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Magnesia-Spinel Composite Refractories for Cement Rotary Kilns

Conference Paper · February 2006

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 Magnesia-Spinel Composite Refractories for
Cement Rotary Kilns

A. Ghosh1, Ritwik Sarkar2, B. Mukherjee1

1
Refractories Division,
2
Clay & Traditional Ceramics Division
Central Glass & Ceramic Research Institute, Kolkata, India
e-mail: arup@cgcri.res.in
Abstract
Synthesized stoichiometric Magnesium Aluminate spinel was incorporated to the Magnesite brick
composition in the range of 5 to 30 wt. %. Additive was also introduced in the composition to
facilitate coating adherence with cement clinker. The refractories were fired between1600 o to
1700oC. The products were characterized by physical, mechanical and thermo-mechanical
properties like hot strength, thermal shock resistance etc. Incorporation of spinel greatly
improves the refractoriness under load and retained strength after thermal shock of the magnesia
refractory. Microstructure shows that spinel phase are present in inter granular position between
the periclase grains. 20% spinel enrichment shows optimum properties. The properties are
considered to be suitable against thermal load, alkali and sulphate attack in rotary cement kilns.

Introduction
Cement is generally produced in rotary kilns all over the world. The harshest condition
faced in these kilns is the burning zone, which is mainly lined with Magnesia-chrome
bricks. Recently chrome free bricks like Magnesia-spinel have attracted interest due to
eco-friendlyness and probably better properties [1]. Magnesium aluminate spinel brick is
known to offer a desirable combination of mechanical, chemical and thermal properties
both at ambient and elevated temperatures. Gonsalves [2] observed that bricks
manufactured from natural magnesite and fused spinel grain exhibit higher resistance to
hydration, carbonation, alkali and sulfate attack than the similar product made from sea
water magnesia and sintered spinel.

Portland cement mainly consists of calcium silicates, CA and some low melting ferrites
[3]. The burning zone of these furnaces has a temperature of 1450oC and transition zone
1200o-1300oC. However, the flame temperature is still higher. Therefore, the basic bricks
may even corrode unless a protective coating is formed on the brick.
Mag-Chrome when comes into contact with cement, Fe2O3 and Al 2O3, which may react
with CaO and form low melting compound C4AF. This compound may quickly
crystallize, when cooled down below its melting point and eventually produces coating
layer on the brick surface. Cr 2O3 increases the viscosity of liquid phase and stable coating
will form.

In magnesia -spinel brick, Al 2O3 from the brick form low melting and low viscous CaO-
Al2O3-SiO2 phase with cement and corrode the refractory. However, coating adherence
may be improved by using Fe2O3 and TiO2 in the brick composition [4]. Fe2O3 favours
the brown millerite formation (C4AF) upon reaction with C 3A. While TiO2 forms CaTiO 3,
which improves melting temperature, but lowers spalling resistance.

The addition of spinel in periclase bricks has been again reported [5,6] to improve the
thermal shock resistance, and it is also claimed that two to three times longer service life
can be obtained in cement rotary kilns compared to conventional magnesite-chrome
bricks. The reason for the improved thermal shock resistance is associated with [7,8] the
large difference in the thermal expansion behaviour between magnesia and spinel.

In the present work synthetic magnesium aluminate spinel was prepared through
calcinations in presence of transition metal oxide, then milled to increase fineness
/reactivity. This fine spinel was then added to sintered magnesia grain composition,
replacing finer fraction of magnesia, at an amount of 10, 20, and 30 wt.%. The magnesia-
spinel bricks developed from these compositions were characterized by various physical,
thermo-mechanical and micro-structural properties.

2. Experimental:
Calcined magnesia and calcined alumina were used to develop spinel. The batch
composition with additive was calcined in electric furnace to form spinel. The fired spinel
was then milled in a pot mill.
Milled spinel was finally mixed with sintered magnesia granulometric composition for
brick making. Four different batches were prepared (symbol - A, B, C and D) containing
0, 10, 20 and 30 wt.% of milled spinel respectively (Table 1). Spinel replaces the finest
fraction of magnesia grain in the grain composition. Batches were then mixed with binder
and pressed in hydraulic press to standard brick shape, 230 mm ×115 mm ×75 mm. Then
the green bricks were dried and fired at 1600, 1650 and 1700°C with 2 h soaking time.
The refractory was characterized in terms of bulk density, refractoriness under load,
thermal shock resistance and microstructure.

Table 1. Batch composition (%)

Constituents A B C D
Sintered MgO (0 – 5mm) 100 88 78 68
Milled Spinel 0 10 20 30
Additive 0 2 2 2

Table 2. Physico-chemical properties of the starting materials

Results and discussion

Physico-chemical properties of the starting raw materials (Table 2) show that they are
more than 98% pure. Calcined MgO contains lime and iron oxide as major impurities and
has very little B2O3 content. Calcined alumina has alkali as a major impurity. Specific
gravity and phase analysis of the raw materials for spinel also reflect the higher purity and
specific surface area indicates sub-micron size of the starting materials. Sintered MgO has
also lime and iron oxide as major impurities with very little B2O3 content and sintered to
above 96% of true density. Specific gravity and phase analysis also reflect the high purity
of the material.

