Ceramics International 45 (2019) 3459–3464

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effect of magnesia-alumina spinel precursor sol on the sintering property of T

fused magnesia refractory
Qingdong Houa, Xudong Luoa, , Zhipeng Xieb, Di Anb, Xiaofang Zhanga, Zijun Penga
⁎

a
School of High Temperature Materials and Magnesium Resource Engineering, University of Science and Technology Liaoning, Anshan 114051, China
b
State Key Lab of New Ceramics and Fine Processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

ARTICLE INFO ABSTRACT

Keywords: The sintering property of fused magnesia refractory was investigated by the fused magnesia powder as matrix
Magnesia-alumina spinel precursor sol and the synthetic magnesia-alumina spinel precursor sol as binder. The spinel precursor sol was prepared by co-
Fused magnesia refractory precipitation method and was characterized by its particle size, thermal analysis, microstructure, phase devel-
Sintering property opment with temperatures, and so on. The effect of spinel precursor sol on the sintering property of fused
Microstructure
magnesia refractory were studied after heat treatment at 1450 °C and 1550 °C. The results showed that the bulk
density, flexural strength and linear shrinkage of the sintered samples firstly increase and then decrease with
increasing spinel precursor sol. The bulk density and flexural strength (cold modulus of rupture) of the sample
sintered at 1550 °C, introduced with 1 wt% spinel precursor sol, reached 3.10 g/cm3 and 47.25 MPa, respec-
tively. From the experimental results, magnesia-alumina spinel precursor sol can replace the traditional binders
and improve the sintering property of fused magnesia products.

1. Introduction refractory, but it is not suitable to be used in actual production due to

Magnesium oxide is the main component of fused magnesia re-
fractories, which are widely applied in steel making industry due to
good corrosion resistance and high refractoriness under load [1,2].
However, the use of MgO refractory for many applications are restricted
due to its poor sintering performance [3]. Many scholars have done
much work to improve the sintering property of MgO refractory. Robert
et al. [4] investigated that the properties of magnesia improved with
the addition of zirconia. High cold crushing strength, good dimensional
stability, extremely high values of thermal shock resistance and corro-
sion resistance are exhibited for the obtained samples. Eden et al. [5]
found that the sintering process of magnesia improved with the pre-
sence of nano-titania. A fine-grained microstructure with intergranular
second phase particles, significantly raised the mechanical properties of
the MgO with 5 wt% η-TiO2. Yao et al. [6] found that the sintering
activation energy of magnesia decreased with the addition of activated
carbon, because the occurrence of alternating oxidation-reduction re-
action and the rapid diffusion of grain boundary. C. Gómez et al. [7]
investigated that the sintering process of dense magnesia composite are
improved with the addition of Fe2O3 and Al2O3 nanoparticles owing to
the formation of magnesioferrite spinel. The enhancement of bonding
structure are also influenced by nano-iron oxide.
The above researches improved the properties of magnesia
the high cost of some additives and the complex operation process.
Akhilesh et al. [8] found that refractory bonded with a kind of spinel sol
exhibited excellent performance. As is known to all, MgAlO4 is a
technologically momentous material due to its excellent chemical and
thermo-mechanical properties, such as high melt point, excellent cor-
rosion resistance and transmittance, high thermal shock resistance, and
so on [9–11]. Therefore, magnesia-alumina spinel is mainly applied to
refractory in the cement rotary kiln, glass furnace regenerators, steel
teeming ladles, and so on [12]. A lot of investigators used various non-
conventional methods such as hydro-thermal synthesis, co-precipita-
tion, sol-gel process to prepare pure spinel [13,14]. The precursor sol of
magnesia-alumina spinel was prepared by coprecipitation with simple
operation and good dispersion in this paper. Related research reported
[15] that, some precursor sol as a binding agent at normal temperature
can promote the sintering of materials at high temperature. Using the
precursor sol in place of traditional sulfite lye binders can not only
improve the properties of materials, but also satisfy the current global
policy requirements of low carbon environmental protection.
In this work, a novel magnesia refractory was prepared by using the
fused magnesia as the matrix and the spinel precursor sol as binder. The
effect of precursor sol on the sintering property of fused magnesia re-
fractory was characterized.

