Materials and Design 53 (2014) 1005–1025

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Materials and Design

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A comprehensive overview about the influence of different admixtures

and additives on the properties of alkali-activated fly ash
Alaa M. Rashad ⇑
Building Materials Research and Quality Control Institute, Housing & Building National Research Center, HBRC, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: The development of new binders, as an alternative to Portland cement (PC), by alkaline activation, is a
Received 18 May 2013 current researchers interest. Alkali-activated fly ash (AAFA) binder is obtained by a manufacturing pro-
Accepted 22 July 2013 cess less energy-intensive than PC and involves lower greenhouse gasses emission. Utilizing AAFA system
Available online 31 July 2013
as binder material can limit the consumption of virgin materials (limestone and sand) required in PC
manufacture. AAFA belongs to be prospective material in the field of Civil Engineering where it can resist
Keywords: aggressive acids, resist sulfate attacks, resist aggregate alkali reaction, and resist elevated temperatures.
Alkali-activated fly ash
Researchers have employed different fibers, chemical admixtures, mineral admixtures, additives and
Fibers
Admixtures
other materials in AAFA system aiming to modify special properties of this system. This paper presents
Additives a comprehensive overview of the previous works carried out on using different admixtures and additives
in AAFA system.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction In addition to consuming considerable amounts of virgin mate-

Currently, PC is still the leading material for industrial concrete
demand worldwide, fulfilling a demand of over 1.6 billion tonnes
annually [1]. The production of cement is increasing about 3%
annually [2]. The projections for the global demand of PC show that
in the next 40 years it will have a twofold increase reaching 6 Gt/
year [3]. The cement industry is the second largest producer of the
green house gas [1]. Among the green house gases, CO2 contributes
about 65% of global warming. Additionally, cement production and
resulting emissions are expected to increase by 100% from the cur-
rent level by 2020 [4]. On the same line with this, the global de-
mand will have increased almost 200% by 2050 from 2010 [3].
Beside the emission of CO2, cement industry launches SO3 and
NOx which can cause the greenhouse effect and acid rain [5,6]. This
is particularly serious in the current context of climate change
caused by CO2 emissions worldwide, causing a rise in sea level
and the occurrence of natural disasters and being responsible for
future meltdown in the world economy [7,8]. Not only CO2, SO3
and NOx are launched into the atmosphere from cement industry,
but also about 5% to 10% of the by-products. These by-products
are dusts from the dryers, mills, kilns, coolers and transportation
facilities. These dusts arise from different sources; altogether,
6000–14,000 m3 dust-containing airstreams are generated per
1 tonne cement which contains 0.7 and 800 g/m3 of dust (depend-
ing on source and technology) [9].
⇑ Tel.: +20 2 33351564; fax: +20 2 33367179.
E-mail addresses: alaarashad@yahoo.com, a.rashad@hbrc.edu.eg
rials (limestone and sand) and energy (energy demand about
1700–1800 MJ/tonne clinker [10,11]), producing each tonne of PC
of which about 1.5 tonnes of raw material is needed [6]. The ce-
ment production account about 5% of worldwide industrial energy
consumption [12,13]. The PC industry ranks third in the sector
(after aluminum and steel) for the energy consumption [14]. Fur-
ther, concrete made from PC is subjected to certain durability prob-
lems that are difficult to solve. In the light of these problems, the
scientific community has undertaken to seek new processes, tech-
nologies and materials to provide the construction industry with
alternative binders. One avenue that is expected to significant
reduce cement is use of blended cement [15–22]. The second
alternative is use new cementless binder material based on the
by-products as FA, slag [11,23–26] or burned clay [27] and other
aluminosilicate materials [28,29]. The new binder materials that
can replace PC, by alkali activation, can generate less carbon diox-
ide than PC [6,30–36]. Comparison to PC concrete, the global
warming potential of alkali-activated concrete is 70% lower [37].
The energy consumption of alkali activation system is calculated
to be approximately 60% less than that of PC [38].
FA is a by product of thermal power plants resulting from the
combustion of pulverised coal in the coal-fired furnaces. Around
one billion tonnes of FA are produced annually worldwide in
coal-fired steam power plants [39–42]. The environmental impact
of FA in terms of its massive generation, large usage of land dis-
posal with short and long term impact on surrounding areas is a
major concern for everyone. One option to eliminate this ash in
an ecologically sensitive manner is to reuse it. FA can replace

0261-3069/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2013.07.074
1006 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
cement content up to 30%. The current European standard ENv197
(2000) allows a replacement level up to 55% cement by FA in ce-
ment mixture CEM IV. FA can replace 50–70% cement in high vol-
ume fly ash (HVFA) concrete. However, the best option to eliminate
FA disposal is to reuse it as a binder material, without PC, activated
with alkaline activators.
The alkali activation of aluminosilica materials is a chemical pro-
cess that transforms partially or wholly vitreous structures into
compact cementitious skeletons. Researchers reported that AAFA
concretes can achieve compressive strength over 60 MPa after ther-
mally curing [43,44]. The AAFA concrete is durable, can resist
aggressive acids, resist aggregate alkali reaction [45,46] resist sul-
fate attacks [47,48] and resist elevated temperatures [6]. This sys-
tem performs better than PC mortars in reinforcement steel
bonding [49]. AAFA can protect steel reinforcement from corrosion
[50] and can be used to fix toxic elements [51–55]. The dry shrink-
age of AAFA binders can be lowered than that of PC binders [56–59].
On the other hand, AAFA requires rather long heat curing to obtain
reasonable strength development at early age. The long heat curing
period limits the application of the AAFA. To achieve comparable
strength to PC concrete, it is necessary to provide geopolymer con-
crete with elevated temperature curing between 40 and 80 °C for at
least 6 h [41,60,61]. Further, the question of whether geopolymer
concretes are durable remains the major obstacle to recognition
in standards for structure concrete, and hence to their commercial
adoption. Geopolymer cannot possibly have the availability of dec-
ades of in-service testing and durability data to prove its long-term
stability. Most standard methods of testing paste and concrete
durability involve exposing small samples to very extreme condi-
tions for short periods. Higher-risk application such as high rise
building, which constitutes a smaller fraction of total concrete mar-
ket, will follow only when the market is comfortable with the real-
world track record of the material in low risk application [62]. In
addition, in some countries as UK, FA production does not exceed
its consumption in cement, which limits the wider adoption of geo-
polymer technology until this bottleneck is resolved [62]. However,
researchers tried to modify special properties of AAFA by adding
different admixtures and additives aiming to produce blended
materials have more advantages than the neat AAFA. Different
admixtures and additives were employed in AAFA and investigated
by numerous researchers.
Although there are numerous numbers of review papers in the
literature regarding to AAFA system [43,51,63,64] there is no pub-
lished literature review paper that reviewed the previous works
curried out on AAFA modified with different types of admixtures
and additives. However, in this investigation, the author conducted
a comprehensive literature review focused on the effect of different
admixtures and additives on some special properties of AAFA sys-
tem. A review on fibers, chemical admixtures, mineral admixtures
and additive materials that were added into FA in alkali activation
system was presented.
2. Fibers
Yunsheng et al. [65–67] investigated the behavior of short
polyvinyl alcohol (PVA) fibers reinforced FA-metakaolin (MK)
geopolymer boards manufactured by extrusion technique. Fiber
length was 6 mm with average diameter of 14 lm and a density
of 1300 kg/m3. The average tensile strength and elastic modulus
of the fiber were 1500 MPa and 36 GPa, respectively. MK, in
mortars, was partially replaced with FA at levels of 0%, 10%,
30% and 50%, by weight. Fibers volumes were 0%, 1% and 2%
in neat MK geopolymer, whilst they were 2% in FA-MK geopoly-
mers. NaOH was used as alkaline activator. The fresh geopoly-
mer composites were fed into the pugmill chamber of
single-screw vacuum extruder. After mixing, de-airing and com-
paction, the composites were pushed through a thin sheet die
with a cross-sectional size of 75  6 mm. The specimens were
cured at 20 °C and 99% RH. They concluded that the addition
of high volume fraction PVA fibers changed the impact failure
mode of FA–MK-geopolymer boards from brittle pattern to duc-
tile pattern, resulted in great increase in impact toughness.
Short PVA fibers reinforced geopolymer boards without or with
low percentage of FA possessed very high impact strength and
stiffness, but when much FA was incorporated, the impact
resistance was reduced.
Vaidya and Allouche [68] added carbon fibers to geopolymer
concrete to enhance its electrical conductivity. They employed
carbon fibers at level of 0.4%, by dry weight of FA. The FA to sand
to coarse aggregate was 1:2:2. The activator was a solution of so-
dium silicate and NaOH. Specimens of cylinders and rectangular
beams were cast and cured at 60 °C for 24 h, then at room tem-
perature. The results showed that the electrical resistance fol-
lowed a descending trend with the increase in bending stresses.
Electrical resistance appeared to fluctuate with the application
of axial compressive stresses. This behavior could be attributed
to densification of the geopolymer paste on one hand, and the
development of micro-cracks within the matrix on the other.
They concluded that the conductive geopolymer could serve as
a smart material in health monitoring applications of concrete
structures.
Puertas et al. [69] modified AAFA mortars with polypropylene
fibers at levels of 0%, 0.5% and 1%, by mortar volume. The results
showed higher compressive and flexural strengths at age of 2 days
in AAFA mortar with the increase in fiber content, whilst lower
compressive and flexural strengths were obtained at age of
28 days. The compressive and flexural strengths decreased as the
fiber content increased. Puertas et al. [69] used 4  4  16 cm pris-
matic specimens to determine the elastic modulus of AAFA mortars
modified with 0% and 1% polypropylene fibers, by mortar volume.
The results showed that the presence of polypropylene fibers re-
duced the elastic modulus. The polypropylene fibers had a low
modulus of elasticity; they were easily deformed and reduced
the compatibility of the material. They also studied the impact
strength of AAFA mortars before and after 50 wet/dry cycles; and
before and after 50 cycles of freezing/thawing. Mortars were mod-
ified with polypropylene fibers at levels of 0% and 0.5%, by mortar
volume. The results showed an increase in fracture with the inclu-
sion of fibers either before or after 50 wet/dry cycles. On the same
line with this, the results showed an increase in both compressive
and flexural strengths with the inclusion of fibers before and after
50 cycles of freezing/thawing. They also studied the drying shrink-
age of alkali-activated FA/slag without or with 1% polypropylene fi-
bers under two different curing conditions of humidity condition
(95% RH) and laboratory condition (21 °C and 50% RH). The results
showed that the specimens modified with fibers cured in labora-
tory condition gave lower drying shrinkage than that specimens
without fibers. On the contrary, at humidity curing condition, the
specimens modified with fibers gave higher drying shrinkage than
that without fibers (Fig. 1).
Li and Xu [70,71] prepared sodium silicate activated FA/slag
blends with less than 0.3% basalt fibers. Tests using a split Hop-
kinson pressure bar (SHPB) system revealed no change in dy-
namic compressive strength, but improvements in energy
absorption were observed. 0.3% was estimated to be the optimal
fiber loading based on energy absorption. Strain hardening was
not observed. The composite properties (energy absorbed etc.)
were determined to be strain rate dependent under impact load-
ing. Table 1 summarizes the previous studies about the effect of
different types of fibers on some properties of AAFA system.
 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
Fig. 1. Effect of 1% polypropylene fibers on alkali-activated FA/slag mortars under
different curing conditions [69].
3. Chemical admixtures
Criado et al. [72] investigated the rheological behavior of AAFA
pastes under the effect of chemical admixtures. FA was activated
with 85% of 12.5 M NaOH solution and 15% of waterglass. Some
commercial chemical admixtures as lignosulphonates, melamines
(first and second generation products) and polycarboxylates (latest
generation) were employed. The flow table spread results showed
that the polycarboxylates admixture gave the highest spread, AAFA
without admixture came in the second place, melamines admix-
ture came in the third place, whilst lignosulphonates admixture
came in the last place.
Memon et al. [73], Demie et al. [74] and Nuruddin et al. [75]
prepared SCC from FA-geopolymers. Sodium silicate and NaOH
solution was employed as alkaline activator. Different dosages of
commercial superplasticizer (Sika Viscocrete-3430) of 3%, 4%, 5%,
6% and 7% were used. Concrete specimens were cured at 70 °C
for 48 h. The results of slump flow showed higher flow with higher
dosage of superplasticizer. On the same line with this, the com-
pressive strength at ages of 1, 3, 7 and 28 days increased as the
dosage of superplasticizer increased. Demie et al. [74] cured some
specimens of the previous mixtures, that had 7% superplasticizer,
at 60 and 80 °C for 48 h. The compressive strength results showed
that specimens cured at 70 °C gave the highest compressive
strength, specimens cured at 80 °C came in the second place, whilst
specimens cured at 60 °C came in the last place. Nuruddin et al.
Table 1
Effect of different types of fibers on some properties of AAFA system.
Author Fiber type Positive effects
Yunsheng et al. PVA – Changed the impact failure mode from brittle pattern to ductile
[65–67] pattern
– Great increase in impact toughness
Vaidya and Carbon – Enhanced the electrical conductivity
Allouche [68]
– Densification the geopolymer paste
Puertas et al. [69] Polypropylene – Increased the compressive and flexural strengths at age of 2 days
– Increased the fracture before and after 50 wet/dry cycles
– Increased the compressive and flexural strengths before and after 50
freezing/thawing cycles
– Lower drying shrinkage of FA/slag, in the case of laboratory curing
Li and Xu [70,71] Basalt – Improved energy absorption
1007
[75] employed different molarities of 8, 10, 12 and 14 in some
specified mixtures of the previous mixtures, that containing 6%
superplasticizer and cured at 70 °C for 48 h. The slump flow results
showed that mixture containing 10 M gave the highest flow, mix-
ture containing 8 M or 12 M came in the second place. Finally, mix-
ture containing 14 M came in the last place. On the other hand,
specimens containing 12 M gave the highest compressive strength,
specimens containing 14 M came in the second place, whilst spec-
imens containing 10 M came in the third place.
Reddy et al. [76] activated low lime based FA geopolymer con-
crete with a mixture of NaOH and sodium silicate solution. 1.5%
superplasticizer (CONPLAST SP-430) was employed, by FA weight.
They reported that the addition of high-range water reducer had
slightly impact on the compressive strength of the hardened con-
crete, but improved workability of fresh geopolymer concrete.
Puertas et al. [77] studied the effect of two superplasticizers based
on vinyl copolymers and polycarboxylates on alkaline-activated
aluminum silicate FA. NaOH was used as alkaline activator with
concentration of 8 M. The dosage of the admixtures was constant
and equivalent 2% in solid mass of FA. They concluded that the
presence of vinyl copolymers and polycarboxylates in activated
FA mortars did not cause any substantial modifications to the
strength behavior of these mortars, compared to that which did
not contain any admixture. The two types of admixtures did not in-
crease the fluidity of AAFA pastes. Wallah and Rangan [78] re-
ported that the addition of more than 2% superplasticizer based
on naphthalene in FA geopolymer mixtures had a few benefits in
term of workability and deleterious for the compressive strength.
Montes et al. [79] reported that the addition of superplasticizer
based on naphthalene sulfonate in FA paste goepolymers increased
the paste viscosity and induced flash set, whilst the addition of
superplasticizer based on polycarboxilate slightly decreased the
viscosity of the paste. Table 2 summarizes the previous researches
that studied the effect of chemical admixtures on the workability
and compressive strength of AAFA system.
4. Slag
4.1. Workability
Yang and Song [80] studied the workability of AAFA and alkali-
activated slag (AAS) activated with a combination of sodium sili-
cate and NaOH powders. They noted that lower initial flow in
AAS than that in the AAFA. Yang et al. [81] reported that AAS mor-
tars exhibited slightly lower flow than AAFA mortars, for the same
mixing condition. Yang et al. [82] used sodium silicate powder to
activate either FA or slag mortars. They used constant w/b ratio
of 0.5 and sand to binder of 3. They reported that AAS mortars
had lower workability than AAFA mortars. Collins and Sanjayan
[83] reported that pure AAS concrete activated with powdered
No or negative effects
– Decreased the compressive and flexural strengths
at age of 28 days
– Reduced the elastic modulus
– Higher drying shrinkage of FA/slag, in the case of
humidity curing
– No change in dynamic compressive strength
1008 A.M. Rashad / Materials and Design 53 (2014) 1005–1025