Densification:
Bulk density plot of the batches (Fig. 1) shows a little but gradual increase in density
value with increasing spinel content up to 20 wt.%. Increase in sintering temperature is
also beneficial up to 1650 °C, but further increase in temperature does not show any
further improvement. For all the compositions a sintering temperature of 1650 °C was
found to be optimum. Little increase in density value of the sintered products on
incorporation of spinel may be associated with better sintering of the body due to the
presence of fine spinel phase in presence of additive. However the densification study
does not show any significant difference among the batches, which may be due to the
similar true density values for both spinel and periclase phases.

Fig 1. Densification of Magnesia Spinel Refractory

Refractoriness Under Load:

Fig.2 shows that incorporation of spinel in pure magnesia composition greatly improves
the RUL. The spinel content above 20 wt.% shows a decrease in RUL. Use of spinel
powder replacing fine magnesia reduces the chances of low melting phase formation from
impurities. Thus incorporation of spinel reduces the chances of deterioration and
increases the strength against deformation. Moreover, thermal expansion mismatch
between magnesia and spinel phases results in microcracking in the body that helps to
restrict the crack propagation by interlinking during failure.

Fig 2. RUL study of Magnesia Spinel Refractory

Thermal shock resistance

Cold strength (MOR) of the batches show (Fig.3) nearly similar strength values for the
compositions containing up to 20 wt.% spinel. The relatively lower value of 30 wt.%
spinel containing D batch may be due to the large population of microcracks, which can
propagate to failure at a comparatively lower stress level. Introduction of thermal shock
results in a drastic fall in strength value for the batch containing no spinel (A). Thermal
shock imparts cracking in the fired body (A) due to high -value and poor thermal
conductivity, that causes failure at a lower stress level. Microcracks present in the spinel
containing batches prevents the propagation of crack generated during thermal shock, and
thereby increases the retained strength. A large population of microcracks in D batch
causes a lower retained strength value.

Microstructure
The microstructure of magnesia-spinel refractory is shown in Fig,4. Spinel grains are
mainly observed in small sizes and mostly present in the intergranular spaces between the
 Fig 3. Thermal Shock Resistance of Magnesia Spinel Refractory

periclase grains. Exsolved spinel is also observed in Periclase grains. Spinel at high
temperature becomes soluble to periclase, but on cooling spinel comes out of the periclase
grains as exsolved phase.

Fig 4. SEM study of Magnesia Spinel Refractory

 Conclusion
1. Incorporation of spinel greatly improves the refractoriness under load and retained
strength after thermal shock of the magnesia-spinel composite refractory.

2. Microstructure shows spinel as intergranular particles in between the periclase

grains as well as the exsolved phase on the periclase grains. Spinel also causes
significant growth for the periclase grains.

3. Spinel (20 wt.%) containing body showed superior properties. Thermal expansion
mismatch between the periclase and spinel phases causes micro-cracking and
tensile hoop stresses around the spinel grains that strengthens the composite body
by interlinking of microcracks. But the very large extent of microcracking in
30wt% spinel containing body causes extension/propagation of existing
microcrack in the body at a lower stress level resulting in relatively lower
mechanical/thermo-mechanical properties.

4. The coating of liquid phase over the brick surface may be enriched through
introducing transition metal oxide in the brick composition.

5. It may be concluded that for transition zone, reactive spinel with additive in the
magnesia composition is suitable. However, for the burning zone, sintered / fused
spinel may be beneficial for improved corrosion resistance and coating adherence
in the brick.

References
1. D.J. Bray, Toxicity of chromium compounds formed in refractories. Am. Ceram.
Soc. Bull. 64 7 (1985), pp. 1012–1016
2. G.E. Gonsalves, A.K. Duarte and P.O.R.C. Brant, Magnesia spinel brick for
cement rotary kiln. Am. Ceram. Soc. Bull. 72 2 (1993), pp. 49–54.
3. Y. Kajita, F. Ozeki, T. Honda, The present and future of chrome free linings for
rotary cement kilns, J. Technical Association of Refractories Japan, 20 [4] 266-270
(2000).
4. Kaneyasu, Trends of basic refractory raw materials – Magnesia aggregates for
chrome free bricks, J. Technical Association of Refractories Japan, 20 [4] 245-248
(2000).
5. D.R. Wilson, R.M. Evans, I. Wodsworth and J. Cawley, Properties and
applications of sintered magnesia alumina spinels. Proceedings of UNITECR-93
(1993), pp. 749–760.
6. M. Kimura, Y. Uasuda and H. Nishio, Development of magnesia spinel bricks for
rotary cement kilns in Japan. Interceram Special Issue 33 (1984), pp. 344–376.
7. C. Aksel,. R. W. Davidge, P. D. Warren and F. L. Riley, Investigation of thermal
shock resistance in model magnesia–spinel refractory materials, in IV. Ceramic
Congress, Proceedings Book, Part 1, 1998, pp. 193–199, Turkey.
8. Aksel and P.D. Warren, Thermal shock parameters (R, R and R'''') of magnesia–
spinel composites. J. Eur. Ceram. Soc. 23 2 (2003), pp. 301–308

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