⁎
Corresponding author.
E-mail address: luoxudong@aliyun.com (X. Luo).

https://doi.org/10.1016/j.ceramint.2018.11.001
Received 7 October 2018; Received in revised form 29 October 2018; Accepted 1 November 2018
Available online 02 November 2018
0272-8842/ © 2018 Published by Elsevier Ltd.
Q. Hou et al. Ceramics International 45 (2019) 3459–3464

Fig. 1. The preparation process of spinel precursor sol.

Table 1
The physical and chemical properties of raw materials.
Constituent MgO CaO SiO2 Fe2O3 Al2O3 Particle Phase
size (μm) analysis

Fused Magnesia 97.47 1.02 0.68 0.45 0.16 75.00 Periclase

(wt%)

2. Experimental procedure

2.1. Synthesis of magnesia alumina spinel precursor sol Fig. 3. Grain size distribution of spinel precursor sol.

The precursor sol applied in this study were obtained using the co- Table 2
precipitation method. For the spinel precursor sol, aluminum sulfate Properties of spinel precursor sol.
(Al2(SO4)3⋅18H2O) and magnesium chloride (MgCl2⋅6H2O) were used
Macro apparent precursor sol sintered at 1000 °C
as raw materials. The specific preparation method was as follows:
Firstly, the magnesium chloride and aluminum sulfate were -dissolved Grain size (range) 35–85 nm
in the deionized water. Subsequently, the magnesium chloride solution, Solid content 39.43%
aluminum sulfate solution and ammonia were mixed to prepare mag- Phase analysis Spinel
Specific surface area 47.12 m2/g
nesium hydroxide and aluminum hydroxide, respectively. After that,
the hydroxide was stirred for 1 h and then filtered to prepare the pre-
cursor. The preparation process of precursor sol is shown in Fig. 1.
2.3. characterization

2.2. Sample making
In this study, fused magnesia with the particle size less than
0.075 mm were used as the raw materials. (Anshan aohai refractories
co. Ltd, China). The physical and chemical properties of fused magnesia
were given in Table 1. Then coped spinel precursor sol (0, 1 wt%, 2 wt
%, 3 wt%) was gradually dispersed into fused magnesia powder with
blending for 10 min. After well stirring, the premix was poured into a
mould and pressed uniaxially under a pressure of 8 MPa in a tablet
machine type 769YP-24B formed a refractory block (φ30 mm × 10
mm, Fig. 2). Finally, the samples were dried at 110 °C for 24 h
(Fig. 2(a)) and sintered at 1450 °C and 1550 °C for 2 h with the heating
rate of 4 °C/min. Fig. 2(b) exhibited the picture of sintered sample at
1550 °C.
The solid content of the synthetic precursor sol was estimated by
loss-on-ignition method on firing at 1000 °C. Thermal decomposition
behavior was evaluated by thermo-gravimetric analysis (STA 449 F3,
Netzsch, Germany). X-ray diffraction (XRD) were used to study the
spinel powder at different temperatures (X′pert-Powder, Netherlands,
Cu Kα-radiation, 40 kV, 40 mA, 0.01°, 10°≤ 2θ≤ 90°). Field emission
scanning electron microscopy (FESEM, ∑IGMA HD, Germany) was ex-
amined the microstructure with energy dispersive x-ray (EDX). The
grain size were measured with 80 grains of spinel precursor sintered at
1000 °C. The bulk density (BD) and apparent porosity (AP) of the
samples was calculated by using Archimedes’ method. The linear
shrinkage of samples was tested (accuracy of 0.02 mm) as per standard
GB/T5072-2008. The flexural strength was measured in a DPK digital

Fig. 2. The picture of the samples (a) dried at 110 °C and (b) sintered at 1550 °C.

