Effect of Fly Ash on Rheological Properties

of Magnesium Oxychloride Cement

Jiayu Wu 1; Huaxin Chen, Ph.D. 2; Bowen Guan 3; Yu Xia 4;
Yanping Sheng 5; and Jianhong Fang 6

Abstract: This paper studies the effect of fly ash on rheological properties of magnesium oxychloride cement (MOC) paste. Six different
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dosages of fly ash (0%, 15%, 20%, 25%, 30%, and 35% by weight of MgO) samples are prepared to investigate the rheological properties
of fly ash–magnesium oxychloride cement (FA-MOC) paste. The effects of fly ash on fluidity, setting times and mechanical properties of
MOC paste are measured. Phases and microstructures of FA-MOC paste are analyzed by X-ray diffraction (XRD) and scanning electronic
microscopy (SEM). An optical microscope is used to evaluate the flocculation of fresh FA-MOC paste. The results reveal that fly ash can
improve fluidity and retard the setting time of MOC paste. The water-absorbing ability and the morphology effect of fly ash have combined
effects on the rheological properties of FA-MOC paste. At the same time, the results show that fly ash used in MOC paste does not change
the phases composition of hardened paste, but increases the amount of 5MgðOHÞ2 · MgCl2 · 8H2 O (Phase 5). However, fly ash weakens the
structure of hydration products and results in poor mechanical properties of MOC paste. DOI: 10.1061/(ASCE)MT.1943-5533.0002597.
© 2018 American Society of Civil Engineers.
Author keywords: Magnesium oxychloride cement (MOC); Rheological property; Fly ash; Microstructure; Mechanical property.

Introduction
Magnesium oxychloride cement (MOC) has unique advantages
of rapid hardening and high early strength compared with ordinary
cement that gain it more attention from researchers (Tan et al.
2014). MOC is an air-hardening cementitious material (Zhang et al.
2017). The strength of MOC decreases rapidly when it is exposed
to water for a long time (Beaudoin and Ramachandran 1975).
Therefore, the water-resistance of a MOC system is a key problem
which seriously affects how widely MOC products can be used
(Chau et al. 2009). The raw materials of MOC are light-burned
MgO, MgCl2 , and water. As does ordinary cement, magnesium
oxychloride cement gets strength through chemical reactions and
hydration products (Liu et al. 2015). 3MgðOHÞ2 · MgCl2 · 8H2 O
(Phase 3) and 5MgðOHÞ2 · MgCl2 · 8H2 O (Phase 5) are the two
main hydration products in the system (Demediuk et al. 1955).
1 behavior, stability, and even compactability of cement paste, mor-
Ph.D. Student, School of Materials Science and Engineering,
Chang’an Univ., Xi’an, Shaanxi 710061, PR China. ORCID: https://
orcid.org/0000-0002-5047-9588. Email: wjy1991@chd.edu.cn
2 of cement. For example, Shang et al. (2015) studied the rheological
Full Professor, School of Materials Science and Engineering,
Chang’an Univ., Xi’an, Shaanxi 710061, PR China (corresponding author).
Email: chenhx_paper@163.com
3
Associate Professor, School of Materials Science and Engineer-
ing, Chang’an Univ., Xi’an, Shaanxi 710061, PR China. Email:
guanbowen2001@163.com
4
Lecturer, Dept. of Road and Bridge Engineering, Shaanxi Railway
Institute, Weinan, Shaanxi 714000, PR China. Email: 676989940@qq.com
5
Full Professor, School of Materials Science and Engineering,
Chang’an Univ., Xi’an, Shaanxi 710061, PR China. Email: 26701080@
qq.com
6
Senior Engineer, Transportation Development Institute, Qinghai
Research Institute of Transportation, Xining, Qinghai 810008, PR China.
Email: 13709719909@163.com
Note. This manuscript was submitted on March 30, 2018; approved on
August 7, 2018; published online on December 31, 2018. Discussion per-
iod open until May 31, 2019; separate discussions must be submitted for
individual papers. This paper is part of the Journal of Materials in Civil
Engineering, © ASCE, ISSN 0899-1561.
Hydration products interlaced with each other are the main source
of strength of hardened MOC paste (Hu et al. 2016). However,
different mix proportion of MOC generate different hydration
products which affect the strength and water-resistance of MOC
(Zhou et al. 2015). Li and Chau (2007) found that the molar ratio
of H2 O=MgCl2 and MgO=MgCl2 of the MOC system had a
significant effect on the strength of hardened MOC. Zhou et al.
(2015) studied the formation conditions of Phase 3 and Phase 5 of
MOC. The results showed that the minimum MgCl2 concentrations
needed for Phases 5 and 3 to form are 1.47 and 2.25 mol · kg−1 ,
respectively.
Modern concrete has properties of high fluidity and good homo-
geneity (Wang et al. 2017). Sufficient viscosity of cement paste
avoids segregation of the aggregate, and good fluidity of cement
paste maintains workability until concrete hardens. The fluidity
of concrete can be characterized by rheology. In addition, the flow
tar, and concrete can be predicted by rheology (Jiao et al. 2017).
There have been many studies relating to the rheological properties
properties of common portland cement pastes mixed with graphene
oxide. The results showed that graphene oxide caused poor fluidity
of the cement paste and increased the rheological parameters of
the paste. Jiang et al. (2018) tested the rheology of cement pastes
containing different kinds of nanofillers and microfillers, and used
a modified Bingham model to describe the rheological behaviors.
Lu et al. (2017) investigated the effect of colloidal polymers on
rheological properties of fresh cement pastes. Tan et al. (2014)
found that phosphoric acid had the ability to retard the hydration
process of MOC. These systematic studies concerned the rheologi-
cal properties of portland cement or the fluidity of MOC; however,
the rheological properties of MOC rarely are found in the literature.
Furthermore, the rapid-setting property of MOC limits its use in
engineering services. Therefore, it is very important to study the
rheological properties of MOC and the modified workability
of MOC.

