Journal of Wuhan University of Technology-Mater. Sci. Ed. www.jwutms.

net June 2016 689

DOI 10.1007/s11595-016-1430-8

Fly Ash-based Geopolymers: Effect of Slag

Addition on Efflorescence

YAO Xiao1, YANG Tao1, ZHANG Zhuhua2

(1.Faculty of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China; 2.Faculty of Engineering and Surveying,
University of Southern Queensland, Toowoomba 4350, Australia)

Abstract: Blended fly ash/blast-furnace slag geopolymers are focused on due to their excellent
mechanical and chemical resistant properties. We investigated the effect of slag partial substitution for fly ash
on the efflorescence of the resulting geopolymers. The efflorescence of geopolymer binders was inspected and
evaluated through leaching tests. The efflorescence deposits on surface of the geopolymer binders were analyzed
using XRD and SEM-EDS. The results showed that sodium and calcium cations leached from geopolymer
binders reacted with the atmospheric CO2 and formed the crystal deposits, gaylussite and calcite, in the forms of
granular and angular crystal particles. The slag addition led to a refinement of the pore structure of fly ash-based
geopolymers, but an increment in the concentration of alkali leaching. The crystal deposits gradually developed
in the pore volume of the binders, and finally exceeded the capacity of pore volume. The extent of efflorescence
on the surface of specimens increased with the slag substitution. The visible efflorescence is therefore a result
of available alkalis and pore sizes and volumes. Higher concentration of available alkalis and smaller pores (and
volume) will lead to more intensive efflorescence.
Key words: geopolymer; efflorescence; pore structure; fly ash; slag