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Fig. 4. DSC-TG pattern of spinel precursor powder dried at 60 °C.
Fig. 5. XRD pattern of spinel precursor powder sintered at different tempera-
tures.
display electric strength meter (GB/T3810.4-2016/ISO10545-4:2014,
China).
3. Results and discussion
3.1. Characterization of magnesia alumina spinel precursor sol
The grain size distribution plot of Fig. 3 showed that all the pre-
cursor sol particles were within the size range of 35–85 nm with a peak
around 50 nm. The properties of the synthetic precursor sol were pro-
vided in Table 2.
The DSC-TG pattern of the spinel precursor sol dried at 60 °C was
shown in Fig. 4. The weight loss range of TG curve were about 61.03%.
It could be seen that an endothermic peak at 70–80 °C [16,17] due to
the dehydration of the precursor. The endothermic conversion of
amorphous Al(OH)3 to AlO(OH) at 200–210 °C might be corresponded
to the evaporation of physically bound water [16–18]. The weight loss
between 300 °C and 430 °C was attributed to dehydroxylation of mixed
hydroxides-AlO(OH) to γ-Al2O3 and Mg(OH)2 to MgO [16–19]. The
broad exothermic peak in the temperature range 900–1000 °C was due
to the mass MgAlO4 formed by the solid-state reaction of γ-Al2O3 and
MgO. The endothermic peak formed at 1060 °C was due to the crystal
growth of MgAlO4 [20,21].
The XRD pattern of the spinel powder calcined at different tem-
peratures was shown in Fig. 5. The spinel precursor sol after drying was
nearly amorphous and poorly crystalline under a calcination tempera-
ture of 600 °C. The formation of MgAlO4 by solid-state reaction reduced
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the diffusion path of the particles and enhanced the volume diffusion.
Nano-sized spinel with high specific surface area had high reactivity,
which lowered the temperature of spinellization reaction. The obtained
precursor powder transforms to well crystalline material at and above
800 °C. The further increase of sintering temperature enhanced the in-
tensity of diffraction peak, indicative of spinel crystallite growth [22].
The microstructure of precursor sol sintered at 1000 °C was shown
in Fig. 6(a). It revealed that the particles agglomerated in the field of
view due to the formation of ultrafine spinel particles. The elemental
mapping of microstructural frame (Fig. 6b) showed that nearly homo-
genous distribution of aluminum and oxygen ions all through the mi-
crostructural frame with lesser extent of magnesium ions. EDX analysis
of Fig. 6(c) confirmed that there were only three elements (Mg, Al and
O) in the samples (elemental of Au coming from the gold-sprayed
coating), and the atomic ratio of these elements was consistent with the
structural composition of MgAlO4. Furthermore, the precursor sol sin-
tered at 1000 °C was completely transformed into magnesia-alumina
spinel.
3.2. The effect of spinel precursor sol on the sintering property of fused
magnesia refractory
The effect of different additions of precursor sol on the bulk density
and apparent porosity of samples sintered at 1450 °C and 1550 °C was
shown in Fig. 7(a). The bulk density of sintered samples firstly increase
and then decrease with increasing precursor sol addition at the same
sintering temperatures, but the apparent porosity was of the opposite
trend. The bulk density and apparent porosity of the sintered sample at
1550 °C, introduced with 1 wt% spinel precursor sol, respectively
reached 3.10 g/cm3 and 21.88%. The analysis indicated that there was
a significant relationship between sintering temperature and diffusion
coefficient, among which self-diffusion coefficient (D), pre-exponential
factor (D0), gas constant (R), sintering temperature (T) and self-diffu-
sion activation energy ( G ) satisfied the relational expression (1).
Higher sintering temperature resulted in higher diffusion coefficient of
ions in particles and faster the sintering speed. At certain sintering
temperatures, greater the diffusion coefficient of the substance leaded
to stronger the diffusion capacity of the ions.
G
D = D0exp( )
RT (1)
The addition in spinel precursor sol less than 1 wt%, the precursor
sol particles rapidly diffused into the gap of magnesia particles to im-
prove the densification of matrix and also aided in the sintering of the
samples. However, the addition in spinel precursor sol more than 1 wt
%, the excessive spinel particles decreased the compactness of samples.
This was because the synthetic magnesia-alimina spinel by solid-state
reaction at high temperature with 5% volume expansion hindered the
sintering process [23].
Fig. 7(b) represented the effect of different additions of precursor sol
on the linear shrinkage of samples at different sintering temperatures. It
was observed that higher sintering temperature results in greater linear
shrinkage at the same addition of precursor sol. With the increase of
spinel precursor sol addition, the linear shrinkage of sintered samples
firstly increase and then decrease at the same sintering temperature.
The linear shrinkage of the sample sintered at 1550 °C, introduced with
1 wt% spinel precursor sol, reached 6.34%. It was acknowledged that
there were internal relations among sintering temperature, reaction
rate and linear shrinkage, among which reaction rate (K), material
constant (A), gas constant (R), sintering temperature (T), sintering ac-
tivation energy (Q), linear shrinkage ( L / L ) and time (t) satisfied the
relational expression (2) and (3) [24]. The increase of sintering tem-
perature accelerated the solid-state reaction rate of spinel particles and
periclase particles in the raw material of fused magnesia, promoting the
process of sintering and shrinkage.
Q. Hou et al. Ceramics International 45 (2019) 3459–3464

