Materials Characterization 54 (2005) 354 359

Microstructure and properties of hercynitemagnesiacalcium

zirconate refractory mixtures
J.E. Contreras, G.A. CastilloT, E.A. Rodrguez, T.K. Das, A.M. Guzman
Doctoral Programme of Materials Engineering, Faculty of Mechanical and Electrical Engineering, Autonoma University of Nuevo Leon,
66450 San Nicolas de los Garza, N.L., Mexico
Received 11 January 2004; accepted 17 December 2004

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

Chemical analysis (wt.%)

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

J.E. Contreras et al. / Materials Characterization 54 (2005) 354359

Table 2
Composition of the different formulation, wt.%
Formulation

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

become more competitive, have implanted new

operational practices based on the use of new fuels
and new raw materials. These practices have a
direct impact on the performance of refractory
bricks as impurities are introduced into the kiln
and their presence may lead to structural and
compositional changes in the refractories, and to
the formation of unstable compounds. These harsh
operational conditions considerably diminish the
service life of the refractory lining, causing kilns
to shutdown more frequently, which causes economic losses due to the decrease of production
levels. It is clear that there is great importance for
both the development and investigation of new
chrome-free mixtures suitable to withstand the
various kiln operation conditions. Besides, they
must compete with refractory bricks used nowadays
not only in regards to properties but also in the
cost-performance ratio.
Taking these aspects into account, the present work
describes a laboratory study on the feasibility to
develop novel refractory combinations based on
magnesia (MgO), calcium zirconate (CaZrO3) and
electrofused hercynite (FeAl2O4), which could serve
as the basis for the production of refractories for the
cement industry.

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.

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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

2A, 2B and 2C). The chemical compositions for each

refractory formulation are shown in Table 2. The
addition of high-purity zirconia was made to avoid
being lime-free in all formulations, since zirconia has
a high affinity for lime to form a high-melting point
compound, calcium zirconate [2].
The mixtures were made by combining the various
compounds in accordance with the compositions
shown in Table 2. Fine particles of 53 Am or less were
used for each raw material. Alcohol was added to bind
the mixtures and aid in holding the shape of the green
samples during subsequent handling prior to firing.
Each refractory composition was formed into cylindrical samples with a diameter of 11.5-mm and a height

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.

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357

Fig. 3. Schematic illustration of hercynite location in boundaries of

MgO and CaZrO3 grains.

of 10.5-mm in a metallic mold; a pressure of 283 MPa

was used. The green samples were then fired in an
industrial tunnel kiln at a temperature of 1650 8C for 7 h
to simulate the real conditions of a refractory brick.
Phase identification of sintered samples was done
by means of powder X-ray diffraction (XRD).
Morphological analysis of the sintered microstructure
was carried out using scanning electron microscopy
(SEM). To appreciate the influence of hercynite as an
additive on both mechanical and chemical properties
of MgOCaZrO3 refractory mixtures, two laboratory

Fig. 5. Effect of electrofused hercynite on cold crushing strength of

MgOCaZrO3 combination.

tests were carried out: cold crushing strength and

chemical attack.

3. Results and discussion

The XRD spectra obtained from each refractory
composition showed the same phases prior to sintering.

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.

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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

This indicates that there was no formation of new

compounds. Diffraction patterns of formulation with
additive (2A, 2B and 2C) did not show the relative
peaks of hercynite, which may be due to the small
amount used; however, chemical analysis confirmed
the presence of the spinel. Fig. 1 compares the X-ray
diffraction patterns of the different formulations after
sintering where the broadening of the peak for CaZ and
CZ can be appreciated.
Fig. 2a shows a SEM image of the sintered
microstructure of the formulation without additive.
A microstructure formed by two well-distributed
phases in the refractory matrix can be observed.
These phases were identified as magnesia (obscure
grains) and calcium zirconate (white grains) according
to energy-dispersive spectroscopy (EDS) analysis
(Fig. 2b and c, respectively). A SEM image at higher
magnification of this formulation is shown in Fig. 2d.
This micrograph shows a good bond between
magnesia and calcium zirconate particles, which is
attributed to the sintering in the tunnel kiln.
Analysis by SEM of formulations with addition of
electrofused hercynite (2A, 2B and 2C) revealed, as in
the formulation without this spinel, the presence of
well-distributed grains of magnesia and calcium
zirconate in the microstructure. Hercynite spinel was
not identified at low-magnifications; however, SEM
analysis at higher magnifications revealed that hercynite was located in the boundaries between MgO
and CaZrO3 particles acting as bond linkage for these
phases (Fig. 3). FeAl2O4 spinel situates by diffusion
in these zones of the microstructure because its
melting temperature is lower than that of both
magnesia and calcium zirconate. Fig. 4a is a high
magnification SEM image of formulation 2C, in
which hercynite spinel is identified in the boundaries
and between the particles of magnesia and calcium
zirconate. This was corroborated by EDS analysis
(Fig. 4b).
It is important to mention that there was no
evidence of either free-lime conditions, nor of any
other new compound in the sintered microstructures

of the refractory formulations according to these

analysis.
The results of cold crushing strength (cold compressive strength) tests carried out on a group of
sintered samples revealed that this property increased
not only when hercynite is added in MgOCaZrO3
refractory mixture, but that this property depends on
the amount of the spinel. Addition of hercynite
permits formation of a stronger bond linkage between
magnesia and calcium zirconate particles improving in
this manner the cold crushing strength. Fig. 5 shows
the effect of hercynite addition on the MgOCaZrO3
refractory combination.

Fig. 6. DTA graph of the formulation attacked with cement raw

meal. (a) Formulation 1; (b) formulation 2C.

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359

penetration of clinker into the sintered samples.

However, the samples were cut and analyzed by
SEM to determine if the sintered microstructure of
each composition had been attacked by cement
clinker. SEM observations revealed that the microstructures of the four formulations were not altered
by the clinker, since no new compounds were
identified by EDS analysis. Fig. 7 is an SEM
micrograph that shows the cross-section of one of
the formulation 2C samples after the test. The
microstructure remained stable in presence of the
clinker compounds.
Fig. 7. SEM micrograph of the cross-section of a formulation 2C
sample. It can be observed that the microstructure was not altered by
clinker phases.

Chemical stability of each formulation in the

presence of cement raw meal was evaluated by the
following chemical attack test. The sintered samples
were ground and mixed with cement raw meal
powders (Table 3); then the mixtures were analyzed
by DTA at a rate of 10 8C/min from ambient
temperature to 1300 8C and were held at this
temperature for 3 h.
According to DTA results, the four refractory
compositions exhibited good chemical stability in
the presence of this type of cement raw meal in this
temperature range. There were no unexpected peaks
detected in the DTA graphs of each composition,
indicating the lack of reaction among sintered samples
and the cement meal compounds to form new phases
(Fig. 6).
In addition to these analyses, chemical attack tests
by the static method were carried out on the sintered
samples to evaluate both the degree of penetration
and the chemical attack by the cement clinker. A
hole was made in the upper face of the samples. It
was filled with cement raw meal and the samples
were held at 1450 8C for 4 h in an electric furnace.
When the test was finished and the samples were
taken out from the electric furnace, it was observed
that the clinker pellet was not strongly adherent, as it
was easily removed when the samples were inverted
upside down. This means that there was no

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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