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A Study on Spinel Formation and Sintering Behavior of Ozan Uylas,, Muharrem Timuin, Ender Suvac,
Al2O3-MgO System for Induction Furnace Linings Muammer Bilgi5, Beyhan zdemir4, Oktay Uysal,
Uur Cengiz5, zkan Kurukavak4, Hasan Erdoan4,
Yakup Yalnkaya4
Anadolu University, Entekno Endstriyel Ltd. ti.,
Middle East Technical University, 4Ktahya Manyezit Sanayi A..,
5Bilecik Demir elik A.. - Trkiye

Abstract SiO2, MgO and Al2O3 based Dry vibrating mixes for
linings of induction furnaces may be based on silica,
Alumina (Al2O3) is the most fashionable material for magnesite or alumina. Due to high working temperature
producing neutral linings of induction furnaces used in and slag chemistry, SiO2 based and MgO based
steel industry. This type of lining has very high melting refractories not favorable in steel melting induction
temperature, high strength, high hardness, and relatively furnaces [4]. In contrast, alumina based neutral linings
high resistance to slag attack. In induction furnace featuring in situ MgAl2O4 spinel forming capability have
applications chemical durability, thermal shock become materials of choice due to their high thermal
resistance, and mechanical strength of Al2O3 based shock resistance, high corrosion resistance, longer
neutral linings can be improved by direct addition of pre- service life, and high chemical stability in both acidic and
reacted spinel (MgAl2O4), or by adding fine MgO to basic media [5,6].
form an in situ spinel phase. When using in situ spinel
forming alumina based neutral linings factors such as MgAl2O4 spinel is called as mullite of 21st century
control of spinel formation kinetics, distribution of the because of its outstanding chemical, thermal, and
spinel phase in the microstructure, and sintering kinetics mechanical properties [7]. It maintains its lattice
in the Al2O3-MgO system are critical issues. structure even at elevated temperatures. In alumina
Accordingly, the objective of this research was to study based refractories differences between thermal expansion
the spinel MgAl2O4 formation behavior and the sintering coefficients of alumina and spinel creates microcracks in
of alumina based Al2O3-MgO type induction furnace microstructure. The microcrack network imparts a
ramming materials in terms of the controllable variables toughening mechanism and improves mechanical
like particle size distribution in the ramming mix, properties of the refractory body [8]. The in situ spinel
sintering temperature, and sintering time. formed in the alumina ramming mix at service
temperature has a defective structure with a tendency of
1. Introduction forming substitutional solid solutions while in contact
In steel industry, refractories gain importance for many with molten steelmaking slag [9]. When Fe2+ and Mn2+
reasons, including product quality, energy saving, and cations migrate into A-site of spinel they form (Mg, Mn,
cost effectiveness. About 75 percent of world refractory Fe)O(Al, Fe)2O3. Also Ca2+ cations in the slag react with
production is consumed in iron and steelmaking. In excess Al2O3 for forming Hibonite (CA6). Depletion of
recent years, induction furnaces have become MnO, FeO and CaO causes increment in relative SiO2
indispensible tools of melting units for the steel industry content of the slag which limits the slag penetration and
owing to their high efficiency, low energy consumption, thereby reduces slag corrosion [9, 10]. Although spinel is
easy operational control, and compatibility with a vast known to exhibit superior properties in refractory bodies
variety of scrap types [1-3]. In induction furnaces the the knowledge on the formation of in situ spinel and
most preferred refractory lining type is dry vibrating sintering behavior of alumina based Al2O3-MgO dry
mixes. This is due to their ease of application, low cost of vibrating mixes is still far from being complete.
lining production, and absence of junction points [4]. Preliminary studies on Al2O3-MgO refractory systems
have concentrated on Al2O3-MgO castables or on
ceramic systems with fine particle size [11, 12].

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The success of neutral ramming mixes in steel melting change (PLC) in dimensions of the sintered bodies. PLC
induction furnaces depends critically on the formation of in neutral ramming mixes is an important index, because
in situ spinel during service. A better understanding of in addition to dimensional change it provides clue on
spinel formation and sintering kinetics is essential for sintering behavior and sintering depth. Phases in the
designing Alumina based Al2O3-MgO spinel forming dry sintered specimens were determined by powder XRD
vibrating mixes for induction furnace linings with techniques, using an X-ray difractometer (Rigaku Rint
improved thermal, chemical, and mechanical properties 2200) with Cu - K
radiation.
compared to those in the commercially available
products. The objective of this study is to examine the Spinel transformation rates were calculated according to
effect of particle size range, sintering time and sintering Eqn. (1) which is an internal standard method based on
temperature on spinel formation and sintering behavior ratio of highest intensity peaks of the components
of these particulate refractories. periclase (200), corundum (113), and spinel (311) in their
XRD patterns [13].
2. Experimental Procedure
Fused Al2O3 and sinter MgO with particle size 0-5 mm  
 
