ACI MATERIALS JOURNAL
Title No. 111-M25
Effects of Material Ratio, Fly Ash, and Citric Acid on
Magnesium Oxysulfate Cement
by Chengyou Wu, Hongfa Yu, Jinmei Dong, and Lina Zheng
The effects of material ratio, fly ash, and citric acid on the
compressive strength and phase composition of magnesium oxysul-
fate (MOS) cement have been studied. From these results, when
the molar ratio of active MgO/MgSO4 increases from 3 to 5, the
compressive strength of magnesium oxysulfate cement increases.
When the molar ratio of active MgO/MgSO4 is 3, the main crystal
phase contributing to the mechanical strength is 3Mg(OH)2·Mg-
SO4·8H2O; when the molar ratio increases to 5, the main crystal
phase is a new magnesium subsulfate that can be expressed as
yMg(OH)2·MgSO4·zH2O (Y phase). The compressive strength of
MOS cement by adding fly ash decreases from 56.89 to 33.75 MPa
(8.251 to 4.895 ksi) by 39.29% when the dosage of fly ash increases
to 40%, because SiO2 in fly ash can form magnesium silicate hydrate
gel, which can adsorb onto the surface of the Y phase nucleus and
inhibit its growth. In the presence of 0.5% weight citric acid (CA),
the compressive strength of MOS cement increases, because CA
may facilitate the formation of yMg(OH)2·MgSO4·zH2O (Y phase).
Keywords: citric acid; compressive strength; fly ash; magnesium oxysul-
fate cement; material ratio.
INTRODUCTION
Magnesium oxysulfate (MOS) cement is a type of magnesia
cementitious material prepared by active magnesia (a-MgO)
and magnesium sulfate solution. Due to light density, good
fire resistance, strong water resistance, low corrosion to steel,
and low thermal conductivity,1,2 this cementitious material is
widely used in producing insulation board and fire-resistive
materials. Low mechanical strength and high cost, however,
have restricted its large-scale practical application.
The compressive strength of MOS cement depends
on the category and content of magnesium subsulfate in
cement.3,4 According to Demediuk and Cole’s report,5 four
magnesium subsulfate ternary (MgO-MgSO4-H2O) systems
that commonly exist in MOS cement are 5Mg(OH)2·Mg-
SO4·3H2O (5 phase), 3Mg(OH)2·MgSO4·8H2O (3 phase),
Mg(OH)2·2MgSO4·3H2O, and Mg(OH)2·MgSO4·5H2O.
Urwrong and Sorrel6 studied the phase relations in MOS
cement, and suggested that metastable Mg(OH)2·Mg-
SO4·5H2O and MgSO4·4H2O can also be detected at ambient
temperature besides 3 phase, MgSO4·nH2O (n = 7, 6, 1),
Mg(OH)2, and MgO. They also suggested that it was impos-
sible to prepare MOS cement product that contained more
than 50% weight 3 phase, which resulted in low mechan-
ical strength of MOS cement. Kahle’s report7 showed that
the cement contained 3 phase and 5 phase simultaneously
only in the steam curing condition. An effective method to
ACI Materials Journal/May-June 2014
TECHNICAL PAPER
improve the mechanical strength of MOS cement in normal
condition, however, has not yet been developed.
Magnesia used for preparing MOS cement was normally
light-burned magnesia (LBM) obtained by calcining magne-
site at 700 to 800°C (1292 to 1472°F).8-10 Some inactive
magnesia, which cannot hydrate in water but can be treated
as filler, is typically contained in LBM. To decrease the cost,
high-dosage industrial solid waste, such as fly ash and silica
fume, are usually added into MOS cement.11,12 Given that
the ternary system MgO-MgSO4-H2O of MOS cement does
not easily reach equilibrium, which leads to the uncertainty
of crystal phase composition, it is not practical to prepare
MOS cement with high-content magnesium subsulfate and
high strength according to the ternary system MgO-Mg-
SO4-H2O directly. Above all, it is necessary to study the
effects of material ratio and fly ash on compressive strength
and phase composition of MOS cement. Additionally, citric
acid was selected as an additive for improving the mechan-
ical strength of MOS cement. It is believed that this study
will provide significant information to prepare an MOS
cement product with good properties, and will find related
theoretical principles to study the modification mechanism
of magnesium cement, including MOS and MOC (magne-
sium oxychloride) cement.
