopolymer specimens.
Surfaces of OPC specimens exposed to the acidic solutions indicate severe deterioration compared to geopolymer. After 10 days,
the surface layer of the samples is converted to some reaction
products and is corroded to a depth of 4 mm, however, the surface
layer of geopolymer samples deteriorates to a depth of 2 mm after
28 days. After 28 days, OPC samples are severely deteriorated and
exhibit severely deteriorated surface layer with 3.3% mass change.

Fig. 11. Compressiver strength evolution of the geopolymer and OPC specimens
exposed to sulfuric acid (2%) plus hydrochloric acid (2%) solutions.

Signicant uctuations of strength measured in OPC specimens

are possibly connected to the decomposition of hydration products
and migration of alkalis from the specimens into solution imposed
by the acid attack. Changes of strength measured in geopolymer
specimens are possibly connected to the breakdown of some
geopolymer alkali components and migration of alkalis from the
specimens into acidic solutions.

3.8. Compressive strength exposed to acid

3.9. Water absorption
The results provided in Fig. 11 uncover the evolution of the
compressive strength of the samples exposed to the acidic solutions. The geopolymer samples activated by sodium hydroxide
and sodium silicate solution perform well with about 10.4%
strength decline in the 28-day exposure, which continues over
the next 28 days, reaching 22.2% after the test. Exponent trend
lines can be used to show the trend of strength evolution in
geopolymer specimens because signicant uctuations of strength
are not observed for geopolymer in the acidic solutions.
OPC paste sample shows 34.4% strength loss after 28-day exposure, and about 57.8% after the next 28 days. The OPC samples are
severely deteriorated in the rst 28-day exposure. An exponent
relationship is also found between compressive strength and the
exposure time of OPC.

Sorptivity tests were conducted to determine mass change in the

water absorption process of cement paste and geopolymer. The
results of saturated water absorption on OPC, metakaolin and y
ash geopolymer specimens after several days curing have been presented in Fig. 12. It indicates less water absorption in geopolymer
compared to cement paste. Minor difference between metakaolin
and y ash geoplymer can be observed. Based on the pore structure
results mentioned below, the comparison among metakaolin
geopolymer, y ash geopolymer and OPC paste shows that the total
porosity (cumulative intrusion volume) is decreasing for geopolymer pastes, which indicates that geopolymer possesses denser
microstructure. It also indicates that geopolymer could withstand
outside medium ingress including water and acid, which relates

Fig. 10. Photographs of geopolymer and OPC before and after the acid exposures: (a) geopolymer before acid exposures; (b) geopolymer after acid exposures; (c) OPC before
acid exposures; (d) OPC after acid exposures.

133

P. Duan et al. / Materials and Design 74 (2015) 125137

Fig. 12. Mass change of geopolymer and cement samples in water absorption test.

Fig. 14. Change of mass in water absorption test of geopolymer and cement
samples after acid exposure.

Cumulative intrusion (mL/g)

0.09

(a)

0.08

Cement paste

0.07

Metakaolin
Geopolymer

0.06

Fly ash
Geopolymer

0.05
0.04
0.03
0.02

Fig. 13. Change of mass in water absorption test of geopolymer and cement
samples after thermal exposure.

3.10. Pore structure after acid exposure

Mercury intrusion porosimetry (MIP) has been widely used to
determine pore structure and pore size distribution of porous

0.00
1

10

100

1000

10000

100000

1000000

Pore diameter (nm)

0.18

(b)
0.16

Cement paste

0.14

dV/dlogD (mL/g)

to better permeability resistance, and the results are consistent

with the water absorption test result. It can be concluded that alkali
activated condition is optimum for better pore structure modication. The strength is also higher at this optimal condition.
As the compressive strength of OPC specimens drops considerably after 500 C (see Figs. 4 and 5) because of spalling, water
absorption test after thermal exposure was carried out for geopolymer and OPC samples exposed to 500 C.
The results of saturated water absorption on OPC, metakaolin
and y ash geopolymer specimens exposed to 500 C have been
presented in Fig. 13. It indicates markedly less water absorption
in geopolymer compared to cement paste. Minor difference
between metakaolin and y ash geoplymer can be observed, and
water absorption of samples is relatively higher when exposed to
elevated temperatures.
Water absorption test after acid exposure was also made for
geopolymer and OPC samples exposed to acidic solutions for
28 days. The results of saturated water absorption are presented
in Fig. 14. Similarly, it shows markedly less water absorption in
geopolymer compared to cement paste. Minor difference between
metakaolin and y ash geoplymer can be observed, and water
absorption is relatively higher than samples not exposed to
acidic solutions but lower than samples exposed to elevated temperatures. These results are consistent with the compressive
strength development results (see Figs. 4, 5 and 11), which uncover
that better permeability resistance is closely related to the compressive strength.

