Construction and Building Materials 50 (2014) 169–176

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Construction and Building Materials

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Fresh and hardened properties of alkali-activated fly ash/slag pastes

with superplasticizers
J.G. Jang, N.K. Lee, H.K. Lee ⇑
Department of Civil and Environmental Engineering, Korea Advanced Institute of Science and Technology, Guseong-dong, Yuseong-gu, Daejeon 305-701, South Korea

h i g h l i g h t s

 Higher contents of slag increased the compressive strength, but caused rapid setting.
 Polycarboxylate-based superplasticizer retarded the setting with negligible effect on the heat of hydration.
 The workability was significantly improved with the addition of the polycarboxylate-based superplasticizer.
 Formation of hydration products was not noticeably affected by the addition of superplasticizers.

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

Article history: This paper presents results of an experimental study carried out to investigate fresh and hardened prop-
Received 11 July 2013 erties of alkali-activated fly ash/slag pastes with superplasticizers. The binders were prepared by dry mix-
Received in revised form 17 September ing of slag and fly ash with 5 slag-to-binder ratios, 0, 0.3, 0.5, 0.7, and 1. An alkali activator was prepared
2013
from NaOH solution and sodium silicate solution. The polycarboxylate-based and naphthalene-based
Accepted 24 September 2013
Available online 15 October 2013
superplasticizers were added to the mixes at the levels of 0%, 1%, 2%, 3%, and 4% by the mass of binder.
All specimens were prepared under room-temperature curing conditions. The results showed that the
higher contents of slag increased the compressive strength of alkali-activated fly ash/slag pastes, but
Keywords:
Alkali-activated cement
caused rapid setting and crack due to autogeneous shrinkage in the cases of 70% and 100% of slag to bin-
Ground granulated blast furnace slag der ratios. The polycarboxylate-based superplasticizer showed retarding effect on alkali-activated fly ash/
Fly ash slag pastes with negligible effect on the heat of hydration, and improved the workability more signifi-
Superplasticizer cantly than naphthalene-based superplasticizer. From the results of the SEM/EDS tests, it was observed
Fresh and hardened properties that a higher content of slag led to the formation of denser matrix of hydration products. However, for-
mation of hydration products was not noticeably affected by the addition of superplasticizers.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction past few decades. Both alkali-activated cementitious materials

Alkali-activated cementitious materials, sometimes referred to
by different terms such as ‘‘inorganic polymers’’, ‘‘alkali-bonded
ceramics’’, and ‘‘geopolymers’’, can provide comparable perfor-
mance to ordinary Portland cements (OPC) in a range of
applications, with the added advantage of significantly reduced
carbon-dioxide emissions [1,2]. In addition, alkali-activated
cementitious materials can offer high compressive strength
[3–5], rapid setting and hardening [6], fire resistance [7], resistance
to alkali aggregate reaction [8], low shrinkage [9], low thermal con-
ductivity [10], freeze–thaw resistance [11], and remarkable dura-
bility [12,13]. Among other things, alkali-activated slag and
alkali-activated fly ash, which are well-known alkali-activated
cementitious materials, have been extensively studied during the
⇑ Corresponding author. Tel.: +82 42 350 3623; fax: +82 42 350 3610.
E-mail address: leeh@kaist.ac.kr (H.K. Lee).
have advantages and disadvantages because of different chemical
reactions and mechanical properties. The major features of alkali-
activated slag include rapid setting, high strength, impermeability,
and improved fire resistance [14,15]. On the other hand, the major
features of alkali-activated fly ash are high strength, high acid
resistance, and high heat resistance [6]. In addition, it has been
reported that the disadvantages of each activation process can be
counterbalanced by the advantages of the other process by the
joint activation of fly ash and slag [16,17].
In spite of these advantages of alkali-activated slag and/or fly
ash, the utilization of these materials has been very limited so
far. In general, alkali-activated fly ash needs high temperature cur-
ing to help the activation due to its low activity at room tempera-
ture. However, alkali-activated slag is sometimes sensitively
activated even at room temperature depending on the type and
concentration of alkali activator [18]. Since the type of alkali acti-
vator and its chemical constitution highly affect the strength

