28 Refractories Manual 2011

Review Papers

nate g
the m
tion a
studie
with d
produ
nique
nation
R. Sarkar* fluori

Additives for Magnesium Aluminate Spinel:

peratu
ties. V

a Review
The author
Dr. Ritwik Sarkar, Associate
Professor, NIT, Rourkela, India,
has about 15 years of experi-
ence in Ceramics and Refrac-
tories. He worked with IFGL
Bioceramics Ltd, IFGL Refrac-
tories Ltd, CG & CRI, R&D of
ACC Ltd, and H&R Johnson Ltd,
all in India, and at the IKKM, RWTH Aachen, Ger-
many (DAAD Fellowship). He has received many
awards in his career for academic excellence and
his contributions to Ceramics and Materials Sci-
ence, including the Young Scientist Award. A life
member of the Indian Ceramic Society & Indian
Institute of Ceramics, Dr. Sarkar has more than
80 research publications and 9 patents to his
credit. His current research interests are refrac-
tories, solid waste utilization and bioceramics.
1 Introduction
Additives are foreign substances intention-
ally added to provide promotion effects in
processing and to improve final properties.
An additive can react with the system to
form a solid solution, or a new compound
or a liquid phase either of its own composi-
tion or of a new composition by reacting
with the batch materials. In a solid solution,
both interstitial and substitutional effects
may occur, causing a vacancy and or strain
in the lattice and promoting diffusion de-
pendent processes. The introduction of a
lower valence cation creates anion vacancy
(or cation interstitial), which increases the
diffusivity and all diffusion dependent proc-
esses, as is the case of Li2O doping for sinter-
ing of MgO [1]. Incorporation of a higher
valence cation creates cation vacancies rath-
er than forming anionic interstitial [2] and
thus increases the cation diffusion rate and
* Department of Ceramic Engineering, National Institute
of Technology, Rourkela, India.
Contact: ritwiksarkar@rediffmail.com
BeO a
tempe
ing m
corpo
Abstract Keywords prima
thesis
Additives play a very important role on the formation and sintering of spinel, additives,
magnesium aluminate spinel. Plenty of research has been done on the ­formation, sintering
Zhang
­effect of different additives on spinel and the science associated with. Refractories Manual 2011 in Mg
This paper accumulates many such research works and attempts to cor- [1] MgO
relate them in a sequential manner for a better understanding. 1200–
ments
growt
forms
­effect
forma
Kostic
fluori
id-sta
alumi
ion is
the O
conce
diffus
at a
a high
related processes. The formation of a liquid ence was reported to be complex. They conce
phase acts as a lubricant, produces higher ­reported increased crystal growth on addi- tional
diffusivity than solid phase, attracts the wet- tion of salt vapour, especially alkali fluo- tice)
ted solid particles by capillary force of at- rides. It was suggested that the effectiveness produ
traction and results in better compaction. of the salts follows the following order: the so
For magnesium aluminate spinel system LiX>NaX>KX, MgX2>CaX2>SrX2>BaX2, [11] c
­additives can affect synthesis and formation, AF>ACl and BF2>BCl2, where A is alkali tion r
sintering, growth, properties, etc. Additives metal, B is alkaline earth metal and X is flu- 1000 °
are most important for the formation and orine or chlorine. Sarka
sintering of magnesium aluminate spinel. Helmut [4] studied the effect of different
Additives for spinel can be broadly classified additives on spinel formation and observed
as two types: additives for spinel formation a decreasing order of beneficial effects for Tabl
and additives for sintering. Detailed infor- the additives V2O5, B2O3, MoO3, P2O5, WO3, Tem
mation on the effect of both types of addi- LiF and MgF2. Again MgO, MnO, CaO and
tives on magnesium aluminate spinel is pro- NiO were reported to have little or no effect,
vided herein. and CoO, Li2O, SiO2 and Cr2O3 were report- No
ed to inhibit the reaction. Bhattacharya and addi
2 Additives for spinel formation others [5, 6] studied the mineralization ef-
The effects of various additives on the for- fect of B2O3 up to 1.5 mass-% on spinel for-
mation of magnesium aluminate have been mation. Higher amounts of additive were 1 ma
studied by various researchers for a long reported to form Mg3B2O6 on cooling and AlF3
time. Noda and Hasegawa [3] studied the mineralization was hindered. The authors
effect of salt vapour on the synthesis and confirmed that initially an Mg-borate liquid
crystal growth of magnesium aluminate. phase was formed, which at higher tempera- 3 ma
They observed increased spinellization on tures dissolves alumina, leading to the for- AlF3
the addition of salt vapours, but the influ- mation of a magnesia-modified boroalumi-