RESEARCH SIGNIFICANCE
MOC and MOS cement were developed not long after the
invention of portland cement (PC). In recent years, MOS
cement was reported less than MOC cement because of low
compressive strength and high cost. Compared with MOC
cement, however, MOS cement is a promising material in
the application of producing light insulation board, elec-
trical insulating materials, and fire-resistive materials due to
its outstanding merits such as light weight, good fire resis-
tance, and low thermal conductivity. The authors believe that
methods to improve the compressive strength and to lower
the cost for MOS cement and related mechanisms discussed
in this study will provide helpful information for a later study
about MOS cement by other researchers and will provide
significant findings for preparing MOS cement product with
good properties.
ACI Materials Journal, V. 111, No. 3, May-June 2014.
MS No. 2012-255.R2, doi: 10.14359/51686723, was received August 9, 2012, and
reviewed under Institute publication policies. Copyright © 2014, American Concrete
Institute. All rights reserved, including the making of copies unless permission is
obtained from the copyright proprietors. Pertinent discussion including author’s
closure, if any, will be published ten months from this journal’s date if the discussion
is received within four months of the paper’s print publication.
291
Table 1—Chemical compositions of LBM and
fly ash
LBM Fly ash
MgO, % 80.2 0.47
CaO, % 1.30 2.16
SiO2, % 6.07 52.37
Al2O3, % 0.15 32.13
Fe2O3, % 0.41 4.13
Others, % 11.87 8.74
EXPERIMENTAL INVESTIGATION
Materials
Magnesia used in this study was LBM provided from
calcination of magnesite from Liaoning, China at 750°C
(1382°F). The chemical compositions are listed in Table 1.
Because only a-MgO can hydrate and convert to any magne-
sium subsulfate in a magnesium sulfate solution, it is neces-
sary to test the content of a-MgO in this LBM to make
sure that the material ratio and its effects on MOS cement
have universality when cement products are prepared using
different types of LBM. In this study, the content of a-MgO
is tested with the standardized hydration method according
to Dong et al.13 The result is only 58.50% of a-MgO in LBM,
although the content of total MgO is 80.20%.
Magnesium sulfate (MgSO4·7H2O) and citric acid (CA)
were analytically pure and purchased from Tianjin Hongyan
Ltd. of Tianjin, China. The low-calcium fly ash was from
Jiangsu, China, with the chemical composition listed in
Table 1.
Material ratio choice
To compare the effect of the a-MgO/MgSO4 molar ratio
M on the compressive strength effectively, a different
density of the cement should be avoided by fixing the water-
cement ratio (w/c). In this experiment, the mass of LBM
and MgSO4·7H2O needed was calculated according to the
a-MgO/MgSO4 molar ratio M of 3, 5, 7, 9, 11, and 13. The
results (assuming the sum of LBM and MgSO4 was 100 g
[0.22 lb]) are listed in Table 2. The mass of water mH2O
needed is calculated for w/c of 0.50, 0.60, 0.70, 0.80, 0.90,
and 1.00, respectively, according to the following formula
mH2O = R × (48.78% × mMgSO4∙7H2O) – mMGSO4∙H2O × 51.22%
where R is the w/c and 48.78 and 51.22% are the percentages
of MgSO4 and H2O, respectively, in MgSO4·7H2O.
Sample preparation
First, a quantitative and concentrated magnesium sulfate
solution was prepared according to the results calculated
previously. Pre-weighted LBM and magnesium sulfate solu-
tion were blended and then stirred well to form an MOS
cement paste. This paste was cast into 40 x 40 x 40 mm
(1.576 x 1.576 x 1.576 in.) polyethylene molds and cured at
292
Table 2—Amount of LBM and MgSO4·7H2O needed
in MOS cement with different M*
M mLBM, g mMgSO4·7H2O, g
3 63.0915 75.6625
5 74.0192 53.2605
7 79.9543 41.0937
9 83.6820 33.4519
11 86.2407 28.2065
13 88.1057 24.3832
*
Assuming sum of LBM and MgSO4 is 100 g.
temperature of 20 ± 3°C (68 ± 5.4°F) and relative humidity
of 35 ± 5% for 24 hours before demolding.
ANALYTICAL PROCEDURE
The compressive strength of MOS cement cured for
28 days at room temperature and relative humidity of 35 ±
5% was tested on a testing machine with maximum force of
300 kN (67.42 kip) according to cement strength test method
standard ASTM C109/C109M.14 Triplicate samples were
tested. The crushed cement was reduced to a powder (D90 <
30 μm [0.0012 in.]) for crystal phase composition analyzed
on an X-ray diffractometer with a Cu target.