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.09.048
170 J.G. Jang et al. / Construction and Building Materials 50 (2014) 169–176
development and reaction kinetics of alkali-activated slag [24,25],
it may also cause the workability loss and rapid setting [18]. To
overcome this problem, previous studies have investigated the ef-
fects of admixtures on setting and hardening of the alkali-activated
slag and/or fly ash. Brough et al. [18], studying the retarding effect
of added sodium chloride and malic acid in sodium silicate-based
alkali-activated slag mortars, concluded that in the systems with
added malic acid or sodium chloride, the same calorimetry peaks
were observed, even though retarded, but with similar integrated
heat outputs. These findings suggested that the basic mechanism
of hydration was not altered by the retarding additions. Douglas
and Brandstetr [19] reported that the addition of a water reducer
such as sodium lignosulphonate and a sulphonate naphthalene-
based superplasticizer caused a reduction of compressive strength
without any improvement of workability. Palacios and Puertas
[20], studying the effect of a superplasticizer (polycarboxylate, vi-
nyl copolymers, melamine and naphthalene-based) on alkali-acti-
vated slag pastes and mortars, reported that a NaOH alkaline
solution with naphthalene-based system could provide increased
mechanical strength values, improved workability and retardation
of the initial and final setting times.
To date, however, there have been no published studies dealing
with the effects of superplasticizers on fresh and hardened proper-
ties of the alkali-activated fly ash/slag pastes. Although it is known
that the superplasticizers show workability improvement in
ordinary Portland cement concrete, the effects are not known in
alkali-activated fly ash/slag pastes. In this study, the effects of
superplasticizer addition and slag to binder ratios on setting time,
workability loss, heat of hydration, compressive strength, micro-
structural and mineralogical properties of alkali-activated fly ash/
slag pastes were studied. Ground granulated blast furnace slag
and class F fly ash were used to prepare the samples with sodium
hydroxide and sodium silicate based alkali activator. Polycarboxyl-
ate-based and naphthalene-based superplasticizers were added to
the mixes. The preparation of samples and curing, all were con-
ducted under room temperature condition.
2. Experimental details
2.1. Materials and mix proportion
Ground granulated blast furnace slag and class F fly ash were used as the binder
in this study. The chemical and physical properties of ground granulated blast fur-
nace slag (SG) and class F fly ash (FA) used are given in Table 1. The specific surface
area of the granulated blast furnace slag and class F fly ash were 485 and 290 m2/kg,
respectively. The binders were prepared by dry mixing of SG and FA with 5 different
slag to binder ratios, i.e., SG/binder = 0, 0.3, 0.5, 0.7, and 1.
Sodium hydroxide pearl (99% purity) and sodium silicate solution (Na2O
nSiO2-

