Construction and Building Materials 350 (2022) 128734

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Construction and Building Materials

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Effects and mechanism of superplasticizers and precursor proportions on

the fresh properties of fly ash – slag powder based geopolymers
Guiyan Xiong a, Xiaolu Guo a, b, *
a
School of Materials Science and Engineering, Tongji University, Shanghai 201804, PR China
b
Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, Tongji University, Shanghai 201804, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: To promote the application of green geopolymer materials, the effects and mechanism of commercial super­
Superplasticizers plasticizers on the fresh properties of one-part geopolymers prepared from fly ash (FA), slag powder (Slag) and
Geopolymer anhydrous sodium silicate powder were studied, including flowability, rheological properties and particles
Flowability
packing properties. And the influence of precursor proportion (FA:Slag) i.e. the mass proportion of FA and Slag
Rheology
Water film theory
on the effectiveness of superplasticizers was also considered. The results show the fluidity of geopolymer with
Mechanism 2.4 % liquid naphthalene-based superplasticizer (N-L) increased by 19.20 % when FA:Slag = 85:15, and the 0.20
% one kind of solid polycarboxylate-based superplasticizer (PC-S2) increased the fluidity of geopolymer by
16.47 % when FA:Slag = 95:5. The addition of superplasticizers could improve fluidity, increase plastic viscosity,
and decrease yield stress of the pastes. The particles packing properties, including excess water and water film
thickness (WFT) of the geopolymer pastes with superplasticizers also increase. It is interesting to find that the
effectiveness of superplasticizers varies from different types of superplasticizers. This could be understood by the
mechanism of the two types of superplasticizers based on Zeta, FTIR results, and water film theory. Accordingly,
naphthalene-based superplasticizers guided by the adsorption-dispersion effect, due to their stable molecular
structures and short chains, could improve the workability, while the effectiveness of polycarboxylate-based
superplasticizers guided by the steric hindrance effect of lateral chains may be judged by the combined effects
of the interaction between particles and the effects induced by superplasticizers.

1. Introduction cementitious material, geopolymer has become the focus of domestic

Geopolymer chemical activated from silica-alumina precursors is a
kind of inorganic binding material with the three-dimensionally cross-
linked, highly polymerized, and non-crystal-line alkali aluminosilicate
network structure. Metakaolin is an important aluminosilicate source
material for geopolymer containing sufficient amounts of reactive
alumina and silica [1]. Also, it could also be used as alumina source
additive to increase the geopolymerization extent for ensuring better
performance [2]. Moreover, many other aluminosilicate source mate­
rials are used to prepare geopolymers currently, which means that this
could consume a large number of industrial wastes (fly ash, slag, sludge
[3], red mud [4–6], palm oil fuel ash[7], etc.) and agricultural wastes
(rice husk [8,9], etc.). Besides, the amorphous three-dimensional
network structure after geopolymerization reaction could effectively
solidify/stabilize heavy metals [10,11], which is beneficial for the
disposal and utilization of solid wastes. At present, as an eco-friendly
and foreign experts, which could partially replace Ordinary Portland
Cement (OPC) [12,13].
Admixtures have been recognized as the indispensable fifth compo­
nent of modern concrete technology. Among them, the development of
water-reducing agents makes it possible for OPC concrete to be modern
concrete with high performance [14]. However, the research and
development of superplasticizers are always suitable for OPC concrete
based on the characteristics of cement, which results in the in­
compatibility of superplasticizers for geopolymers [15]. Generally, the
viscosity of geopolymer paste is higher than cement pastes [16] due to
the difference between geopolymerization reaction and hydration re­
action. The hydration products are short chain calcium silicate hydrate
gels (C-–S-–H), while the geopolymer gels (N-A-–S-–H) have three-
dimensional network structures. Besides, the “dissolution-reconstruc­
tion-agglomeration” process of geopolymerization is relatively faster
than hydration reaction. Therefore, it is essential to study the

* Corresponding author at: School of Materials Science and Engineering, Tongji University, 4800 Caoan Road, Shanghai 201804, PR China.
E-mail address: guoxiaolu@tongji.edu.cn (X. Guo).