EXPERIMENTAL RESULTS AND DISCUSSION
Effect of material ratio on MOS cement
Figure 1 shows the effects of the molar ratio a-MgO/MgSO4
M (Fig. 1(a)) and the w/c R (Fig. 1(b)) on the compressive
strength of MOS cement. When M increases from 3 to 5, the
compressive strength increases at the same R. For instance,
the compressive strength increases to 39.91 MPa (5.788 ksi)
by 29.41% from 30.84 MPa (4.473 ksi), as M increases from
3 to 5 when R is 0.8. When M continuously increases from
5 to 13, however, the compressive strength decreases grad-
ually to only 14.5 MPa (2.103 ksi). On the other hand, the
compressive strength decreases with the increase of R at the
same M. For example, the compressive strength decreases by
61.41% from 65.15 to 25.14 MPa (9.449 to 3.646 ksi) as R
increases from 0.5 to 1.0 when M = 5.
Phase composition depending on material ratio is the
most important factor on the compressive strength of MOS
cement. Figure 2 shows the effects of M (Fig. 2(a)) and R
(Fig. 2(b)) on the crystal phase composition in MOS cement.
It can be found that when M = 3, MOS cement is comprised
of a mass of 3 phase, MgCO3, MgO and trace MgSO4·7H2O,
which is similar to the results obtained by Urwong and
Sorrel.6 Compared with M = 3, a large amount of new crystal
phase presents in MOS cement when M = 5. It is likely to be
a new type of magnesium subsulfate crystal phase that can
be expressed as yMg(OH)2·MgSO4·zH2O (Y phase).
This new phase’s characteristic X-ray diffraction (XRD)
peaks are listed in Table 3. Compared with characteristic
XRD peaks of those magnesium subsulfates discovered thus
far (Table 3), it is confirmed that the phase is not 3 phase,
5 phase, Mg(OH)2·2MgSO4·3H2O, or Mg(OH)2·Mg-
SO4·5H2O detected in ternary system MgO-MgSO4-H2O in
ACI Materials Journal/May-June 2014
Fig. 1—Effects of: (a) molar ratio a-MgO/MgSO4 (M); and
(b) w/c (R) on the compressive strength of MOS cement
cured for 28 days. (Note: 1 MPa = 6.895 ksi.)
Fig. 2—Effects of: (a) M (R = 0.8); and (b) R (M = 5) on
Demediuk and Cole’s report.5 The molar ratio Mg(OH)2/ XRD spectra of MOS cement.
MgSO4 (y) in chemical composition of the Y phase,
however, is more likely to be more than 3 and less than Table 3—Characteristic X-ray diffraction peaks of
5, because the Y phase appears in large amounts when M magnesium subsulfates
is greater than 3. Furthermore, active magnesia is partly
aMg(OH)2·bMgSO4·cH2O (a·b·c) d (Å)
converted into Mg(OH2) or MgCO3 with H2O or CO2 in air
when M = 5. When M ≥ 7, the diffraction peak intensity of yMg(OH)2·MgSO4·zH2O 9.36, 7.46, 4.99, 2.40
the Y phase decreases dramatically, and that of Mg(OH)2 or 3·1·8 5.74, 5.44, 4.72, 2.46
MgCO3 increases.
5·1·3 6.85, 5.12, 3.90, 2.26
The pH changes of LBM hydration in water (Fig. 3(a))
and magnesium sulfate solution (Fig. 3(b)) were studied 2·1·8 5.47, 4.72, 2.52, 2.00
in this work. From Fig. 3(a), it can be seen that hydration 3.1·1·8 10.09, 5.41, 4.73, 2.54
of a-MgO in LBM can be divided into 3 stages. Stage 1a 1·1·5 9.03, 5.43, 4.84, 4.55
is the pH rapid-raise stage (pH raises from 6.86 to 11.79
during approximately 1 minute). This stage is the forma- 1·2·3 7.23, 5.79, 4.81, 2.98
tion of [Mg(OH)(H2O)x]+ hydration layer on the surface of 4·1·1 3.34, 3.22
MgO and the release of OH– into liquid phase, which can be
expressed by Eq. (1)15-17 Stage 2a is the pH decline stage (pH declines from 11.79
to 11.06 in 11 minutes after Stage 1a). This stage is the
MgO + (x + 1) H2O → [Mg(OH)(H2O)x]+(surface) + OH– (1) formation of Mg(OH)2 (Eq. (2))

[Mg(OH)(H2O)x]+(surface) + OH–(aq) → Mg(OH)2 (2)

ACI Materials Journal/May-June 2014 293

Fig. 3—pH change of: (a) LBM hydration water; or
(b) magnesium sulfate solution (M = 3, R = 0.8).