Table 2
Effect of chemical admixtures on workability and compressive strength of AAFA system.

Author Activator concentration Admixture Positive effects No or negative effects

Criado et al. 85% of 12.5 M NaOH and Superplasticizer – Improved the workability
[72] 15% waterglass (lignosulphonates)
Superplasticizer – Reduced the
(melamines) workability
Superplasticizer – Reduced the
(polycarboxylates) workability
Memon 12 M NaOH + 143 kg/m3 Superplasticizer (Sika – Improved the workability
et al. sodium silicate Viscocrete-3430)
[73]
-Increased the compressive strength at ages of 1, 3, 7 and 28 days
Demie et al. 12 M NaOH + 143 kg/m3 Superplasticizer (Sika – Specimens cured at 70 °C gave the highest strength, followed by
[74] sodium silicate Viscocrete-3430) specimens cured at 80 °C, followed by specimens cured at 60 °C
Nuruddin 8, 10, 12, 14 M Superplasticizer (Sika – The best workability was obtained when 10 M of activator was
et al. NaOH + 143 kg/m3 Viscocrete-3430) used, followed by 8 M or 12 M and followed by 14 M
[75] sodium silicate
– The highest compressive strength at 12 M of activator was used,
followed by 14 M and followed by 10 M
Reddy et al. 10 M NaOH + 171.42 kg/ Superplasticizer (CONPLAST – Improved the workability – No much impact on
[76] m3 Na2SiO3 SP-430) the compressive
strength
Puertas 8 M NaOH Superplasticizer (vinyl – No increase in the
et al. copolymers and workability
[77] polycarboxylates)
– No much impact on
the compressive
strength
Wallah and 8–16 M NaOH Superplasticizer – No much impact on
Rangan (naphthalene) the workability
[78]
– Deleterious for the
compressive strength
Montes Activator/FA = 0.35 Superpalsticizer – Increased the
et al. (naphthalene sulfonate) viscosity
[79]
– Induced flash set
Superplasticizer – Slightly decreased the viscosity
(polycarboxilate)