0.01

Metakaolin
Geopolymer
Fly ash
Geopolymer

0.12
0.10
0.08
0.06
0.04
0.02
0.00
1

10

100

1000

10000

100000

1000000

Pore diameter (nm)

Fig. 15. The porosity and pore size distribution of geopolymer and OPC paste.

materials. As pointed out by Diamond [91], MIP is the only

available procedure that can cover nearly the whole range of sizes
that must be tallied.
The porosity and pore size distribution measurements performed by MIP of metakaolin and y ash geopolymer samples and
OPC paste are shown in Fig. 15. The results at 28 days are plotted
to identify how pore size distribution varies with ages.

134

P. Duan et al. / Materials and Design 74 (2015) 125137

Fig. 16. The porosity and pore size distribution of geopolymer and OPC paste after
thermal exposure.

Fig. 17. The porosity and pore size distribution of geopolymer and OPC paste after
acid exposure.

The comparison among metakaolin geopolymer, y ash geopolymer and OPC paste shows that the total porosity (cumulative intrusion volume) (Fig. 15(a)) is decreasing for geopolymer pastes, and
y ash geopolymer shows a signicant change. The differential
curves of pore size distribution are almost identical between
different samples. The critical pore diameters, dened as the peaks
in the differential curves (Fig. 15(b)), giving the rate of mercury
intrusion per change in pressure (differential curves) [92], do not
show a signicant change. However, the total pore volume in OPC
is higher than that in geopolymer. It is evident that exposure of
cement to acidic solutions shifts the pore size peak to a higher value
and also leads to the development of a macropore system with pore
size exceeding 100 nm.
Unlike cement pastes which hydrate with time, the strength of
the geopolymer samples remain high after exposure to sulfuric acid
(2%) plus hydrochloric acid (2%) solutions. Geopolymer possesses a
relatively lower strength loss when compared to conventional
cement paste. This is also conrmed by MIP tests with almost identical results, which show the total porosities of the OPC samples are
signicantly higher than the porosities of the y ash and metakaolin
based geopolymer. This is also extremely true for metakaolin and y
ash geopolymer samples and OPC paste exposed to high temperature
(Fig. 16) and acid (Fig. 17). Geopolymer has a relatively lower
strength loss when compared to conventional cement paste after
thermal exposure and acid exposure. This is also conrmed by MIP
test, which shows the total porosities of the OPC samples are signicantly higher than the porosities of the y ash and metakaolin
based geopolymer. Additionally, major difference between OPC and
geopolymer can be observed due to marked strength loss of OPC after
thermal exposure and acid exposure (see Figs. 4, 5 and 11).
Based on the pore structure results by MIP, the total porosity
(cumulative intrusion volume) is lower for geopolymer pastes
compared to OPC, which means that geopolymer possesses denser

microstructure. It indicates that geopolymer could withstand outside medium ingress including water and acid, which relates to
better permeability resistance, and the result of MIP is consistent
with the water absorption and acid exposure test. It can be
concluded that alkali activated condition is optimum for better
pore structure modication.
3.11. Formation of microstructure and simulation
MIP tests have been veried from the formation of microstructure aspect, which was simulated with a numerical model. For the
simulation of the reaction processes and of the formation of the
microstructure in cement and geopolymer systems, the numerical
model HYMOSTRUC was developed [93].
In this model, the degree of hydration was simulated as a function of the particle size distribution, the chemical composition of
geopolymer materials, the water/solid ratio and the reaction temperature. In a computer digitized format of HYMOSTRUC [93], the
raw solid particles were modelled as digitized spheres randomly
distributed in a three-dimensional body and the hydrating
geopolymer grains were simulated as growing spheres.
In this model, the geopolymer particles are modelled as spheres
of different diameters. Metakaolin and y ash are not regular
spheres, and this may be the limitation of this simulation model.
However, the hydration proceeded at the particle/water interface
and the hydration products formed around the original particles
in this model are true when geopolymerization occurs.
The microstructure formation and development in geopolymer
is schematically presented in Fig. 18, which can be described via
simplied mechanisms, geopolymer samples show a homogenous
microstructure with reaction products evenly distributed in the
matrix. Some large cavities form and are seemed as isolated by
aluminosilicate gels.