Fig. 6. (a) Microstructure, (b) elemental mapping and (c) EDX frame analysis of spinel precursor powder sintered at 1000 °C.

Fig. 7. Effect of adding spinel precursor sol on (a) bulk density, apparent porosity and (b) linear shrinkage of samples sintered at different temperatures.

Q
K = Aexp( )
RT (2)

L
ln =K lnt +lnA
L (3)

The effect of different additions of precursor sol on the flexural

Fig. 8. Effect of adding spinel precursor sol on flexural strength of samples
sintered at different temperatures.
strength of samples sintered at 1450 °C and 1550 °C was shown in
Fig. 8. The flexural strength value of samples increased due to the high
combination of spinel particles and magnesia particles with the increase
of sintering temperature. With the increase of spinel precursor sol ad-
dition, the flexural strength of sintered samples firstly increase and then
decrease at the same sintering temperature. The flexural strength of the
sample sintered at 1550 °C, introduced with 1 wt% spinel precursor sol,
reached 47.25 MPa. Based on the variation trend of bulk density, linear
shrinkage after burning and flexural strength at room temperature, a
certain amount of spinel precursor sol promoted the sintering behavior
of the fused MgO refractory matrix, but the volume expansion caused

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Fig. 9. SEM images of fracture surface of the samples sintered at 1550 °C with different formulas (a) 0 wt%; (b) 1 wt%; (c) 2 wt%; (d) 3 wt%.
by excessive spinel precursor sol during the heating process was un-
favorable to the sintering of matrix.
The SEM images of samples fabricated with different additions of
precursor sol were shown in Fig. 9. As could be seen from Fig. 9(a), the
structure of periclase particles was loose due to the presence of obvious
fracture in the samples. In addition, there were partial sintering beha-
vior and a large number of pores among the particles. When the pre-
cursor sol of magnesia alumina spinel was doped, there were traces of
spinel phase participating in solid phase, increasing direct binding de-
gree of magnesia particles (Fig. 4(b)). The microstructure of samples
with 1 wt% spinel precursor sol was the most dense and the less degree
of fracture. It was concluded that the spinel particles formed in the
process of high-temperature sintering diffused to the surface of mag-
nesia particles and the boundary pores, which promoted the sintering of
samples. By Fig. 4(c) and (d), there were a large amount of pores in the
samples with the increase of spinel precursor sol addition. It was ana-
lyzed that the decomposition of precursor sol and the volume expansion
of spinel formed in situ reaction result in the decline in strength and
density of samples sintered.
4. Conclusion
A new magnesia refractory is prepared by co-precipitation method
with the fused magnesia as matrix and the spinel precursor sol as
binder. The effect of magnesia-alumina spinel precursor sol on the
sintering performance of the fused MgO refractory is investigated. The
results show that the sintering of MgO refractory can be promoted with
a certain amount of spinel precursor sol (< 1 wt%). The density of the
sintered samples at 1550 °C, introduced with 1 wt% precursor sol,
reaches to 3.10 g/cm3. Moreover, the microstructure of spinel precursor
sol bonded fused MgO refractory is dense, and the particles are closely
combined to each other. The maximum flexural strength of the sample
is 47.25 MPa.
Acknowledgements
The work is supported by National Natural Science Foundation of
China (51772139).
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