Stage 3a is the pH slow-raise stage (pH rises from 11.06 to
11.64 in more than 120 minutes after Stage 2a). This stage is
the decomposition of Mg(OH)2 (Eq. (3))
Mg(OH)2(s) → Mg2+ + OH–(aq) (3)
The case is different, however, in the presence of MgSO4,
and the whole process is only divided into two stages—
Stage 1b is the pH slow-raise stage. In this stage, Eq. (1)
and (4) occur simultaneously. Equation (4) consumes partial
OH– released by Eq. (1), which makes the pH rise in Stage
1b more slowly than in Stage 1a.18
Mg2+ + OH– + xH2O → [Mg(OH)(H2O)x]+(aq) (4)
Stage 2b is the pH slow-decline stage. When the concen-
tration of OH– in solution and [Mg(OH)(H2O)x]+ on surface
or in solution increases with a-MgO hydration, the crystal
nucleus (for example, 3 phase) generates and grows to grad-
ually be a complete crystal (Eq. (5) and (6))
3[Mg(OH)(H2O)x]+(surface) + [Mg(OH)(H2O)x]+(aq) + 2OH– +
SO42– → 3Mg(OH)2 ∙ MgSO4 ∙ 8H2O(nucleus) + (4x – 8)H2O
(5)
3Mg(OH)2 ∙ MgSO4 ∙ 8H2O(nucleus)
→ 3Mg(OH)2 ∙ MgSO4 ∙ 8H2O(crystal) (6)
When [Mg(OH)(H2O)x]+ on the surface of MgO and OH–
in solution are slightly excessive, the nucleus and complete
crystal of the Y phase will generate by 3 phase with them
(Eq. (7) and (8))
3Mg(OH)2 ∙ MgSO4 ∙ 8H2O(nucleus) + (y – 3)[Mg(OH)
(H2O)x]+(surface) + (y – 3)OH–(aq) → yMg(OH)2 ∙ MgSO4 ∙
zH2O(nucleus) + [x(y – 3) + 8 – z]H2O (7)
yMg(OH)2 ∙ MgSO4 ∙ zH2O(nucleus)
→ yMg(OH)2 ∙ MgSO4 ∙ zH2O(crystal) (8)
According to the stoichiometric relationship of Eq. (5) or
(7), the molar ratio value of Mg(OH)2/MgSO4 in Y phase or
3 phase is equal to [Mg(OH)(H2O)x]+(surface)/SO42– in chem-
ical equation. The molar value of [Mg(OH)(H2O)x]+(surface)
294
Fig. 4—Effect of fly ash on compressive strength of MOS
cement (R = 0.6, M = 5). (Note: 1 MPa = 6.895 ksi.)
is exactly equal to that of a-MgO (Eq. (1)). Thus, when M
increases from 3 to 5, the Y phase will generate in a large
amount, and 3 phase decreases dramatically. Why does the
content of Y phase crystal decrease when M increases from
5 to a large number (for example, 9)? The reason may be that
after the generation of Y phase nucleus, excessive [Mg(OH)
(H2O)x]+ and OH– will react and form an Mg(OH)2 nucleus,
which may form a coating on the surface of the Y phase
nucleus and inhibit Y phase crystal growth. This coating will
absorb CO2 in air and convert to MgCO3.
Figure 2(b) indicates that the XRD peak intensity of Y
phase reduces at the same M with the increase of R. The
reason is that a lower concentration of SO42– and Mg2+ at
a higher R reduces the generation rate of the Y phase. It is
notable that categories of magnesium subsulfates cannot
be changed by only changing R, because the molar ratio
of Mg[(OH)(H2O)x]+(surface)/SO42– is hardly changed by
changing the water content.
Effect of fly ash on MOS cement
Figure 4 shows the effect of fly ash on the compressive
strength of MOS cement. It was found that the compressive
strength of MOS cement decreases as the dosage of fly ash
increases. The strength decreases from 56.89 to 33.75 MPa
(8.251 to 4.895 ksi) by 39.29% when the dosage of fly ash
increases to 40%.