P. Duan et al. / Materials and Design 74 (2015) 125137

135

respectively. Only a little amount of products could be observed

at early ages. However, with the reaction time increases, plenty of
hydration products ll the voids in the matrix and the microstructure becomes denser at 6 h (Fig. 18(e)) and 24 h (Fig. 18(f)), respectively. Obviously, large amount of outer hydration products form at
longer ages and the microstructure at 3 days (Fig. 18(g)), 7 days
(Fig. 18(h)) and 28 days (Fig. 18(i)) can be observed to be much
denser and only a few voids exist in the matrix.
As mentioned in Fig. 9, geopolymer presents denser microstructure compared to OPC paste. Additionally, the comparison
among metakaolin geopolymer, y ash geopolymer and OPC paste
shows that the total porosity (cumulative intrusion volume) in
Figs. 1517 is decreasing for geopolymer pastes. The total pore volume in OPC is higher than that in geopolymer. The differential
curves of pore size distribution also indicate that geopolymer has
optimized pore structure. All these simulation results are demonstrated by the obtained experimental results.
4. Conclusions
This study intends to broaden application of uidized bed y
ash and metakaolin in cement or concrete. Durability and
microstructure of uidized bed y ash and metakaolin geopolymer
exposed to elevated temperatures and acid attack were investigated. Compressive strength and several key durability parameters for
geopolymer and ordinary Portland cement (OPC) were assessed
and compared. Microstructure formation and development was
characterized in terms of morphology by SEM and pore structures
by simulation. The results are summarized below:

Fig. 18. Formation of the microstructure in geopolymer at various curing times

(
un-reacted particles;
inner products;
outer
products;
pores).

The original initial geopolymer particles (Fig. 18(a)) are randomly distributed in a three-dimensional body. Some hydration products form at 1 h (Fig. 18(b)), 2 h (Fig. 18(c)) and 3 h (Fig. 18(d)),

(1) The distribution of temperature is not uniform and a thermal

gradient exists after exposure to high temperature. Water
accumulated inside the geopolymer structure is the main
contributor to heat resistance, geopolymer presents lower
temperature at the same distance to the surface compared
with OPC. OPC suffers strength loss, however, the y ash
and metakaolin geopolymer gains strength after the same
high temperature exposure. OPC shows a higher rate of
shrinkage compared to geopolymer after the thermal exposures. Polynomial trend lines can be used to show the trend
of shrinkage evolution in geopolymer specimens and OPC
with increasing temperature.
(2) The geopolymer microstructures become denser with the
increase of temperature up to 400 C. This change in the
microstructure may be due to sintering and further geopolymerization of y ash and metakaolin with the increasing
temperature.
(3) Geopolymer specimens have very small change in appearance after 28 days of immersion in the acidic solutions, and
there is only 0.7% mass change in geopolymer specimens.
Surfaces of OPC specimens exposed to the acidic solutions
indicate severe deterioration compared to geoplymer and
there is 3.3% mass change in the OPC specimens. An exponent
relationship can be used to show the trend of strength evolution in geopolymer specimens and OPC after exposure to
acidic solutions.
(4) Sorptivity tests on OPC, metakaolin and y ash geopolymer
specimens after several days curing show the lesser water
absorption in geopolymer compared to cement paste. The
comparison among metakaolin geopolymer, y ash geopolymer and OPC paste shows that the total porosity is decreasing for geopolymer pastes, which is closely related to better
permeability resistance.
(5) The total pore volume in traditional OPC is higher than that
in geopolymer. It is evident that exposure of cement to
acidic solutions shifts the pore size peak to a higher value

136

P. Duan et al. / Materials and Design 74 (2015) 125137

and also leads to the development of a macropore system.