https://doi.org/10.1016/j.conbuildmat.2022.128734
Received 28 January 2022; Received in revised form 1 June 2022; Accepted 6 August 2022
Available online 23 August 2022
0950-0618/© 2022 Elsevier Ltd. All rights reserved.
G. Xiong and X. Guo
compatibility of superplasticizers for geopolymers, especially for future
high strength geopolymer concrete.
However, the effectiveness of superplasticizers is strongly influenced
by the chemistry of the aluminosilicate precursors and the activating
solution [17]. The production of geopolymers could effectively utilize
the silicon and aluminum components of solid wastes. While, the
physical and chemical properties of different precursors are really
different, and they are quite different from cement grains. Thus, the
diversity of raw material sources is one of the reasons for the possible
poor compatibility between geopolymers and commercial super­
plasticizers. For example, Xie et al. [18] indicated that naphthalene-
based superplasticizer performed similarly for both fly ash classes, and
polycarboxylate-based superplasticizer was rather effective for Class C
fly ash than for Class F based geopolymers due to the higher Ca2+ con­
tent in Class C fly ash, which could lead to better superplasticizer
dispersion. Palacios et al. [19] indicated that conventional water
reducing agents such as polycarboxylate, melamine and vinyl copolymer
did not improve the flowability of alkali-activated slag, only
naphthalene-based had a slight effect since its formulation was not
altered in NaOH alkaline solution. Besides, the types of alkali activators
also affect the incompatibility between superplasticizers and geo­
polymers [20–22], especially for waterglass with special characteristics
of colloidal solution. For example, Nematollahi et al. [21] indicated that
the effectiveness of superplasticizers depended on the type of binder and
activators in addition to the type and dosage of the superplasticizers as
well as the pH of the alkaline solution. The polycarboxylate-based
superplasticizers were the most effective type in the case of fly ash
based geopolymer activated by NaOH + Na2SiO3 activators. Whereas, in
the case of NaOH solution activated slag, naphthalene-based super­
plasticizers were the most efficient type. Based on these facts, the factors
affecting the compatibility of water reducing agents and geopolymers
can be summarized as the properties of precursor particles and the in­
teractions between water reducing agents and alkali activator solution,
and naphthalene-based and polycarboxylate-based superplasticizers are
relatively effective superplasticizers, although their effectiveness still
depends on the types of precursors and alkali activators. However, it is
worth noting that most scholars paid more attention to the effect of the
types and dosages of water reducing agents, also the type of precursors
and alkali activators. Few studies focused on the effect of precursor
proportion on the effectiveness of superplasticizers, in particular when
anhydrous sodium silicate powder used as the alkali activator.
In addition, flowability test is a common method to evaluate the
effectiveness of water-reducing agents. Unlike the slump and flow tests
only showing the flowability characteristics, rheological properties
reveal the response of internal structures for external forces. Therefore,
the rheological test can reflect the cluster structures between particles of
the fresh pastes by the changes of shear stress and apparent viscosity
[23–26]. Moreover, in cement-based materials, superplasticizers work
by dispersing the solid particles. When no superplasticizer is added, the
solid particles would tend to form agglomerates, thereby causing the
solid particles to be loosely packed, while with superplasticizers added,
agglomeration would be reduced, thus allowing the solid particles to be
more closely packed [27,28]. Thus, particle packing and water film
thickness theories may provide a practical and promising way to char­
acterize and explain the fluidity behavior of fresh pastes. It is evidenced
that water film thickness (WFT) is a reflection of combined effects of
water content, particle size distribution, particle shape, and solid surface
area on the fresh properties of pastes, mortar and concrete [29–32].
However, few studies explained the effects of superplasticizers on the
geopolymers starting from the WFT theory. Therefore, the WFT theory
as a new perspective is used to provide new ideas for studying the fresh
properties of fly ash-slag powder based geopolymers incorporating
superplasticizers.
To dispose of the industrial wastes highly effectively, fly ash (FA) and
slag powder (Slag) were used to prepare one-part geopolymer in this
paper. The effect of commercial superplasticizers including
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Construction and Building Materials 350 (2022) 128734
naphthalene-based and polycarboxylate-based superplasticizers and the
effect of the precursor proportions (FA:Slag), i.e., the mass proportion of
FA and Slag on the fresh properties of geopolymer has been studied,
including flowability, rheological properties and particles packing
properties. And zeta potential and ATR-FTIR tests were implemented to
reveal the charged properties of raw material particles and the stability
of superplasticizers in alkali activator aiming to elucidate the mecha­
nism of superplasticizers in geopolymer pastes and the effectiveness
differences between geopolymer and cement-based materials systems.
2. Materials and methods
2.1. Raw materials
Fly ash (FA) and slag powder (Slag) were all purchased from the
Hengnuo Filter Material Co., ltd. in Zhengzhou, China. The density of FA
and Slag are 2.30 g/cm3 and 2.86 g/cm3 respectively. The chemical
compositions, morphology and particle size distributions of the raw
materials were measured. Table1 presents the chemical compositions of
FA and Slag obtained through XRF analysis. It can be found that the
main chemical composition of FA is SiO2 and Al2O3, and FA contains
about 3.48 % of CaO, which indicates a kind of low calcium fly ash. And
Slag contains about 44.05 % of CaO, 32.95 % of SiO2 and 14.46 % of
Al2O3. Besides, the loss of FA and Slag on ignition at 1000 ◦ C was 6.71 %
and 0.57 %, respectively, according to the standard “Test Methods of
Materials Stabilized with Inorganic Binders for Highway Engineering
JTG E51-2009 (T 0817–2009 The methods for measuring the loss of fly
ash)”[33].
The XRD patterns of raw materials are shown in Fig. 1. Fig. 1(a)
shows the main phase of FA, including quartz and mullite, and from
Fig. 1(b), it can be found that there is an amorphous peak between 25◦ -
35◦ and there are no characteristic diffraction peaks, which indicates
high amorphous contents available in Slag. Fig. 2 demonstrates the
morphology of raw materials, including the common sphere shapes of
FA and irregular shapes of Slag. And the particle size distributions of FA
and Slag are shown in Fig. 3.
Anhydrous sodium silicate powder (Na2O⋅1.4SiO2) with the purity of
greater than 99 % obtained from Usolf Technology Co., ltd (PR China)
was selected as the alkali activator, and its modulus (M = n(SiO2)/n
(Na2O)) is 1.4.
The detailed information of commercial superplasticizers is shown in
Table 2. There are 2 types of superplasticizers, including naphthalene-
based and polycarboxylate-based superplasticizers, and they are in
liquid and powder. The recommended dosages in Table 2 are supported
by sellers.
2.2. Experimental methods
2.2.1. Experimental program
Two groups were set according to the proportion of precursors. The
one is FA: Slag = 85:15 marked as G-15 and the other one is FA: Slag =
95:5 marked as G-5. Based on pre-experiments, 7 wt% alkali activator
(the mass fraction of precursors) and 0.27 of the water-binder ratio is
determined as the basic mix proportion.
The experimental program for each superplasticizer in 2 groups is
shown in Fig. 4. The initial value of a was set as the minimum value of
the recommended dosages and i was set as the dosage gradient ac­
cording to the recommended dosages. This means that the dosages of
each superplasticizer were chosen based on recommended dosages from
sellers and pre-experiments. From Fig. 4, the saturation point of each
superplasticizer was obtained according to the maximum fluidity and
then the rheological test and particles packing test were carried out
based on the saturation point. And it should be stressed that in order to
avoid the influence of the water in liquid superplasticizers on the
workability of geopolymer pastes, the amount of water incorporated was
subtracted the water content of superplasticizers.
G. Xiong and X. Guo Construction and Building Materials 350 (2022) 128734

Table 1
Chemical compositions (by mass) of fly ash (FA) and slag powder (Slag) by XRF analysis.
Compound SiO2 Al2O3 CaO Fe2O3 MgO TiO2 K2O Na2O
(wt%)

FA 56.68 26.92 3.48 6.3 0.811 1.44 2.92 0.706

Slag 32.95 14.46 44.05 0.614 5.45 0.725 0.282 0.324

Fig. 1. The XRD patterns of raw materials (a)Fly ash (b)Slag Powder.