sodium metasilicate and hydrated lime gave lower workability Table 3

than the composite of 90% slag plus 10% ultrafine FA concrete. Effect of slag on the workability of AAFA system.
Rashad [84] studied the workability of alkali-activated FA/slag Author Increased Decreased Fineness Notes
concretes. The ratios of FA/slag were 100/0, 95/5, 90/10 and 85/ workability workability
15, by weight. A mixture of NaOH and sodium silicate was used Yang and Song
p
FA: 3000 cm2/g, AAS had less
as alkaline activator. The results showed higher workability with [80] slag: 4000, 6000, workability
higher FA content. 8000 cm2/g than AAFA
p
Talling and Brandstetr [85] reported that FA may improve the Yang et al. FA: 3388 cm2/g, AAS had less
[81] slag: 4204 cm2/g workability
workability of a fresh mixture of AAS cement. Wang et al. [86] re-
than AAFA
ported that an addition of FA (below 10%) had little effect on p
Yang et al. FA: 4200 cm2/g, AAS had less
improving the workability of the AAS mixture. On the contrary, [82] slag: 4400 cm2/g workability
Parameswaran and Chatterjee [87] reported that an Indian FA did p
than AAFA
not improve the workability even at 40%, by weight of total binder, Collins and UFA:
Sanjayan 90% < 13.7 mm,
implying that the characteristics of FA were important. However,
[83] slag: 4600 cm2/g
in general, the workability of FA/slag mixture is influenced by p
Rashad [84] FA: 3500 cm2/g,
FA/slag fineness. Table 3 summarizes the previous researches that slag 3200 cm2/g
p
studied the effect of slag on the workability of AAFA system. Talling and Unavailable
Brandstetr
[85]
p
4.2. Setting time Wang et al. Unavailable Little
[86] improvement
p
Parameswaran Unavailable
Sugama et al. [88] studied the setting time of alkali-activated and
Class F FA/slag. FA was replaced with slag at levels of 50%, 60%, Chatterjee
70%, 80%, 90% and 100%, by weight. Sodium silicate was used as [87]
alkaline activator with molar ratios (SiO2/Na2O) of 3.22, 2.50 and
2.00. The results indicated that the setting time decreased with
the increase in slag content, when sodium silicate had molar ratios 4.3. Strength
of 3.22 and 2.50. Kumar et al. [89] partially replaced FA with slag at
levels of 0%, 5%, 15%, 25%, 35% and 50%, by weight, in FA/slag-based Goretta et al. [90] measured the compressive strength of Class C
geopolymers. They reported that the setting time decreased as the FA, slag and sodium silicate alkali-activated concrete. The aggre-
content of slag increased. gate constituted 52% and an alkali activator 11.2% of the total
 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
mass; the mass ratio of silicate to FA + slag was 0.29. 50 mm diam-
eter cylinders having a 1:2 diameter-to-length ratio were used for
testing compressive strength. They reported that compressive
strength of 35 MPa could be obtained at 14 days. Smith and Os-
borne [91] and Bijen and waltje [92] found that waterglass-acti-
vated FA/slag blends showed very low strength, but NaOH
activation gave higher strengths. On the contrary, Dai and Cheng
[93] found that waterglass was much more effective than NaOH.
Weiguo et al. [94] replaced FA with slag at levels of 0%, 30%,
60%, 50%, 40%, 70% and 100%, by weight, in alkali-activated FA/slag
cements. Waterglass with SiO2/Na2O ratio of 2.4 and NaOH which
used to adjust the SiO2/Na2O ratio to 1.0, was used as alkaline acti-
vator. The results showed that the compressive and flexural
strengths increased as the slag content increased. Puertas et al.
[95] alkali-activated FA/slag pastes with NaOH solution. The
parameters of this study were: activator concentration (NaOH:
2 M and 10 M), curing temperature (25 and 65 °C) and FA/slag ra-
tios of 100/0, 70/30, 50/50, 30/70 and 0/100, by weight. In the cur-
ing temperature process, the pastes were maintained at 65 °C
during the first 5 h. for the rest of the curing time, the specimens
were maintained at ambient temperature and 98% RH; the same
as the specimens cured at 25 °C. The compressive strength results
at 1 day showed an increase in strength with the increase in slag
content. 65 °C coupled with 10 M of NaOH gave the highest
strength. At 7 days, 30/70 gave the highest strength at 25 °C cou-
pled with 10 M of NaOH. In the remaining conditions, the strength
increased with the increase in slag content. At age of 28 and
90 days, as the slag content increased as the compressive strength
increased. 25 °C coupled with 10 M of NaOH seemed to be the opti-
mum condition, followed by 65 °C coupled with 10 M of NaOH, fol-
lowed by 25 °C coupled with 2 M of NaOH. 56 °C coupled with 2 M
of NaOH came in the last place.
Garía et al. [96] studied the compressive strength of the alkali-
activated FA/slag composites. The FA/slag ratios were 100/0, 75/25,
50/50, 25/75 and 0/100, by weight. Sodium silicate with modulus
(SiO2/Na2O) of 0, 0.75, 1, 1.5 and 2 was used as alkaline activator.
The %Na2O was added at 4%, 6% and 8%, related to the binder
weight. The pastes were cured at 75 °C for 24 h and then at 20 °C
up to 28 days. The results indicated that for 0/100 pastes, the high-
est strengths were for 4% Na2O (80–85 MPa); the optimum modu-
lus was 1.5. For 100/0 pastes, the higher %Na2O, the better the
strength, whereas the highest strength of 25 MPa was reached
using modulus 1. For the composite of 25/75, the strengths were
(56–60 MPa) at 4% Na2O and the modulus 1 and 1.5. For the com-
posite of 50/50 paste, the strengths were (45–48 MPa) at 4% Na2O
and the best modulus was 1–1.5. For the composite of 75/25
pastes, the strength reached 30–35 MPa at 4% Na2O and modulus
1.5. Guerrieri and Sanjayan [97] presented the compressive
strength of geopolymer pastes made of composites FA/slag. The ra-
tios of FA/slag were 100/0, 65/35, 50/50, 35/65 and 0/100, by
weight. The alkaline activators were mixtures of sodium silicate li-
quid and 8 M NaOH. The activators were mixed in proportions so
that Ms were 0, 0.5, 1.0, 1.5 and 2.0. Industrial grade-powdered so-
dium metasilicate with hydrated lime was also used. The activators
concentrations were 4% and 8% Na. After casting, the specimens
were kept at 23 ± 1 °C and 50 ± 5% RH for 2 h and then were cured
at 80 ± 1 °C and 95 ± 3% RH for 22 h, after that the specimens were
allowed to cool down to room temperature. The compressive
strength was measured at 24 h after curing period. The results
showed that the composite of 65/35 achieved the highest compres-
sive strength at 8% Na and Ms 1.0–1.5, followed closely by the 35/
65, followed by 0/100 and 50/50. Chi and Huang [98] presented the
compressive strength and flexural strength, at ages of 7, 14 and
28 days, of geopolymer mortars made of different combinations
of FA/slag ratios of 100/0, 70/30, 50/50, 30/70, 0/100, by weight.
Sodium silicate with modulus ratio of 1 was used as alkaline
1009
activator. Two concentrations of Na2O of 4% and 6%, by cementi-
tious weight, were employed. The results showed that the compo-
sition of 50/50 achieved the highest compressive strength and
flexural strength followed by 30/70, 0/100, 70/30 and 100/0,
respectively, at both 4% and 6% Na2O.
Yang et al. [99] activated FA/slag pastes with alkaline activator
with modulus of 1.2, 1.4 and 2.0. The ratios of FA/slag were 100/0,
80/20, 60/40, 40/60, 20/80 and 0/100, by weight. The pastes were
demoulded after curing for 24 h in room temperature, then they
were cured at 50 °C for 48 h. After that, they were cured at room
temperature until testing. The compressive strength of the pastes
was measured at ages of 3, 7 and 28 days. The results showed that
the composition of 20/80 gave the highest compressive strength
followed by 40/60, 0/100, 60/40, 80/20 and 100/0, respectively, at
Ms of 1.2 and 1.4. At Ms of 2.0, the composition of 20/80 also gave
the highest compressive strength followed by 40/60 or 60/40, 0/
100, 80/20 and 100/0, respectively. Kim and Kim [100] replaced
FA with slag at levels of 0%, 50% and 100%, by weight, in FA/slag-
based geopolymers. 2.78 M NaOH was used as activator. The com-
pressive strength results of the mortars, at ages of 1, 7 and 28 days,
increased as the content of slag increased. Aydın [101] activated
FA/slag mortars with NaOH and sodium silicate. The ratios of FA/
slag were 40/60, 20/80 and 0/100, by weight. The specimens were
cured at 20 °C and 90% RH for 5 h, then in steam at 70 °C for 6 h.
The results showed an increase in the compressive strength with
the inclusion of slag. The compressive strength increased as the
content of slag increased. Smith and Osborne [91] investigated ce-
ment made of the combination of 40% FA and 60% finely slag acti-
vated with 7% NaOH. They found that the early strength properties
were good but there was a little gain in strength beyond 28 days;
though improved strength might be obtained by varying the pro-
portions of slag and FA or by increasing the fineness of the slag. Ku-
mar et al. [89] partially replaced FA with slag at levels of 0%, 5%,
15%, 25%, 35% and 50%, by weight, in FA/slag-based geopolymers.
An increase in the compressive strength was observed with the
inclusion of slag. As slag content increased as the compressive
strength increased. Zhang et al. [102] solidified municipal solid
waste incinerator (MSWI) FA with the Na2SiO3-activated slag.
The Na2SiO3 activated slag was added to MSWI FA at 25%, 30%,
35% and 45%, by weight. The compressive strength results showed
that 45% gave the highest compressive strength at age of 7 days,
whilst 35% gave the highest compressive strength at ages of 28
and 60 days. Rashad [84] studied the compressive strength, split-
ting tensile strength and flexural strength of alkali-activated FA/
slag concretes. The ratios of FA/slag were 100/0, 95/5, 90/10 and
85/15, by weight. A mixture of NaOH and sodium silicate was used
as activator. The results showed that the compressive strength,
splitting tensile strength and flexural strength increased as the slag
content increased.
Wang et al. [103] studied the compressive strength and porosity
of alkali-activated FA–slag–MK cementitious materials prepared
by hydrothermal method. Waterglass was used as alkaline activa-
tor with the modulus adjusted to 1.0 by dissolving NaOH. The ratio
of water to solid was about 0.35. Different mixtures with different
contents of slag, MK and FA were employed. The slag contents
ranging from 16.2% to 31.33%, the FA contents ranging from
20.46% to 73.52%, and MK contents ranging from 7.22% to
49.39%. The compressive strength results indicated that this type
of material had higher mechanical strength. The highest compres-
sive strength value reached nearly 80 MPa. They suggested that the
higher compressive strength was attributed to the addition of slag.
The more contents of slag in the system, the more hydration prod-
ucts of CSH and hydrated aluminates calcium were obtained. Li and
Liu [104] utilized 4% slag, presented by weight of dry powders, as
additive to 90% FA + 10% MK-based geopolymer. Na2SiO3 and
NaOH solution was used as alkaline activator. The paste specimens
1010 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
were cured at 30 or 70 °C for 14 days. After 14 days, the specimens
were tested in compression. The results showed 51.96% and 25.72%
increases in compressive strengths, due to the inclusion of 4% slag,
cured at 30 °C and 70 °C, respectively. 4% slag addition also influ-
enced pore structure of the geopolymer significantly. A refined
pore size and reduced porosity volume were exhibited after 4% slag
addition. On the contrary, Puertas et al. [69] investigated both
compressive and flexural strengths of mortar consisted of 50% FA
coupled with 50% slag activated with 8 M NaOH versus neat FA
mortar activated with 8 M NaOH. The specimens were cured at
85 °C during the first 24 h. The results showed lower compressive
and flexural strengths at ages of 2 and 28 days with the inclusion of
50% slag. Table 4 summarizes the previous researches that studied
the effect of slag on the strength of AAFA system.
4.4. Durability
Sugama et al. [88] exposed FA/slag-based geopolymers to CO2-
laden H2SO4 with pH value of 1.1 for 15 days at 90 °C, after auto-
claving at 100, 200 and 300 °C. The paste specimens were prepared
by varying two parameters, FA/slag weight ratios of 0/100, 10/90,
30/70 and 50/50, by weight, and SiO2/Na2O molar ratios, in the so-
dium silicate, of 3.22, 2.50 and 2.00. The weight loss results
showed that the proportion of 50/50 mixture had the lowest
weight loss among the all studied molar ratios, followed by 30/
70 and followed by 10/90, whilst the mixture of 0/100 came in
the last place. Ismail et al. [105] studied the performance of alka-
li-activated FA/slag geopolymer binders to different forms of sul-
fate exposure immersed in 5 wt% MgSO4 or 5 wt% Na2SO4
solutions for 3 months. Sodium metasilicate was used as alkaline
activator at concentration of 8 wt%. They reported that MgSO4
was more aggressive to geopolymer paste than Na2SO4. The pres-
ence of magnesium led to decalcification of the Ca-rich gel phases
presented in the blended FA/slag geopolymer system, causing deg-
radation of the binder system and the precipitation of gypsum. The
products of magnesium sulfate attack were poorly cohesive and
expansive, led to dimensional instability and loss mechanical per-
formance. On the contrary, immersion of geopolymer pastes in
Na2SO4 did not lead to any apparent degradation of the binder
and no conversion of the binder phase components into sulfate-
containing precipitates. Chi and Huang [98] studied the percentage
of water absorption of geopolymer mortars made of different com-
binations of FA/slag ratios of 100/0, 70/30, 50/50, 30/70, 0/100, by
weight. Sodium silicate with modulus ratio of 1 was used as alka-
line activator. Two concentrations of Na2O of 4% and 6%, by cemen-
titious weight, were employed. The results showed a reduction in
the percentage of water absorption with increasing slag content
at both concentrations.
4.5. Fire resistance and metal leaching
Guerrieri and Sanjayan [97] studied the high temperature per-
formance up to 800 °C, for 1 h, of alkali-activated FA/slag pastes
activated with a combination of sodium silicate and 8 M NaOH.
FA was replaced with slag at levels of 0%, 50%, 65% and 100%, by
weight. They reported that the specimens with very low initial
strengths (<7.6 MPa) experienced an increase in residual strength
up to 90% gain. Specimens with initial strengths in the order of
28 MPa had residual strength losses of approximately 70%, whilst
specimens with higher initial strengths approaching 83 MPa had
residual strength losses in order of 90% after exposure to 800 °C.
Izquierdo et al. [106] studied leaching of FA/slag/K-silicate/H2O
yielded geopolymer bodies. The activator consists of potassium sil-
icate and potassium hydroxide solution with SiO2/K2O = 1.25. The
proportions of slag were differed between specimens, ranging from
12% to 18%. They reported that the geopolymeric matrices gave rise
to a leaching, which inhibited the leaching of heavy metals with
the result that many numbers of traced pollutants such as Ba, Be,
Bi, Cd, Co, Cr, Nb, Ni, Pb, REE, Sr, Th, U, Y and Zr were retained. They
also reported that the main mechanism of immobilization in the
FA/slag/K-silicate/H2O geopolymers could be essentially physical
encapsulation rather than chemical stabilization. Zhang et al.
[102] solidified MSWI FA with the Na2SiO3-activated slag. The Na2-
SiO3 activated slag was added to MSWI FA at 25%, 30%, 35% and
45%, by weight. They reported that the leaching of Pb and Cr de-
creased with increasing curing time. The mixture containing 35%
slag gave the lowest leaching of Pb and Cr.
4.6. Drying shrinkage
As known, shrinkage is the reduction in volume at constant
temperature without external loading. It is as important material
property that significant effects on long-term performance of de-
signed structures. It also influences structural properties and dura-
bility of the material. However, Rashad [84] studied the drying
shrinkage, up to 91 days, of alkali-activated FA/slag concretes.
The ratios of FA/slag were 100/0, 95/5, 90/10 and 85/15, by weight.
A mixture of NaOH and sodium silicate was used as activator. The
results showed that the drying shrinkage increased as the slag con-
tent increased. On the same line with this, Chi and Huang [98] pre-
pared geopolymer mortars made of different combinations of FA/
slag ratios of 100/0, 70/30, 50/50, 30/70, 0/100, by weight. They
measured the drying shrinkage at ages of 7, 14 and 28 days. They
reported that the drying shrinkage increased as the slag content in-
creased. Aydın [101] activated mortars made of different combina-
tions of FA/slag ratios of 40/60, 20/80, 0/100, by weight, with
NaOH. The specimens cured at 20 °C and 90% RH for 5 h, then in
steam at 70 °C for 6 h. After that, the specimens were kept at
20 °C and 55% RH. The measurement of drying shrinkage of the
specimens started from the end of heat treatment up to 4 months.
The results showed an increase in the drying shrinkage with the
inclusion of slag. The drying shrinkage increased as slag content
increased.
5. Metakaolin
5.1. Workability, setting time, strength and durability
Zhang et al. [107] blended FA with MK to produce FA/MK-based
geopolymers. The FA/MK ratios were 66.7/33.3, 50/50, 33.3/66.7
and 0/100, by weight. NaOH and water were mixed into sodium
silicate to adjust the mole ratio of 1.2. Curing conditions were
either in steam at 80 °C or in air at 20 °C for 1, 3 and 6 days. They
concluded that proper addition of MK (66.7%) increased the fluidity
of fresh paste, prolonged its setting time and improved the com-
pressive strength of hardened geopolymer. The compressive
strength of the geopolymer containing 66.7% MK, by steam curing
for 6 days, was improved by 35.5%. Wu and Sun [108] partially re-
placed FA with MK at levels of 0%, 10%, 20% and 30%, by weight, in
FA/MK-based geopolymers. The experimental results showed an
increased in the workability as well as an increase in the 1, 7 and
28 days compressive strength with increasing MK content.
Yunsheng et al. [109] studied some properties of FA/MK mor-
tars. The ratios of FA/MK were 70/30, 50/50, 30/70, 10/90 and 0/
100, by weight. NaOH and sodium silicate solution with the molar
ratio of 3.2 was used as alkaline activator. There were different cur-
ing conditions. They concluded that geopolymer containing 30% FA
and 70% MK that was synthesized at steam curing (80 °C for 8 h),
exhibited higher mechanical strength. The compressive and flex-
ural strengths were 32.2 and 7.15 MPa, respectively. Li et al.
[110] blended FA with MK to produce FA/MK-based geopolymers.
 A.M. Rashad / Materials and Design 53 (2014) 1005–1025 1011