The compressive strength shows agreement with the results
of pore structure.
(6) Geopolymer samples show homogenous microstructure
with reaction products evenly distributed in the matrix.
Only a little amount of products can be observed at early
ages. However, with the reaction time increases, plenty of
hydration products ll the voids in the matrix and the
microstructure becomes denser after 6 h curing ages.

Acknowledgements
This work was supported by the Fundamental Research Funds
for the Central Universities (CUGL150806), China University of
Geosciences, Wuhan, Public Service Project of the Chinese
Ministry of Land and Resources (201311024) and the National
Natural Science Foundation of China (NNSF-51202172).
References
[1] K.H. Yang, J.K. Song, K.I. Song, Assessment of CO2 reduction of alkali-activated
concrete, J. Clean Prod. 39 (2013) 265272.
[2] R.I. Malek, Z.H. Khalil, S.S. Imbaby, D.M. Roy, The contribution of class-F y ash
to the strength of cementitious mixtures, Cem. Concr. Res. 35 (2005) 1152
1154.
[3] X.Y. Wang, Effect of y ash on properties evolution of cement based materials,
Constr. Build. Mater. 69 (10) (2014) 3240.
[4] P.K. Sarker, S. Kelly, Z.T. Yao, Effect of re exposure on cracking, spalling and
residual strength of y ash geopolymer concrete, Mater. Des. 63 (11) (2014)
584592.
[5] P.S. Deb, P. Nath, P.K. Sarker, The effects of ground granulated blast-furnace
slag blending with y ash and activator content on the workability and
strength properties of geopolymer concrete cured at ambient temperature,
Mater. Des. 62 (10) (2014) 3239.
[6] P. Nath, P.K. Sarker, Effect of GGBFS on setting, workability and early strength
properties of y ash geopolymer concrete cured in ambient condition, Constr.
Build. Mater. 66 (9) (2014) 163171.
[7] Z.H. Zhang, H. Wang, Y.C. Zhu, A. Reid, J.L. Provis, F. Bullen, Using y ash to
partially substitute metakaolin in geopolymer synthesis, Appl. Clay Sci. 8889
(2014) 194201.
[8] T. Sun, J.Y. Chen, X.R. Lei, C.Y. Zhou, Detoxication and immobilization of
chromite ore processing residue with metakaolin-based geopolymer, J.
Environ. Chem. Eng. 2 (1) (2014) 304309.
[9] T.W. Cheng, M.L. Lee, M.S. Ko, T.H. Ueng, S.F. Yang, The heavy metal adsorption
characteristics on metakaolin-based geopolymer, Appl. Clay Sci. 56 (2) (2012)
9096.
[10] Z.T. Yao, X.S. Ji, P.K. Sarker, J.H. Tang, L.Q. Ge, M.S. Xia, et al., A comprehensive review on the applications of coal y ash, Earth-Sci. Rev. 141 (2015)
105121.
[11] R.S. Blissett, N.A. Rowson, A review of the multi-component utilization of coal
y ash, Fuel 97 (2012) 123.
[12] R. Kumar, S. Kumar, S.P. Mehrotra, Towards sustainable solutions for y ash
through mechanical activation, Resour. Conserv. Recy. 52 (2) (2007) 157179.
[13] M. Saridemir, Effect of specimen size and shape on compressive strength of
concrete containing y ash: application of genetic programming for design,
Mater. Des. 56 (2014) 297304.
[14] B. Nematollahi, J. Sanjayan, Effect of different superplasticizers and activator
combinations on workability and strength of y ash based geopolymer, Mater.
Des. 57 (2014) 667672.
[15] W. Wongkeo, P. Thongsanitgam, A. Ngamjarurojana, A. Chaipanich,
Compressive strength and chloride resistance of self-compacting concrete
containing high level y ash and silica fume, Mater. Des. 64 (2014) 261269.
[16] W. Chalee, P. Ausapanit, C. Jaturapitakkul, Utilization of y ash concrete in
marine environment for long term design life analysis, Mater. Des. 31 (3)
(2010) 12421249.
[17] P. Lorca, R. Calabuig, J. Benlloch, L. Soriano, J. Paya, Microconcrete with partial
replacement of Portland cement by y ash and hydrated lime addition, Mater.
Des. 64 (2014) 535541.
[18] R.F. Li, G.H. Wu, L.T. Jiang, D.L. Sun, Interface microstructure and compressive
behavior of y ash/phosphate geopolymer hollow sphere structures, Mater.
Des. 65 (2015) 585590.
[19] A. Islam, U.J. Alengaram, M.Z. Jumaat, I.I. Bashar, The development of
compressive strength of ground granulated blast furnace slag-palm oil fuel
ash-y ash based geopolymer, Mater. Des. 56 (2014) 833841.
[20] T. Phoo-ngernkham, P. Chindaprasirt, V. Sata, S. Hanjitsuwan, The effect of
adding nano-SiO2 and nano Al2O3 on the properties of high calcium y ash
geopolymer cured at ambient temperature, Mater. Des. 55 (2014) 5865.
[21] J. Davidovits, Geopolymers-inorganic polymeric new materials, J. Ther. Anal.
37 (8) (1991) 16331656.