1 Introduction It has therefore been widely proposed that geopolymers

Geopolymers are a class of chemical activated
materials produced by the reaction between
aluminosilicate sources, usually fly ash and metakaolin,
with an activator, usually alkali hydroxide and/or
silicate solution[1]. The reaction products are composed
of tetrahedral silicate and aluminate units linked in an
amorphous three-dimensional network structure[2]. As
the term geopolymer was introduced in the 1970s by
Joseph Davidovits, the development and assessment of
these materials become increasingly widespread, due
to their environmental and technological advantages,
compared with traditional Portland cement systems[3,4].
©Wuhan University of Technology and SpringerVerlag Berlin Heidelberg 2016
(Received: Oct. 20, 2015; Accepted: Feb. 18, 2016)
YAO Xiao (姚晓): Prof.; Ph D; E-mail: htmpaper@sina.com
Funded by the Jiangsu Higher Education Institutions for
a project PAPD (Priority Academic Program Development),
Program for Changjiang Scholars and Innovative Research Team
in University (PCSIRT), (No.IRT1146) and Graduate Education
Innovation Project in Jiangsu Province (No.CXLX13_409). The
work by Zhang is supported by University of Southern Queensland
and an ARC-linkage project.
will be used as alternative clinker-free binders in a
variety of applications in terms of both technical and
commercial requirements[3,5].
The role of alkalis in geopolymerization can be
categorized into two parts: the hydroxyl ions as reaction
catalysts will generate a high pH condition to dissolve
the aluminosilicate precursors and produce small
reactive silico and alumino species; and the alkaline
metal cations balance the negative charge in aluminum
tetrahedrals in geopolymer framework [6] . Due to
the high Na2O/Al2O3 ratios used in the geopolymer
mixes and weak binding of alkaline metal cations (Na
or K) in geopolymeric phases [7-9], the binders often
suffer from severe efflorescence, when excess sodium
oxide remains unreacted in the pore network. The
exact effects of efflorescence on the performance of
geopolymers are not yet well understood. Nevertheless,
the formation of visible surface deposits caused by
efflorescence has brought the negative influence on the
appearance, causing some restrictions of this material in
a variety of structural and non-structural applications.
Some researchers have made the attempts to
reduce efflorescence[9-12]. Kani et al reported that the
690
incorporation of aluminate cements can significantly
r e d u c e t h e e ff l o r e s c e n c e s e v e r i t y o f n a t u r a l
pozzolan-based geopolymers, due to their release
of high amounts of alumina into the aluminosilicate
geopolymeric phases[10]. Using potassium hydroxide
instead of sodium hydroxide in the activator is also
beneficial, because potassium cations are more strongly
bound to the nanostructure of gel phases [11,12] . In
addition, hydrothermal curing can enhance the extent
of geopolymerization with less alkali remained in the
material, so is able to mitigate efflorescence[9,10].
Fly ash is one of the most common raw
materials in geopolymer synthesis for construction
applications. It has been proposed that the substitution
of blast-furnace slag is critical to early strength
development and compact structure of fly ash-based
geopolymers[13-15]. Provis et al[14] discovered that slag
incorporation can increase tortuosity of the fly ash-
based binders by using X-ray microtomography.
Alkali diffusion measurements confirm that Ca in
geopolymers is important in the formation of a low-
permeability pore system to hinder the movement of
ions through the paste[7]. This suggests the likelihood
that the extent of efflorescence from geopolymers could
be reduced. However, the exact relationship between
the slag addition and efflorescence of fly ash-based
geopolymer binders is not yet well understood.
2 Experimental
2.1 Materials
Fly ash used in this study was obtained from
Guohua Power Station (Jiangsu, China) and ground
granulated blast-furnace slag was obtained from
Nanjing Steel (Jiangsu, China). Their compositions
were tested by X-ray fluorescence analysis with the
results given in Table 1. The particle size ranges
of the fly ash and slag, as determined through laser
granulometry, are 0.1-325.2 and 0.1-132.4 μm, with d50
of 14.7 and 17.4 μm, respectively.
An alkaline activating solution was prepared
by mixing a sodium silicate solution (with 30.3
wt% SiO2, 12.8 wt% Na2O and 56.9 wt% H2O) with
Vol.31 No.3 YAO Xiao et al: Fly Ash-based Geopolymers: Effect of Slag Addition on...
sodium hydroxide pellets ( 96% purity) and distilled
water, to reach the desired molar ratio of Ms=1.4 (i e,
Na2O·1.4SiO2) at a constant concentration of 30 wt%.
The solution was allowed to cool to room temperature
prior to use.
2.2 Sample synthesis
The precursor blends with 0, 5, 10, 20, 30 and 50
wt% slag substitution were dry-mixed for 5 min and
then mixed with the alkali silicate solutions at a liquid
to solid mass ratio (l/s) of 0.42, which gave a suitable
workability. The pastes were transferred into the molds
with a size of 20×20×20 mm, and cured in an air-
conditioned fog room at 20 ℃ and RH > 95% for 28
days.
2.3 Analytical methods
Mercury intrusion porosimetry (MIP) was
performed using a Poremaster GT-60. Before testing,
the samples were crushed into small pieces. The
samples were stored in ethanol for 24 h to extract free
water, and dried at 60 ℃ for 4 h. This relatively low
drying temperature is expected to have little or no
effect on the pore structure of geopolymer binders.
To investigate the severity of efflorescence, 28-