mH2O, SiO2/Na2O = 2.16, water content = 61.5 wt%, specific gravity 1.38 g/mL) were
used as the alkali activator. The alkali activator was prepared as follows: NaOH
solution of 4 M was prepared and left overnight to cool down to room temperature.
The sodium silicate solution was then mixed with the NaOH solution to form an al-
kali activator (mass of NaOH solution/sodium silicate solution = 2). Superplasticiz-
ers were added to the alkali activator before mixing. The properties of
polycarboxylate and naphthalene-based superplasticizers used in this study are gi-
ven in Table 2. Each superplasticizer was added to mixes at the levels of 0%, 1%, 2%,
3%, and 4% by the mass of binder. The mix proportion of the samples is listed in
Table 3.
Ground granulated blast furnace slag and fly ash were synthesized using the al-
kali activator with or without superplasticizer. The mass ratio between the alkali
activator solution and binder was 0.5. The binder was premixed for 1 min, the alkali
Table 1
Chemical and physical properties of ground granulated blast furnace slag and class F fly ash.
Chemical composition (wt.%)
SiO2 Al2O3 CaO Fe2O3 SO3 K2O TiO2
SG 21.00 17.00 56.10 0.62 0.77 0.60 0.84
FA 46.00 33.00 2.60 10.50 – 4.80 2.60
Table 2
Properties of superplasticizer used.
Polycarboxylates-based Naphthalene-based
Specific gravity (25 °C) 1.10 ± 0.05 1.20 ± 0.02
pH (25 °C) 6.5 ± 1.0 8.0 ± 1.0
Content of chloride ion (%) 60.01 –
Content of alkaline (%) 60.20 –
activator was then added, and the paste was mixed for a further 2 min. Fresh pastes
were cast into molds (50 mm cube), consolidated, and cured under atmospheric
pressure and laboratory humidity at 20 °C for 24 h.
2.2. Test procedures
The initial and final setting times were measured using a Vicat needle as de-
scribed in ASTM C191-08 [26]. Values of penetration distances were measured
every 10 min considering rapid setting and hardening. The determined initial and
final setting times were an average of three separate tests. Flow tests as described
in ASTM C1437-07 [27] were conducted to determine workability loss of fresh
pastes after 3, 10, 20, 40, and 60 min. Diameter was measured along the 4 lines
and the final value was an average of 4 readings. The compressive strength was
measured on the paste at ages of 1, 7, 14, and 28 days using a 300 kN universal test-
ing machine (UTM) in accordance with ASTM C109 [28]. All the values collected
were the averages of three separate tests.
Heat of hydration was monitored using an Isothermal Conduction Calorimetry
apparatus. A multi-micro calorimeter (Model MMC-511SV6) from TOKYO RIKO
was used. The test conditions of the Isothermal Conduction Calorimetry were as fol-
lows: the mass of binder used and alkali activator used were 20 g and 10 g, respec-
tively; the dry-mixed binder (SG and FA) and the pre-mixed alkali activator
prepared 1 day earlier than the test were automatically mixed in the calorimetry
equipment; the initial scanning rate was 30 s; the final recording rate was 300 s;
the bath water temperature was 20 °C; and the test time was 72 h. In addition,
microstructural and mineralogical analyses using scanning electron microscopy
and energy dispersive X-ray spectroscopy (Nova 230 SEM/EDS, manufactured by
FEI Company) were carried out on the hardened pastes after 28 days.
3. Results and discussion
3.1. Setting time
Fig. 1 shows the effect of superplasticizer addition on setting
time of alkali-activated fly ash/slag (SG/binder = 0.5). It is shown
from Fig. 1 that the initial and final setting times were relatively
un-affected by the presence of the naphthalene-based superplast-
icizer for the alkali-activated fly ash/slag paste. Setting was, how-
ever, retarded by the presence of the polycarboxylate-based
superplasticizer. In the case of the polycarboxylate-based superp-
lasticizer at 4% addition, the initial and final setting times were re-
tarded by 50 min and 70 min, respectively.
The naphthalene-based superplasticizer in ordinary Portland
cement hinders flocculation with electrostatic repellency.
Although Palacios and Puertas [20] reported that the retardation
of setting and improvement of workability were achieved by addi-
tion of the naphthalene-based superplasticizer in NaOH based
alkali-activated slag, it did not affect NaOH and sodium silicate
based alkali-activated fly ash/slag prepared in this study. It can
be inferred that high alkaline media from the NaOH and sodium
silicate based activator negatively affected adsorption between
the naphthalene-based superplasticizer and fly ash/slag particle.
On the other hand, polycarboxylate-based superplasticizer showed
Specific gravity (SSD) Surface area (m2/kg) Particle size (lm)
10% 50% 90%
2.90 485 2.45 12.12 32.89
2.38 290 2.74 19.96 95.33
 J.G. Jang et al. / Construction and Building Materials 50 (2014) 169–176 171

Table 3
Mix proportion of the samples.