Fig. 2. The morphology of raw materials (a)Fly ash (b)Slag Powder.

2.2.2. Preparation process 2.3. Testing methods

The paste mixer used in this work is a kind of planetary mixer
meeting the standard JC/T 729–2005 “Mixer for cement paste” [34].
According to the mix proportion, the dry materials, i.e., FA, Slag and
activator were blended in the stirring pot at low speed for 1 min to
ensure mixing evenly. Then water was incorporated and mixed with the
dry mix for around 1 min at low speed. Finally, the mixture was mixed
for 2–3 min at high speed. It should be noted that for the specimens with
superplasticizers, the powder superplasticizers and liquid super­
plasticizers should be mixed with water in advance and the mixing so­
lution was poured in twice into the pot.
2.3.1. Flowability
According to JC/T 1083–2008 “Test method for compatibility of
cement and water-reducing agent” [35], the paste fluidity method was
used to evaluate the effect of superplasticizers on the flowability of
geopolymer pastes. The average value of the longest diameter and its
vertical diameter was regarded as the fluidity value.
2.3.2. Rheological properties
After mixing, the paste was poured into the outer cylinder matched
with rotational viscometer to implement rheological test. The RVDV-2
type rotational viscometer was used to measure the rheological prop

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G. Xiong and X. Guo Construction and Building Materials 350 (2022) 128734

was added to forming geopolymer pastes. After mixing 2 min, the paste
was poured into a cylindrical test-tube to be centrifuged at 4000r/min
for 10 min. After centrifuging, the excess water on the top of the com­
pacted solid particles was removed and the particles packing parameters
were measured according to the remained compacted solid particles
[40].
The maximum particle packing density (φmax ) was calculated by Eq.
(4).
Mb /ρb
φmax = (4)
Mb /ρb + Ml /ρl

where Mb is the mass of the solid blends; ρb is the density of the solid
blends, which is calculated by Eq. (5); Ml is the mass of the liquid
remaining in the compacted solid particles; ρl is the density of the
remaining liquid, which is assumed to be uniform at 1.16 g/cm3.
ρb = Vf • ρf + Vs • ρs (5)

where Vf , Vs are the volumetric ratios of FA and Slag to the blends

Fig. 3. The particle size distributions of raw materials.
erties of the fresh fly ash-slag powder based geopolymer paste at
ambient temperature. And the precise data cannot be collected limited
by the viscometer when the shear stress is smaller than 10 Pa⋅s. There­
fore, the shear stress data in this study was obtained from the viscometer
collected. The data of apparent viscosity is directly obtained by exper­
imental instruments, and the data of yield stress τ0 and plastic viscosity η
are calculated by rheological models and formulas. The detailed infor­
mation about setup can be found in the previous paper [36].
The commonly used constitutive models of rheological curve of
cementitious material are as follows [37,38]:
The expression of Bingham (BH) fluid model is Eq. (1).
τ = τ0 + ηγ(1)
The expression of Herschel-Bulkley (HB) model is Eq. (2).
n
τ = τ0 + mγ (2)
Larrard et al. [39] used Herschel-Bulkley model to study the rheo­
logical behavior of fresh cementitious materials. The results show that
the plastic viscosity can be calculated by Eq. (3):
3m n− 1
η= γ (3)
n + 2 max
In these formulas (1)-(3), τ is the shear stress, Pa; γ is the shear rate,
s− 1; τ0 is the yield stress, Pa; η is the plastic viscosity, Pa⋅s; m is the
consistency coefficient, Pa⋅sn; n is the flow index of the fluid.
2.3.3. Particles packing properties
To clarify the effect of superplasticizers on the particles packing
properties of fresh geopolymer pastes, the particle packing test was
carried out following the Fig. 5. Certain amounts of FA and Slag were
mixed for 2 min to ensure mixed evenly. Then the pre-prepared alkali
activator (The density of the alkali activator solution with 7 % anhy­
drous sodium silicate powder under ambient temperature is 1.16 g/
cm3.) at a fixed liquid–solid ratio of 0.5 with/without superplasticizers
respectively; ρf , ρs are the density of FA and Slag respectively.
For the maximum particle packing density, the minimum void ratio
(Vmin ) is determined by Eq. (6):
1 − φmax
Vmin = (6)
φmax
The volume ratio of excess water (We ) is defined by Eq. (7):
We = (w/s)v − Vmin (7)
where (w/s)v is the volume ratio of alkali activator to the solid blends.
The water film thickness (WFT) is calculated by Eq. (8):
We
WFT = (8)
SSAb
where SSAb is the specific surface area of solid blends calculated by Eq.
(9), and SSAf , SSAs are specific surface area of FA and Slag respectively
determined by the density and D (3,2) of their particle size distributions.
SSAb = Vf • SSAf + Vs • SSAs (9)
2.3.4. Zeta potential
Zeta potential is an important parament for characterizing the elec­
trostatic repulsion between charged particles. In order to clarify the
mechanism of superplasticizers in geopolymer systems, the zeta poten­
tials of precursors were measured and experimental details are as fol­
lows. Malvern Zetasizer Nano ZS 90δ was used to test the zeta potential
of FA and Slag. 1 g of the precursor was mixed with 100 mL ethanol.
After mixing them fully, 3–5 mL of the supernatant was taken to measure
zeta potential [41].
2.3.5. ATR-FTIR
In order to evaluate the stability of superplasticizers in alkali media
[42], the FTIR of superplasticizers in different media was measured
using Thermo Fisher Scientific Nicolet 6700 and experimental details
are as follows. Based on the above basic mix proportion, experimental