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 Fly ash is an industrial by-product with the ability to improve
the fluidity of cement paste (Hou et al. 2013; Sabet et al. 2013). It is
environmentally friendly by adding fly ash into MOC. Chau et al.
(2009) used fly ash to modify MOC mortars and showed that when
fly ash content was 30% by weight of MgO, the fluidity of mortar
was improved and the setting time was retarded. Wang et al. (2017)
measured the effect of fly ash on the properties of graphene oxide
cement and found that the reduction of paste fluidity caused by
graphene oxide was compensated by fly ash. Zheng et al. (2017)
found that cement paste containing a high volume of circulating
fluidized bed fly ash exhibited Bingham fluid characteristics when
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the dosage of fly ash was less than 50%. Considering the prominent
benefits of fly ash, i.e., it can significantly modify the rheological
properties of cement paste, this study used it to modify MOC paste.
MOC paste containing various percentages of fly ash was prepared
to investigate the effect of fly ash on the rheological properties
of MOC paste. A modified Bingham model was applied to de-
scribe the shear stress-shear rate relationship of fly ash–magnesium
oxychloride cement (FA-MOC) pastes. An optical microscope was
used to observe the distribution and morphology of fly ash in MOC.
The phase characterizations of FA-MOC were analyzed based
on scanning electronic microscopy (SEM), and X-ray diffraction
(XRD) was used to explain the mechanism of the effects of fly ash
on FA-MOC. In order to better analyze the effect of fly ash on the
properties of MOC, the strength of MOC was determined after

being cured for 28 days.

Experiment

Raw Materials
Light-burned magnesia powder, magnesium chloride hexahydrate,
and tap water were used to prepare MOC paste. The specific sur-
face area of the light-burned magnesia powder was 340 m2 =kg and
the reactivity index of the light-burned magnesia was 59.3%, which
was determined by (Wu et al. 2017)
w2 − w1
w¼ × 100% ð1Þ
0.45w1
where w1 and w2 = mass of light-burned magnesia powder before
and after reacting with water for 3 h at 105°C, respectively (g); and
0.45 is a conversion factor, which is the ratio of the relative molecu-
Fig. 1. Particle-size distribution curves of magnesia and fly ash.
lar masses of H2 O and MgO.
The magnesium chloride was MgCl2 · 6H2 O, with a purity of
99%. Class F fly ash was provided by Xi’an Hongyuan (Xi’an,
Shaanxi, China), and the specific surface area of the fly ash was
425 m2 =kg. Fig. 1 shows the particle-size distribution curves of
magnesia and fly ash. The micromorphology of fly ash is shown
in Fig. 2. The chemical compositions of the raw materials are listed
in Table 1.