Table 4
Effect of slag on the strength of AAFA system.

Author % incorporation Positive effects Negative Fineness Notes

effects
p
Weiguo et al. [94] 0, 25, 50, 75 and 100 0.08 sieve residue was controlled
below 2%
100% optimal
p
Puertas et al. [95] 0, 30, 50, 70 and 100 FA: 3980 cm2/g, slag: 4600 cm2/g Cured at 65 °C coupled with 10 M, at age of
1 day
100% optimal
p
Cured at 25 °C coupled with 10 M, at age of
7 days
70% optimal
p
For the remaining conditions, at age of
7 days
100% optimal
p
At ages of 28 and 90 days
100% optimal
p
Garía et al. [96] 0, 25, 50, 75 and 100 FA: 2600 cm2/g, slag: 3700 cm2/g At 4% Na2O, Ms = 1.5
100% optimal
p
At 4% Na2O, Ms = 1–1.5
75% second
place
p
At 4% Na2O, Ms = 1–1.5
50% third place
p
Guerrieri and 0, 35, 50, 65 and 100 Unavailable At 8% Na2O, Ms = 1–1.5
Sanjayan [97]
35% optimal
p
At 8% Na2O, Ms = 1–1.5
65% second
place
p
At 8% Na2O, Ms = 1–1.5
100% third
place
p
At 8% Na2O, Ms = 1–1.5
50% fourth
place
p
Chi and Huang [98] 0, 30, 50, 70 and 100 FA: 2370 cm2/g, slag: 4350 cm2/g
50% optimum
p

100% second
place
p

30% Third
place
p
Yang et al. [99] 0, 20, 40, 60, 80 and Unavailable At Ms = 1.2 or 1.4
100
80% optimal
p

60% second
place
p

100% third
place
p

40% fourth
place
p

20% fifth place

p
Kim and Kim [100] 0, 50 and 100 FA: 10–50 lm, slag: less than 20 lm
100% optimum
p

50% Second
place
p
Aydın [101] 60, 80 and 100 FA: 3230 cm2/g, slag: 4100 cm2/g
100% optimum
p

80% Second
place
p
Smith and Osborne 60 FA: 3980 cm2/g, slag: 4600 cm2/g At early ages, but little strength gain
[91] beyond 28 days
p
Kumar et al. [89] 0, 5, 15, 25, 35 and FA: 13,000 cm2/g, slag: 9200 cm2/g
50
50% optimal

(continued on next page)

1012 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
Table 4 (continued)
Author % incorporation Positive effects Negative
effects
p
Zhang et al. [102] 25, 30, 35 and 45
45% optimal
p
35% optimal
p
Rashad [84] 0, 5, 10 and 15
15% optimal
p
Wang et al. [103] 16.2–31.33
p
Li and Liu [104] 4 Particle size (lm) FA: 11.69, slag: 0.94
p
Puertas et al. [69] 0 and 50
The ratios of FA/MK were 50/50, 30/70, and 10/90, by weight. 2%
short polyvinyl alcohol (PVA) fibers were used as reinforcements.
The fiber length was 6 mm, whilst its average diameter was
14 lm. Solution of NaOH and sodium silicate was used as alkaline
activator. Extrusion method was used to manufacture the geopoly-
mers. The experimental results showed that the inclusion of high
content of MK in the geopolymer gave good fiber–matrix bond.
This led to a higher flexural strength. On the other hand, the inclu-
sion of small MK content in the geopolymer, led to lower flexural
strength. Zhang et al. [111] studied some properties of alkali-acti-
vated FA/MK. The ratios of FA/MK were 70/30, 50/50, 30/70, 10/90
and 0/100, by weight. Chemical-grade NaOH and sodium silicate
solution were used as alkaline reagents. The compressive and flex-
ural strengths at 2 days showed that the composite 0/100 gave the
highest compressive strength and flexural strength followed by 30/
70, 10/90 and 50/50, respectively, whilst the composite of 70/30
came in the last place. The incorporation of FA increased the elec-
trical resistivity of geopolymeric pastes, whereas FA content had a
little impact on the electrical resistivity.
Aguilar et al. [112] produced lightweight concretes based on
binders of FA/MK activated with 15.2% of Na2O using sodium sili-
cate of modulus SiO2/Na2O = 1.2. The ratios of FA/MK were 25/75
and 0/100. Concretes with densities of 1200, 900 and 600 kg/m3
were obtained by aeration by adding aluminum powder, in some
formulations lightweight aggregate of blast furnace slag was added
at a ratio binder: aggregate 1:1; curing was carried out at 20 and
75 °C. The compressive strength development was monitored for
180 days. They concluded that it is possible to produce concrete
based on geopolymers of different densities. The substitution of
FA with 75% MK was viable to form reactive cementitious pastes.
The increment in the curing temperature from 20 to 75 °C acceler-
ated the development to the compression strength during the first
day; in the long term curing at 20 °C similar results were obtained.
Yunsheng et al. [66] studied the durability of FA/MK-based geo-
polymers reinforced with short PVA fibers. Sodium silicate and
NaOH solution was used as alkaline activator. The incorporations
of MK in FA were 50%, 70%, 90% and 100%, by weight. They reported
that impact strength, impact stiffness and impact toughness of
control specimens, specimens exposed to acid solution attack and
specimens exposed to 20 freeze/thaw cycles increased with the
inclusion of MK. 10% FA coupled with 90% MK showed the best
mixture followed by 30/70 and 50/50, respectively. They also re-
ported that the 10/90 gave lower porosity. Table 5 summarizes
the previous researches that studied the effect of MK on the work-
ability, setting time, strength and durability of AAFA system.
5.2. Immobilization
Bankowski et al. [113] activated FA/MK with solution of sodium
silicate and NaOH. The solution had 0.76 M and the sodium silicate
Fineness Notes
Unavailable At age of 7 days
At ages of 28 and 60 days
FA: 3500, slag: 3200
FA, slag and MK: particle size less
than 74 lm
FA: 3980 cm2/g, slag: 4600 cm2/g
concentration was 4.25 M. This geopolymer was used to encapsu-
late brown coal FA containing high concentrations of heavy metals.
The results indicated that leaching of calcium and potassium has
been reduced by this geopolymer. Significant reductions in leach-
ing were found for calcium, arsenic, strontium, selenium and bar-
ium. The geopolymer was effective at stabilizing low percentages
of FA, but effective as the percentage of FA increased. Phair et al.
[114] studied the effect of incorporation of Al sources, such as
metakaolinite, kaolinite and K-Feldspar, with FA geopolymers on
solidification stabilization of heavy metals. They reported that for
increasing the efficiency of immobilisation, it was suggested that
the metal waste be pre-treated with the Al source/clay before
being added to the geopolymer mixture. This would maximize
the sportive capacities of the Al source. They also reported that
all matrices were generally found to be highly efficient in retaining
Pb within the matrix with the order of effectiveness: FA > kaolin-
ite > K-feldspar > metakaoline.
Xu et al. [115] studied some factors affecting the immobiliza-
tion of heavy metals in FA/MK-based geopolymers. They used a
solution of KOH and K2SiO3 as activator. The results showed that
the heavy metals could be effectively immobilized into the geo-
polymeric matrices. The concentrations of alkali activator and dif-
ferent types of heavy metals had impact on the immobilization
behavior to one metal in the same system. Yunsheng et al. [109]
studied the immobilization behavior of FA/MK mortars activated
with NaOH and sodium silicate solution. The ratios of FA/MK were
70/30, 50/50, 30/70, 10/90 and 0/100, by weight. They concluded
that the synthesized geopolymer could effectively immobilize Cu
and Pb heavy metals. Van Jaarsveld [116] reported that the inclu-
sion of MK affected the propensity of the geopolymer matrix to
immobilize heavy metals effectively. The inclusion of MK actively
improved the stability of the geopolymer matrix against chloride
attack.
6. Silica fume
Nuruddin et al. [117] partially replaced FA, in geopolymer con-
cretes, with SF at levels of 0%, 3%, 5% and 7%, by weight. Sodium sil-
icate and NaOH solution was used as alkaline activator. Sugar
based material was incorporated, 3% of total binder, to increase
the setting time of concrete. There were three different curing con-
ditions named hot gunny, ambient and external exposure curing. In
hot gunny curing, specimens were covered with gunny sack,
dipped in warm water which removed in the third day. In ambient
curing, specimens were placed in the shade. In external exposure
curing, specimens were put in plastic coated shelve and exposed
to direct sunlight. The compressive strength results showed that
the optimal replacement level with SF that gave the highest com-
pressive strength depended on curing condition. In hot gunny cur-
ing, 3% SF was the optimal. In ambient temperature curing, 7% SF
 A.M. Rashad / Materials and Design 53 (2014) 1005–1025 1013

Table 5
Effect of MK on the workability, setting time, strength and durability of AAFA system.