Figure 5 displays XRD spectra of the MOS cement
containing fly ash. Compared with the cement without fly
ash, there are three obvious changes in phase composition
of the cement with fly ash: 1) the Y phase’s diffraction peak
intensity reduces and that of 3 phase appearance; 2) a mass
of hydrated magnesium silica (MSH) appears, which is
also found in MOC cement in Xu et al.’s study18 and in the
mixture system of MgO and silica fume in low pH19; and
3) the diffraction peak intensity of Mg(OH)2 and MgCO3
decreases dramatically.
Active SiO2 in fly ash can dissolve and convert to hydrated
silica (SiO2·2H2O) in the basic system of MOS cement paste.
In PC,20 hydrated calcium silica (CSH) gel generates through
the reaction between SiO2·2H2O and calcium hydrate. Simi-
larly, in MOS cement, MSH generates through the reaction
of SiO2·2H2O and magnesium hydrate (Eq. (9))
ACI Materials Journal/May-June 2014
 Fig. 7—XRD spectra of MOS cement (R = 0.6) with and
Fig. 5—XRD spectra of MOS cement with or without fly ash. without CA.

Fig. 6—Effect of CA on compressive strength of MSH (R =

0.6) with different M. (Note: 1 MPa = 6.895 ksi.)
3[Mg(OH)(H2O)x]+(surface) + 2SiO2 + 3OH– Fig. 8—pH changes of LBM hydration in magnesium sulfate
(9)
→ 3MgO ∙ 2SiO2 ∙ 2H2O + (3x – 5)H2O solution before final setting in presence of 0.5% CA (M = 3,
R = 0.8).
MSH crystallizes as MSH gel increases. From Eq. (9), the
the generation of Y phase and inhibits 3 phase. In addition,
generation of MSH consumes OH– and Mg[(OH)(H2O)x]+ in
when M = 5 and 7, the diffraction peak intensity of Mg(OH)2
solution, which inhibits the generation of Mg(OH)2 (Eq. (4))
or MgCO3 in MOS cement with CA becomes weak.
and, consequently, MgCO3. The reduction of Mg[(OH)(H2O)
+ + Figure 8 presents the pH change of LBM hydration in
x] leads to the decrease of molar ratio Mg[(OH)(H2O)x] (sur-
2– magnesium sulfate solution before final setting in the pres-
face)/SO4 , which is favorable to the generation of 3 phase.
ence of CA. The case is different from MgO hydration in
Another important effect is that the content of Y phase
magnesium sulfate solution without CA (Fig. 3(b)). The pH
decreases because MSH gel adsorbs onto the surface of the
change can be divided into five stages. Stage 1 is the pH raise
Y phase nucleus and forms the coating, which inhibits the Y
stage (pH increases from 5.86 to 9.40 before 205 minutes).
phase crystal growth such as the effect of Mg(OH)2 stated
In this stage, the acid group ion, CAn–, adsorbs onto the
previously.
magnesia surface to form a type of organic magnesium
hydration [CAn– → Mg(OH)(H2O)x–1]21 (Eq. (10)), besides
Effect of citric acid on MOS cement
Eq. (1) and (5). Amaral et al.22 proved by testing zeta poten-
The effect of the addition of 0.5% citric acid (CA) on the
tial that adding CA can decrease the positive charge of the
compressive strength of MOS cement with different M is
magnesia surface because of the formation of [CAn– →
shown in Fig. 6. The compressive strength of MOS cement
Mg(OH)(H2O)x–1]
increases by adding CA as an additive. When M = 3, 5, and
7, the compressive strength increases by 59.88, 58.45, and
CAn– + [Mg(OH)(H2O)x](surface)
175.64%, to 75.37, 90.14, and 98.79 MPa (10.931, 13.073,
→ [CAn– → Mg(OH)(H2O)x–1](surface) + H2O (10)
and 14.328 ksi), respectively.
Figure 7 shows the crystal phase composition of MOS
It is notable that the pH of MOS cement paste with
cement of with different M, with or without CA. When M = 3,
CA reaches a higher value than that without CA. Taking
the peak diffraction intensity of 3 phase becomes weak, and
into account that adding CA is helpful for the gener-
that of the Y phase becomes strong after adding CA. There-
ation of magnesium subsulfates and the inhibition
fore, it can be inferred that the incorporation of CA benefits
of Mg(OH)2 in MOS cement, it can be inferred that

ACI Materials Journal/May-June 2014 295

Fig. 9—SEM images of MOS cement (M = 7, R = 0.6): (a) without CA; and (b) with CA.