Magnesium Oxychloride Cement Specimen Preparation

The molar ratio of MgO∶MgCl2 ∶H2 O was 7∶1∶15 for all specimens.
It was obtained by testing the water resistance of MOC with differ-
ent molar ratios of MgO∶MgCl2 ∶H2 O. Fly ash was adopted from
15% to 35% by weight of MgO in 5% by weight intervals to pre-
pare the FA-MOC paste specimens. A cement paste mixer was
used for mixing. Water and MgCl2 were first added into the mixer
and stirred evenly. Then MgO was added and stirred with the
MgCl2 solution to form MOC paste. Finally, fly ash was added and
stirred with the MOC paste to form FA-MOC paste. After being
fabricated, the FA-MOC paste was transferred to a container for
performance testing. The flow chart of FA-MOC paste preparation
Fig. 2. SEM image of fly ash particles.
is shown in Fig. 3.

Table 1. Chemical compositions of raw materials

Mass fraction (%)
Materials MgO SiO2 Al2 O3 CaO K2 O Na2 O Fe2 O3 P2 O 5 SO3 MgCl2 H2 O CaCl2
MgO 85.43 6.65 1.82 1.33 0.18 0.25 1.31 0.11 0.09 — — —
MgCl2 · 6H2 O — — — — — — — — — 45.6 52.0 1.5
Fly ash 1.93 49.1 21.9 8.53 1.98 0.35 11.8 0.94 1.12 — — —