day cured cube specimens from each set were half-
immersed in distilled water, and kept in an open-
air atmosphere at 20 ℃ for 7 days to accelerate the
efflorescence. The results were obtained by visual
comparison of efflorescence deposits on top surface of
the specimens. To quantitatively measure the extent of
efflorescence, 1.000 ± 0.004 g ground hardened paste
was mixed with 10.000 ± 0.004 g distilled water in a
covered container, and stirred each for 8 hours. After
7 days, the solutions for each set were centrifuged
to remove solids, and measured using a PHS-3C pH
meter. The concentrations of cations (Na+, Ca2+, Si4+
and Al3+) in the solutions after dilution were determined
by inductively coupled plasma optical emission
spectroscopy (ICP-OES), using a PE Optima 2000DV
instrument.
X-ray diffraction (XRD) analysis of efflorescence
crystal deposits scratched from top surface of the half-
immersed geopolymer samples was conducted on a
Thermo ARL’tra machine with Cu Kα radiation, at
Journal of Wuhan University of Technology-Mater. Sci. Ed. www.jwutms.net June 2016
a scanning rate of 10°/min from 8° to 80° (2-theta).
A ZEISS EVO MA18 scanning electron microscope
(SEM) was used to analyze the surface of the
geopolymer specimen with 50 wt% slag substitution.
The elemental composition analysis was performed
using an equipped energy dispersive spectroscope
(EDS). The sample was coated with gold.
3 Results and discussion
3.1 Pore structure
Fig.1 depicts the pore size distribution in the fly
ash-based geopolymers with slag substitution. All of
the mixes exhibit unimodal profiles with one peak,
reflecting pore sizes with diameter in the range of 8
to 100 nm, which represent gel pores formed in the
interstices of the colloidal particles in geopolymeric
phases [16]. Capillary pores, 100-1 000 nm, are not
detectable by the MIP method. This is because the gels
occupy most of the bulk space in capillary pores in the
well-reacted alkali-silicate activated geopolymers after
28 days[14,16,17].
The substitution of slag for fly ash leads to a more
refined pore structure. In the mixes with less than 20%
slag, the diameters of distribution-maximal pores in
differential curves decrease slightly from 47.1 nm in
100% FA binder to 38.1 nm in 10% slag containing
binder; a marked decrease is found when slag addition
is higher than 20%. More very fine pores that may exist
in these binders are not able to be detected by MIP, due
to the limitation of this method[16,17].
The cumulative porosity of the binders measured
by MIP is shown in Fig.2. The overall porosities in the
mixes with less than 20% slag are almost the same,
and slag substitution leads to the reduction of volume
of pores in the macopores interval. When slag addition
691
increases from 20% to 50%, the overall porosities
decrease sharply from 21.2% to 8.1%. This trend is
more significant in the amount of mesopores. The
pore refinement effect of slag incorporation on fly ash-
based geopolymers was also reported by Provis et
al using X-ray microtomography[14]. It was revealed
from their study that a space-filling Al substituted
calcium silicate hydrate (C-A-S-H) gel formed in fly
ash-slag system leads to porosity reduction which is
not observed in fly ash systems with the predominant
sodium aluminosilicate (geopolymer) phases without
chemically binding water of hydration[14]. Fly ash-based
binders with more than 20% slag substitution could
demonstrate the formation of coexisting C-A-S-H and
geopolymer gels[18], which determines the compact pore
structure. However, with ≤10% slag added, it seems
that there is not enough C-A-S-H gel formed to present
the coexistence situation.
3.2 Extent of efflorescence
3.2.1 Visual inspection
The results obtained from the efflorescence
observation show that the amount of efflorescence
products on the top surface of half-immersed specimen
increases with slag content. In conjunction with the
MIP results, geopolymers with more refined pore
structure form more crystal deposits on their surface.
However, this relationship seems conflict to the general
acceptations that a compact structure could slow
down efflorescence occurring[5,10]. In order to obtain
a better understanding of the effect of slag addition
on efflorescence of fly ash-based geopolymer, it is
essential to apply techniques which are sensitive to
leaching behavior of alkalis in the pore structure of
materials.
3.2.2 Alkalis leaching
The pH value of leaching solution (Fig.3) provides
important information regarding the concentrations
692 Vol.31 No.3 YAO Xiao et al: Fly Ash-based Geopolymers: Effect of Slag Addition on...
of hydroxyl ions leached from geopolymers. The slag
substitution leads to an increment in pH values, which
is in agreement with the increased concentration of
sodium cations. This implies that more alkalis (sodium
hydroxide) are released from the slag-containing
pastes, compared with the 100% fly ash-based paste.
During geopolymerization, a large amount of
alkalis supplied by activators make a major contribution
to the dissolution of aluminosilicate source and produce
reactive silico and alumino species[6]. The incorporation
of slag into the fly ash-based geopolymers leads to a
significant effect. The reactive slag favors consuming
more silicate, leading to higher availability of alkali
supplied by the activator for reaction with the fly ash.
In addition, the C-A-S-H type gels formed in the slag-
containing binders do not bind the alkalis as strongly
as the N-A-S-H (geopolymer) type gels do[19]. Thus,
more excessive alkalis exist in the pore network of
