Materials Chemistry and Physics 86 (2004) 399–408

Thermochemical stability of spinel (MgO·Al2 O3)

under strong reducing conditions
M.A. Sainz a , A.D. Mazzoni b,∗ , E.F. Aglietti b , A. Caballero a
a Instituto de Cerámica y Vidrio (CSIC), Campus de Cantoblanco, Camino de Valdelatas, S/N—28049, Madrid, Spain
b Centro de Tecnologı́a de Recursos Minerales y Cerámica (CETMIC, CONICET-CICPBA-UNLP) Camino Parque Centenario y 506,
CC 49 (B1897ZCA) M.B. Gonnet, Prov. Buenos Aires, Argentina
Received 23 April 2003; received in revised form 20 June 2003; accepted 12 April 2004

Abstract
The thermochemical stability of the main refractory oxides and some of their compounds under strong reducing conditions has become
increasingly important in recent years. In the present work, the formation, sintering and stability of magnesium–alumina spinel (MgAl2 O4 )
under very low oxygen partial pressure were studied using Ellingham diagrams. Reduction processes of spinel at high temperatures
1500–1650 ◦ C were discussed. The experimental treatments were carried out with spinel and equimolar mixtures of MgO and Al2 O3 .
The effect of the oxygen partial pressure on stability of spinel was evaluated using different atmospheres: air (PO2 = 0.21 atm), CO/CO2
(80/20), PO2 < 10−10 atm), CO (PO2 < 10−15 atm) and C–CO (PO2 < 10−20 atm). Finally, the results were compared with the experimental
observations of spinel formation in MgO–C refractories with the addition of aluminium.
© 2004 Elsevier B.V. All rights reserved.
Keywords: Spinel; Stability; Sintering; Reducing atmospheres; Volatilization

1. Introduction the formation of high density materials, therefore, an in-

termediate calcination operation is necesary to obtain high
Magnesium–alumina spinel (MgAl2 O4 ) is one of the com- density spinel bodies [5]. It was found [6] that a partial re-
mon compounds in a family of mixed oxide spinels having a action (55–70% completion) of the oxides was enough to
cubic structure [1]. This compound offers a good combina- overcome the volume expansion barrier while they could re-
tion of physical and chemical properties, such as high melt- tain enough reactivity at sintering temperatures lower than
ing point, high resistance to chemical attacks, high mechan- 1640 ◦ C.
ical strength, permitting its use in metallurgical, cement and Although several works about spinel had been published
glass industries, etc [2,3]. This spinel is a crystalline phase [7,8], its formation and thermochemical stability at very low
which is important to the life of magnesia–graphite refrac- oxygen partial pressure were not well established.
tories at high temperatures containing aluminium metal as The thermochemical stability of oxide/non oxide refracto-
antioxidant. ries under strong reducing conditions has recently become of
The preparation of spinel can be made by reaction of mag- great importance due to the use of carbon as a component of
nesium and aluminium compounds. When relatively cheap high performance refractories. Applications such as vacuum
raw materials, such as burned magnesite, sea water magne- melting of steels, melting of alloys or the behaviour of ox-
sia, calcined alumina or gibbsite were used, the minimun ide/non oxide refractory materials, as MgO–C, with or with-
calcination temperature necessary to obtain complete con- out metal additions are examples of the importance of the
version was about 1450–1600 ◦ C [4]. The reaction of MgO reducing conditions on the refractory materials stability [9].
and Al2 O3 to form spinel is accompanied by a volume ex- The sintering of spinel has been mainly studied in air at-
pansion of approximately 5%, this volume expansion stops mosphere. It is well known that reducing atmospheres cause
the reduction and volatilization of Mg from MgO. This fact
∗ Corresponding autor. Tel.: +54 221 484 0247/0167;
can be easily verified in thermodynamic studies and it is
fax: +54 221 471 0075.
frequently observed in ceramics and refractories based on
E-mail addresses: [email protected], MgO at high temperature [10]. However, there exists few
[email protected] (A.D. Mazzoni). data and studies of the magnesium spinel behaviour under

0254-0584/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2004.04.007
400 M.A. Sainz et al. / Materials Chemistry and Physics 86 (2004) 399–408

reducing atmospheres with respect to its stability as well as

its microchemistry.
In the present work, the thermochemical stability and
its influence on the stoichiometry of the magnesium spinel
at high temperature under strong reducing conditions were
studied. The behaviour of this compound in reducing atmo-
spheres of different PO2 was observed. Experimental tests
were carried out to study the formation, sintering and sta-
bility of synthetic spinel and equimolar mixture of alumina
and magnesia under low oxygen partial pressure.