[CAn– →Mg(OH)(H2O)x–1] formed with the participation
of CAn– is more stable than [Mg(OH)(H2O)x]+ in a solution
with a higher pH.
Stage 2 is the pH decline stage (pH decreases from 9.40 to
9.27 between 205 and 230 minutes). This stage may be the
formation process of 3 phase nucleus by consuming OH– in
the solution and [Mg(OH)(H2O)x-1]+ in the surface (Eq. (11))
3[CAn– → Mg(OH)(H2O)x–1](surface) + [Mg(OH)(H2O)x]+(aq)
+ 2OH–(aq) + SO42–(aq) → 3Mg(OH)2 ∙
MgSO4 ∙ 8H2O(nucleus) + (4x – 8)H2O + 3CAn– (11)
Stage 3 is the pH again-raise stage (pH increases from
9.27 to 9.37 between 230 and 250 minutes). According to
Eq. (11), the generation of 3 phase nucleus consumes [CAn–
→ Mg(OH)(H2O)x–1] on the magnesia surface and releases
CAn–. The magnesia continues to hydrate and release
[Mg(OH)(H2O)x]+ and OH–. According to Thomas’s report,
this type of organic metal hydrate, like R-O-Ca-OH,23 can
adsorb onto the Ca(OH)2 nucleus surface, CSH nucleus, and
other metal hydrate, which inhibits their complete crystal
growth in PC. Similarly, [CAn– → Mg(OH)(H2O)x–1] can
adsorb onto the surfaces of 3 phase nucleus and the Mg(OH)2
nucleus and inhibit their growth. This explains the decrease
in 3 phase in the MOS cement with M = 3 and Mg(OH)2 in
the MOS cement with M = 5 or 7.
Stage 4 is the pH alternate-raise-fall stage (between 250
and 560 minutes). This stage can be regarded as the circu-
lation of Stages 2 and 3. In these circulations, a mass of
3 phase nucleus can hardly generate to be complete crystal,
because the 3 phase nucleus reacts with OH– and [Mg(OH)
(H2O)x]+ in the solution or on the surface to eventually form
the Y phase (Eq. (12))
3Mg(OH)2 ∙ MgSO4 ∙ 8H2O(nucleus) + (y – 3)OH–(aq) + (y – 3)
[Mg(OH)(H2O)x] → yMg(OH)2 ∙ MgSO4 ∙ zH2O(nucleus) +
[x(y – 3) + 8 – z]H2O (12)
Stage 5 is the pH rapid-decline stage (after 560 minutes).
In this stage, OH– in the solution is consumed by the growth
of the Y phase nucleus.
Figure 9 displays scanning electron microscope (SEM)
images of MOS cement (M = 7) with or without CA. There
is a mass of flake Mg(OH)2 crystals in MOS cement without
296
Fig. 10—Compressive strength of MOS cement (R = 0.6,
M = 5) containing 40% fly ash with or without CA. (Note:
1 MPa = 6.895 ksi.)
CA; the flake Mg(OH)2 crystals disappear, and plenty of
needle-like crystals appear, which is likely to be the Y phase
in MOS cement with CA.
The effect of CA on MOS cement containing 40% fly ash
has been studied (Fig. 10) to verify the similarity between
[(CAn– → Mg (OH)(H2O)x–1] and R-O-Ca-OHR-O–Ca2+–
OH reported.22 After adding CA, the compressive strength
of MOS cement (containing 40% fly ash) increases from
33.75 MPa to 84.16 MPa (4.895 to 12.203 ksi), which
is close to the compressive strength of MOS cement
(containing CA) without fly ash. One conclusion is that the
addition of CA can also improve the compressive strength of
MOS cement containing fly ash, and can reduce the adverse
effect of adding fly ash. From XRD spectra of MOS cement
containing fly ash with or without CA (Fig. 11), the diffrac-
tion peak intensity of the MSH phase that can inhibit the
growth of the Y phase becomes weak after adding CA. It
can be inferred that [(CAn– → Mg (OH)(H2O)x–1] can also
adsorb onto MSH gel and inhibit its growth like the effect of
R-O-Ca-OHR-O–Ca2+–OH on CSH gel. As the result of this
adsorb-inhibit effect on MSH, the Y phase can grow well.