[22] P. Duxson, J. Provis, G. Lukey, J.S.J. van Deventer, The role of inorganic polymer
technology in the development of green concrete, Cem. Concr. Res. 37 (2007)
15901597.
[23] F. Pacheco-Torgal, J.P. Gomes, S. Jalali, Alkali-activated binders: a review. Part
2: About materials and binders manufacture, Constr. Build. Mater. 22 (2008)
13151322.
[24] F. Pacheco-Torgal, J.P. Gomes, S. Jalali, Alkali-activated binders: a review. Part
1: Historical background, terminology, reaction mechanisms and hydration
products, Constr. Build. Mater. 22 (2008) 13051314.
[25] M. Shojaei, K. Behfarnia, R. Mohebi, Application of alkali-activated slag
concrete in railway sleepers, Mater. Des. 69 (2015) 8995.
[26] C. Bilim, O. Karahan, C.D. Atis, S. Ilkentapar, Inuence of admixtures on the
properties of alkali-activated slag mortars subjected to different curing
conditions, Mater. Des. 44 (2013) 540547.
[27] A. Nazari, Compressive strength of geopolymers produced by ordinary
Portland cement: application of genetic programming for design, Mater. Des.
43 (2013) 356366.
[28] P. Posi, C. Teerachanwit, C. Tanutong, S. Limkamoltip, S. Lertnimoolchai, V.
Sata, et al., Lightweight geopolymer concrete containing aggregate from
recycle lightweight block, Mater. Des. 52 (2013) 580586.
[29] P. Sukmak, S. Horpibulsuk, S.L. Shen, Strength development in clay-y ash
geopolymer, Constr. Build. Mater. 40 (3) (2013) 566574.
[30] D. Hardjito, S.E. Wallah, D.M.J. Sumajouw, On the development of y ash-based
geopolymer concrete, ACI Mater. J. 101 (6) (2004) 467472.
[31] D. Hardjito, S.E. Wallah, D.M.J. Sumajouw, Fly ash-based geopolymer concrete,
Aust. J. Struct. Eng. 6 (1) (2005) 7786.
[32] B.V. Rangan, Studies on low-calcium y ash-based geopolymer concrete,
Indian Concr. Inst. J. 4 (2006) 917.
[33] D.M.J. Sumajouw, D. Hardjito, S.E. Wallah, Fly ash-based geopolymer concrete:
study of slender columns, J. Mater. Sci. 42 (9) (2007) 31243130.
[34] P.K. Sarker, Analysis of geopolymer concrete columns, Mater. Struct. 42 (2009)
715724.
[35] A. Bagheri, A. Nazari, Compressive strength of high strength class C y ashbased geopolymers with reactive granulated blast furnace slag aggregates
designed by Taguchi method, Mater. Des. 54 (2014) 483490.
[36] E. Papa, V. Medri, E. Landi, B. Ballarin, F. Miccio, Production and
characterization of geopolymers based on mixed compositions of metakaolin
and coal ashed, Mater. Des. 56 (2014) 409415.
[37] S. Pangdaeng, T. Phoo-ngernkham, V. Sata, P. Chindaprasirt, Inuence of curing
conditions on properties of high calcium y ash geopolymer containing
Portland cement as additive, Mater. Des. 53 (2014) 269274.
[38] J.J. Feng, R.F. Zhang, L.L. Gong, Y. Li, W. Cao, X.D. Cheng, Development of porous
y ash-based geopolymer with low thermal conductivity, Mater. Des. 65