2. Structure and thermodynamic considerations

Fig. 1. Ellingham diagram for the oxidation-reduction equilibria occurring
The spinel structure occurs in many systems as magnetite in an equimolecular mixture of MgO and Al2 O3 at PMg = 1.0 atm and
in the Fe–O system, hercynite in the Al2 O3 –FeO system, pi- at PMg = 10−4 atm.
crocromite in the MgO–Cr2 O3 system, etc. In normal spinel
the oxygen ions form a face centered cubic (fcc) structure
with aluminium ions occupying one-half of the octahedral tions corresponding to various plots can easily be identified
interstitial sites and magnesium ions occupying one eighth from the phases occurring in the adjacent fields. Then, the
of the tetrahedral sites. This configuration changes when boundary line between the fields labelled as “MgO + Al”
normal spinel is heated at high temperature; aluminium and represents the reaction:
magnesium ions start to change sites giving rise to a random
3 MgO(s) + 3 Al(l) +O2 ⇔ 23 MgAl2 O4(s)
2 4
distribution of the cations and under cooling this distribu- (1)
tion persists. This means that thermodynamic properties of and that between the fields labeled as “Mg + Al2 O3 ” and
the spinel depend on its cation distribution. “MgAl2 O4 ”
The cation distribution in stoichiometric spinel has been
measured by Wood et al. [11]. They found that below 723 ◦ C 2Al2 O3(s) + 2Mg(g) + O2 ⇔ 2MgAl2 O4(s) (2)
the redistribution of the cations was almost negligible and
that above 923 ◦ C a considerable redistribution took place and finally between the fields labelled as “Al + Mg” the
during quenching. Therefore, the approximate equilibrium reaction is
cation distribution was observed in the samples heated above 1
+ Al(l) + O2 ⇔ 21 MgAl2 O4(s)
2 Mg(g) (3)
923 ◦ C and quenched. At room temperature the equilibrium
distribution must be normal in accordance with what was According to White [15] deductions it could be observed
found in samples of natural spinel. that at PMg = 1.0, the reduction of MgAl2 O4 at temperatures
The Gibbs formation energy of stoichiometric spinel below 1450 ◦ C took place following the reaction (1) obtain-
from oxides has been measured by Taylor and Schmalzned ing MgO(s) + Al, whereas at temperatures above 1650 ◦ C it
[12] at low temperature (530 ◦ C). The value obtained (G gave Mg(g) + Al2 O3 . It is very important to notice the strong
= −10 kJ mol−1 ) is higher than the results obtained by influence of the magnesium partial pressure on the temper-
Rosen and Muan [13] who had calculated the formation atures at which the reactions occurred. At PMg = 10−4 atm
energy of spinel using rather extensive simplification em- these temperatures were lowered up to 1060 and 1280 ◦ C,
ploying mixtures of MgO, CoO and Al2 O3 . The value respectively.
obtained by these authors (G = −37 kJ mol−1 ) is in good The volatility diagram of magnesia–alumina spinel was
agreement with that calculated by Haldsted [14] based on made using the thermodynamic data of: alumina, magne-
the thermodynamic assessment of the MgO–Al2 O3 system sia and spinel. Fig. 2 shows such diagram that represent
(G = −42.5 kJ mol−1 ). the different equilibria as a function of the temperature, the
It is well known that the Gibbs formation energy of a com- oxygen partial pressure and the partial pressures of the dif-
pound from the elements is extremely lower compared with ferent species that may be formed during reduction. From
the formation energy from oxides. Employing the JANAF this diagram it can be deduced that at high temperatures,
tables, the G0 of MgAl2 O4 formation from the oxides T > 1250 ◦ C and at oxygen partial pressures between 10−10
at 1400 ◦ C is near – 25 kJ mol−1 . White [15] studied var- and 10−20 atm, the spinel decomposition would lead to the
ious oxidation reduction equilibria in equimolecular mix- formation of Mg gas, Al gas or AlO2 gas.
tures of MgO and Al2 O3 (Fig. 1) and observed that the G Finally, the studies performed by Guba [16] in the
of MgAl2 O4 formation at two different Mg pressures (1.0 Mg–Al–O–C system in argon atmosphere (PO2 < 10−3 atm)
and 10−4 atm) was lower than −669 kJ mol−1 . This author permitted to determine the compatibilities in solid state of
defined the phases occurring in different fields and the reac- the spinel up to 1600 ◦ C. This author found that the spinel,
 M.A. Sainz et al. / Materials Chemistry and Physics 86 (2004) 399–408 401