28-32_RP_Sarkar.indd 28 10.05.11 15:04

 Refractories Manual 2011 29

Review Papers

nate glass. These observations suggest that
the mechanism of mineralization is dissolu-
tion and precipitation. Lepkova et al. [7]
studied the effect of B2O3 in combination
with different fluorides and TiO2 on spinel
produced by solid phase or sol gel tech-
niques. They reported that B2O3 in combi-
nation with others TiO2 and different metal
fluorides reduces the spinel formation tem-
tion from oxide reactants with AlF3 as min-
eralizer up to 3 mass-%. AlF3 was found to
reduce the spinel formation temperature
from above 1400 °C to 1100 °C. A higher
amount of additive has a greater effect, but
sintering (measured as shrinkage) was also
reported to start at lower temperatures.
­Table 1 shows the effect of AlF3 on the phase
content of the spinel at various tempera-
equally as effective in spinel formation as
AlF3 and in increasing sintered density. They
indicated that the hygroscopic nature of
­AlCl3 is probably responsible for the forma-
tion of OH− ions at the surface of the Al2O3
particles and the removal of these OH− ions
during the sintering process leads to an
­increase in defect concentration, resulting in
improved density.

el:
perature and improves the sintered proper- tures. Stamenkovic [18] studied the effect of LiF
ties. Vereshchagin et al. [8] found that SrO, addition on spinel and found enhanced
BeO and Y2O3 reduce the spinel formation 3 Additives for spinel sintering densification and infrared transmission for
temperature when oxides are used as start- The densification of reaction sintered and spinels at temperatures where LiF was
ing materials. They concluded that the in- pre-synthesized stoichiometric spinels was present as a liquid phase. Huang and co­
corporation of these additives is one of the studied by Sarkar et al. [13] using various workers [19] examined the effects of LiF
s primary condition for low temperature syn- oxides as additives, namely, B2O3, V2O5, and LiF/CaCO3 on the phases formed, the
thesis of MgAl2O4 from oxide reactants. TiO2, Cr2O3 and calcined co-precipitated microstructure developed, and the sintering
ng
Zhang et al. [9] studied the inter-diffusion spinel. They reported that TiO2 showed the and activation energy of the magnesia-alu-
al 2011 in MgO-Al2O3 spinel using polycrystalline greatest beneficial effect followed by Cr2O3 mina compacts with a magnesia to alumina
MgO and Al2O3 in the temperature range on densification for both the pre-synthe- molar ratio of 1:9. The authors suggested
1200–1600 °C by diffusion couple experi- sized and reaction sintered spinels. How­ that formation of a liquid phase in the pres-
ments. They found that Zn2+ increases the ever, V2O5 and B2O3 were reported to have ence of additives decreased the spinel for-
growth rate of the spinel thickness but Si4+ detrimental effects. The phase composition mation temperature and increased the spi-
forms a glassy phase and has a negligible and densification behaviour of reaction sin- nel content. They also observed spinel grains
­effect on the diffusion process and spinel tered spinels (with MgO:Al2O3 molar ratios with stoichiometric composition with zero
formation. of 2:1, 1:1 and 1:2) were investigated by additives, but with higher alumina content
Kostic et al. [10] worked on the influence of Sarkar and Banerjee [14–15] in the presence for those additives. The authors also ob-
fluorine ion (using AlF3 or CaF2) on the sol- of different additives. They reported that the tained much lower activation energy for spi-
id-state reaction synthesis of magnesium additives have nearly no influence on the nel formation in the presence of additives.
aluminate spinel. According to them the F- phase content but affect the densification Villalobos et al. [20] found that LiF reacts