Author % Fineness Effects Notes

incorporation
Zhang et al. 33.3, 50, 66.7 FA: 0.787 m2/g, MK: – Increased the workability 66.7% optimal, steam
[107] and 100 1.37 m2/g curing for 6 days
– Prolonged the setting time
– Increased the compressive strength
Wu and Sun 0, 10, 20 and Unavailable – Increased the workability
[108] 30
– Increased the compressive strength
2
Yunsheng 50, 70, 90 and FA: 4000 cm /g, MK: – Increased the compressive and flexural strengths 70% optimal
et al.[109] 100 3500 cm2/g
Li et al. [110] 50, 70 and 90 FA: 4000 cm2/g, MK: – Increased the flexural strength 90% optimal
3500 cm2/g
Zhang et al. 30, 50, 70, 90 FA: 26.7 m2/kg, MK: – 100% MK gave the highest compressive and flexural strengths, followed by
[111] and 100 65.1 m2/kg 70%, 90%, 50%, and 30%, respectively
Yunsheng 30, 50, 70, 90 FA: 4000 cm2/g, MK: – Increased the impact strength, impact stiffness and impact toughness 90% optimal
et al. [66] and 100 3500 cm2/g
– Resist acidic solution attach
– Resist 20 freeze/thaw cycles
– Lowered the porosity

was the optimal, whilst 100% FA was the optimal at the external of the paste mixture containing 40% SF and 10 M NaOH versus con-
exposure curing. Dutta et al. [118] and Thokchom et al. [119] par- trol mixture. The results showed that the inclusion of SF increased
tially replaced FA with SF, in pastes and mortars, at levels of 0%, initial setting time by about 17.86%, but decreased final setting
2.5% and 5%, by weight. Sodium silicate and NaOH solution was time by about 20%. Table 6 summarizes the previous researches
used as activator. The activator concentration was 8% Na2O, while that studied the effect of SF on the workability, compressive
molar ratio was 1. The specimens were cured at 85 °C for 48 h then strength and water absorption of AAFA system.
allowed to cool inside the oven. The compressive strength results
indicated that as the SF content increased in the pastes as the com- 7. Portland cement
pressive strength marginally decreased. On the contrary, as the SF
content increased in the mortars as the compressive strength in- Lohani et al. [121] replaced FA, in concretes, with PC at levels of
creased. The water absorption results showed an increase with 0%, 10%, 25%, 40%, 60% and 100%, by weight. NaOH was used as
introduction of SF in the pastes, whilst they showed a reduction alkaline activator. The slump results indicated higher workability
with introduction of SF in the mortars.
Wu and Sun [108] prepared activator from sodium silicate solu-
tion by mixing predetermined amounts of NaOH flake and SF in Table 6
distilled water. The mixture was sealed and placed in a furnace Effect of SF on the workability, compressive strength and water absorption of AAFA
system.
at 75 °C for approximately 12 h, to achieve a complete reaction be-
tween NaOH and SF, and then left to be cooled at room tempera- Author % Effects Notes
ture. They partially replaced FA, in mortars, with MK at levels of Incorporation
0%, 10%, 20% and 30%, by weight, in which SF/(FA + MK) ratios of Nuruddin et al. 0, 3, 5 and 7 – Increased the compressive Hot gunny
0%, 5%, 7.5%, and 10% and NaOH/(FA + MK) ratios of 5%, 7.5%, 10% [117] strength, 3% optimal curing
– Increased the compressive Ambient
and 12.5% were obtained. The experimental results showed an in-
strength, 7% optimal curing
crease in slump with increasing SF content from 0% to 12.5%. In the – Increased the compressive External
case of NaOH/(FA + MK) ratio of 5%, the 7 days compressive strength, 0% optimal exposure
strength increased as SF increased from 5% to 7.5%, then decreased curing
as SF further increased to 10%, whereas the 28 days compressive Dutta et al. 0, 2.5 and 5 – Increased the compressive In mortars
strength increased monotonically as SF increased from 5% to 10%. [118] and strength, 5% optimal
In case of NaOH/(FA + MK) ratio of 7.5%, both the 7 and 28 days Thokchom
et al. [119]
compressive strengths increased as SF increased from 5% to 10%, – Reduced the water
with the exception of 10% MK. Both the 7 and 28 days compressive absorption
strengths decreased as SF increased from 10% to 12.5% in the case – Decreased the In pastes
of 20% MK. For NaOH/(FA + MK) ratio of 10%, 7 and 28 days com- compressive strength
– Increased the water
pressive strengths increased with SF from 0% to 7.5%, followed by
absorption
a reduction as SF/(FA + MK) further increased from 7.5 to 10% for
Wu and Sun 0, 5, 7.5, 10 – Increased the workability
the same MK content except 0%. They concluded that the optimal
[108] and 12.5
SF content depended on NaOH content, where optimal SF content – Increased the compressive Depended
shifted from 10% to 7.5% when NaOH was increased from 7.5% to strength at SF levels 7.5–10% on NaOH
10% or higher. Songpiriyakij et al. [120] partially replaced FA with content
SF, in pastes at levels of 0%, 10%, 20%, 30% and 40%, by weight. Mix- Songpiriyakij 0, 10, 20, 30, – Increased the compressive
ture of Na2OSiO2 and NaOH was used as activator. The NaOH con- et al. [120] 40 and 50 and bonding strengths with
centration was 10 M or 18 M. The Na2OSiO2/NaOH ratio was 2.5. increasing SF content
40 – Increased the initial
The compressive strength and bonding strength, at ages of 1, 3,
setting time, but decreased
7, and 28 days, increased with increasing SF content and NaOH the final setting time
concentration. They also studied the initial and final setting times
1014 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
with decreasing PC content. On the other hand, compressive
strength increased with increasing PC content. Palomo et al.
[122] partially replaced FA with PC clinker at level of 30%, by
weight. The composite was activated with either NaOH solution
or waterglass + NaOH solution. Mixture hydrated with deionised
water was employed for comparison. The compressive strength re-
sults showed that the highest compressive strength was obtained
when waterglass + NaOH was used as activator. Mixture mixed
with deionised water came in the second place, whilst mixture
activated with NaOH came in the last place.
Guo et al. [123] studied the compressive strength, at ages of 3, 7
and 28 days, of FA/PC-based geopolymers activated with NaOH
solution and sodium silicate solution. FA was partially replaced
with PC at levels of 0%, 10%, 20%, 30%, 40% and 50%, by weight.
The specimens were cured at 23 °C. They reported that the 40%
PC gave better mechanical performance compared to the binders
using other mixture ratios. In another investigation, Guo et al.
[124] partially replaced Class C FA with PC at levels of 0%, 10%,
20%, 30%, 40% and 50%, by weight. NaOH solution and sodium sil-
icate solution were used to activate the composites in which the
amount of Na2O was fixed at 10 wt%. The pastes were cured at
75 °C for 4, 8 and 24 h or at 23 °C for 3, 7 and 28 days. At curing
temperature of 75 °C, the compressive strength increased with
increasing PC content up to 40%. The composition of 60% FA plus
40% PC gave the highest compressive strength at ages of 4, 8 and
24 h. At curing temperature of 23 °C, the compressive strength in-
creased with increasing PC content up to 40% at ages of 3 and
7 days, whilst it increased with increasing PC content up to 50%
at age of 28 days. However, the composition of 60% FA plus 40%
PC gave the highest compressive strength at ages of 3 and 7 days.
The composition of 50/50 gave the highest compressive strength
at age of 28 days, whilst the composition of 60/40 (FA/PC) came
in the second place (Fig. 2). They concluded that specimens made
of 60/40 had better mechanical performance compared to binders
using other mixture ratios.
Owens et al. [125] studied the early ages compressive strength
of FA/PC pastes activated with different activators and cured at
either 20 °C up to testing date or at 60 °C for initial 24 h and then
at 20 °C for the remaining period. The activators were 1% sodium
sulfate, 10% calcium sulfate (anhydrite), from binder weight and
1 M NaOH. The FA was partially replaced with PC at level of 50%,
by weight. Neat FA/PC paste without activator was employed for
comparison. At 20 °C curing temperature, the compressive strength
results showed that 1% sodium sulfate, which used as activator,
gave the highest compressive strength at age of 1 day, followed
by 1 M NaOH, followed by neat FA/PC without activator and fol-
lowed by 10% calcium sulfate. At ages of 3 and 7 days, the neat
FA/PC without activator gave the highest compressive strength,
Fig. 2. Compressive strength of FA/PC binders [124].
followed by 1% sodium sulfate, followed by 1 M NaOH, whilst
10% calcium sulfate came in the last place. At 60 °C curing temper-
ature for 1 day and then 20 °C for the remaining period, 10% cal-
cium sulfate gave the highest compressive strength at age of
1 day, followed by 1% sodium sulfate, followed by neat FA/PC with-
out activator, whilst 1 M NaOH came in the last place. At ages of 3
and 7 days, 10% calcium sulfate gave the highest compressive
strength, followed by neat FA/PC without activator, followed by
1% sodium sulfate. Finally, pastes activated with 1 M NaOH came
in the last place. They concluded that sodium sulfate seemed to
be the optimum activator when curing temperature was 20 °C,
whilst calcium sulfate seemed to be the optimum activator when
curing temperature was 60 °C for 1 day and then 20 °C for the
remaining period.
Saraswathy and Song [126] studied the corrosion performance
of steel embedded in different FA/PC concrete mixtures. The ratios
of FA/PC were 10/90, 20/80, 30/70 and 40/60, by weight. The mix-
tures were activated with NaOH and calcium oxide. They also acti-
vated the mixtures with physical activation and thermal activation.
The results showed that FA/PC ratios of 20/80 and 30/70 improved
the corrosion resistance properties of concrete. The FA/PC chemi-
cally activated gave the lowest corrosion rate, lower absorption
and lower coulomb values compared to either physical activation
or thermal activation.
Fernández-Jiménez et al. [127] studied the residual compressive
strengths, after exposure to elevated temperatures, of different
three types of binders. These binders were PC, AAFA and alkali-
activated FA/PC. The neat AAFA binder was activated with a mix-
ture of 15% liquid sodium silicate and 85% NaOH solution. The
composite of FA/PC (59/25) was activated with 16% solid activator
(8% solid sodium silicate + 8% Na2CO3). They concluded that neat
AAFA performed better than PC. Residual compressive strength
was maintained or even raised in this material after exposure to
elevated temperatures. The hybrid FA/PC exhibited intermediate
behavior between the neat AAFA and PC.
Wu and Nail [128] studied the effect of sulfate attack and ASR
on blended cements consisted of 20–60% Type I cement, 40–80%
Class C FA and spray-dryer ash (SDA) activated with 2–4% sodium
sulfate. Neat Type I cement was employed as a control. They con-
cluded that the blended cements showed superior resistance to
sulfate attack. With 60% cement replacement, the 1-year mortar
bar expansion was significantly lower than limit of 0.1% specified
in ASTM C 1157 for Type high sulfate resistance blended cement.
The mortar bar expansion of blended cements in alkali solution
was lower than the control Type I cement. The expansion values
were still beyond the limit that is considered safe for ASR. The
addition of sodium sulfate depleted Ca2+, increased the pH value
in cement past and promoted the dissolution of PC minerals and
pozzolan minerals. It also accelerated the formation of early ages.
Table 7 summarizes the previous researches that studied the effect
of PC on some properties of AAFA system.
8. Cement kiln dust
Wang et al. [129] studied the effect of curing temperature and
NaOH addition on the compressive strength of FA blended with ce-
ment kiln dust (CKD) binders. The ratio of FA/CKD was 50/50.
NaOH was used as alkaline activator with two different concentra-
tions of 2% and 5%. The curing temperatures were 14, 38 and 50 °C.
The results indicated that curing temperature was more effective
for FA/CKD binder strength improvement than NaOH addition.
Addition of 2% NaOH increased the strength of the binder at both
early and later ages, whilst addition of 5% NaOH increased the
strength only at early age when the pastes cured at 24 °C or
38 °C. 2% NaOH reduced the strength when curing temperature
 A.M. Rashad / Materials and Design 53 (2014) 1005–1025 1015

Table 7
Effect of PC on some properties of AAFA system.