Table 2
Detailed information about commercial superplasticizers.
Name Types Model Appearance Solid Recommended dosages* Water-reducing rate*
content

N-L Naphthalene-1 – Brown liquid 40 % 0.5–3.0 % 15 %

N-–S Naphthalene-2 FDN-C Brown powder – 0.5–1.0 % 18–28 %
PC-L Polycarboxylate-1 PCA-Q8081 Light yellow liquid 40 % 0.2–0.5 % 37 %
PC-S2 Polycarboxylate-2 Sika-325C White powder – 0.05–0.50 % 25 %
PC-S3 Polycarboxylate-3 CQJ-JSS White powder – 0.16–0.30 % 25 %

*supported by sellers.

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G. Xiong and X. Guo Construction and Building Materials 350 (2022) 128734

Fig. 4. Experimental program.

5
G. Xiong and X. Guo
Fig. 5. The illustration for particles packing test.
groups were the mixing solution of superplasticizer and alkali activator
solution, where the anhydrous sodium silicate powder of alkali activator
solution was set the same as the solid content of superplasticizers. And
the control groups were the mixing solution of superplasticizer and
deionized water, and the amount of deionized water was the same as the
alkali activator solution.
3. Results
3.1. Effect of types and dosages of superplasticizers on flowability
Fig. 6 shows the fluidity of geopolymers with different super­
plasticizers and different dosages in the G-15 group. When the mass ratio
of FA:Slag was 85:15, the fluidity of geopolymer paste without super­
plasticizer (Control-15) was 161.5 mm. From Fig. 6, the liquid naph­
thalene superplasticizer (N-L) has the best plasticizing effect on
improving the flowability of geopolymer. The fluidity of geopolymer
paste with 2.4 wt% N-L was 192.5 mm, increasing by 19.20 % compared
with Control-15 in the G-15 group. While polycarboxylate-based
superplasticizers have few effects on the flowability of geopolymer.
And the status of the superplasticizer, solid or liquid, seems to have few
effects.
In the G-5 group, the fluidity of geopolymers with different super­
plasticizers and different dosages is shown in Fig. 7. The fluidity of
geopolymer paste with no superplasticizer (Control-5) was 173.0 mm in
the G-5 group. From Fig. 7, the polycarboxylate-2 superplasticizer (PC-
S2) has the best plasticizing effect on improving the flowability of
geopolymer. The fluidity of geopolymer paste with 0.20 wt% PC-S2 was
201.5 mm, increasing by 16.47 % compared with Control-5. Next, the
fluidity of geopolymer paste with 2.4 wt% N-L was 192.0 mm,
increasing by 10.98 % compared with Control-5.
Fig. 6. The effect of each superplasticizer at different dosages on the flowability of fresh geopolymer pastes with FA:Slag = 85:15 (G-15).
6
Construction and Building Materials 350 (2022) 128734
To clarify the effect of precursor proportion on the flowability and
the effectiveness of each superplasticizer, Table 3 summarizes the op­
timum dosage of each superplasticizer in the G-15 and G-5 group and
their corresponding fluidity values. When the content of Slag replace­
ment decreased from 15 % to 5 %, the Control geopolymer pastes
without superplasticizer increased from 161.5 mm to 173.0 mm, which
indicates that high content sphere FA has positive effects on the work­
ability of geopolymer. Besides, it can be seen from Table 3 that the
fluidity values of geopolymer pastes with the same superplasticizer are
different in the G-15 and G-5 groups, but the optimum dosage of the
same superplasticizer is similar. In particular, the optimum dosages of N-
L, N-–S, and PC-S2 in the G-15 and G-5 group are the same, which are
2.4 %, 1.6 % and 0.20 %, respectively. Moreover, it is interesting to find
that the compatibility of polycarboxylate-based superplasticizers seems
to be more sensitive to the precursor proportion, especially for PC-S2. In
the G-15 group, the effect of polycarboxylate-based superplasticizer on
the improvement of workability is negligible, while in the G-5 group,
PC-S2 exhibits the best plasticizing effect.
3.2. Effect of superplasticizers on rheological properties
Based on the optimal dosages of each superplasticizer in Table 3, the
influence of different superplasticizers on the rheological properties of
geopolymer pastes were studied. Fig. 8 shows the curves of “shear rate-
apparent viscosity” (Fig. 8 (a)), “shear rate-shear stress” (Fig. 8 (b)) and
the fitting results by Bingham model (BH) (Fig. 8 (c)) and Herschel-
Bulkley model (HB) (Fig. 8 (d)) in the G-15 group. From Fig. 8 (a), the
apparent viscosity of geopolymer pastes gradually decreased with the
increase of shear rate, which confirms the “shear thinning” behavior,
indicating the pseudoplastic fluid characteristics of geopolymer pastes.
From Fig. 8 (c) and Fig. 8 (d), the R2 fitted by BH model was greater than
G. Xiong and X. Guo Construction and Building Materials 350 (2022) 128734

Fig. 7. The effect of each superplasticizer at different dosages on the flowability of fresh geopolymer pastes with FA:Slag = 95:5 (G-5).