mum temperature was of 2 h. Samples were put into an alu-

mina crucible and were so put inside an alumina closed tube
(sintering) that was heated in Si2 Mo furnace. The temper-
atures were controlled by thermocouple of Pt–Pt Rh (Type
B). Gases, dry air, CO/CO2 (80/20) mixture and CO (car-
bon monoxide) circulated through the tube. The purity of
these gases and mixtures were all of 99.8%. The flow rate of
these gases was near 1.0 l min−1 at a pressure of 0.2–0.4 atm.
Pressures and gas flow were controlled with a manometer
and with ball flowmeters respectively. The oxygen partial
pressures are: air PO2 =0.21 atm; CO/CO2 : PO2 = 10−10 atm
and CO PO2 = 10−15 atm. Dense BA spinel (>98% theo-
retical density) blocks were obtained by isostatic pressing
at 200 MPa and firing at 1600 ◦ C for 4 h. Plates of 10 mm
× 10 mm × 2 mm were diamond machined from the spinel
blocks and the surfaces were subsequently polished up to
Fig. 2. Volatility diagram of Mg–Al spinel. 1 ␮m.
Carbon containing inks were obtained by mixing ethylene
under the conditions studied here, is compatible with carbon glycol and carbon powder with 1% deflocculant in an agate
and with the different phases appearing in the system. mortar. The carbon containing inks were screen printed, on
the different spinel structures and then dried at 60 ◦ C for
48 h. The samples, packed around with carbon, were placed
3. Experimental into closed alumina crucibles. Then, samples were fired in
air at temperature ranging from 1250 to 1600 ◦ C for 4 h.
A16SG calcined alumina (ALCOA Aluminium Co., Polished cross sections of all specimens were studied. Un-
>99.55 purity; average particle size d50 =0.5 ␮m and spe- der these conditions (C–CO atmosphere) the PO2 was near
cific surface area (BET) Sg = 9.0 m2 g−1 ), magnesium hy- 10−20 atm.
droxide (analytical grade >99.85% purity, d50 = 35 ␮m and DTA–TG analyses were carried out using a Netzsch STA
Sg = 5 m2 g−1 ), magnesia–alumina spinel BA (Baikowski 409 equipment.
>99.5%, d50 = 0.4 ␮m and Sg = 49.4 m2 g−1 ) and carbon The Hg picnometry method was used to determine
(Asbury Micro 750: >98% purity, d50 = 3–5 ␮m) powders densities. XRD patterns were obtained using a PW 1140
were used as starting materials. diffractometer. Diffraction peaks were indexed according to
Stochiometric spinel was prepared from equimolar mix- powder diffraction file data card of MgAl2 O4 spinel [17].
ture of aluminium oxide and magnesium hydroxide in sto- The lattice parameters were determined by the Rietveld
ichiometric composition. The mixture was homogenized in method [18], using all reflections of the compound, the
a ball mill for 4 h. Alumina balls and 0.1% of deflocculant error was of ±0.002 A. A SEM was used for microstruc-
were used. The suspension was vacuum filtered and dried at tures and photographs. A EPMA equipment was employed
60 ◦ C. The dried mixture was passed through a 60 ASTM for chemical analysis. The results obtained came from the
sieve. The EE spinel was obtained by calcination of the mix- average of three different determinations.
ture at 1300 ◦ C, without soaking time.
Table 1 shows the chemical analyses of BA spinel and
the resultant EE spinel. Both spinels are near stoichiometry. 4. Results and discussion
XRD patterns show that BA had MgO as a second phase.
The EE spinel contains MgAl2 O4 as the only phase present. 4.1. Spinel formation
EE and BA spinels were isostatically pressed at 200 MPa
in cylinders of 5 mm (diameter) and 10 mm length for sin- The formation of the equimolar spinel EE from mag-
tering process. No pressing additives were used. nesium hydroxide and alumina in air was studied. Fig. 3
Thermal treatments and sintering were performed at a shows DTA–TG analyses of the mixture, where the en-
heating rate of 5 ◦ C min−1 . The soaking time at the maxi- dothermic bands observed at 269 and 435 ◦ C were attributed