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Fig. 3. Flow chart of preparing FA-MOC paste.
Characterizations
Fluidity Measurements
The fluidity of the FA-MOC paste was characterized according
to Chinese standard GB/T8077-2000 (AQSIQ 2000). The mold for
measuring the fluidity was a round cone mold with top inside diam-
eter 36 mm, bottom inside diameter 60 mm, and height 60 mm. The
mold was put on a glass plate after fresh FA-MOC paste was poured
into the mold, and then the mold was lifted from the glass plate
slowly, leaving the cement paste on the glass plate. The paste
flowed freely for 30 s and then the maximum diameter of the sam-
ple and the maximum width perpendicular to that diameter were
measured. The average of these two results was defined as the
fluidity value. The fluidity of cement paste at 0, 30, and 60 min
was recorded.
Setting Time
The setting time of the FA-MOC paste was determined according
to GB/T50080-2011 (AQSIQ 2011). After preparation, FA-MOC
paste was poured into molds and cured in air. The temperature of
curing was 24°C  1°C and the relative humidity was 55%  5%.
After 30 min, the cement paste was taken out of the moisture curing
box to test the initial setting time. A Vicat needle was placed in
contact with the surface of the paste, and the needle was released.
When the needle was 4  1 mm from the bottom of the mold,
the cement paste reached the initial setting state, and the time
was the initial setting time. Then the mold was turned over 180° to
test the final setting time. When the needle inserting depth was
0.5 mm, the cement paste reached the final setting state, and the
time was denoted as the final setting time.
Microcharacterizations
The solid particle morphology of FA-MOC paste after being
hydrated for 0 min and 60 min was examined using an optical
microscope. The FA-MOC paste should be diluted 100-fold. Fur-
thermore, the micromorphology of FA-MOC cement paste after
28 days of curing was characterized using SEM.
Rheology and Thixotropic Properties Measurements
The rheological parameters of the FA-MOC paste were tested us-
ing a rotary viscometer. The test process is shown in Fig. 4. First,
the rotation rate was accelerated from 0 to 100 rotations=min in
30 s and then reduced to 0 in 30 s. This phase was a preshearing
cycle, intended to get the same shear state for each mixture before
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Fig. 4. Rheology property test processes.
testing. After standing still for 30 s, the shear rate was increased
from 0 to 150 rotations=min in 75 s and then returned to 0 in
another 75 s. Data obtained in this phase formed the two flow
curves (up-curves and down-curves) which reflect the rheological
properties of the slurry, and a suitable rheological model was
applied to fit rheological parameters.
Strength Measurements
The size of the specimens for compressive strength measurements
was 40 × 40 × 40 mm, whereas the size of specimens for flexural
strength measurements was 40 × 40 × 160 mm. At the curing age
of 28 days, the strength of hardened paste was tested according to
GB/ T17671-1999 (AQSIQ 1999). Each test group was repeated
three times and the average was taken to be the representative value.
Results and Discussion
Fluidity of FA-MOC
The effect of fly ash on the fluidity of MOC paste was investigated,
and the results are shown in Fig. 5. The fluidity of MOC paste
increased with the increase of fly ash content (Fig. 5). With the
use of fly ash, the fluidity of fresh MOC paste ranged from 176
to 204 mm. After curing for 30 min, the fluidity of the MOC varied
from 97 to 181 mm. After 60 min, the fluidity of the MOC paste
ranged from 70 to 153 mm. Comparing the fluidity of MOC with
varied contents of fly ash showed that the flow loss at 30 min and
60 min was 44.9% and 60.2%, respectively, when the fly ash con-
tent was 0. When the fly ash content was 35%, the flow loss at
30 min and 60 min was 11.3% and 25.0%, respectively. The fluidity
loss of the control sample was larger than that of the sample modi-
fied with fly ash. This finding confirms the results by Hemalatha
and Ramaswamy (2017) that fly ash can enhance the paste and con-
crete workability. The addition of fly ash decreased the content of
MgO, resulting in a diluted system, thus reducing the flocculation
forming by cement particles. In addition, the spherical shape of fly
ash particles facilitates the movement of neighboring particles by a
morphology effect. Therefore, the fly ash can effectively improve
the fluidity of MOC paste (Yu et al. 2017).
Setting Time of FA-MOC
Table 2 lists the setting time of FA-MOC paste. The results show
that fly ash has a strong retardation effect on the setting of MOC
J. Mater. Civ. Eng.
 with the dilution effects resulting from cement replacements with
fly ash (Naik and Singh 1997). Another reason is that, in a MOC
paste system, fly ash does not react with cement particles. Fly ash,
existing between hydration products, do not contribute to building
the bridges between the cement particles (Gurney et al. 2018), and
hence the setting of FA-MOC is retarded. However, after adding
fly ash, MgO and MgCl2 react to develop more Phase 5. Without
fly ash, less Phase 5 develops in MOC paste. From this result, it can
be concluded that fly ash has the ability to promote hydration re-
actions in the MOC system. This may be ascribed to the fact that the
average grain size of fly ash is smaller than MgO particles. The size
gradation of composite particles is improved by adding fly ash to
the system. In addition, fly ash between MgO particles can disperse
gathered MgO particles into independent particles. Thus, water
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wrapped by MgO particles is released and participates in the

hydration process, leading to more hydration products. However,
the use of fly ash dilutes the system, prolonging the setting time
(Xu et al. 2017). Magnesium carbonate was found in the XRD data.
Fig. 5. Effect of fly ash on the fluidity of MOC paste. This may be because of carbon dioxide dissolved in the water dur-
ing preparation of the specimen, or because the large void area in
solidified cement paste led to internal carbonization of the sample
(Liu et al. 2015).
Table 2. Setting time of MOC with various fly ash contents
Content of Initial setting Final setting
fly ash (%) time (min) time (min) Rheological Properties of FA-MOC Paste
0 76 107
15 85 125 Rheology Models of FA-MOC Paste
20 100 145 Due to the hydration of MOC paste, the rheological behavior of
25 107 168 MOC paste evolves with time. In addition, fresh MOC is a com-
30 101 195 plicated system that contains various particulate materials, so the
35 108 234 rheological behavior of MOC paste is a complicated subject (Jiao
et al. 2017). Fig. 7 shows the down-curve of rheology measurement
results of the FA-MOC paste. There was a nonlinear relationship
between the shear rate and shear stress of the FA-MOC paste.
Therefore, non-Newtonian fluid models were used to fit the rheol-
ogy curves of FA-MOC paste. On the basis of previous studies
(Feys et al. 2013; Wallevik et al. 2015), a modified Bingham (M-B)
model is suitable to describe the rheological properties of FA-MOC
paste. The model is
τ ¼ τ 0 þ μγ̇ þ cγ̇ 2 ð2Þ