the “shear rate shear stress” curve fitted by BH model deviated greatly
Table 3
from 1, which indicates that BH model is not suitable. Therefore, the
The optimum dosage of each superplasticizer in G-15 and G-5 and corresponding
rheological parameters of the G-5 group only consider the fitting results
fluidity of the pastes.
by HB model.
Specimens Optimum dosage/ Corresponding fluidity/ The fitting results are listed in Table 5. The R2 fitted by HB model was
wt% mm
basically greater than 0.99, indicating HB model was suitable for fitting
G-15 (FA:Slag = Control- 0 161.5 the rheological curve of geopolymer pastes. The plastic viscosity and
85:15) 15
yield stress of geopolymer paste without superplasticizer (Control-5) are
N-L-15 2.4 192.5
N-–S- 1.6 180.0 0.27 Pa⋅s and 6.06 Pa, respectively. After adding superplasticizers, the
–15 plastic viscosity basically increased and the yield stress decreased,
PC-L-15 0.30 165.0 which is consistent with the conclusion in the G-15 group.
PC-S2-15 0.20 165.0
As mentioned above, the incorporation of superplasticizers could
PC-S3-15 0.24 164.0
G-5 (FA:Slag = Control-5 0 173.0
result in a decrease in yield stress and an increase in plastic viscosity.
95:5) The effect of superplasticizers on the yield stress of pastes could be easily
N-L-5 2.4 192.0 understood since the yield stress of the pastes reflects the minimum force
N-–S-–5 1.6 185.5 required for flowing generally. When superplasticizers were incorpo­
PC-L-5 0.10 182.0
rated, the plasticizing effect led to the reduction of yield stress, thus, the
PC-S2-5 0.20 201.5
PC-S3-5 0.22 187.5 pastes tended to flow. While it is interesting to find that there is an in­
crease in plastic viscosity induced by superplasticizers, since both yield
stress and plastic viscosity exhibited a reduction in common cement-
0.97 and the R2 fitted by HB model was greater than 0.99, indicating HB based pastes when superplasticizers were incorporated [29,32]. This
model was more suitable for fitting the rheological curve of geopolymer may be understood that raw material particles would adsorb super­
pastes than BH model. And if R2 is used as the evaluation index of the plasticizers, so the plastic viscosity increased. A similar phenomenon
applicability of the rheological model, the rheological curves of G-15 could be found in Chen et al.’s [43] research. They revealed that higher
fresh geopolymer pastes are more consistent with HB model. viscosity with FA was observed with more adsorbed superplasticizers,
The fitting results of the model are listed in Table 4. From the fitting and this was closely related to the fineness and density of the ash.
results of BH model, the plastic viscosity of geopolymer paste without Adjoudj et al. [32] also observed an increase of the plastic viscosity in
superplasticizer (Control-15) was 0.68 Pa⋅s, and the plastic viscosity of the high substitution rate of ordinary cement with silica fume, and they
geopolymer with superplasticizers increased. The yield stress of geo­ explained that much adsorption of superplasticizer by silica fume
polymer paste without superplasticizer (Control-15) was 5.20 Pa, and occurred, leading to an increase of the rheological parameters of the
the yield stress of geopolymer with superplasticizers decreased, among mixtures.
which the yield stress of geopolymer with N-L (N-L-15) decreased by To clarify the effect of precursor proportion on the rheological
83.65 %. From the fitting results of HB model, the plastic viscosity of properties of pastes, it can be found that the values of rheological pa­
geopolymer paste without superplasticizer (Control-15) was 0.41 Pa⋅s, rameters in the G-15 group are generally higher than that of in the G-5
the plastic viscosity of geopolymer also increased with the addition of group by comparing the fitting results in the G-15 and G-5 group, no
superplasticizers. The yield stress of Control-15 was 12.85 Pa, and the matter apparent viscosity, calculated plastic viscosity or yield stress.
yield stress of geopolymer with superplasticizers decreased. Comparing From Fig. 8(a) and Fig. 9(a), the initial apparent viscosity of all speci­
the obtained results fitted by the two models, the plastic viscosity ob­ mens in the G-15 group was more than 2.6 Pa⋅s, and that of in the G-5
tained by BH model is generally larger than that of HB model, and the group was less than 2.6 Pa⋅s. And compared with G-15, the plastic vis­
yield stress obtained by BH model is smaller than that of HB model. The cosity of G-5 was lower, which indicated that high content FA was
same conclusion could be drawn from the fitting results of the two beneficial to reduce the viscosity of fresh geopolymer paste due to its
models that the addition of superplasticizers in geopolymer pastes positive ball-bearing effect. On the other hand, it is also probably due to
would result in an increase in plastic viscosity and a decrease in yield the fact that there is less Slag in G-5, leading to less adsorption of
stress. superplasticizers and lower viscosity. Vance et al. [44] also indicated
Fig. 9 shows the curves of “shear rate-apparent viscosity” (Fig. 9(a)), that the spherical nature of fly ash particles likely compensated against
“shear rate-shear stress” (Fig. 9 (b)) and the fitting results by Herschel- other “viscosity enhancing” effects. Moreover, compared with G-15, the
Bulkley model (HB) (Fig. 9 (c)) in the G-5 group. From Fig. 9(a), the yield stress of G-5 was lower, revealing that the pastes were more likely
apparent viscosity of geopolymer paste gradually decreased with the to flow with high content of FA. This is because the ball-bearing effect of
increase of shear rate, indicating that the pseudoplastic fluid charac­ spherical fly ash particles effectively reduces the friction between par­
teristics would not change with different precursor proportions. When ticles, which is conducive to the destruction of cluster structures.
the content of Slag replacement is 5 %, i.e., in the G-5 group, the R2 of

7
G. Xiong and X. Guo Construction and Building Materials 350 (2022) 128734

Fig. 8. The effect of each superplasticizer on rheological properties of fresh geopolymer pastes with FA:Slag = 85:15 (G-15) (a)Apparent viscosity (b)Shear stress (c)
The fitting of Bingham (BH) model (d)The fitting of Herschel-Bulkley (HB) model.