Table 1
Chemical analysis of spinels
Sample (%) Al2 O3 MgO SiO2 CaO Na2 O K2 O TiO2 P2 O5 LOI Fe2 O3 MgO + Al2 O3
BA 71.90 26.01 0.16 0.20 0.005 0.011 0.004 0.001 0.39 1.11 97.91
EE 71.69 27.83 0.17 0.17 0.03 0.02 <0.01 <0.01 0.60 0.06 99.52
402 M.A. Sainz et al. / Materials Chemistry and Physics 86 (2004) 399–408

Fig. 3. DTA–TG of equimolecular alumina–magnesia mixture.

to dehydration and brucite decomposition, respectively. At (not shown) indicated that brucite decomposition causes a
1055 ◦ C a small exothermic effect was detected associated small contraction near 400 ◦ C. Then, the expansion due to
with nucleation and formation of spinel by reaction be- spinel formation begins at 950 ◦ C. The total expansion of
tween alumina and magnesia. This fact was confirmed by the bar reached 5% of the initial length and finished near
dilatometric and XRD diffraction studies. The dilatometry 1300 ◦ C [19]. It could be concluded that spinel formation

Fig. 4. Rietveld plot for EE mixture treated at 1300 ◦ C.

 M.A. Sainz et al. / Materials Chemistry and Physics 86 (2004) 399–408 403

was completed at 1300 ◦ C (XRD). Fig. 4 shows diffrac- parameter ao for both spinels at 1650 ◦ C and the densities
tograms of EE spinel, no MgO or Al2 O3 unreacted were obtained during sintering.
present. The crystalline phases in the sintered samples were ana-
The EE spinel formation was carried out in CO/CO2 and lyzed with XRD. Sample EE showed spinel as the unique
CO atmospheres up to 1300 ◦ C. The mechanism of spinel crystalline phase present.
nucleation and formation was similar to that occurred in air The BA spinel sintered in CO did not present free MgO or
previously described. It can be concluded that no appreciable Al2 O3 at 1500 ◦ C as well as at 1650 ◦ C (XRD); this spinel
differences in the process of spinel nucleation and formation presents MgO as minority phase at the same temperatures
were observed by comparing XRD phase evolution under in air.
both conditions. XRD results only showed stoichiometric The lattice parameters (ao ) measured at 1500 and 1650 ◦ C
spinel with a lattice parameter for EE of ao = 8.082 A in the were very near to the stoichiometric spinel (ASTM standard
three experimental conditions employed (air, CO/CO2 and ao = 8.083 A) EE = 8.082 A and BA = 8.079 A, this indi-
CO). cates that the sintering in air did not produce stoichiometric
changes.
4.2. Sintering in air and reducing atmospheres Fig. 5 shows that ao remains approximately constant
when air or CO/CO2 are employed. The ao decreases
EE spinel obtained at 1300 ◦ C and the BA spinel were at PO2 = 10−15 atm (CO). Thus, at 1650 ◦ C and at PO2
sintered in different atmospheres (air, CO/CO2 and CO) at = 10−15 atm (CO) the ao values were 8.074 for EE and 8.046
1500 and 1650 ◦ C. Fig. 5 shows the evolution of the lattice for BA, indicating a slight shift towards an alumina-rich