(2015) 529533.
[39] A.M. Fernandez-Jimenez, A. Palomo, C. Lopez-Hombrados, Engineering properties
of alkali-activated y ash concrete, ACI Mater. J. 103 (2) (2006) 106112.
[40] M. So, J.S.J. van Deventer, P.A. Mendis, Engineering properties of inorganic
polymer concretes (IPCs), Cem. Concr. Res. 37 (2007) 251257.
[41] A.M. Rashad, A comprehensive overview about the inuence of different
admixtures and additives on the properties of alkali-activated y ash, Mater.
Des. 53 (2014) 10051025.
[42] M.O. Yusuf, M.A.M. Johari, Z.A. Ahmad, M. Maslehuddin, Evolution of alkali
activated ground blast furnace slag-ultrane palm oil fuel ash based concrete,
Mater. Des. 55 (2014) 387393.
[43] M.O. Yusuf, M.A.M. Johari, Z.A. Ahmad, M. Maslehuddin, Effects of H2O/Na2O
molar ratio on the strength of alkali activated ground blast furnace slagultrane palm oil fuel ash based concrete, Mater. Des. 56 (2014) 158164.
[44] P. Duxson, A. Fernndez-Jimnez, J.L. Provis, G.C. Lukey, A. Palomo, J.S.J. van
Deventer, Geopolymer technology: the current state of the art, J. Mater. Sci. 42
(9) (2007) 29172933.
[45] K.C. Goretta, F. Gutierrez-Mora, D. Singh, J.L. Routbort, G.C. Lukey, J.S.J. van
Deventer, Erosion of geopolymers made from industrial waste, J. Mater. Sci. 42
(9) (2007) 30663072.
[46] D.L.Y. Kong, J.G. Sanjayan, K. Sagoe-Crentsil, Comparative performance of
geopolymers made with metakaolin and y ash after exposure to elevated
temperatures, Cem. Concr. Res. 37 (12) (2007) 15831589.
[47] Sindhunata, J.S.J. van Deventer, G.C. Lukey, H. Xu, Effect of curing temperature
and silicate concentration on y-ash-based geopolymerization, Ind. Eng.
Chem. Res. 45 (10) (2006) 35593568.
[48] C.K. Yip, G.C. Lukey, J.S.J. van Deventer, Effect of blast furnace slag addition on
microstructure and properties of metakaolinite geopolymeric materials,
Ceram. Trans. 153 (2004) 187209.
[49] T.W. Cheng, J.P. Chiu, Fire-resistant geopolymer produce by granulated blast
furnace slag, Miner. Eng. 16 (3) (2003) 205210.
[50] J.W. Ginacaspro, P.N. Balaguru, R.E. Lyon, Use of inorganic polymer to improve
the re response of balsa sandwich structures, J. Mater. Civ. Eng. 18 (3) (2006)
390397.
[51] R.E. Lyon, P.N. Balaguru, A. Foden, U. Sorathia, J. Davidovits, M. Davidovics,
Fire-resistant aluminosilicate composites, Fire Mater. 21 (2) (1997) 6773.
[52] P.G. He, D.C. Jia, T.S. Lin, M.R. Wang, Y. Zhou, Effects of high-temperature heat
treatment on the mechanical properties of unidirectional carbon ber
reinforced geopolymer composites, Ceram. Int. 36 (4) (2010) 14471453.
[53] N. Ranjbar, M. Mehrali, U. Johnson Alengaram, H.S.C. Metselaar, M.Z. Jumaat,
Compressive strength and microstructural analysis of y ash/palm oil fuel ash
based geopolymer mortar under elevated temperatures, Constr. Build. Mater.
65 (8) (2014) 114121.