 

and 0-500 m were used as raw materials. Particle size  









(1)
range of the raw materials resemble those in commercial
dry vibrating mixes. Particle size range in experimental
mixes, designated as K1, K2, K3 and K4, was defined as Definition of particle
shown in Table 1. size of raw materials

Weighing and
Name of Particle Size Particle Size Mixing
Compositions of Al2O3 of MgO

Pressing of
K1 0-5 mm 0-500 m
mixtures

K2 0-500 m 0-5 mm Measuring

dimensions

K3 0-5 mm 0-5 mm
Sintering

K4 0-500 m 0-500 m

Table 1. Compositions and particle size range of raw materials. Sintering Sintering Time
o
Temperature 1550 C(1h, 2h, 3h, 4h)
Flow chart of the experimental procedure is shown in 1350,1450, o
Fig. 1. According to the flow chart experimental o 1650 C(1h, 2h, 3h, 4h)
1550, 1650,1700 C o
compositions were mixed with stoichiometric molar ratio 1700 C (1h 2h 3h 4h)
of Al2O3 to MgO in a rotating high density polyethylene
(HDPE) bottle, then pressed uniaxially under 150 bar
into the form of cylinders measuring 50 mm in diameter Characterisations
and 50 mm in height. The cylindrical compacts were
sintered at temperatures in the range 1350 C to 1700 C.
The longest dwell time at the peak sintering temperature
was 4 hours. Samples fired at 1550, 1650, and 1700 C % Permanent
Linear Change XRD
were withdrawn from the furnace at 1 hr intervals. The
sintering operation was carried out in a programmable (PLC)
muffle furnace heated by MoSi2 elements.

The dimensions of the samples were measured before Calculation of

and after sintering for determining the permanent linear Phase Phase
Analysis Transformation
Rate

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PLC determination is important for understanding the

thermo-mechanical behavior of neutral ramming mixes in
Fig. 1. Summary of experimental procedure the induction furnace. The results of calculations on PLC
values of sintered bodies in the present study are shown
3. Results and Discussion in Fig. 3.
3.1. Spinel Conversion Rate

Spinel conversion rate is important in understanding the   
 




spinel formation mechanism. The spinel conversion rates

of experimental compositions are shown in Fig. 2. It can
be seen that K4 has the highest spinel conversion rate at
all temperatures. K1 follows as the the second highest in
conversion rate, while K2 and K3 exhibit the least
conversion rates. The conversion rates of the latter two
compositions are very close to each other for all sintering
temperatures.   


These results show that particles size of components has Fig 3. PLC values of compositions according to temperature
a major effect on spinel conversion rate. When we
compare the conversion rates of K1 and K2 it can be seen In case of experimental mix K1, until 1650C volume
that particle size of MgO is predominant. With fine expansion due to spinel formation is dominant
MgO the rate is higher. As MgO gets coarser the effect mechanism on PLC behavior, above this temperature K1
of particle size of Al2O3 on conversion kinetics becomes starts to shrink, because the dominant mechanism shifts
lesser. to densification instead of volume expansion. When K2
is compared with K1, the expansion is lesser, and the
sintering shrinkage starts at 1550C. Hence, when Al2O3
particles are coarse the spinel formation becomes slower

 


and densification mechanism of sintering becomes
effective on PLC at lower temperature.

The details of the PLC behavior were studied at

temperatures 1500, 1650 1700C for sintering times at
peak temperature between 1 to 4 hours. The results of
PLC determinations obtained under these conditions are
shown in Fig. 4, Fig. 5, and Fig 6, at 1500C, 1650 C,
and 1700 C, respectively.
  


Fig. 4 shows that at 1550C, in K4 which has both Al2O3

Fig. 2. Spinel conversion rate of compositions according to temperature and MgO particles in fine fraction, the PLC exhibits a
maxima at hours of firing, therefore at this temperature
These results show that the Wagner mechanism [14],
initially the spinel formation mechanism is dominant. In
which explains spinel formation mechanism in fine MgO
fact, within 2 hours all reactants are transformed totally
+ Al2O3 particulate mixtures, works for the dry vibrating
into spinel phase. Following the maxima in PLC, the
mixes used in the present study.
sintering shrinkage takes over. At 1550 C, the
3.2. Permanent Linear Change compositions show relatively moderate PLC values.
Interestingly, however, these mixes maintain their PLC at
PLC represents a combination of dimensional variations longer retention times at temperature.
due to sintering shrinkage and volume expansion
encountered during spinel formation. Because of
differences in density of MgO, Al2O3, and MgAl2O4
phase the thermal synthesis of spinel is associated with a   
 




volume expansion [15]. The magnitude of this expansion

is governed by the particle size of the components MgO
and Al2O3. Thus, PLC can be controlled and monitored
by adjustments in particle size distributions.