Fig. 5. Evolution of the lattice parameter ao and the densities obtained vs. oxygen partial pressure. (a) BA spinel; (b) EE spinel.
404 M.A. Sainz et al. / Materials Chemistry and Physics 86 (2004) 399–408

Fig. 6. Lattice parameters of Mg–Al spinel vs. chemical composition.

spinel. Fig. 6 shows the lattice parameters of Mg-Al spinel cates undoubtedly the Mg loss and the Al2 O3 enrichment of
reached by different authors [20]. This parameter is directly spinel.
related with the spinel composition, that is to say, with the At 1650 ◦ C (in air), a density of 3.45 g cm−3 (96.4% of
Al2 O3 content which enters in solid solution forming an TD) for EE spinel and a density of 3.56 (99.8% of TD)
alumina-rich spinel. The shift of the ao value would indi- for BA spinel were reached. The highest densities were
cate that EE reached an alumina content of 73% and BA of reached at 1650 ◦ C for both spinels. The densities obtained
75%. The reducing character of the atmosphere produces at 1500 ◦ C were smaller (2.97 g cm−3 for EE spinel and
the Mg volatilization by PO2 decrease. The reaction that 3.20 g cm−3 for BA spinel). The BA densities better at both
occurs under low PO2 may be interpreted by Eq. (4). temperatures and atmospheres due to their small particle
size. A tendency for density to decrease at lower PO2 was
∗∗
Mg2+ (Al3+ )2 O4 → VO + Al∗Mg + VAl + 21 O2 observed in both spinels. This effect was more noticeable in
+ Mg(g) + 2AlxAl + 3OxO (4) EE spinel.
Fig. 7 shows the microstructure of EE spinel sintered at
The lattice parameters measured showed that spinels were 1650 ◦ C in air. The EE spinel shows a good grain size dis-
stable at T ≤ 1650 ◦ C and PO2 ≥ 10−10 atm (CO/CO2 ) and tribution of with relative amount of intergranular and intra-
that they were unstable at T = 1650 ◦ C and PO2 ≤ 10−15 atm granular pores.
(CO) and thus the reaction (4) took place. The sintered samples at PO2 = 10−15 (CO) analyzed by
Measurements of weight losses (WL) were analyzed. Sin- SEM present a microstructure different than that of the sam-
tering in air showed the lowest WL and in CO the highest ples sintered in air. The BA microstructure in CO presents
WL. This fact is in agreement with the behaviour of lattice zones of high porosity and grain boundaries not well defined.
parameters (ao ). However, these measurements had an error This porosity may be produced by magnesium volatiliza-
so that it is not possible to establish a quantitative relation tion. In order to obtain oxygen partial pressures lower than
between WL and ao BA presents the highest WL (up to 10−20 atm the tests were performed using C–CO.
2% w/w) and consequently the great decrease of crystalline Dense spinel substrates were screen printed with carbon
parameter and MgO disappearance. This ao decrease indi- and treated in air between 1300 and 1550 ◦ C for 6 h. Dur-
 M.A. Sainz et al. / Materials Chemistry and Physics 86 (2004) 399–408 405

Fig. 7. SEM micrograph of EE spinels sintered at 1650 ◦ C in air (scale bar = 10 ␮m).