P. Duan et al. / Materials and Design 74 (2015) 125137

[54] O.A. Abdulkareem, A.M. Mustafa Al Bakri, H. Kamarudin, I. Khairul Nizar, A.A.
Saif, Effects of elevated temperatures on the thermal behavior and mechanical
performance of y ash geopolymer paste, mortar and lightweight concrete,
Constr. Build. Mater. 50 (11) (2014) 377387.
[55] L. Zeng, D.Y. Cao, Y. Xu, C.W. Fan, X.Q. Peng, Novel method for preparation of
calcined kaolin intercalation compound-based geopolymer, Appl. Clay Sci. 101
(11) (2014) 637642.
[56] Z. Pan, J.G. Sanjayan, Stressstrain behaviour and abrupt loss of stiffness of
geopolymer at elevated temperatures, Cem. Concr. Compos. 32 (9) (2010)
657664.
[57] Z. Pan, J.G. Sanjayan, F. Collins, Effect of transient creep on compressive
strength of geopolymer concrete for elevated temperature exposure, Cem.
Concr. Res. 56 (2) (2014) 182189.
[58] C.C. Mao, H. Ran, H.W. Te, C.F. Toun, Utilization of circulating uidized bed
combustion (CFBC) y ash and coal-red y ash in Portland cement, Key Eng.
Mater. 629630 (2014) 306313.
[59] M. Shaswata, M. Saroj, U.B. Adhikari, Study on the physical and mechanical
property of ordinary Portland cement and y ash paste, Int. J. Civ. Struct. Eng. 2
(3) (2012) 731736.
[60] . Eren, Strength development of concretes with ordinary Portland cement,
slag or y ash cured at different temperatures, Mater. Struct. 35 (9) (2002)
536540.
[61] W. Sha, G.B. Pereira, Differential scanning calorimetry study of ordinary
Portland cement paste containing metakaolin and theoretical approach of
metakaolin activity, Cem. Concr. Compos. 23 (6) (2001) 455461.
[62] A.M. Mustafa Al Bakri, H. Kamarudin, M. Binhussain, N.I. Khairul, A.R. Raza, Y.
Zarina, Comparison of geopolymer y ash and ordinary Portland cement to the
strength of concrete, Adv. Sci. Lett. 19 (12) (2013) 35923595.
[63] V. Kirk, K. Aditya, S. Gaurav, N. Narayanan, The rheological properties of
ternary binders containing Portland cement, limestone, and metakaolin or y
ash, Cem. Concr. Res. 52 (2013) 196207.
[64] G.S. David, W. Stan, O.F. Martin, Heat of hydration of Portland cement
metakaoliny ash (PCMKPFA) blends, Cem. Concr. Res. 38 (6) (2008) 832
840.
[65] V. Kirk, A. Matthew, O. Tandre, S. Gaurav, N. Narayanan, Hydration and
strength development in ternary Portland cement blends containing limestone
and y ash or metakaolin, Cem. Concr. Compos. 39 (2013) 93103.
[66] R.D. Hooton, W. Ma, D. Sample, R. Martin, P.W. Brown, Calorimetric study of
cement blends containing y ash, silica fume, and slag at elevated
temperatures, Cem. Concr. Aggr. 16 (2) (1994) 9399.
[67] N.I. Fattuhi, B.P. Hughes, Ordinary Portland cement mixes with selected
admixtures subjected to sulfuric acid attack, ACI Mater. J. 85 (6) (1988) 512
518.
[68] S. Wild, B.B. Sabir, J. Bai, J.M. Kinuthia, Self-compensating autogenous
shrinkage in Portland cementmetakaoliny ash pastes, Adv. Cem. Res. 12
(1) (2000) 3543.
[69] R. Mateusz, O. Jan, Effects of curing conditions on the properties of ternary
(ordinary Portland cement/y ash/silica fume) concrete, ACI Mater. J. (2014),
http://dx.doi.org/10.14359/51687307.
[70] P. Sandor, Portland cementy ashsilica fume systems in concrete, Adv. Cem.
Based Mater. 1 (2) (1993) 8391.
[71] M.S. Sudarshan, R.V. Ranganath, Properties of y ash based geopolymer
concrete exposed to sustained elevated temperatures, Adv. Mater. Res. 250
253 (2011) 962968.
[72] D.L.Y. Kong, J.G. Sanjayan, S.C. Kwesi, Comparative performance of
geopolymers made with metakaolin and y ash after exposure to elevated
temperatures, Cem. Concr. Res. 37 (12) (2007) 15831589.