CONCLUSIONS
Effects of material ratio, fly ash, and CA on MSO cement
have been studied. When the molar ratio of a-MgO/MgSO4
increases from 3 to 5, the compressive strength increases
at the same w/c because of the generation of new magne-
sium subsulfate phase (Y phase). When the molar ratio
ACI Materials Journal/May-June 2014

Fig. 11—XRD spectra of MOS cement (R = 0.6, M = 5)
containing 40% fly ash with or without CA.
increases continuously above 5, however, the compressive
strength decreases because of the reaction between exces-
sive [Mg(OH)(H2O)x]+ and OH– to form Mg(OH)2 coating
that inhibits the crystal growth of the Y phase. At the same
molar ratio of a-MgO/MgSO4, the compressive strength of
MOS cement decreases as the w/c increases. The w/c cannot
change the category of magnesium subsulfate, but can change
the concentration of SO42– and Mg2+ in the cement slurry.
The compressive strength of MOS cement with the addi-
tion of fly ash decreases from 56.89 to 33.75 MPa (8.251 to
4.895 ksi) by 39.29% when the dosage of fly ash increases to
40%, because SiO2 in fly ash can form MSH gel, which can
adsorb onto the surface of the Y phase nucleus and inhibit
its growth.
The compressive strength of MOS cement can be enhanced
by adding CA because of the generation of [CAn– →
Mg (OH)(H2O)x–1]. [CAn– → Mg (OH)(H2O)x–1] can adsorb
onto the surface to inhibit the growth of 3 phase, Mg(OH)2,
and MSH nucleus (if MOS contains fly ash), and can facili-
tate the conversion of 3 phase to Y phase.
MOS cement with high content of Y phase possesses high
strength, which can be obtained by choosing the appropriate
material ratio and additive. In this study, however, the molar
ratio of Mg(OH)2/MgSO4 in the Y phase inferred is more
than 3, and the precise chemical composition and crystal
structure of the Y phase needs to be studied further.
AUTHOR BIOS
Chengyou Wu is a PhD student in the Inorganic Materials Division,
Qinghai Institute of Salt Lake, Chinese Academy of Sciences, Xining,
China. He received his BS from Shandong University, Jinan, China, and
his MS from the Chinese Academy of Sciences Institute, Beijing, China.
His research interests include structures and performance of magnesium
oxychloride and oxysulfate cement.
Hongfa Yu is a Professor in the Civil Engineering College at Qinghai
University, Xining, China, and at Nanjing University of Aeronautics and
Astronautics, Nanjing, China. He received his BS and MS from Shenyang
Engineering University, Shenyang, China, and his PhD from Southeast
University, Nanjing, China. His research interests include durability of
reinforced concrete structures in frozen salt environments.
Jinmei Dong is a Researcher in the Inorganic Materials Division, Qinghai
Institute of Salt Lake, Chinese Academy of Sciences. She received her BS
and MS from Shandong University, and her PhD from Chinese Academy
of Sciences Institute. Her research interests include structures and perfor-
mance of magnesium oxychloride cement.
ACI Materials Journal/May-June 2014
Lina Zheng is a Graduate Student at Inorganic Materials Division,
Qinghai Institute of Salt Lake, Chinese Academy of Sciences. She received
her BS from Xian University, Xian, China. Her research interests include
industrial minerals and processing.
REFERENCES
1. Beaudion, J. J., and Ramachandran, V. S., “Strength Development in
Magnesium Oxysulfate Cement,” Cement and Concrete Research, V. 8, No.
1, 1977, pp. 103-112.
2. Newman, E. S., “Preparation and Heat of Formation of a Magnesium
Oxysulfate,” Journal of Research of the National Bureau of Standards,
V. 68A, No. 6, 1964, pp. 645-650.
3. Li, Z. J., and Chau, C. K., “Influence of Molar Ratios on Properties of
Magnesium Oxychloride Cement,” Cement and Concrete Research, V. 37,
No. 6, 2007, pp. 866-870.
4. Li, H. Q.; Li, G. Z.; and Yu, Y. Z., “The Influence of Compound
Additive on Magnesium Oxychloride Cement/Urban Refuse Floor Tile,”
Construction and Building Materials, V. 22, No. 4, 2008, pp. 521-525.
5. Demediuk, T., and Cole, W. F., “A Study of Magnesium Oxysulfate,”
Australian Journal of Chemistry, V. 10, No. 3, June 1957, pp. 287-294.