ing heating the carbon layer was evaporated and the original ichiometric (71.84/28.16) in the center of the sample to
cross-section of interaction between spinel and carbon was slightly rich alumina in the middle of interaction zone up
studied. No evidence of reaction was observed in samples to an alumina-richer spinel in zones near to the original
fired at temperatures lower than 1500 ◦ C. However, at tem- spinel–carbon interface.
peratures higher than 1500 ◦ C an important interaction area This fact was confirmed and observable later in samples
was detected. screen printed with carbon, packed around with carbon pow-
In samples treated at 1550 ◦ C the depth of penetration der and finally heated into a closed alumina crucible at dif-
of reaction zone varied between 300 and 325 ␮m (Fig. 8). ferent temperatures (1250–1650 ◦ C).
Scanning electron microscopy of the interaction zone makes The reaction area in samples fired at temperatures below
clear (Fig. 9) the presence of relative big grains (5–10 ␮m) 1425 ◦ C was not observed. However, at temperatures above
dispersed in a regular matrix of smaller grains (2–3 ␮m). 1450 ◦ C, the interaction area was clearly defined. Neverthe-
An homogeneous and continuous intergranular porosity was less, samples treated at 1550 and 1650 ◦ C denoted a com-
also observed. pleted bulk interaction (Fig. 10). Both samples showed a
Furthermore, no evidence of an intergranular glass phase high and mainly intergranular porosity, and only at a high
was found and the grain boundaries appeared free of sec- magnification it was possible to observe a scarce propor-
ondary phases. X-ray diffractogram only showed peaks cor- tion of intergranular porosity. No other phases except for
responding to the spinel phase. spinel were detected by XRD. However, a displacement in
Microchemical analysis of spinel in different zones the spacing of the peaks was observed due to the changes
of the sample was performed by SEM–EPMA on the in the stoichiometric composition of the spinel.
polished cross-sections of the surface sample heated at Other important aspect is the one related with microstruc-
1550 ◦ C. The results (Table 2) confirmed the XRD ob- tural evolution of spinel phase submitted to reducing atmo-
servations. Spinel composition changed from almost sto- spheres and increasing temperatures. Starting from a spinel
with a relative homogeneous microstructure, samples treated
below 1500 ◦ C and oxygen partial pressure higher than PO2
> 10−10 atm started to develop intragranular porosity mainly
Table 2
SEM–EPMA microanalysis of Al2 O3 ·MgO at 1650 ◦ C
between fine grains. The microstructure (Fig. 9) tends to be
Location Al2 O3 MgO bimodal with large and fine grains, with a high porosity be-
Stoichiometric 71.67 28.33 tween the last ones.
No reaction zone 71.84 28.16 Both facts were especially evident in samples treated
Middle of reaction zone 72.17 27.83 at temperatures above 1500 ◦ C under strong reduction at-
Interface spinel–carbón 72.95 27.05
mosphere PO2 = 10−16 atm. This evolution took place at
406 M.A. Sainz et al. / Materials Chemistry and Physics 86 (2004) 399–408

Fig. 8. SEM micrograph corresponding to a cross-section of screen-printed sample heated at 1550 ◦ C in air (scale bar = 50 ␮m). (a) Middle of reaction
zone; (b) no reaction zone.

the same time that the processes of reduction of spinel in Finally, the high proportion of porosity generated during
presence of carbon. The vaporization of Mg(g) and O2 , as reduction would be explained by the faster diffusion of Mg
CO, produced vacant sites in the crystal which enhances (compared with Al) against the high oxygen potential [22].
grain growth. The largest grains were formed by coalescence The reduction of spinel mainly took place on surface layer,
of small grains (Fig. 11), probably by Ostwald Rippening this area would contain a higher concentration of Mg vacan-
mechanism [21], while small grains maintain their size al- cies than the bulk of the particle, and therefore the porosity
most constant. would be generated in the zones.

Fig. 9. SEM micrograph of spinel morphology in interaction (scale bar = 5 ␮m).

 M.A. Sainz et al. / Materials Chemistry and Physics 86 (2004) 399–408 407

Fig. 10. SEM micrograph of sample treated at 1650 ◦ C showing intergranular porosity and the presence of large grains in a matrix of finer grains (scale
bar = 20 ␮m).