Table 4
Rheological parameters of the G-15 group fitted by two models.
Specimens Rheological modela Fitting data Plastic viscosity (Pa⋅s) Yield stress (Pa)

G-15 (FA:Slag = 85:15) Control-15 BH y = 5.20 + 0.68x R2 = 0.976 0.68 5.20

HB y = 12.85 + 0.02x1.87 R2 = 0.992 0.41 12.85
N-L-15 BH y = 0.85 + 0.76x R2 = 0.982 0.76 0.85
HB y = 8.83 + 0.02x1.90 R2 = 0.998 0.45 8.83
N-S-15 BH y = 0.92 + 0.92x R2 = 0.986 0.92 0.92
HB y = 6.78 + 0.11x1.53 R2 = 0.998 0.66 6.78
PC-L-15 BH y = 1.06 + 1.29x R2 = 0.976 1.29 1.06
HB y = 7.13 + 0.05x1.68 R2 = 0.995 0.53 7.13
PC-S2-15 BH y = 1.09 + 0.76x R2 = 0.971 0.76 1.09
HB y = 7.55 + 0.03x1.84 R2 = 0.996 0.45 7.55
PC-S3-15 BH y = 0.83 + 0.77x R2 = 0.983 0.77 0.83
HB y = 5.59 + 0.09x1.52 R2 = 0.995 0.55 5.59

Notea:BH is Bingham model and HB is Herschel-Bulkley model.

3.3. Effect of superplasticizers on particles packing properties
The particles packing parameters of geopolymer pastes in G-15 and
G-5 group are shown in Table 6. The role of superplasticizers is to reduce
agglomerations, changing the solid particles from the loosely packed to
closely packed. From Table 6, it can be found that no matter in the G-15
group or the G-5 group, when superplasticizers were added into the
geopolymer pastes, the packing density (φmax ), excess water (We ) and
water film thickness (WFT) of the geopolymer pastes with super­
plasticizers almost increase, indicating the workability improvement
induced by superplasticizers.
When the precursor proportion changed from FA:Slag = 85:15 to
95:5, the packing density (φmax ) increased generally, while WFT
decreased generally. This is mainly because the specific surface area

8
G. Xiong and X. Guo Construction and Building Materials 350 (2022) 128734

Fig. 9. The effect of each superplasticizer on rheological properties of fresh geopolymer pastes with FA:Slag = 95:5 (G-5) (a)Apparent viscosity (b)Shear stress (c)
The fitting of Herschel-Bulkley model (HB).

Table 5
Rheological parameters of the G-5 group fitted by Herschel-Bulkley model.
Specimens Rheological model Fitting data Plastic viscosity (Pa⋅s) Yield stress (Pa)

G-5 (FA:Slag = 95:5) Control-5 HB y= 6.06 + 0.002x2.43 R2 = 0.995 0.27 6.06

N-L-5 HB y= 4.64 + 0.008x2.10 R2 = 0.996 0.34 4.64
N-S-5 HB y= 7.01 + 0.004x2.34 R2 = 0.998 0.39 7.01
PC-L-5 HB y= 5.55 + 0.05x2.33 R2 = 0.984 0.38 5.55
PC-S2-5 HB y= 5.26 + 0.03x2.19 R2 = 0.991 0.29 5.26
PC-S3-5 HB y= 2.94 + 0.09x1.85 R2 = 0.994 0.36 2.94

negatively charged, which is − 0.658 mV, and the surface of slag powder
Table 6 particles is positively charged, which is 1.740 mV. Habbaba et al. [45]
Particles packing parameters of geopolymer pastes in G-15 and G-5 group.
explained that slag attains a positive zeta potential in pore solutions
Specimens Specific Particles Excess Water film containing Ca2+ ions, and onto this positively charged layer of adsorbed
surface area packing water thickness
Ca2+ ions, anionic dispersants adsorb, producing a Langmuir-type
(m2/m3) density (We ) (μm) (WFT)
(SSAb ) (φmax ) adsorption isotherm. The superplasticizers used in this study, i.e.,
naphthalene-based and polycarboxylate-based superplasticizers are
G-15 (FA: Control- 1,040,408 0.602 0.106 0.102
Slag = 15
both anionic surfactants, indicating the adsorption of superplasticizers is
85:15) dominated by the content of slag powder in fly ash-slag powder based
N-L-15 0.606 0.142 0.136 geopolymers. Moreover, compared with cement grains (25.03 mV in
N-–S- 0.603 0.148 0.143 [41]), the zeta potential value of FA and Slag particles are comparatively
–15
small. This indicates that the adsorption capacity of the raw materials
PC-L-15 0.602 0.114 0.110
PC-S2- 0.601 0.114 0.110 for geopolymers is much worse than that of cement grains, leading to
15 only a little improvement of workability performance of pastes influ­
PC-S3- 0.602 0.114 0.110 enced by water reducing agents. Chen et al. [43] also revealed that the
15 fly ash particles have smooth surfaces and are normally negatively
G-5 (FA: Control- 1,089,697 0.617 0.101 0.093
Slag = 5
charged, so that their adsorbing capacity is much weaker than the
95:5) Portland cement particles.
N-L-5 0.625 0.134 0.123
N-–S- 0.626 0.135 0.124 3.4.2. Molecular stability of superplasticizers under different media
–5
The alkalinity of geopolymers, alkali-activated materials, is stronger
PC-L-5 0.618 0.105 0.097
PC-S2-5 0.617 0.106 0.098 than cement-based materials comparatively and ATR-FTIR could be
PC-S3-5 0.616 0.105 0.097 used to characterize the change of molecular structures of water
reducing agents in different media. In order to verify the effectiveness of
naphthalene-based superplasticizers in sodium silicate solution in this
(SSAb ) changed from 1040408 m2/m3 in G-15 to 1089697 m2/m3 in G-5, study, the FTIR spectrums of solid and liquid naphthalene-based
resulting from the relative increase of FA. According to Eq.(8), WFT is superplasticizers were measured.
inversely proportional to the SSAb , thus, WFT of the pastes in the G-5 Fig. 10 shows the FTIR spectrums of naphthalene-based super­
group is generally lower than that of G-15 group. Further analysis about plasticizers in deionized water and alkali activators solution, and the
the effect of superplasticizers and precursor proportion based on the peaks in the spectrums and their corresponding assignments. The
water film theory is discussed in Section 3.4.3. mechanism of naphthalene-based superplasticizers is that the sulfonic
groups (SO-3) on its chains adsorb on the surface of positively charged
3.4. The mechanism analysis of superplasticizers in geopolymers cement particles, which makes the surface of particles with the same
charge and produce repulsion, thus dispersing the particles. Therefore, it
3.4.1. Charged properties of precursors can be considered that sulfonic groups are the main functional groups of
As mentioned before, zeta potential is an important parameter to naphthalene-based superplasticizer, and its corresponding wavenumber
characterize the electrostatic repulsion between charged particles. The in the FTIR spectrum is about 1185 cm− 1 and 1034 cm− 1. Comparing the
zeta potential results show that the surface of fly ash particles is