Samplesa SG/binder (wt%) Superplasticizer/binder (wt%) Unit weight (kg/m3)

Alkali activator Binder Superplasticizer
Water NaOH Sodium silicate FA SG
S0 0 0 338.1 54.1 196.1 1176.6 0 0
S30 30 0 347.3 55.6 201.5 846.2 362.7 0
S50 50 0 353.8 56.6 205.2 615.6 615.6 0
S70 70 0 360.5 57.7 209.1 376.3 878.1 0
S100 100 0 371.0 59.4 215.2 0 1291.1 0
S50P1 50 1 353.8 56.6 205.2 615.6 615.6 12.3
S50P2 50 2 353.8 56.6 205.2 615.6 615.6 24.6
S50P3 50 3 353.8 56.6 205.2 615.6 615.6 36.9
S50P4 50 4 353.8 56.6 205.2 615.6 615.6 49.2
S50N1 50 1 353.8 56.6 205.2 615.6 615.6 12.3
S50N2 50 2 353.8 56.6 205.2 615.6 615.6 24.6
S50N3 50 3 353.8 56.6 205.2 615.6 615.6 36.9
S50N4 50 4 353.8 56.6 205.2 615.6 615.6 49.2
S0P4 0 4 338.1 54.1 196.1 1176.6 0 47.0
S30P4 30 4 347.3 55.6 201.5 846.2 362.7 48.4
S70P4 70 4 360.5 57.7 209.1 376.3 878.1 50.2
S100P4 100 4 371.0 59.4 215.2 0 1291.1 51.6
S0N4 0 4 338.1 54.1 196.1 1176.6 0 47.1
S30N4 30 4 347.3 55.6 201.5 846.2 362.7 48.4
S70N4 70 4 360.5 57.7 209.1 376.3 878.1 50.2
S100N4 100 4 371.0 59.4 215.2 0 1291.1 51.6
S0P1 0 1 338.1 54.1 196.1 1176.6 0 11.8
S0P2 0 2 338.1 54.1 196.1 1176.6 0 23.5
S0P3 0 3 338.1 54.1 196.1 1176.6 0 35.3
S30P1 30 1 347.3 55.6 201.5 846.2 362.7 12.1
S30P2 30 2 347.3 55.6 201.5 846.2 362.7 24.2
S30P3 30 3 347.3 55.6 201.5 846.2 362.7 26.3
S70P1 70 1 360.5 57.7 209.1 376.3 878.1 12.5
S70P2 70 2 360.5 57.7 209.1 376.3 878.1 25.1
S70P3 70 3 360.5 57.7 209.1 376.3 878.1 37.6
S100P1 100 1 371.0 59.4 215.2 0 1291.1 12.9
S100P2 100 2 371.0 59.4 215.2 0 1291.1 25.8
S100P3 100 3 371.0 59.4 215.2 0 1291.1 38.7
a
P: polycarboxylate-based superplasticizer, N: naphthalene-based superplasticizer.

250 1600
Initial-N Final-N Initial-N Final-N
Initial-P Final-P 1400 Initail-P Final-P
200
Setting time (min)

1200
Setting time (min)

150 1000

800
100
600 setting time described in ASTM C150

50 400 setting time of OPC with w/c=0.485

200
0
0 1 2 3 4 0
0 30 50 70 100
Superplasticizer (%)
SG/binder (%)
Fig. 1. Effect of superplasticizer addition on setting time (SG/binder = 0.5. N:
Fig. 2. Effect of SG/binder on setting time (content of superplasticizers = 4 wt%. N:
Naphthalene-based superplasticizer. P: Polycarboxylate-based superplasticizer).
Naphthalene-based superplasticizer. P: Polycarboxylate-based superplasticizer).