Microchemical analysis was performed by SEM–EPMA even in crystals located close to the surface packed around
on large spinel grains in sample fired at 1650 ◦ C (Table 3). It with carbon powder.
was observed that spinel composition strongly changed from From the results obtained in spinel samples prepared
stoichiometric to 76.40/23.60 in the center of the sample and from oxides it can be concluded that spinel formation
up to 88.93/11.07. This high alumina spinel is produced from without reduction took place in the reducing conditions
large crystals located near the surface coating with carbon or defined by CO/CO2 (80/20) atmosphere (PO2 > 10−10 atm

Fig. 11. SEM micrograph of sample heated at 1650 ◦ C showing the grain growth of largest grains (scale bar = 10 ␮m).
408 M.A. Sainz et al. / Materials Chemistry and Physics 86 (2004) 399–408

Table 3 spinel. Mg-spinels are the most affected by reducing condi-

SEM–EPMA microanalysis of Al2 O3 ·MgO at 1550 ◦ C tions and Mg volatilization took place.
Location Al2 O3 MgO Employing carbon as reducing agent the lowest PO2 was
Stoichiometric 71.67 28.33 reached causing important changes in the spinel microstruc-
Middle of reactions zone 76.40 23.60 ture. Grain growth and intergranular porosity due to Mg
Interface spinel–carbon 88.43 11.07 volatilization were observed according to the equilibria di-
agram.
at T < 1600 ◦ C). Under CO atmosphere (PO2 = 10−15 )
reduction and volatilization of Mg at 1650 ◦ C are clearly Acknowledgements
observed, thus the occurrence of reaction (4) is accompa-
nied by a decrease in ao . However, in the presence of carbon
We want to thank Susana Conconi for the measurement
(PO2 = 10−20 ), spinel reduction starts between 1425 and
with the Rietvelt method and Maria E. Ghirimoldi (CICPBA)
1450 ◦ C; these temperatures are slightly higher than those
for their assistance.
reported by Colin [23].
Considering G of spinel formation from oxides as
G = −42.5 kJ mol−1 and considering our experimental References
results as well as the White [15] deductions, it can be
expected a magnesium partial pressure in equilibium of [1] T.J. Gray, Oxide Spinels in High Temperature Oxides 77-1101,
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at 1425–1450 ◦ C. However, processes of spinel reduction [2] R.M. Evans, Am. Ceram. Soc. Bull. 72 (4) (1993) 59–63.
[3] S.C. Cooper, P.T.A. Hodson, Trans. J. Br. Ceram. Soc. 81 (1982)
do not directly lead to Al2 O3 , and the results achieved up 121–126.
to 1650 ◦ C showed that reduction processes produce richer [4] E. Ryskhewitch, Oxide Ceramics: Physical Chemistry and
and richer alumina spinel (Table 3) when temperature and Technology, Academic Press Inc., New York, 1960.
reducing conditions are increased (>T and <PO2 ). This evo- [5] G.R. Rigby, G.H.B. Lovell, A.T. Green, Trans. Br. Ceram. Soc. 45 (4)
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[6] J.T. Bailey, R. Russel Jr., Ceram. Bull. 47 (11) (1968) 1025.
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As reduction of double spinel starts on divalent cation Soc. 69 (5) (1986) 418–422.
[24], spinel reduction process produces magnesium evapora- [8] M. Lejus, Rev. Int. Haut. Temp. Ref. 1 (1) (1964) 53–95.
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[10] V.L.K. Lou, T.E. Mitchell, A.H. Heuer, J. Am. Ceram. Soc. 68 (2)
generated to maintain electroneutrality in the lattice. From (1985) 49–58.
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by the following reaction: 1006.
[12] R.H. Taylor, Schmalzned, J. Phys. Chem. 68 (9) (1964) 2444–
∗∗
Mg2+ (Al3+ )2 O4 + C → VO + Al∗Mg + VAl + CO 2449.
[13] E. Rosen, A. Muan, J. Am. Ceram. Soc. 49 (2) (1966) 107–108.
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refractory materials [9]. [18] Rietveld, J. Appl. Crystallogr. 2 (1969) 65–71.
[19] A.D. Mazzoni, M.A. Sainz, A. Caballero, E.F. Aglietti, Mat. Chem.
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