Author Replacement levels (%) Positive effects Negative Studied property and notes
effects
p
Lohani et al. [121] 0, 10, 25, 40, 60 and 100 – Workability
p
– Compressive strength
p
Palomo et al. [122] 30 – Compressive strength (activator: waterglass + NaOH)
p
Guo et al. [123] 0, 10, 20, 30, 40 and 50 – Compressive strength
40% optimal
p
Guo et al. [124] 0, 10, 20, 30, 40 and 50 – Compressive strength
– 40% optimal at ages of 3, 7 days, whilst 50% optimal at age of 28 days
p
Owens et al. [125] 50 – Compressive strength
20 °C curing – 1% Na2SO4 optimal at age of 1 day
p
– Compressive strength
20 °C curing – At ages of 3, 7 days
p
– Compressive strength
60 °C then – 10% calcium sulfate optimal at ages of 1, 3, 7 days
20 °C
p
Saraswathy and Song [126] 60, 70, 80 and 90 – Corrosion resistance
– 70–80% optimal
p
Fernández-Jiménez et al. 0 and 25 – After exposure to elevated temperatures
[127]
p
Wu and Nail [128] 20–60 – Sulfate attack resistance

was 50 °C (Fig. 3). Wang et al. [130] investigated three different
methods and their effects on the strength development of nonclin-
ker cements made of 50% Class F FA and 50% CKD. These activation
methods included ball mill cogrinding, chemical addition and ele-
vated temperature curing. In chemical addition method, FA/CKD
was activated with 2% or 5% NaOH, by weight. The compressive
strength results showed that the inclusion of 2% NaOH was more
effective than the inclusion of 5% NaOH, to improve the compres-
sive strength (Fig. 4).
9. Lime
Shi [131] prepared FA/lime at ratio of 80/20 without activation
or with activation by 4% Na2SO4. The water to solid ratio of 0.35
was used to produce a paste with normal consistency. Paste spec-
imens were cured in fog room at temperature of 23 °C, up to test-
ing date. The results indicated that the addition of Na2SO4 did not
affect the initial setting time, but shortened the final setting time.
Activated pastes showed much higher strength than un-activated
pastes at ages of 3 and 28 days. The addition of Na2SO4 raised
the alkalinity of pore solutions, accelerated initial pozzolanic reac-
tion and resulted in the formation of AFt, which gave the high early
strength of the FA/lime paste. Shi and Day [132] studied the effect
of addition of lime on the strength development and hydration of
FA/slag mixtures activated with NaOH and sodium silicate. They
concluded that the addition of a small amount of hydrated lime
significantly increased the early-age strength, but slightly de-
creased the later-age strength of the cements. Fan et al. [133] pre-
sented new method of FA activation with addition of lime and a
small quantity of Na2SiO3. FA/lime pastes without or with small
quantity of Na2SiO3 were tested in compression at ages of 3, 14,
28, 56, 90 and 120 days. The results indicated that the inclusion
of Na2SiO3 increased the compressive strength at ages of 3, 14
and 28 days, whilst no effect on the compressive strength at age
of 56 days. On the other hand, the inclusion of Na2SiO3 decreased
the compressive strength at ages of 90 and 120 days, in comparison
with FA/lime without Na2SiO3. Table 8 summarizes the previous

Fig. 3. Effect of curing temperature on alkali-activated FA/CKD compressive

strength (a) 2% NaOH (b) 5% NaOH [129]. Fig. 4. Effects of NaOH addition on strength of FA/CKD [130].
1016 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
Table 8
Effect of lime on the compressive strength of AAFA system.
Author % Positive effects
incorporation
Shi [131] 20 – Increased early strength
Shi and Day [132] Small amount – Increased early strength
Fan et al. [133] – Increased the compressive strength at ages of 3, 14 and 28 days
researches that studied the effect of lime on the compressive
strength of AAFA system.
10. Natural pozzolan
Nazari et al. [134] partially replaced FA with rice husk-bark ash
(RHBA) at levels of 20%, 30% and 40%, by weight, in geopolymers
activated with waterglass + NaOH. The compressive strength re-
sults showed that 30% RHBA combined with 70% FA gave the high-
est compressive strength at 7 and 28 days. The composition of 20%
RHBA coupled with 80% FA came in the second place, whilst the
composite of 40% RHBA coupled with 60% FA came in the last place.
In another investigation, Nazari and Rohani [135] studied the flex-
ural strength of the same mixtures and concluded similar conclu-
sions. Riahi et al. [136] measured the percentage of water
absorption of the same mixtures that activated with the solution
of waterglass and NaOH. The SiO2/Al2O3 ratios were 2.38, 2.99
and 3.81. The experimental results showed that SiO2/A2O3 ratio
of 2.99 gave the lowest water absorption percentage, the SiO2/
Al2O3 ratio of 2.38 came in the second place, whilst the ratio of
3.81 came in the last place. The 30% RHBA coupled with 70% FA
gave the lowest water absorption, the combination of 20% RHBA
with 80% FA came in the second place, whilst the combination of
40% RHBA with 60% FA came in the last place.
Songpiriyakij et al. [120] partially replaced FA with RHBA, in
pastes at levels of 0% and 40%, by weight. The ratio of RHBA was
70:30. The treated temperature was around 400 °C. Mixing of Na2-
OSiO2 and NaOH was used as activator. The NaOH concentration
was 10 M or 18 M. The Na2OSiO2/NaOH ratio was 2.5. The results
showed an increase in the compressive strength and bonding
strength, at ages of 1, 3, 7 and 28 days, with the inclusion of RHBA.
The specimens activated with 18 M NaOH exhibited lower
strengths, at ages of 1 and 3 days, in comparison with that acti-
vated with 10 M NaOH. On the other hand, the specimens activated
with 18 M NaOH showed higher strengths, at ages of 7 and 28 days,
than that activated with 10 M NaOH. They also studied the initial
setting time and final setting time of the paste mixture containing
40% RHBA and 10 M NaOH compared to control mixture. The re-
sults showed that the inclusion of RHBA increased both initial
and final setting times by about 21.43% and 6.67%, respectively.
Kusbiantoro et al. [137] partially replaced FA, in concretes, with
microwave incinerated rice husk ash (MIRHA) at levels of 0%, 3%
and 7%, by weight. The composites were activated with solution
of sodium silicate and NaOH. The geopolymer concrete specimens
were exposed to three different curing conditions that were ambi-
ent, external exposure and oven curing. In ambient curing, the
specimens were placed at the shaded area with maximum temper-
ature of 35 + 1 °C. In external exposure curing, the specimens were
placed in plastic chamber exposed to direct sunlight with maxi-
mum temperature of 55 + 1 °C. In oven curing, the specimens were
placed, after casting by 1 h, in an oven at temperature of 65 °C for
24 h, then in ambient temperature. The results showed that the
improvement in the compressive strength of MIRHA-based geo-
polymer concrete was up to 22.34% higher than that of non-MIR-
No or negative effects
– Slightly decreased the later strength
– No effect on the strength at age of 65 days
– Decreased the compressive strength at ages of 90 and
120 days
HA-based geopolymer concrete at ambient temperature, whilst
the inclusion of MIRHA in FA had adversely impact on compressive
strength at external exposure curing. In oven curing, the inclusion
of MIRHA in FA had significantly improvement in compressive
strength. 3% MIRHA had compressive strength up to 14.17% higher
than that of non-MIRHA concrete, whilst 7% gave 19.41% higher, re-
lated to non-MIRHA concrete. They also studied the bonding
strength between FA-MIRHA based geopolymers and steel. They
found that 3% MIRHA had marginal improvement in bonding
strength, whilst 7% had significant improvement which reached
38.31% higher than that of non-MIRHA, at ambient curing
(Fig. 5). In external exposure curing, the non-MIRHA geopolymer
mixture gave the highest bonding strength, followed by 7% MIRHA
and 3% MIRHA (Fig. 6). The 7% MIRHA presented only 4.29% lower
bonding strength than that of non-MIRHA concrete. In oven curing,
the 3% MIRHA gave the highest bonding strength at 3 and 7 days,
whilst the bonding strength of all mixtures was comparable at
age of 28 days. Nuruddin et al. [138] presented the compressive
strength development (from age of 3 days up to 56 days) through
polymerization process of alkaline solution and FA blended with
MIRHA. FA was blended with MIRHA at levels of 3%, 5% and 7%.
A solution of NaOH and Na2SiO3 was used as alkaline activator.
Concrete specimens were cured at three different conditions
named hot gunny curing (33–38 °C), ambient curing (27–32 °C)
and external exposure curing (39–44 °C). At hot gunny and ambi-
ent curing, the results indicated that the addition of 5% MIRHA
gave the highest compressive strength, followed by 0%, followed
by 3% and 7%. At external exposure curing, the results indicated
that the addition of MIRHA at level of 0% gave the highest compres-
sive strength, followed by 7%, followed by 3% and 5%. Table 9 sum-
marizes the previous researches that studied the effect of RHBA
and MIRHA on some properties of AAFA system.
11. Nanoparticles
Riahi and Nazari [139] studied the compressive strength of ash-
based geopolymers containing rice husk ash + FA and nanoalumi-
Fig. 5. Bonding strength of FA-MIRHA-based geopolymer concrete in ambient
curing [137].
 A.M. Rashad / Materials and Design 53 (2014) 1005–1025 1017

suspension in the solution during the early ages of reaction and

Fig. 6. Bonding strength of FA-MIRHA-based geopolymer concrete in external
exposure curing [137].
then released silica later in the reaction process.
Chindaprasirt et al. [141] investigated the effect of silica derived
from nanosilica and rice husk ash and alumina (nanoalumina) on
the setting time and compressive strength of Class C FA geopoly-
mers. Sodium silicate and NaOH were used as alkaline activators.
The setting and compressive strength were investigated by adjust-
ing SiO2/Al2O3 ratio of the starting mixture, via series of mixtures
formulated with varying SiO2 or Al2O3 contents. The results
showed that the increasing in both alumina and silica, accelerated
the setting. The control specimen with SiO2/Al2O3 = 4 had com-
pressive strength of 62.6 MPa. The compressive strength decreased
with the addition of silica content from 4.8 to 5.8 (SiO2/Al2O3 from
4 to 4.79). On the other hand, the increasing Al2O3 content did not
show any significant effect on the compressive strength. Table 10
summarizes the previous researches that studied the effect of
nanoparticles on some properties of AAFA system.

na + nanosilica. Four factors including the percentage of nanosilica
(at 3 levels of 1, 2 and 3 wt%), oven curing temperature (at 3 levels
of 25, 70 and 90 °C), oven curing time (at 3 levels of 2, 4 and 8 h)
and NaOH concentration (at 3 levels of 5, 8 and 12 M) were consid-
ered. The alkali activating was done by a mixture of NaOH and so-
dium silicate solutions. The experimental results showed that the
oven curing time was not important factor affecting the compres-
sive strength. The optimum NaOH concentration of 8 M showed
the most effect on the compressive strength. Utilizing of 3 wt%
SiO2 nanoparticles resulted in obtaining the highest strength.
Al2O3 nanoparticles had no effect on the compressive strength.
The optimum level of nano silica, oven curing temperature and
oven time were 3 wt%, 90 °C and 8 h, respectively. Rodríguez
et al. [140] assessed the effect of the use of an alternative activator
based on nanosilica/MOH (M = K+ or Na+) blended solutions on the
performance of AAFA binders. Sodium silicate and potassium sili-
cate were used as reference soluble silica sources. They reported
that the production of high mechanical strength and low perme-
ability could be achieved using alternative activators based on
modified nanosilica. These binders showed an extent of reaction
which was slightly lower than that of binders produced from using
sodium silicate activators, but mechanical strengths were similar.
The water demand and porosity of the samples prepared with
the nanosilica-based activators were lower than for the case of sil-
icate activators, which was attributed to the slightly delayed re-
lease of silica from the solid nanosilica particles, which remain in
12. Bottom bed and fluidized bed combustion
Boonserm et al. [142] studied the improvement of the geopoly-
merization of bottom ash (BA) by incorporating FA. The ratios of
FA/BA were 100/0, 75/25, 50/50, 25/75 and 0/100, by weight. NaOH
solution at 10 M concentration and sodium silicate solution were
used as alkaline activators. The results indicated that the compres-
sive strength decreased with increasing BA content. Chindaprasirt
et al. [143] presented utilization of FA obtained from fluidized
bed combustion (FBC) as a source material for geopolymer. FBC
FA has low reactivity and high content of CaO and CaSO4 which
limits its use. However, they blended FBC FA with pulverized coal
combustion (PCC) FA in different contents. The ratios of PCC/FBC
were 100/0, 80/20, 60/40, 20/80 and 0/100, by weight. A solution
of NaOH and Na2SiO3 was used as alkaline activator. They reported
that the compressive strength decreased with increasing FBC FA
content (Fig. 7).
Chindaprasirt and Rattanasak [144] blended FBC FA with BA at
ratio of 60/40. The blended FBC/BA was partially replaced with PCC
FA at levels of 50%, 60%, 70% and 80%, by weight. Sodium silicate
and 10 M NaOH solutions were used as alkaline activators. The re-
sults indicated that the inclusion of 60% PCC FA gave the highest
compressive strength. Xu et al. [145] investigated compressive
strength, at age of 7 days, of low-reactive circulating FBC FA
blended with different contents of MK activated with sodium sili-
cate solution. The ratios of FBC FA/MK were 30/70, 40/60, 50/50,

Table 9
Effect of RHBA and MIRHA on some properties of AAFA system.