where τ and τ 0 = shear stress (Pa) and yield stress (Pa), respec-
tively; μ = plastic viscosity (Pa · s); γ̇ = shear rate (s−1 ); and c is
a correction factor (Pa · s2 ).
Table 3 gives regression analysis results of rheological param-
eters of FA-MOC paste at different hydration times based on the
M-B model. A high value of regression coefficient R2 means that
the regression results are well correlated with flow curve. Table 3
shows that the fluid characteristics exhibited by FA-MOC paste
follow the M-B model very well. Therefore, the plastic viscosity (μ)
Fig. 6. XRD diffraction patterns of MOC with and without fly ash and yield stress (τ 0 ) were obtained from the M-B model in this
at 28 days. study.

Effect of Fly Ash on Rheological Properties

paste. The setting time increased with the increase of fly ash
content. The initial setting time of the FA-MOC paste increased
by 11.84%–42.11%, and the final setting time increased by
16.82%–118.69% with the addition of fly ash from 15% to 35%
compared with the setting time of MOC paste without fly ash. Fig. 6
shows the XRD test result of MOC paste with 35% fly ash content
and of MOC paste without fly ash, both cured for 28 days. Using
fly ash in MOC paste did not change the composition of the hy-
dration products. In general, the delay in setting time is associated
of FA-MOC Paste
In this study, data obtained from the down-curve were used to
evaluate the rheological parameters. The yield stress and plastic
viscosity of FA-MOC paste were obtained by fitting with the
M-B model. Fig. 8 shows the effect of different fly ash contents
on the yield stress of FA-MOC paste with different hydration
times. The yield stress of cement paste is produced by adhesive
force and frictional force among cement particles. The cement
particles sustain a certain amount of stress before they start to
flow, which defines the yield stress (Qian and Kawashima 2018).