geopolymers containing slag. This mechanism is
consistent with the Na+ leaching behavior of alkali-
activated fly ash/slag blends[7].
When the specimens are half-immersed in
distilled-water under open-air atmospheric conditions,
the alkali-rich pore solution in the pore structure
will react with the atmospheric CO2, forming crystal
deposits. Following the gradual growth of efflorescence
product, the deposits will finally exceed the space of
the pores, and then emerge on the surface of specimens.
The porous N-A-S-H gel formed in fly ash-based
geopolymers, has a larger capacity of carrying higher
extent of efflorescence compared with the compact pore
structure in system containing slag. It means that slag
substitution increases the pore solution alkalinity and
decreases the capacity of pores to hold crystal deposits.
3.2.3 Leaching of other cations
Fig.4 shows the concentrations of Ca, Si and Al of
leaching solutions. The availability of Ca, Si and Al is
much lower than that of Na when geopolymers contact
with water. The slag addition leads to an increment in
the concentration of leached Ca, which indicates that a
part of calcium cations dissolved from the slag particles
present in pore solution.
It is interesting to note that the concentrations of
leached Si and Al increase as slag content increases
from 0% to 20%, then sharply decrease as slag
substitution increases. With less than 20% slag used,
the alkali-rich pore solution resulted from the presence
of more reactive slag enhances the dissolution of solid
precursors to produce more Si and Al cations[13,19]. In
the mixes containing 20% slag content, a C-A-S-H
gel with tobermorite type structure is formed to co-
exist with N-A-S-H gel, and the Al-O-Si linkages in the
crosslinked tobermorites will strongly bind the network
forming ions (Si4+ and Al3+)[19]. In the meanwhile, the
gel coexistence forms a more compact pore structure in
geopolymers, which will hinder the leaching of Si and
Al[14].
3.2.4 XRD and SEM-EDS analysis
Fig.5 presents the X-ray diffraction patterns of
Journal of Wuhan University of Technology-Mater. Sci. Ed. www.jwutms.net June 2016
efflorescence crystal deposits. The Na+ and Ca2+ react
with atmospheric CO 2 to form the crystal phases,
gaylussite Na2Ca(CO3)2(H2O)5 and calcite CaCO3, in the
forms of granular and angular crystal particles (shown
in Fig.6). Fig.6(a) shows that the granular crystals are
likely to eject out from one pore which connects the
surface with gel phase, and grow sustainably around the
centre. It confirms that the alkali-rich pore solution in
the binders reacts with the atmospheric CO2 to form the
crystal deposits, which will finally exceed the capacity
of the pore volume and then emerge on the surface of
specimens.
EDS results obtained for multiple points selected
from the surface of 50% slag specimen studied are
shown in Table 2. Sodium, calcium, silicon and
aluminum contents of gel phase and crystal deposits
are reported. The gel compositions confirm that a C-A-
693
S-H type gel is formed due to the slag substitution, as
suggested by other studies[18,19]. Both of the granular
and angular crystals contain sodium and calcium
cations, with Na/Ca ratios in a wide range between 0.1
and 2.05. It indicates that the coexistence of gaylussite
with calcite crystal phases is feasible, consistent with
the XRD results.
The XRD and SEM-EDS analysis, combined
with the pore structure and efflorescence extent results
presented throughout this paper, suggest that slag
incorporation could give a refinement of the pore
structure of fly ash-based geopolymers, but aggravate
the efflorescence on the surface of binders at the same
time. Although there is not detailed study of the effects
of efflorescence on the performance of geopolymers,
including mechanical strength and volume stability
etc. leaching of pore solution and growing of crystal
deposits on the surface of specimens could result in
degradation of the structure, affecting the appearance
and durability negatively. That is to say, given a
sufficiently dense and impermeable matrix with slag
substitution, efflorescence is still a problem within the
lifetime of a structure.
4 Conclusions
Excess sodium cations are kept in the pore
solution, which are mobile within the pore network of
geopolymers. When geopolymer specimens are placed
in contact with water under atmospheric conditions,
the alkali-rich pore solution will react with dissolved
atmospheric CO 2 to form the crystal deposits. In
addition to sodium, certain amount of calcium cations
also leach out from the pore structure to react with CO2,
so that the crystal efflorescence deposits, gaylussite and
calcite are formed.
This study shows that slag substitution leads
to a refinement of the pore structure of fly ash-based
geopolymers, but an aggravation for efflorescence
on the surface of specimens. The growth of crsystal
deposits is therefore a result of available alkalis and
pore sizes and volumes. Higher concentration of
available alkalis and smaller pores (and volume) will
lead to more intensive efflorescence. The efflorescence
is still an essential problem to be solved in the lifetime
of fly ash/slag blended geopolymers with a sufficiently
dense and impermeable matrix. Moreover, further
studies about the pore structure of geopolymers after
suffering a long-term efflorescence are recommended to
estimate the effects of efflorescence on the performance
694 Vol.31 No.3 YAO Xiao et al: Fly Ash-based Geopolymers: Effect of Slag Addition on...
of geopolymers, including mechanical strength and
volume stability etc.
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