137

[73] F.U.A. Shaikh, V. Vimonsatit, Compressive strength of y-ash-based

geopolymer concrete at elevated temperatures, Fire Mater. (2014), http://
dx.doi.org/10.1002/fam.2240.
[74] Y.C. Choi, J.H. Kim, S. Choi, Mechanical performance of y-ash-based green
geopolymer composites subjected to elevated temperatures, Asian J. Chem. 26
(17) (2014) 55175521.
[75] J.Z. Kuang, X.C. Zhao, F. Shi, H.Y. Cao, Study on inuence factors of y ash and
metakaolin based geopolymer, Adv. Mater. Res. 538541 (2012) 23222328.
[76] C. Prinya, R. Ubolluk, Utilization of blended uidized bed combustion (FBC) ash
and pulverized coal combustion (PCC) y ash in geopolymer, Waste Manage.
30 (4) (2010) 667672.
[77] X.H. Yuan, W. Chen, Z.A. Lu, H.G. Chen, Shrinkage compensation of alkaliactivated slag concrete and microstructural analysis, Constr. Build. Mater. 66
(15) (2014) 422428.
[78] A. Palomo, M.W. Grutzeck, M.T. Blanco, Alkali-activated y ashes: a cement for
the future, Cem. Concr. Res. 29 (8) (1999) 13231329.
[79] H. Rahier, B. van Mele, J. Wastiels, Low-temperature synthesized aluminosilicate glasses. Part II: Rheological transformations during low-temperature
cure and high temperature properties of a model compound, J. Mater. Sci. 31
(1) (1996) 8085.
[80] P. Duxson, G.C. Lukey, J.S.J. van Deventer, Physical evolution of Na-geopolymer
derived from metakaolin up to 1000 C, J. Mater. Sci. 42 (9) (2007) 30443054.
[81] R.D. Recommendation, P.D.R. De La Rilem, 129-MHT: test methods for
mechanical properties of concrete at high temperatures, Mater. Struct. 28
(1995) 410414.
[82] F. Collins, J.G. Sanjayan, Microcracking and strength development of alkali
activated slag concrete, Cem. Concr. Res. 23 (4) (2001) 345352.
[83] E. Douglas, A. Bilodeau, V.M. Malhotra, Properties and durability of alkaliactivated slag concrete, ACI Mater. J. 89 (5) (1992) 509516.
[84] S.D. Wang, X.C. Pu, K.L. Scrivener, P.L. Pratt, Alkali-activated slag cement and
concrete: a review of properties and problems, Adv. Cem. Res. 7 (27) (1995)
93102.
[85] Y. Xu, Y.L. Wong, C.S. Poon, M. Anson, Impact of high temperature on PFA
concrete, Cem. Concr. Res. 31 (2001) 10651073.
[86] M. Bouasker, P. Mounanga, P. Turcry, A. Loukili, A. Khelidj, Chemical shrinkage
of cement pastes and mortars at very early age: effect of limestone ller and
granular inclusions, Cem. Concr. Compos. 30 (1) (2008) 1322.
[87] F.G. Collins, J.G. Sanjayan, Effect of pore size distribution on drying shrinkage
of alkali-activated slag concrete, Cem. Concr. Res. 30 (9) (2000) 14011406.
[88] Z. Jiang, Z. Sun, P. Wang, Autogenous relative humidity change an autogenous
shrinkage of high-performance cement pastes, Cem. Concr. Res. 35 (8) (2005)
15391545.
[89] J.L. Provis, J.S.J. van Deventer, Direct measurement of the kinetics of geopolymerisation by in-situ energy dispersive X-ray diffractometry, J. Mater. Sci. 42
(2007) 29742981.
[90] J. Davidovits, Geopolymers and geopolymeric materials, J. Ther. Anal. 35
(1989) 429441.
[91] S. Diamond, Mercury porosimetry: an inappropriate method for the
measurement of pore size distributions in cement-based materials, Cem.
Concr. Res. 30 (10) (2000) 15171525.
[92] Y. Akkaya, K. van Bui, S.P. Shah, Rheological model for self-consolidating
concrete, ACI Mater. J. 99 (6) (2002) 549559.
[93] G. Ye, P. Lura, K. van Breugel, A.L.A. Fraaij, Study on the development of the
microstructure in cement-based materials by means of numerical simulation
and ultrasonic pulse velocity measurement, Cem. Concr. Compos. 26 (5) (2004)
491497.