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Fig. 7. Effect of fly ash on the shear stress of FA-MOC paste at different hydration times: (a) 0 min; and (b) 60 min.
Table 3. Rheological parameters of FA-MOC paste based on M-B model
Hydration for 0 min
Fly ash content (%) Fitting equation
0 τ ¼ 12.394 þ 1.565γ − 0.00145γ̇ 2
15 τ ¼ 6.372 þ 1.235γ − 7.36 × 10−4 γ̇ 2
20 τ ¼ 3.712 þ 1.113γ − 0.00111γ̇ 2
25 τ ¼ 2.189 þ 0.827γ − 8.87 × 10−4 γ̇ 2
30 τ ¼ 7.687 þ 0.571γ − 1.9 × 10−4 γ̇ 2
35 τ ¼ 2.442 þ 0.719γ − 6.72 × 10−4 γ̇ 2
Fig. 8. Yield stress of FA-MOC paste at different hydration times.
The value of yield stress is significantly related to the workability
of cement paste. The yield stress of FA-MOC paste decreased as a
whole (Fig. 8). For the paste hydrated for 0 min, the yield stress
decreased when the dosage of fly ash was less than 25%, sub-
sequently increased when the dosage of fly ash was 30%, and then
decreased when fly ash content was 35%. This is because when
the fly ash content was less than 25%, the size gradation of
composite particles was improved by addition of fly ash into the
© ASCE
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Hydration for 60 min
2
R Fitting equation R2
0.999 τ ¼ 32.431 þ 2.545γ̇ − 0.00548γ̇ 2 0.997
0.999 τ ¼ 31.039 þ 2.429γ̇ − 0.00564γ̇ 2 0.989
0.999 τ ¼ 6.35 þ 1.152γ̇ − 8.8 × 10−5 γ̇ 2 0.999
0.999 τ ¼ 16.1 þ 1.099γ̇ − 0.00169γ̇ 2 0.999
0.999 τ ¼ 8.13 þ 0.842γ̇ − 0.00161γ̇ 2 0.999
0.999 τ ¼ 3.634 þ 0.733γ̇ − 8.95 × 10−4 γ̇ 2 0.999
system, and fly ash filled the voids between the cement particles,
resulting in a more compact FA-MOC system. As a result, water
wrapped by particles was released and the FA-MOC paste was
more flowable, so that the yield stress decreased. However, when
the fly ash content is more than 25%, FA-MOC paste needs more
mixing water due to the larger specific surface area of fly ash,
which absorbs a lot of free water. Therefore, free water in the
FA-MOC paste decreased, leading to greater friction between the
particles, so that the yield stress increased. When the FA-MOC
paste hydrated for 60 min, the yield stress of the paste with 25%
and 30% fly ash content was higher than that of the paste with
20% fly ash content. The reason for this phenomenon is the same
as for the FA-MOC paste hydrated for 0 min. However, the yield
stress of FA-MOC paste with a 60-min hydration time was much
higher than that with 0 min hydration time. Free water was not
only absorbed by fly ash, but also participated in the hydration
process. Thus, less free water played a role in lubrication, causing
a higher yield stress of FA-MOC paste with a 60-min hydra-
tion time.
The plastic viscosity of samples containing different dosages of
fly ash is shown in Fig. 9. Plastic viscosity is a measure of particles’
resistance to flow. It is strongly influenced by the solid loading and
particle separation (Vance et al. 2015). The plastic viscosity of FA-
MOC paste decreased with the increase of fly ash content (Fig. 9).
The plastic viscosity of the paste without fly ash was 2.46 Pa · s,
which was about 3 times that with a fly ash content of 35% when
the hydration time was 60 min. This is also attributed to the mor-
phology effect of fly ash. When the paste is under flowing condi-
tions, fly ash particles in the system can act as ball bearings
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Fig. 9. Plastic viscosity of FA-MOC paste at different hydration times.
between cement particles, thereby reducing the viscosity of the
paste (Genovese 2012). The test results of yield stress and plastic
viscosity of the FA-MOC paste showed that the morphology effect
of fly ash can improve the rheological properties of the paste, but
more fly ash absorbs more free water, resulting in poor workability
of the paste. However, the rheological properties of FA-MOC paste
were improved as a whole. It can be deduced that the morphology
effect and water-absorbing property of fly ash had a combined
influence on the rheological properties of MOC paste. Furthermore,
the morphology effect of fly ash has a stronger influence on the
rheological properties of FA-MOC paste than does its water-
absorbing property.
In order to demonstrate the effect of fly ash on the rheological
properties of MOC paste, optical characterizations were carried out
on fresh FA-MOC paste. Fig. 10 shows the optical microstructures
of fresh FA-MOC paste with different fly ash contents. There were
single cement particles and flocculation in the system (Fig. 10). The
flocculation structure was agglomerated cement particles formed
by van der Waals force and the Coulomb force. The amount of
flocculation decreased with the increase of fly ash content. When
the fly ash content was 0, cement particles with different particle
sizes combined with each other, forming a great deal of flocculation
and wrapping water inside. Different sizes of the flocculation struc-
ture were evenly distributed, and there were few separate cement
particles in the paste. With the increase of fly ash content, the floc-
culation structure gradually decreased. There were many cement
particles with a regular geometric shape individually dispersed in
the system.
Usually, more flocculation structure would lead to a high yield
stress. However, the yield stress of the fresh paste with 25% fly
ash content was lower than that of paste in which the fly ash con-
tent was 30%, even though there was less flocculation in the paste
with 30% fly ash content. This phenomenon can be explained
by rheological properties test results which showed that the mor-
phology effect of fly ash and its water-absorbing ability had a
combined effect on the rheological properties of MOC paste.
When the fly ash content was 30%, more free water was absorbed
by fly ash, so the yield stress of FA-MOC paste increased. How-
ever, the yield stress and plastic viscosity of the paste had a
downward trend overall. Therefore, the main factor affecting the
rheological properties of FA-MOC paste was the morphology ef-
fect of fly ash.
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Thixotropic Properties of FA-MOC Paste
When cement particles are exposed to water, the hydration reaction
begins. Early hydration products are on the surface of cement par-
ticles. Those hydration products bridge cement particles together to
form a rigid network (Qian and Kawashima 2018). With the hydra-
tion of cement particles, microstructures are built up in MOC paste,
such as Phase 5. When the paste is under shear flow, the rigid net-
work and microstructures are broken down. However, when the
shear force is removed, the rigid network and microstructures are
built up again. The property of fresh cementitious materials in
which the microstructure and viscosity changes with shear stress
time history is termed thixotropy (Wallevik 2005). Understanding
the thixotropy of FA-MOC paste that it is related to the degree of
internal structure of the material it will provide a better understand-
ing of the time-dependent rheological properties of FA-MOC.
Fig. 11 shows the effect of fly ash on the thixotropy of FA-MOC
paste at hydration times of 0 and 60 min. There was a loop between
the up-curve and down-cure (Fig. 11). The area of the loop repre-
sents the level of thixotropy (Ferron et al. 2007). A larger loop area
represents higher thixotropic of the fresh cement paste. The inte-
gration method to obtain the area of the loop is
Z γ̇
2
S¼ ðT 1 − T 2 Þdγ̇ ð3Þ
γ̇ 1
where S = level of thixotropy of the paste (Pa=s); γ̇ 1 and γ̇ 2 = initial
shear rate and final shear rate, respectively; and T 1 and T 2 = fitting
equations of the up-curve and down-curve, respectively.
Table 4 lists the values of loop areas for different dosages of fly
ash at different hydration times. Adding fly ash to MOC paste no-
tably reduced the thixotropy loop area of the paste, which indicates
that the stability of the MOC paste decreased. FA-MOC pastes with
35% fly ash content had the minimum thixotropy, whereas pure
MOC paste possessed the maximum thixotropy. Previous results
suggested that an appropriate amount of fly ash can delay the struc-
ture recoverability of MOC paste. The higher the fly ash content,
the less flocculation existed in the system. This conclusion is con-
sistent with the experimental results of optical characterizations
tests of fresh FA-MOC paste. It is due to two reasons. On the one
hand, the fly ash partly replaced the MgO, decreasing the content of
raw materials, thus decreasing the quantity of flocculation structure.
On the other hand, fly ash filled the voids between the cement par-
ticles, making the particles separate in the system, reducing the
amount of flocculation.
Mechanical Properties of FA-MOC Paste
To better determine the effect of fly ash on MOC paste, the
mechanical properties of FA-MOC paste were tested. Fig. 12 shows
the effects of fly ash on the compressive strength and flexural
strength of hardened FA-MOC paste cured in air for 28 days. The
mechanical properties of FA-MOC paste decreased with the in-
crease of fly ash content. The compressive strength of FA-MOC
with 35% fly ash content decreased by 48% compared with the
control sample. The flexural strength of FA-MOC paste content
35% fly ash decreased by 24.5% compared with the control sample.
The results show that fly ash had a negative effect on the compres-
sive strength of MOC paste. Fig. 13 shows the SEM images of
MOC with 35% fly ash content and without fly ash content cured
in air for 28 days. Well-crystallized needlelike hydration products,
which are Phase 5 in hardened paste, and fly ash existed independ-
ently in the MOC paste (Fig. 14). Phase 5 has been described as
whiskers, and it is responsible for the high strength of MOC paste
(Tan et al. 2015). However, the hydrated crystals were thin and
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Fig. 10. Optical microstructures of fresh FA-MOC paste with different fly ash contents: (a) pure MOC paste; (b) 15% fly ash content; (c) 20% fly ash
content; (d) 25% fly ash content; (e) 30% fly ash content; and (f) 35% fly ash content.