9
G. Xiong and X. Guo
Fig. 10. FTIR spectrums of naphthalene superplasticizers in different media (a)N-L (b)N-–S.
FTIR spectra of naphthalene-based superplasticizer in deionized water
and alkali activator solution, it can be drawn that the sulfonic groups
could still be found in alkali activator solution (dotted line in Fig. 10 (b)
and Fig. 10 (d)), which reveals that naphthalene-based superplasticizers
still remain the main molecular structures under alkali activator solution
media. Palacios et al. [46] found that when the alkaline solution used is
NaOH, the formulation of naphthalene-based admixtures is not altered,
while naphthalene-based admixtures undergo alterations in the SO3
groups when the alkaline solution is waterglass.
As for the molecular stability of polycarboxylate-based super­
plasticizers, Palacios et al. [46] found that the molecular structure of
polycarboxylate-based superplasticizers changed under alkali media.
The same conclusion about the stability of polycarboxylate-based
superplasticizers could be found in the research of Carabba et al. [47].
However, the lateral effect of polycarboxylate-based superplasticizers
may be different in different geopolymers. For alkali-activated slag
material, the main chain, which contained the carboxylate groups, was
adsorbed on to the surface of the slag particles, while the steric hin­
drance was practically nonexistent [19,46]. For alkali-activated fly ash
material, while a certain degree of main chain degraded, the lateral
chains still remained bound and able to exert its action of steric hin­
drance. This may be attributed to different properties of slag and fly ash
[47].
10
Construction and Building Materials 350 (2022) 128734
3.4.3. Discussions of the effect of superplasticizers based on water film
thickness theory
According to the water film thickness (WFT) theory [30], water in
the suspension system can be divided into void filling water and excess
water. Void filling water refers to the amount of water required to fill the
void of solid particles (which does not contribute to the fluidity of the
paste), while excess water refers to the amount remaining, which coated
around the surface of the particles to form water film. Therefore, the
effects and mechanism of superplasticizers are discussed based on water
film thickness theory. And it is worth noting that the analysis is dis­
cussed based on the assumption, i.e., the excess water coats around the
surface of each particle to form a water film, in other words, the particles
are completely dispersed without flocculation.
Fig. 11 shows the relationship between water film thickness (WFT)
and the fluidity of fly ash-slag powder based geopolymer pastes. Zhu
et al. [48] revealed that the adsorption amount of the polycarboxylate-
based superplasticizers may be the decisive factor for WFT. Therefore,
the adsorption amount of superplasticizers on precursors may be re­
flected by WFT. According to the relationship between WFT and fluidity,
WFT of pastes increased and fluidity of pastes increased when super­
plasticizers were incorporated. While the increment is quite different
with different types of superplasticizers. For naphthalene-based super­
plasticizers, there is an obvious increase in WFT. Moreover, the WFT in
G-5 is lower than that in G-15 as a whole, revealing that the decrease of
Slag leads to less adsorption of naphthalene-based superplasticizers.
G. Xiong and X. Guo
Fig. 11. The relationship between water film thickness (WFT) and the fluidity of fly ash-slag powder based geopolymer pastes (a)G-15 (b)G-5.
This is a piece of good evidence to illustrate the mechanism of
naphthalene-based superplasticizers in fly ash-slag powder based geo­
polymer, which improves fluidity by adsorbing and dispersing via
electrostatic repulsion. For polycarboxylate-based superplasticizers, the
increment of WFT is almost negligible, revealing little adsorption
amount of polycarboxylate-based superplasticizers, which may be
mainly because of the destroyed main chains under high alkali media. It
is interesting to find that the fluidity with solid polycarboxylate-based
superplasticizers obtained an obvious increase, while the rise of WFT
could be almost negligible. This indicates the adsorption effects may be
not dominated mechanism of polycarboxylate-based superplasticizers in
fly ash-slag powder based geopolymers.
3.4.4. The mechanism of superplasticizers
For cement-based materials, the main mechanism of water reducing
agents can be explained by the theory of electrostatic repulsion and
steric hindrance [14,49]. These agents adsorbed on the surface area of
cement grains results in the inter-particle electrostatic repulsion and
steric hindrance, which are helpful in releasing the water trapped in the
agglomeration of flocculation. The plasticizing mechanism of the first
and second generations water reducing agents, e.g., naphthalene-based
superplasticizers are guided by the electrostatic repulsion theory, and
the plasticizing mechanism of the third generations, i.e.,
polycarboxylate-based superplasticizers are the dual mechanism of
adsorption/electrostatic repulsion and steric hindrance, between which
steric hindrance is the domination. From the above results, commercial
superplasticizers have a few positive effects on the workability of geo­
polymers, but the effectiveness is far from that of cement-based mate­
rials. The discrepancy in raw material particles and solution between
geopolymers and cement-based materials are the main reason for the
effectiveness differences of water reducing agents in geopolymers and
cement systems.
For the mechanism of naphthalene-based water reducing agents in
fly ash-slag powder based geopolymers, they would be adsorbed in raw
materials particles, mainly slag powder, and then dispersing particles by