sufficient retarding effect on alkali-activated fly ash/slag pastes
even in high alkaline media.
The effect of SG/binder on setting time is shown in Fig. 2. In
addition, the criteria of the initial and final setting times of OPC de-
scribed in ASTM C150 [29] and the measured initial and final set-
ting times of OPC with w/c = 0.485 are shown in Fig. 2. In the
case of SG/binder = 0 with naphthalene-based and polycarboxyl-
ate-based superplasticizers, the initial setting times recorded were
720 min and 1020 min, respectively, while final setting times re-
corded were 960 min and 1560 min, respectively. However, in
the case of SG/binder = 0.3 with naphthalene-based and polycar-
boxylate-based superplasticizers, the initial setting times recorded
were 90 min and 160 min, respectively, and final setting times re-
corded were 170 min and 250 min, respectively. The results for the
setting time in relation to different slag and fly ash ratios indicate
that the setting time decreased dramatically with the increase of
SG/binder ratio from 0 to 0.3. However, the decrease was slow
but steady as SG/binder ratio increases from 0.3 to 1. While alka-
li-activated fly ash/slag pastes with SG/binder ratios from 0.3 to
0.5 satisfied the criteria of the initial and final setting times of
172 J.G. Jang et al. / Construction and Building Materials 50 (2014) 169–176

ordinary Portland cement described in ASTM C150 [29], they
showed relatively rapid setting compared with the measured ini-
tial and final setting times of the OPC with w/c = 0.485. It can thus
be said that the setting and hardening of alkali-activated cementi-
tious materials with slag and fly ash are significantly affected by
the slag content. It can also be said that the polycarboxylate-based
superplasticizer had a retarding effect regardless of SG/binder.
3.2. Workability
Fig. 3 shows the effect of superplasticizer addition on flow loss
of fresh alkali-activated fly ash/slag paste with SG/binder = 0.5. The
flow of alkali-activated fly ash/slag paste without superplasticizer
decreased rapidly after mixing for 3 min. In case of adding polycar-
boxylate-based superplasticizer, the initial values of flow increased
depending on the superplasticizer contents, and flow losses de-
creased. In case of adding naphthalene-based superplasticizer,
the initial values of flow increased similar to the case of polycar-
boxylate-based superplasticizer addition. However, the flow losses
occurred more sharply than the case of naphthalene-based superp-
lasticizer addition. Here, it can be explained that this difference is
derived from the existence of retarding effect of the
superplasticizer.
In general, the naphthalene-based superplasticizer used in a
fresh concrete using ordinary Portland cement has a water reduc-
ing effect but does not retard the setting and hardening, while the
polycarboxylate-based superplasticizer retards setting and harden-
ing, resulting in decreased slump loss [21]. This can be explained
by the chemical structure of polycarboxylate-based superplasticiz-
er, i.e., absorption by carboxyl group (–COOH) and dispersion by
hindering flocculation due to ethylene oxide (–CH2CH2O–)
[21,22]. It could thus be said that the polycarboxylate-based
superplasticizer can retard the setting and increase the workability
of fresh pastes with high alkaline media using NaOH and sodium
silicate based alkali activator.
The effect of SG/binder on flow loss of fresh alkali-activated fly
ash/slag paste with 4% superplasticizer addition is shown in Fig. 4.
The workability of fresh alkali-activated fly ash/slag paste was
greatly affected by SG/binder. Fly ash can improve the workability
of fresh cement paste and concrete due to its globular shape.
Although slag does not in general remarkably affect the workabil-
ity of fresh cement paste and concrete, the slag having large spe-
cific surface area may improve the workability. It should be
noted that the effect of both materials on the workability of alka-
li-activated fly ash/slag pastes is different from that of ordinary
Portland cement pastes. The initial values of flow decrease and
flow loss increases dramatically with an increase of SG/binder,
since the flow and its loss of alkali-activated fly ash/slag were dom-
inantly affected by the rapid reaction between the slag and the al-
kali activator. In addition, the polycarboxylate-based
superplasticizer could more significantly mitigate the flow loss
than the naphthalene-based superplasticizer.
3.3. Heat of hydration
The isothermal conduction calorimetry of alkali-activated fly
ash/slag with added polycarboxylate-based or naphthalene-based
superplasticizer is shown in Fig. 5. The initial peaks appeared at
around 20 min regardless of the presence of superplasticizaers.