6. Urwong, L., and Sorrell, C. A., “Phase Relations in Magnesium
Oxysulfates Cements,” Journal of the American Ceramic Society, V. 63,
No. 2, 1980, pp. 523-526.
7. Kahle, K., “Mechanism Formation of Magnesium-Sulfate Cements,”
Silikatechnik, V. 23, No. 5, 1972, pp. 148-151.
8. Chau, C. K., and Li, Z. J., “Accelerated Reactivity Assessment of
Light Burnt Magnesium Oxide,” Journal of the American Ceramic Society,
V. 91, No. 5, 2008, pp. 1640-1645.
9. Daspoddar, K.; Chowdhury, B. N.; and Basu, R., “Effect of Calcina-
tion Temperature of Magnesium Carbonate on the Properties of Magnesium
Oxides for Use in Magnesium Oxychloride Cements,” Journal of the Indian
Chemical Society, V. 69, No. 9, 1992, pp. 550-551.
10. Birchal, V. S. S.; Rocha, S. D. F.; and Ciminelli, V. S. T., “The Effect
of Magnesite Calcination Conditions on Magnesia Hydration,” Minerals
Engineering, V. 13, No. 14-15, 2000, pp. 1629-1633.
11. Chau, C. K.; Chan, J.; and Li, Z. J., “Influences of Fly Ash on Magne-
sium Oxychloride Mortar,” Cement and Concrete Research, V. 31, No. 4,
2009, pp. 550-551.
12. Li, C. D., and Yu, H. F., “Influence of Fly Ash and Silica Fume on
Water-Resistance Property Magnesium Oxychloride Cement,” Journal of
Wuhan University of Technology—Materials Science Edition, V. 25, No. 4,
2010, pp. 721-724.
13. Dong, J. M.; Yu, H. F.; and Zhang, L. M., “Study on Experimental
Conditions of Hydration Methods of Determining Active Magnesium Oxide
Content,” Journal of Salt Lake Research, V. 18, No. 1, 2010, pp. 38-41.
14. ASTM C109/C109M, “Standard Test Method for Compressive
Strength of Hydraulic Cement Mortars (Using 2-in. or [50-mm] Cube Spec-
imens),” ASTM International, West Conshohocken, PA, 2012, 10 pp.
15. Fruhwirth, O.; Herzog, G. W.; Hellerer, I.; and Rachetti, A., “Disso-
lution and Hydration Kinetics of MgO,” Surface Technology, V. 24, No. 3,
1985, pp. 301-317.
16. Heidberg, B.; Bredow, T.; Littmann, K.; and Jug, K., “Ceramic
Hydration with Expansion: The Structure and Reaction of Water Layers
on Magnesium Oxide. A Cyclic Cluster Study,” Materials Science-Poland,
V. 23, No. 2, 2005, pp. 501-508.
17. Salomão, R.; Bittencourt, L. R. M.; and Pandolfelli, V. C., “A Novel
Approach for Magnesia Hydration Assessment in Refractory Castables,”
Ceramics International, V. 33, No. 5, 2007, pp. 803-810.
18. Xu, K. J.; Xi, J. T.; and Guo, Y. J., “Effects of a New Modifier on the
Water-Resistance of Magnesite Cement Tiles,” Solid State Sciences, V. 14,
No. 1, 2012, pp. 10-14.
19. Tingting, Z.; Cheeseman, C. R.; and Vandeperre, L. J., “Development
of Low pH Cement System Forming Magnesium Silicate Hydrate,” Cement
and Concrete Research, V. 41, No. 4, 2011, pp. 439-442.
20. Harold, H. F. W., Cement Chemistry, Acadmic Press, London, UK,
1990, 123 pp.
21. Salomão, R., and Pandolfelli, V. C., “Citric Acid as Anti-Hydration
Additive for Magnesia Containing Refractory Castables,” Ceramics Inter-
national, V. 37, No. 6, 2011, pp. 1839-1842.
22. Amaral, L. F.; Oliveira, I. R.; Bonadia, P.; Salomão, R.; and Pandol-
felli, V. C., “Chelants to Inhibit Magnesia (MgO) Hydration,” Ceramics
International, V. 37, No. 6, 2011, pp. 1537-1542.
23. Thomas, N. L., and Birchall, J. D., “The Retarding Action of Sugars
on Cement Hydration,” Cement and Concrete Research, V. 13, No. 6, 1983,
pp. 830-842.
297
Reproduced with permission of the copyright owner. Further reproduction prohibited without
permission.