Author % incorporation Studied property Positive Negative Notes

effects effects
p
Nazari et al. [134] 20, 30 and 40 – Compressive strength – 30% optimal, followed by 20%
RHBA
p
Nazari and Rohani 20, 30 and 40 – Flexural strength – 30% optimal, followed by 20%
[135] RHBA
p
Riahi et al. [136] 20, 30 and 40 – Water absorption – 30% optimal, followed by 20%
RHBA
p
Songpiriyakij et al. 0 and 40 RHBA – Compressive and bonding
[120] strength
p
Kusbiantoro et al. 0, 3 and 7 MIRHA – Compressive and bonding – Ambient curing
[137] strength
p
– External exposure curing
p
– Oven curing
p
Nuruddin et al. [138] MIRHA – Compressive strength – Hot gunny and ambient curing
– 5% optimal, followed by 0%, 3% and 7%,
respectively
p
– External exposure curing
– 0% optimal, followed by 7%, 3% and 5%,
respectively
1018 A.M. Rashad / Materials and Design 53 (2014) 1005–1025

Table 10
Effect of nanoparticles on some properties of AAFA system.

Author Nanoparticles Positive effects No or negative

type effects
Riahi and Nanosilica – Increased the
Nazari compressive
[139] strength
Nanoalumina – No effect on the
compressive
strength
Rodríguez Nanosilica (as – Reduced the
et al. [140] activator) permeability
– Decreased water
demand
Chindaprasirt Nanosilica and – Accelerated the
et al. [141] rice husk ash setting
– Decreased the Fig. 8. Compressive strength of geopolymer specimens with different zeolite
compressive contents [146].
strength
Nanoalumina – Accelerated the
setting phase improved the geopolymerization through the mechanism of
– No effect on the providing nucleation sites for geopolymer formation. However, the
compressive
15% 5A zeolite gave the highest compressive strength. The efflores-
strength
cence extent geopolymer specimen decreased with 5A zeolite addi-
tion, which by the reason of the Na+ fixation into the zeolite
structure through Ca2+/Na+ exchange and the lesser pore volume
60/40 and 70/30, by weight. The ratio of 40/60 gave the highest of macrospores. Mingyu et al. [147] synthesized geopolymers by
compressive strength, the ratio of 30/70 came in the second place, using FA as the main starting material, zeolite as supplementary
the ratio of 50/50 came in the third place, whilst the ratio of 60/40 material, and NaOH and CaO together as activator. An orthogonal
came in the fourth place. Finally, the ratio of 70/30 came in the last array testing protocol was used to analyze the influence of the mix-
place. ture proportion on some properties of the geopolymer mortars. The
results indicated that the concentration of NaOH solution and the
CaO content played an important role on the strength of the mate-
13. Zeolite rials. Zeolite as additive, the geopolymer showed the highest
strength and the best sulfate resistance.
Huang et al. [146] studied the compressive strength and efflo-
rescence extent of the FA/5A zeolite geopolymer pastes. FA was
partially replaced with 5A zeolite at levels of 0%, 5%, 10% 15% 14. Gypsum and flue gas desulfurization
and 20%, by weight. NaOH solution and sodium silicate solution
were mixed to prepare liquid activator with Na2O/SiO2 = 2.0 and Boonserm et al. [148] studied the compressive strength of
H2O/Na2O = 10. The specimens were cured at 80 °C for 24 h then blended FBC FA and PCC FA geopolymers containing gypsum as
at ambient temperature. The results showed that the addition of an additive. The gypsum additions were 0%, 5% and 10%, by weight.
5A zeolite served to increase the compressive strength (Fig. 8), NaOH and Na2SiO3 were used to activate the aluminosilicate
which resulted from micro-aggregate effect of fine zeolite particles sources. The results indicated that the inclusion of 5% gypsum gave
on one hand and the enhancement of geopolymerization extent on the highest compressive strength, whilst the inclusion of 10% came
the other hand. The Ca2+ diffused from 5A zeolite through ion ex- in the second place. Boonserm et al. [142] studied the improve-
change with Na+ in activator solution was assumed to be incorpo- ment of the geopolymerization of FA/BA that used as the blended
rated into the alumino-silicate framework as a charge-balancing source materials at ratios of 50/50, 25/75 and 0/100, by weight.
cation to form a new fiber-like phase in the zeolite-contained geo- The source materials were then partially replaced with 0%, 5%,
polymer specimens. The fiber-like phase was suggested to be the 10% and 15%, by weight, with the flue gas desulfurization gypsum
amorphous zeolite-like hydrate products and the formation of this (FGDG). The results indicated that the compressive strength in-
creased with increasing FGDG content up to 10%, then decreased
beyond this level. Boonserm et al. [142] studied the improvement
of the geopolymerization of FA incorporating FGDG as additive. FA
was partially replaced with FGDG at levels of 0%, 5%, 10% and 15%,
by weight. The results indicated that the compressive strength de-
creased as the content of FGDG increased. Guo et al. [124] partially
replaced Class C FA with flue FGDG and water treatment residual
(WTR) at levels of 0%, 10%, 20%, 30%, 40% and 50%, by weight. NaOH
and sodium silicate solution were used to activate the composi-
tions in which the amount of Na2O was fixed at 10 wt%. The pastes
were cured at 75 °C for 4, 8 and 24 h or at 23 °C for 3, 7 and
28 days. The results showed a reduction in the compressive
strength with the inclusion of either FGDG or WTR in FA matrix.
They concluded that specimens made of either 10% FGDG or 10%
WTR had better mechanical performance compared to binders
using other mixture ratios, but neat AAFA was still gave the
Fig. 7. Compressive strength of geopolymer mortars at age of 7 days [143]. highest compressive strength. Table 11 summarizes the previous
 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
researches that studied the effect of gypsum and FGDG on the com-
pressive strength of AAFA system.
15. Other materials
Mingyu et al. [147] synthesized geopolymers by using FA as the
main starting material, bentonite as supplementary material, and
NaOH and CaO together as activator. An orthogonal array testing
protocol was used to analyze the influence of the mixture propor-
tion on some properties of the geopolymer mortars. The results
indicated that the concentration of NaOH solution and the CaO
content played an important role on the strength of the materials.
Bentonite simply acted as filler in which led the geopolymer to be
more contact, but did not show improvement on the compositions
and the microstructures of the geopolymer. Srinivasan and Sivak-
unar [149] studied setting time and compressive strength of the
FA/bentonite-based geopolymer mortars. The ratios of FA/benton-
ite were 30/70, 20/80, 10/90 and 0/100, by weight. NaOH was used
as alkaline activator. They reported that the inclusion of bentonite
increased the initial and final setting times. The compressive
strength values at ages of 1, 3, 7, 14 and 28 days decreased with
increasing bentonite content.
Zhang et al. [150] replaced FA with mine tailings, waste materi-
als produced from mining and screening operations, at levels of 0%,
25%, 50%, 75% and 100%, by weight. NaOH was used as alkaline
activator with different concentrations of 5, 10 and 15 M. The spec-
imens were cured at 60 °C. Unconfined compressive strength (UCS)
was measured at different ages of 2, 7, 14 and 28 days. The results
showed a reduction in the UCS with the inclusion of the mine tail-
ings. The reduction in the UCS increased as the mine tailings con-
tent increased (Fig. 9). Higher activator concentration led to higher
compressive strength.
Jiao et al. [151] replaced FA with silica-rich vanadium tailing at
levels of 50%, 60%, 70%, 80%, 90% and 100%, by weight. Sodium sil-
icate was used as alkaline activator. The specimens were cured at
room temperature. The test results showed that the mass ratio of
30/70 (FA/vanadium tailing) corresponded to the highest compres-
sive strength. This mixture was selected and subjected to elevated
temperatures of 150, 300, 450, 600, 750, 900 and 1050 °C for 1 h,
after curing for 7 days. The results showed that the residual com-
pressive strength did not change substantially before 600 °C. From
600 to 900 °C, the residual compressive strength increased and
reached its peak at 900 °C. From 900 to 1050 °C, the residual com-
pressive strength sharply decreased.
Oh et al. [152] partially replaced two types of Class C FA with
two levels of Na-aluminate, by weight. The first type of FA was par-
tially replaced with 18%, whilst the second type was partially re-
placed with 10%. Solution of 10 M NaOH was used as alkaline
Table 11
Effect of gypsum and FGDG on the compressive strength of AAFA system.
Author % incorporation Positive effect Negative
effect
p
Boonserm et al. 0, 5 and 10 (gypsum)
[148]
5% optimal
followed by 10%
p p
Boonserm et al. 0, 5, 10 and 15 (FGDG)
[142]
up to 10% beyond
10%
p shrinkage. The drying shrinkage decreased as the content of waste-
Boonserm et al. 0, 5, 10 and 15 (FGDG)
[142]
p
Guo et al. [124] 0, 10, 20, 30%, 40 and
50 (FGDG)
1019
Fig. 9. Unconfined compressive strength of geopolymer specimens with different
mine tailings contents at10 M NaOH concentration [150].
activator. The specimens were cured at 80 °C and 100% RH, up to
testing time. Compressive strength was measured at 6 h, 1 day, 7,
14 and 32 days. They reported that the inclusion of Na-aluminate
reduced the compressive strength of the specimens, with the
reduction magnitude relatively constant regardless of length of
curing period (Fig. 10). Rovnaník [153] activated FA pastes with so-
dium silicate. Calcium aluminate C12A7 (mayenite) was added at
different incorporations of 0.1%, 0.15% and 0.2%, by weight. They
reported that the inclusion of C12A7 accelerated the setting times.
The 24 h compressive strength increased, whilst 28 days compres-
sive strength reduced with the inclusion of C12A7.
Ahmari et al. [154] replaced FA with ground waste concrete
(GWC) powder, in concretes, activated with NaOH and sodium sil-
icate solution. The GWC powder was obtained by crushing and
grinding the tested PC concrete specimens. FA was replaced with
GWC at levels of 0%, 25%, 50%, 75% and 100%, by weight. They con-
cluded that the inclusion of GWC improved the UCS of the geopoly-
mer binder up to 50% replacement level. Further increase of GWC
content led to decrease the UCS (Fig. 11). Increased NaOH concen-
tration resulted in higher UCS, especially at GWC content less than
50%. Addition of sodium silicate also improved the UCS due to pro-
vision of additional SiO2 and delayed setting. The optimum initial
Si/Al (the Si/Al ratio at the highest UCS for the FA/GWC geopolymer
was around 3.38). Lampris et al. [155] manufactured geopolymer
from grind silt which was used as source material. Silt powder
was partially replaced with PFA at levels of 0% and 20%, by weight.
The grind silt without or with FA were activated with NaOH and
sodium silicate solution. The paste specimens were cured at room
temperature or at 60 °C for three days and then at room tempera-
ture for four days. The compressive strength results at 7 days
showed an increase in strength with the inclusion of FA. The inclu-
sion of 20% FA raised the compressive strength by 17.11% and
4.63% for specimens cured at room temperature and 60 °C for
3 days then at room temperature for 4 days, respectively. Yan
and Sagoe-Crentsil [156] partially replaced sand in AAFA mortars
with wastepaper sludge. Dry wastepaper sludge ranging from 0%
to 10% was added as sand replacement. NaOH and sodium silicate
was used as alkaline activator. Both fresh and hardened geopoly-
mer mortars properties were evaluated. The results showed that
the addition of wastepaper sludge to geopolymer mortars reduced
flow properties and compressive strength. These reductions in-
creased with increasing wastepaper sludge content. On the other
hand, the addition of wastepaper sludge decreased the drying
paper sludge increased (Fig. 12).
Lee and van Deventer [157] synthesized alkali-activated cement
systems to study the effect of the inorganic salts (KCl, K2CO3, KNO3,
1020 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
Fig. 10. Compressive strength development of alkali-activated FA/Na-aluminate (a)
first type FA, (b) second type FA [152].
Fig. 11. UCS versus GWC content in FA/GWC geopolymers at age 7 days [154].
KOH, CaCl2, Ca(OH)2, CaCO3, CaSO3, CaO, MgCl2.6H2O, Mg(NO3)2.6-
H2O and MgO) on some properties of control mixture did not con-
tain these inorganic salts. FA and kaolin of the appropriate ratio
were mixed (FA/kaolinite ratios were 2.02, 4 and 9). Potassium
hydroxide solution of 15 M was mixed with sodium silicate. This
solution was used to activate the source materials. They concluded
that ionic contamination during manufacturing of AAFA cements
was found not to adversely affect the product early strength. The
setting and rheological properties of the early pastes were changed
significantly by Ca and Mg salts through heterogeneous nucleation
effects. Setting was accelerated by these salts once the right solu-
tion composition was achieved through solid dissolution. Potas-
sium salts were found to delay setting only when the initial
solution for solid activation was low in soluble silicate concentra-
tion. The anions of Cl, CO2 3 and NO3 could affect the alkaline
solution to achieve the right composition and thus retarded
setting.
Ariffin et al. [158] replaced the pulverized fuel ash with palm oil
fuel ash. The ratios of pulverized FA/palm oil fuel ash were 70/30,
50/50, 30/70 and 0/100, by weight. The compositions were acti-
vated with sodium silicate and NaOH solution. The results indi-
cated that the composition of 70/30 gave the highest
compressive strength, the composition of 50/50 came in the sec-
ond place and the composition of 30/70 came in the third place. Fi-
nally, the composition of 0/100 came in the last place. Srivastava
et al. [159] investigated experimental study related to inorganic
species in sludge generated from Common Effluent Treatment
Plant contaminated with hazardous wastes at relatively high con-
centration. The environmental sensitive metals studied in the
sludge were Pb, Fe, Ni, Zn and Mn. The solidification/stabilization
(S/S) of heavy metals within FA-cement-based matrix was con-
ducted for low cost treatment and reuse of sludge. The sludge con-
tents ranging from 0% to 50%, cement contents ranging from 30% to
15%, whilst low calcium FA contents ranging from 70% to 35%. A
solution of NaOH and sodium silicate was used as alkaline activa-
tor. The results indicated that with increasing sludge from 14.2% to
25% the UCS was almost the same. The mixture containing 56% FA,
20% sludge and 24% cement cured at 28 days showed increase in
strength as well as rate of stabilization within range of 95–99%
for zinc, iron and manganese at pH 7. The order of fixation of toxic
metals in the alkali-activated matrix was Zn > Mn > Fe > Ni > Pb.
Criado et al. [160] evaluated the inhibitive of two mixtures of or-
ganic compounds, disodium b-glycerol phosphate (GPH) with
sodium 3-aminobenzoate (3AMB) and GPH with sodium N-pheny-
lanthranilate (PhAMB), on the corrosion of carbon steel reinforce-
ment bars embedded in carbonated chloride-polluted AAFA
mortars. Mortar carbonation was achieved by maintaining the
specimens in CO2 atmosphere for 60 days at room temperature
and 65% RH. The mortars were partially immersed in water solu-
Fig. 12. Variation of drying shrinkage with curing time and wastepaper sludge
content [156].
 A.M. Rashad / Materials and Design 53 (2014) 1005–1025 1021