(a) 120 (a) 120 SG/binder 0% 30%

Superplasticizer content 50% 70%
0% 1% 2% 100%
100 3% 4% 100

80 80
Flow (%)
Flow (%)

60 60

40 40

20 20

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (minutes) Time (minutes)

(b) 120 (b) 120 SG/binder 0% 30%

Superplasticizer content 50% 70%
100%
0% 1% 2%
100 3% 4%
100

80 80
Flow (%)
Flow (%)

60 60

40 40

20 20

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (minutes) Time (minutes)
Fig. 3. Effect of superplasticizer addition on flow loss of fresh alkali-activated fly Fig. 4. Effect of SG/binder on flow loss of fresh alkali-activated fly ash/slag paste
ash/slag paste with SG/binder = 0.5: (a) polycarboxylate-based superplasticizer and with 4% superplasticizer addition: (a) polycarboxylate-based superplasticizer and
(b) naphthalene-based superplasticizer. (b) naphthalene-based superplasticizer.
 J.G. Jang et al. / Construction and Building Materials 50 (2014) 169–176 173

(a)

Compressive strength (MPa)

Heat evolution rate (J/sec/g)
0.007
none 60
0.006 N
P 50
0.005
40
0.004
30
0.003 Superplasticizer content
20
0% 1%
0.002 10 2% 3%
4%
0.001 0
0 7 14 21 28
0
0 20 40 60 80 Time (days)
Time (h)
Fig. 7. Effect of polycarboxylate-based superplasticizer content on compressive

(b) 200
none
strength (SG/binder = 0.5).
Integrated heat (J/g)

N
P
150

Compressive strength (MPa)

70
100
60
50
50
40
0 30
0 20 40 60 80 Superplasticizer content
20 0% 1%
Time (h) 10 2% 3%
4%
0
Fig. 5. Isothermal conduction calorimetry of alkali-activated fly ash/slag with 0 10 20 30 40 50 60 70 80 90 100
addition of polycarboxylates or naphthalene-based superplasticizers: (a) Heat
evolution rate and (b) Integral heat output (content of superplasticizers = 4 wt%. N:
SG/binder (%)
Naphthalene-based superplasticizer. P: Polycarboxylate-based superplasticizer).
Fig. 8. Effect of SG/binder on compressive strength at 28 days in the case of
polycarboxylate-based superplasticizer.

(a)
Heat evolution rate (J/sec/g)

0.007
SG/binder=0
0.006 SG/binder=0.5
SG/binder=1
0.005
0.004
0.003
0.002
0.001
0
0 20 40 60 80
Time (h)

(b) 200
Integrated heat (J/g)

150

100
50
0 (SG/binder of (a) 0, (b) 0.3, (c) 0.5, (d) 0.7 and (e) 1).
0 20
Time (h)
Fig. 6. Isothermal conduction calorimetry of different replacement ratios of SG/
binder with addition of 4 wt% polycarboxylate-based superplasticizer: (a) heat
evolution rate and (b) integral heat output.
The heat evolution curves then slightly declined to an induction
period. The second peaks appeared at around 13 h (without the
superplasticizer), at 15.5 h (with the addition of the 4 wt% naph-
thalene-based superplasticizer), and at 17 h (with the addition of
the 4 wt% polycarboxylate-based superplasticizer), respectively.
In addition, the integrated heats were 155.8 J/g, 140.6 J/g and
SG/binder=0
SG/binder=0.5
SG/binder=1
Fig. 9. Surface images of alkali-activated fly ash/slag with different SG/binder ratios
40 60 80
136.8 J/g at 72 h, respectively. From these results, it could be con-
cluded that both superplasticizers had a negligible effect on the
heat of hydration, although the polycarboxylate-based superplast-
icizer slightly lowered the enthalpy.
Fig. 6 shows the isothermal conduction calorimetry for different
replacement ratios of SG/binder with the addition of the 4 wt%
polycarboxylate-based superplasticizer. It is shown from Fig. 6
that, in the case of alkali-activated fly ash/slag, the activation pro-
cesses were strongly affected by SG/binder. Although the initial
peaks appeared at similar time (18–20 min) regardless of the SG/
binder, the heat evolution rates were quite different. The
174 J.G. Jang et al. / Construction and Building Materials 50 (2014) 169–176