few when there was no fly ash in the MOC paste, and the structure
of the MOC paste was loose. When MOC paste was modified with
fly ash, the needles became thicker and larger. This indicates that
fly ash improved the hydration process of the MOC paste. This
result coincides with the result of XRD measurement. Furthermore,
the optical microscope test result demonstrated that the morphol-
ogy effect of fly ash can release the water wrapped by cement par-
ticles and improve the hydration process of MOC paste. Comparing
the hydration products in Fig. 13 and the mechanical properties in
Fig. 12, although there were more hydration products in the hard-
ened paste which contained fly ash, the corresponding compressive
strength of the paste decreased by 48% compared with the control
sample. This large reduction in compressive can be explained by
the fact that MgO was partly replaced by fly ash, resulting in a
dilute system, and fly ash does not participate in the hydration pro-
cess in a MOC system; therefore the bridges between hydration
products were cut off by fly ash, casing poor mechanical properties
of the FA-MOC paste.
A mechanism model of the interaction between fly ash and
MOC paste is shown in Fig. 14. When the hydration time was
0 min, there were no obvious hydration products in the system
(Fig. 14). Fly ash can improve the dispersivity of cement particles
because of the morphology effect of fly ash. When the dosage of fly
ash was 35%, water wrapped by cement particles was almost com-
pletely released and the cement particles existed independently in
the system, improving the rheological properties of the MOC paste.