Table 12
Effect of different materials on some properties of AAFA system.

Author % Additive Positive effects No or negative effects

Mingyu et al. 0, 10 and 15, bentonite – Acted as a filler in which led the geopolymer more contact – Did not show improvement on the
[147] compositions and the microstructures
Srinivasan and 70, 80, 90 and 100, bentonite – Increased the initial and final setting times – Decreased the compressive strength
Sivakunar
[149]
Zhang et al. 0, 25. 50, 75 and 100, mine tailings – Decreased the compressive strength
[150]
Jiao et al. [151] 50, 60, 70, 80, 90 and 100, vanadium – 70% gave the highest compressive strength and good fire
tailing resistance
Oh et al. [152] 10 and 18, Na-aluminate – Decreased the compressive strength
Rovnaník [153] 0.1, 0.15 and 0.2, calcium aluminate – Increased 24 h compressive strength – Accelerated the setting times
(mayenite)
– Decreased 28 days compressive
strength
Ahmari et al. 0, 25, 50, 75 and 100, GWC – Increased the UCS up to replacement level of 50% – Decreased the UCS beyond 50%
[154] replacement level
– Delayed the setting time
Lampris et al. 80 and 100, grind silt – 80% increased the compressive strength at age of 7 days
[155]
Yan and Sagoe- 0–10, wastepaper sludge (as sand – Decreased the drying shrinkage – Reduced the workability
Crentsil [156] replacement)
– Decreased the compressive strength
Lee and van Inorganic salts – Increased the early strength – Ca and Mg salts shortened the setting
Deventer time
[157]
– Potassium salts retarded the setting time
Ariffin et al. 30, 50, 70 and 100, palm oil fuel ash – Compressive strength decreased with
[158] increasing palm oil fuel ash content
Srivastava et al. 0–50, Common Effluent Treatment – 20% sludge, 24% cement and 56% FA, cured at 28 days, showed – 14.2–25% sludge, no effect on UCS
[159] Plant sludge and 15–30, cement increase in strength as well as rate of stabilization
Criado et al. GPH with 3AMB and GPH with – Good inhibitive effects on rebar corrosion (0.05 M GPH with
[160] PhAMB 0.05 M 3AMB and 0.05 M GPH with saturated PhAMB)
Dutta and Ghosh 0, 10 and 15, lime stone dust – Increased the compressive strength
[161]
– Decreased the percentage of water absorption

tion containing 1% NaCl, both in the absence and in the presence of
the inhibitors. The results achieved in synthetic solution suggested
that the mixtures of 0.05 M GPH with 0.05 M 3AMB and, particu-
larly, 0.05 M GPH with saturated PhAMB exhibited good inhibitive
effects on rebar corrosion. Dutta and Ghosh [161] studied the com-
pressive strength and the percentage of water absorption, at age of
28 days, of AAFA pastes modified with lime stone dust. FA was par-
tially replaced with lime stone dust at levels of 0%, 10% and 15%, by
weight. A mixture of NaOH and sodium silicate solution was used
as activator. The silicate modulus was fixed at 1. Specimens were
cured along with the molds at 65 °C for 48 h and allowed to cool
before being removed and stored at room temperature at dry place
before testing. The compressive strength results of the pastes
showed 20% and 44% enhancement with the inclusion of 10% and
15% lime stone dust, respectively. On the same line with this, the
inclusion of 10% and 15% lime stone dust reduced the percentage
of water absorption by 16% and 40.1%, respectively. Table 12 sum-
marizes the previous researches that studied the effect of different
materials on some properties of AAFA system.
16. Conclusions
The admixed FA as a source of alkali activation has been widely
investigated in the recent years. The conclusions of the current lit-
erature review can be summarized as following:
(1) PVA fiber changed the impact failure mode from brittle pat-
tern to ductile pattern. Carbon fiber enhanced the electrical
conductivity and densification the geopolymer paste. Poly-
propylene fiber increased the fracture before and after 50
wet/dry cycles, but reduced the elastic modulus. Basalt fiber
improved energy absorption, but did not affect the dynamic
compressive strength.
(2) Superplasticizer of lignosulphonates-based improved the
workability (depending on activator concentration), whilst
superplasticizer of melamines and polycarboxylates-based
reduced it. Superplasticizer (Sika Viscocrete-3430) improved
the workability and increased the compressive strength of
AAFA concrete.
(3) The inclusion of slag into AAFA matrix decreased the work-
ability and shortened the setting time.
(4) Most of researchers believed that as the slag content
increased into AAFA matrix, as the compressive strength
increased. Other researchers believed that the optimal con-
tent of slag depends on activator type, activator concentra-
tion, modulus ratio and curing condition.
(5) Alkali-activated FA/slag (50/50) gave the lowest weight
loss after exposure to CO2-laden H2SO4. On the other hand,
FA/slag geopolymer exhibited dimensional instability after
magnesium sulfate attach, whilst sodium sulfate attack did
not cause any degradation.
(6) FA/slag/K-silicate/H2O geopolymers inhibited the leaching of
heavy metals, with the result that many numbers of traced
pollutants, such as Ba, Be, Bi, Cd, Co, Cr, Nb, Ni, Pb, REE, Sr,
Th, U, Y and Zr were retained.
(7) The inclusion of MK in AAFA matrix improved the workabil-
ity (depending on its fineness), prolonged the setting time
and increased the compressive and flexural strengths.
1022 A.M. Rashad / Materials and Design 53 (2014) 1005–1025
(8) The inclusion of MK into AAFA matrix could immobilize Cu
and Pb heavy metals.
(9) The optimal inclusion of SF into AAFA matrix, that gave the
highest compressive strength, ranging from 3–10%, depend-
ing on activator concentration and curing condition.
(10) The inclusion of PC into AAFA matrix decreased the work-
ability and increased the compressive strength. On the other
hand, the inclusion of PC into AAFA matrix decreased the
residual compressive strength after firing.
(11) The compressive strength development of alkali-activated
FA/CKD (50/50) depends on the curing temperature and acti-
vator concentration. 3% NaOH showed an increase in the
compressive at early and later ages at curing temperatures
of 24 °C and 38 °C, whilst 5% NaOH showed an increase in
early age only.
(12) The inclusion of lime into AAFA matrix shortened the final
setting time, increased the early age compressive strength,
but slightly decreased the later age compressive strength.
(13) Nano silica is more effective than Al nano in AAFA matrix.
The optimum level of nano silica is 3%, which gave the high-
est compressive strength. If nano silica was used as a part of
activator, it decreased water demand and the porosity.
(14) The inclusion of FA obtained from FBC or BA or its combina-
tion into AAFA matrix reduced the compressive strength.
(15) The inclusion of zeolite into AAFA matrix increased the com-
pressive strength and enhanced the sulfate resistance.
(16) Replacing FA with 5% gypsum in AAFA matrix increased the
compressive strength. On the other hand, the inclusion of
FGDG into AAFA matrix decreased the compressive strength.
(17) The inclusion of bentonite or potassium salts into AAFA
matrix increased the setting time, whilst the inclusion of
mayenite or calcium and magnesium salts into AAFA matrix
shortened the setting time.
(18) Replacing FA with 70% vanadium tailing in AAFA matrix
increased the compressive strength, whilst replacing FA with
Na-aluminate in AAFA matrix decreased the compressive
strength.
(19) Although the inclusion of wastepaper sludge as sand
replacement in AAFA mortars decreased the compressive
strength and reduced the workability, this inclusion
decreased the drying shrinkage.
(20) Replacing FA with either 50% GWC or 80% grind silt in AAFA
matrix increased the compressive strength. On the same line
with this, replacing FA with lime stone dust enhanced the
compressive strength and reduced the percentage of water
absorption.
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