(a) SG/binder=1

(b) SG/binder=0.7

2 3

(c) SG/binder=0.5

(d) SG/binder=0.3

(e) SG/binder=0

Fig. 10. SEM images of alkali-activated fly ash/slag with different SG/binder ratios and 4 wt% polycarboxylate-based superplasticizer (left: 800–1000  magnification, right:
30,000 magnification).

second peaks appeared at around 9 h (SG/binder = 1) and at 17 h
(SG/binder = 0.5), but no second peak appeared in the case of SG/
binder = 0.
3.4. Compressive strength
The effect of the polycarboxylate-based superplasticizer con-
tent on compressive strength is shown in Fig. 7. In the case of poly-
carboxylate-based superplasticizer at 2–4 wt% addition, the
compressive strength was recorded as 3.4–4.9 MPa at 1 day,
34.8–41.6 MPa at 7 day and 32.8–46.7 MPa at 28 day. Although
the compressive strength at 1 day in case of 2–4 wt% addition of
the superplasticizer was lower than that in the case of 0–1 wt%
addition, the compressive strength at 7 day in the case of 2–4
wt% addition of the superplasticizer was higher than in the case
of 0–1 wt% addition. In addition, the compressive strength after
7 days in the case of 2–4 wt% addition of the superplasticizer
was not remarkably changed. These results indicate that increasing
the polycarboxylate-based superplasticizer content beyond 2 wt%
could positively affect the development of compressive strength
before 7 days, whereas it could have adverse effects after this
point. These results may be due to conflicting effects of the poly-
carboxylate-based superplasticizer on the fresh and hardened
pastes. In general, the superplasticizer plays a role for dispersing
 J.G. Jang et al. / Construction and Building Materials 50 (2014) 169–176 175

Table 4
The elemental compositions of the points 1, 2, 3, and 4 shown in Fig. 10.

Point SG/Binder Elemental compositions (wt%) Ca/Si Al/Si

Oxygen (O) Aluminium (Al) Silicon (Si) Calcium (Ca)
1 1 30.65 6.33 15.64 30.37 1.94 0.40
2 0.5 42.99 8.36 16.58 14.55 0.88 0.51
3 0.5 30.77 27.69 20.99 3.51 0.17 1.32
4 0 30.51 12.80 21.10 3.61 0.17 0.61

the cement (or fly ash/slag) particles through the adsorption
mechanism, resulting in improvement of compressive strength at
early age. However, addition of large amount of superplasticizer
negatively affects the development of the strength, and/or de-
creases the long-term strength, mainly due to increase entrained
air or entrapped air contents in the pastes.
Fig. 8 shows the effects of SG/binder on the compressive
strength at 28 day (in the case of the polycarboxylate-based
superplasticizer). When SG/binder = 0%, 1.6–3.1 MPa of the com-
pressive strengths were recorded. Although the fly ash slightly re-
acted with the alkali activator at room temperature, the
compressive strengths were markedly smaller than those observed
in the cases of the SG/binder = 30–100% and ordinary cement
pastes. On the other hand, the compressive strengths increased
with an increase of the slag content. In the cases of SG/binder = 30%
and 50%, the compressive strengths exceeding 30 MPa were re-
corded. Specimens with SG/binder = 70% and 100% showed high
compressive strengths (50–60 MPa), but had surface cracks due
to shrinkage, regardless of the superplasticizer content (see
Fig. 9). Puertas et al. [16], Zhao et al. [30], and Lee and Lee [17],
who investigated the effect of the slag content on the compressive
strength of alkali-activated fly ash/slag, reported that the compres-
sive strengths increased with the increase of slag content, which
coincide with the results of the present study. From the results
of the setting time and compressive strength, it could be said that
a higher content of slag increases the compressive strength, but
causes rapid setting and crack due to autogeneous shrinkage.
gested that the phase present at the point 1 could be some form
of calcium silicate hydrate (Ca/Si = 1.94). On the other hand, it is
suggested that the phase present at the point 4 could be some form
of alumino silicate hydrate (Al/Si = 0.61). It was also found that the
elemental composition of the point 2 was dominated by silicon and
calcium (Ca/Si = 0.88), while the elemental composition of the
point 3 was dominated by aluminium and silicon (Al/Si = 1.32).
Although the points 2 and 3 were in the same matrix, the phases
present at the points 2 and 3 were clearly different in terms of their
elemental composition. These observations coincide with the re-
port by Yip et al. who noted the coexistence of a geopolymeric
gel and calcium silicate hydrate gel formed simultaneously within
a single binder [23].
4. Concluding remarks
The present study investigated the fresh and hardened proper-
ties of alkali-activated fly ash/slag pastes with superplasticizers.
The binders were prepared by dry mixing of ground granulated
blast furnace slag and class F fly ash with 5 different slag to binder
ratios, i.e., SG/binder = 0, 0.3, 0.5, 0.7, and 1. An alkali activator was
prepared from NaOH solution and sodium silicate solution. The
polycarboxylate-based and naphthalene-based superplasticizers
were added to the mixes at the levels of 0%, 1%, 2%, 3%, and 4%
by the mass of binder. The main conclusions extracted from this
work are as follows.