the electrostatic repulsion. For the mechanism of polycarboxylate-based
superplasticizers, as mentioned above, although a certain degree of main
chain degraded, the lateral chains still remain bound and able to exert its
action of steric hindrance. Here, it may be understood that the steric
11
Construction and Building Materials 350 (2022) 128734
hindrance of polycarboxylate-based superplasticizers is the dominated
mechanism in fly ash-slag powder based geopolymer.
When the precursor proportion changes from FA:Slag = 85:15 to FA:
Slag = 95:5, Slag with adsorption of superplasticizers decreases and FA
with ball-bearing effect increases. For geopolymer pastes with
naphthalene-based superplasticizers, the comparative increase of FA
would enhance the positive ball-bearing effect. On the other hand, the
amount of negatively charged FA particles in the system increases
comparatively, which is not conducive to the adsorption of water
reducing agents. This combined net effect may explain why the fluidity
of geopolymer pastes with naphthalene-based water reducing agents
guided by electrostatic repulsion theory is not almost affected by the
proportion of precursors. For geopolymer pastes with polycarboxylate-
based superplasticizers, it is worth noting that the plasticizing effect of
polycarboxylate-based superplasticizers is quite different in G-15 and G-
5, especially for PC-S2. There is little improvement in the fluidity of G-15
with PC-S2, while PC-S2 exhibits the best plasticizing effect in G-5. This
may be understood that the steric resistance provided by
polycarboxylate-based superplasticizers is not enough to overcome the
friction between the particles in G-15. While in G-5, high content of
spherical fly ash with ball-bearing effect may assist the steric hindrance
to overcome the friction, thereby improving the fluidity. Therefore, the
effectiveness of polycarboxylate-based superplasticizers is very sensitive
to the precursor proportion.
According to the above discussions, the mechanism schematic dia­
gram of superplasticizers is shown in Fig. 12. It is supposed that the
effectiveness of the water-reducing agents in the geopolymers could be
judged by the combined effects of the interaction between particles and
the effects induced by superplasticizers. For the naphthalene-based
superplasticizers, due to their stable molecular structures and short
chains, it can change the interaction between particles through the
adsorption-dispersion effect, thereby improving the workability. For
polycarboxylate-based superplasticizers, if the steric hindrance effect
could overcome the friction between particles, then there are positive
effects on the workability improvement of geopolymer pastes. Other­
wise, it doesn’t work. This also may explain why the effectiveness of
polycarboxylate-based superplasticizers is very sensitive to the precur­
sor proportion.
G. Xiong and X. Guo
Fig. 12. The schematic mechanism diagram of superplasticizers in cement and geopolymer systems (G-15 and G-5).
4. Conclusions
In this paper, the effects of commercial superplasticizers and pre­
cursor proportions on the flowability and rheological properties were
evaluated and the mechanism was revealed by zeta potential and ATR-
FTIR results. Based on the results from this study, the following con­
clusions were obtained:
(1) The fluidity of geopolymer with 2.4 % N-L increased by 19.20 %
when FA:Slag = 85:15, and 0.20 % PC-S2 increased the fluidity of
geopolymer by 16.47 % when FA:Slag = 95:5. While the effec­
tiveness of polycarboxylate-based superplasticizers was closely
related to the precursor proportion.
(2) The addition of superplasticizers increased the plastic viscosity
and decreased the yield stress of the pastes, and the packing
density (φmax ), excess water (We ) and water film thickness (WFT)
of the geopolymer pastes with superplasticizers almost increase,
indicating the workability improvement induced by
superplasticizers.
12
Construction and Building Materials 350 (2022) 128734
(3) The zeta potential value of FA and Slag particles are compara­
tively small compared with cement grains, indicating lower
adsorption capacity. And the molecular structures of super­
plasticizers may be destroyed in alkali activators, especially for
polycarboxylate-based superplasticizers.
(4) The naphthalene- and polycarboxylate-based superplasticizers
have positive effects on the workability improvement of fly ash-
slag powder geopolymer pastes, and it is supposed that the
effectiveness of the water-reducing agents in the geopolymers
could be judged by the combined effects of the interaction be­
tween particles and the effects induced by superplasticizers.
Overall, this study pays attention to the effect of superplasticizers
and precursor proportion on the fresh properties and their qualitative
relationships of one-part fly ash-slag powder geopolymers, which un­
derlies the selection of superplasticizers for geopolymers with various
precursors including fly ash and provides a new perspective to under­
stand the mechanism of superplasticizers based on water film theory.
While further researches should focus on the time effect, detailed
quantitative relationship and the hardened properties of geopolymers as
G. Xiong and X. Guo
well as geopolymerization in the future.
CRediT authorship contribution statement
Guiyan Xiong: Conceptualization, Methodology, Investigation,
Visualization, Writing – original draft. Xiaolu Guo: Conceptualization,
Supervision, Writing – review & editing, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgements
The authors acknowledge the financial supports received from the
National Natural Science Foundation of China (No.52178241) and Na­
tional Key Research and Development Program of China (No.
2019YFE0112600 and 2021YFB3802001).
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