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18. Uluslararas Metalurji ve Malzeme Kongresi | IMMC 2016
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Fig 4. PLC values for 1550C
Fig. 5 shows that when firing temperature is raised to
Fig 6. PLC values for 1700C
1650C the spinel conversion rate in the mixture
designated as K4 becomes very high, therefore 4. Conclusion
spinelization occurs within a very short period followed
by sintering shrinkage. Thus, negative PLC values are The focus of the present study was examining the effect
encountered due to the dominant mechanism of
of parameters like particle size, firing temperature, and
densification. In the early stages of thermal exposure,
firing time on the spinelization and sintering kinetics of
the mixes K1, K2, and K3 all develop certain amount of
stoichiometric particulate mixtures of MgO and Al2O3.
spinel phase within a period shorter than 1 hour. This is
The results are important for the design of neutral
because of the fact that, in the early stages, the spinel
ramming mixes of induction furnace linings. It is known
formation is faster than densification. Pass this period, that in neutral type dry vibrating mixes spinel formation
the spinel formation in mixture K1 continues with rising and sintering are two competing mechanisms.
PLC. The other mixtures attain a stable PLC which may Spinelization is important because it provides the bonds
indicate that the spinel formation and densification rates necessary for strength development in the lining.
are almost equal Shrinkage determines the level of microstructure
development. Present study revealed that MgO particle
size plays a key role in the spinelization and sintering
processes. The rates of these may be kept under control
by adjusting the temperature. Thus linings with different
internal structures may be produced.



 


These investigations provide fundamental knowledge for

producing alumina based spinel forming induction
furnace linings with controllable mechanical, chemical
and thermal properties.

References

[1] Lil, X.C., Wang,T.X., Zhu B.Q., Effect of Electromagnetic Field on

    the Slag Resistance of MgO-C Refractories, IOP Conf. Series:


Materials Science and Engineering 18, 2011.
Fig 5. PLC values for 1650C [2] Stark, R. A., Optimizing Induction Furnace Refractories, Modern
. Casting , June 1, 1994
[3] Refractory failure in induction furnaces can be
Fig. 6 shows that, at 1700C, for K4 the volume change limited.http://www.thefreelibrary.com/Refractory+failure+in+induction
behavior is same as the one observed at 1650C. The +furnaces+can+be+limited.-a010913837
remaining mixes attain a higher level of spinelization in [4] Reference of Furnace Lining, Anonim.
the early stages. Later in the firing process, in all [5]A. Bahatia, B.E., Overview of refractory materials, 2011
[6] Krause.T., Rieke K., Use of Spinel Forming Dry Vibrating Mixes in
mixtures densification becomes dominant over spinel 20-40 t Crucible InductPon Furnaces Anonim.
conversion so that shrinkage, at a low overall rate, occurs [7] R.C. Bradt, MgAl spinel: is it the mullite of 21st century?
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[8]Zhang, S., Lee, W.E., Spinel Containing Refractories, Refractories
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[9] Matsumoto, O., Isobe, T., Nishitani, T., and Genba, T., Alumina-
spinel monolithicrefractories. US Patent 4 990 475 (1991).



 


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Bildiriler Kitab TMMOB Metalurji ve Malzeme Mhendisleri Odas

[10] Kurata, K., Matsui, T., and Sakki, S., Castable lining technique to
bottom of teeming ladle, Taikabutsu Overseas, 12, pp.29 39 (1992).
[11]Sako E.Y., Braulio M.A.L., Zinngrebe E., van der Laan S.R.,
Pandolfelli V.C., Fundamentals and Applications on in situ spinel
formation mechanisms in Al2O3-MgO refractory castables, Ceramics
Internatioal, , 38, 2243-2251, 2012
[12]Braulio, M.A.L., Bittencourt, L.R.M., Pandolfelli V.C., Magnesia
grain size effect on in situ spinel refractory castables, Journal of the
European Ceramic Society, 28, 2845-2852, 2008
[13] Domanski, D., Urretavizcaya, G., Castro,F.J., Gennari, F.C.,
Mechanochemical Synthesis of Magnesium Aluminate Spinel Powder
at Room Temperature 87, 11, 2020-2024, 2004
[14]C. Wagner, The mechanism of formation of ionic compounds of
higherorder (Double salts, spinel, silicates), Zeitschrift Fur
Physikalische Chemie B34 , 209316, 1936
[15] R.E. Carter, Mechanism of solid-state reaction between
magnesium oxide and aluminum oxide and between magnesium oxide
and ferric oxide,Journal of the American Ceramic Society 44 (3) 116
120, 1961.

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