(1) Setting time and compressive strength were significantly

affected by the mixing ratio of slag. Higher contents of slag
3.5. SEM/EDS analysis
increased the compressive strength of alkali-activated fly
ash/slag pastes, but caused rapid setting and crack due to
Fig. 10 shows SEM images of alkali-activated fly ash/slag with
autogeneous shrinkage in the cases of 70% and 100% of slag
different SG/binder ratios. It should be noted that all mixtures of
to binder ratios.
Fig. 10 contain 4 wt% of polycarboxylate-based superplasticizer.
(2) The polycarboxylate-based superplasticizer showed retard-
In addition, the formation of hydration products was not notice-
ing effect on alkali-activated fly ash/slag pastes with negligi-
ably affected by the addition of superplasticizer. As can be ob-
ble effects on the heat of hydration, and improved the
served in Fig. 10, the alkali-activated fly ash/slag samples have
workability more significantly than the naphthalene-based
quite different microstructures according to the SG/binder. When
superplasticizer.
the SG/binder = 1 and 0.7 (see Fig. 8(a and b)), the products of alka-
(3) The polycarboxylate-based superplasticizer content beyond
li-activation were angular and honeycomb microstructures could
2 wt% positively affected the development of compressive
be observed. When the SG/binder = 0.5 and 0.3 (see Fig. 8(c and
strength before 7 days, whereas it could have adverse effects
d)), the products of alkali-activation were amorphous gel and a lay-
after this point.
ered hexagonal microstructure could be observed. When the SG/
(4) rom the results of the SEM/EDS tests, it was observed that a
binder = 0 (see Fig. 8(e)), the products of alkali-activation had a
higher content of slag led to the formation of denser matrix
porous microstructure and a fly ash agglomerate surrounded by
of hydration products. However formation of hydration
partially reacted particles could be observed. The observed differ-
products was not noticeably affected by the addition of the
ences among the samples with different slag/binder ratios suggest
superplasticizers.
that with higher slag contents, a denser matrix is formed.
An EDS analysis was conducted at points 1–4 (see Fig. 10) and
the results are summarized in Table 4. It is found from Table 4 that
for the points 1–4, which mixed at different SG/binder of 1, 0.5, and Acknowledgements
0, the reaction products were different. It was found that the ele-
mental composition of the point 1 was dominated by silicon and This research was supported by a grant (Code 11-Technology
calcium, while the elemental composition of the point 4 was dom- Innovation-F04) from Construction Technology Innovation
inated by aluminium and silicon. From the Ca/Si ratio, it is sug- Program (CTIP) funded by Ministry of Land, Transportation and
176 J.G. Jang et al. / Construction and Building Materials 50 (2014) 169–176
Maritime Affairs (MLTM) of Korean government. The authors
would like to thank Dr. Jaedam Ha at Ssangyong Cement Industrial
Co., Ltd. for the cooperation in the test involved in this study.
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