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J. Mater. Civ. Eng., 2019, 31(3): 04018405

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Fig. 11. Effect of fly ash on thixotropy of FA-MOC paste at different hydration times: (a) 0 min; and (b) 60 min.

Table 4. Thixotropy loop area of FA-MOC paste with different dosage of Conclusions
fly ash at different hydration times
Integrated area (Pa=s)
A series of experiments was carried out to evaluate the effectiveness
Content of fly ash on increasing the rheological properties of MOC paste.
(% by weight) 0 min 60 min The test results demonstrated that the rheological properties of
0 1,769.08 2,220.23 MOC paste increased with the increase of fly ash content due to
15 1,449.03 1,550.31 the morphology effect of fly ash. However, due to the water absorb-
20 1,209.39 1,360.06 ability of fly ash, with greater fly ash content, more water was ab-
25 1,123.91 1,349.16 sorbed by the fly ash, which led to little increase of the yield stress
30 1,049.45 1,100.86 of the FA-MOC paste. However, the morphology effect of fly ash
35 910.4 925.82
improved the rheological properties of FA-MOC paste at the same
time, so the addition of fly ash improved the rheological properties
of FA-MOC paste on the whole.
When the hydration time was 60 min, more hydration products Thixotropy of the MOC paste was reduced by adding fly ash to
were generated in the cement paste. The amount of hydration prod- the system. Fly ash filled the gaps between cement particles, reduc-
ucts increased with the increase of fly ash content due to more re- ing flocculation structures in fresh MOC paste. The setting time of
leased water and independent cement particles participating in the MOC paste was also retarded due to fly ash blocking cement par-
hydration process. Although more hydration products will lead to ticle connections and diluting the system.
poor workability of MOC paste, fly ash particles exist between the Adding fly ash to MOC paste does not change the composition
hydration products and do not participate in hydration process, of the hydration products, but increases the amount of hydration
which weakens the stability of the hydration products and improves products. However, fly ash breaks the bridges between the hydra-
the rheological properties of the MOC paste. tion products, weakening the hydration structure. The mechanical

Fig. 12. Mechanical properties of FA-MOC paste cured in air for 28 days: (a) compressive strength; and (b) flexural strength.

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J. Mater. Civ. Eng., 2019, 31(3): 04018405

Downloaded from ascelibrary.org by Iowa State University on 01/03/19. Copyright ASCE. For personal use only; all rights reserved.

Fig. 13. SEM images of FA-MOC paste cured in air for 28 days: (a) without fly ash; and (b) with 35% fly ash content.

Fig. 14. Effect of fly ash on cement particle dispersion at different hydration times.

properties results revealed that the strength decreased as the fly ash Foundation (2017-ZJ-764 and 2017-ZJ-763), and the Special Fund
content increased. Hence, adding fly ash to MOC paste leads to for Scientific Research of Central Colleges, Chang’an University
poor mechanical properties of FA-MOC paste. (Nos. 310831172201 and 300102318501).

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