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Abstract
Refractory manufacturers have focused their investigations on the development of chrome-free products that suitably meet the
refractory lining requirements of cement rotary kilns. The experimental development of refractory mixtures based on magnesia
and calcium zirconate, to which electrofused hercynite was added, was carried out in this work. Formulations, in which various
amounts of hercynite were added to study its influence on MgOCaZrO3 microstructure and properties, were prepared. Samples
were obtained by compacting powders and sintering in an industrial tunnel kiln. The samples were characterized via XRD and
SEM. The strength of the refractory was determined at room temperature. Resistance to attack by cement raw meal at 1300 8C
was studied. According to the results, formulations with the addition of hercynite show superior cold crushing strength compared
to those without the additive, moreover, all compositions showed good chemical resistance to the presence of cement raw meal.
D 2005 Elsevier Inc. All rights reserved.
Keywords: Hercynite; Calcium zirconate; Chrome-free refractories
1. Introduction
The manufacture and production of cement
clinker in rotary kilns is one of the most important
industrial processes at world level. Several technological innovations have been developed to lower
costs and increase the production of this process.
Some of these innovations include the development
and use of chrome-free basic bricks suitable to
T Corresponding author. Tel.: +52 81 83294252; fax: +52 81
10523321.
E-mail address: acastill@gama.fime.uanl.mx (G.A. Castillo).
1044-5803/$ - see front matter D 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2004.12.005
Table 1
Characterization of raw materials
Raw materials
XRD
MgO
97.90% MgO
1.64% CaO
0.30% SiO2
72.80% ZrO2
26.50% CaO
52.30% Al2O3
45.70% FeO
1.26% MgO
97.70% ZrO2
2.10% SiO2
MgO
CaZrO3
FeAl2O4
ZrO2
CaZrO3
Ca0.15Zr0.85O1.85
FeAl2O3
ZrO2
MgO
CaZrO3
FeAl2O3
ZrO2
1
2A
2B
2C
78
75.5
75.0
74.5
21.5
21.5
21.5
21.5
2.5
3.0
3.5
0.5
0.5
0.5
0.5
withstand the severe operational conditions occurring within cement rotary kilns. For many years, the
cement industry used magnesia-chrome bricks, since
they were products with excellent refractory characteristics for facing the refractory linings. However, the use of these bricks has been reduced in
many countries due to environmental considerations
and governmental regulations concerning the
chrome-wastes that they generate. Therefore, in
recent years there has been an increase in the
development of chrome-free products for refractory
lining of cement rotary kilns, since they do not
generate dangerous wastes.
At the present time, there are several types of
chrome-free refractory bricks especially developed
to fulfill the demands of the cement clinker process
[19]. However, cement producers, in order to
355
Fig. 1. XRD patterns of the refractory formulations sintered at 1650 8C for 7 h. (1) 0.0% FeAl2O4, (2) 2.5% FeAl2O4, (3) 3.0% FeAl2O4, (4)
3.5% FeAl2O4.
356
2. Experimental procedure
It is well known that the raw material purity of a
refractory brick influences the final characteristics of
the product. High-purity raw material powders were
used in this work (Table 1). It is important to mention
that the calcium zirconate used in this study was
produced in the laboratory using zirconia (ZrO2) and
calcium oxide (CaO) as raw materials.
In order to evaluate the influence of hercynite
spinel on the combination of MgOCaZrO3 phases,
four refractory formulations were prepared, one without addition of hercynite (formulation 1), and the rest
with various amounts of this compound (formulations
Fig. 2. (a) Sintered microstructure of formulation 1; (b) EDS spectrum obtained from the obscure phase identified as MgO; (c) EDS spectrum
obtained from the white phase identified as CaZrO3; (d) sintered microstructure of formulation 1 at a higher magnification.
357
Fig. 4. (a) SEM image of the sintered microstructure of the formulation 2C; it can be appreciated the electrofused hercynite situated between
MgO and CaZrO3 grains; (b) EDS spectrum obtained from the boundaries of magnesia and calcium zirconate grains showing the presence
of the spinel.
358
Table 3
Composition of cement raw meal, wt.%
CaO
SiO2
Al2O3
Fe2O3
MgO
K2O
NaO2
65.8
22.5
4.68
3.87
1.49
0.47
0.06
359
4. Conclusion
This study demonstrated that the addition of
electrofused hercynite improves the cold crushing
strength of MgOCaZrO3 refractory mixtures. All
compositions studied in this work showed a good
chemical stability in the presence of this type of
cement raw meal, as SEM and EDS analyses
demonstrated that the microstructure was not altered.
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