ion is incorporated in the lattice instead of behaviour. Dy2O3, Cr2O3, TiO2, etc., increase with the aluminium in the spinel matrix to
the O2- ion and increases the cation vacancy the sintered density but V2O5 shows strong create Mg rich areas, which causes opacity in
concentration, which intensifies the cation inhibition of sintering for all the composi- the densified material due to poor sintering.
diffusion and completes spinel formation tions. Moreover, LiAlO2 precipitates from that
at a much lower temperature. However, Kenya et al. [16] studied the effect of the same reaction contribute to the formation
a higher concentration of fluorine ions (a ­addition of chlorides on the sintering of spi- of opaque regions. The authors proposed
They concentration range more than the substitu- nel using hydroxide reactants. Chlorine ions that a more homogeneous initial distribu-
addi- tional solid solution in the anion sub-lat- decreased the decomposition temperature tion should decrease the total amount of LiF
fluo- tice) was found to be detrimental since it of magnesium hydroxide, reduced the spinel requirement and reduce the hold times,
veness produces MgF2 and reduces the product of formation temperature and finally helped in thereby producing high optical quality spi-
order: the solid-state reaction. Bakker and Lindsay sintering. Ganesh et al. [17] studied the ef- nel samples with high reproducibility. Reac-
BaX2, [11] claimed to complete the spinel forma- fect of addition of 0.01–0.03 mol-% of AlCl3 tions between LiF and MgAl2O4 at tempera-
alkali tion reaction from the hydroxides within in the conventional double stage densifi­ tures up to 1500 °C were examined by Ro-
is flu- 1000 °C in presence of 1.5 mass-% AlF3. cation process of magnesium aluminate zenburg et al. [21]. LiAlO2 and MgF2 were
Sarkar et al. [12] studied the spinel forma- ­spinel. The authors reported that AlCl3 is reported to be the active reaction products
ferent
erved
ts for Table 1 • Effect of AlF3 on the phase content of spinel
WO3, Temperature 1000 °C 1100 °C 1200 °C 1300 °C 1400 °C
O and
effect, Periclase & Periclase & Periclase & Spinel, Periclase
major Spinel
eport- No Corundum Corundum Corundum & Corundum
a and additive Periclase &
minor Spinel Spinel
on ef- Corundum
el for-
major Spinel Spinel Spinel Spinel Spinel
were 1 mass-%
g and AlF3 Periclase &
minor
uthors Corundum
liquid major Spinel Spinel Spinel Spinel Spinel
mpera- 3 mass-%
e for- AlF3 Periclase &
minor
Corundum
lumi-

28-32_RP_Sarkar.indd 29 10.05.11 15:04

 30
at these temperatures. A transient liquid
phase comprising MgF2 and LiF forms at in-
termediate temperatures but is then con-
sumed at higher temperatures during the
reformation of MgAl2O4. Rozenburg et al.
[22] reported that oxygen lattice diffusion is
the limiting step in the densification of spi-
nel, and oxygen vacancies are likely to form
when LiF is added during the sintering
process. In addition to forming a transient
liquid phase, LiF leads to the formation of
oxygen vacancies that promote late-stage
sintering in MgAl2O4. Reimanis and Kleebee
reported [23] that the presence of LiF at el-
evated temperatures leads to the formation
of a defective MgAl2O4 spinel phase contain-
ing oxygen vacancies due to the incorpora-
tion of both Li and F ions into the crystal
lattice. Consequently, densification is pro-
moted via the diffusion of oxygen vacancies.
Neither of the other lithium aluminate
phases, LiAlO2 and Li2Al4O7 were reported
to be detected.
Yu and Hiragushi [24] worked on the sinter-
ing behavior of spinel with TiO2 addition in
the range of 0.2 to 2 mass-%. They observed
an increasing densification for TiO2 con-
taining batches up to 1.5 mass-% and con-
cluded that exsolution of alumina and dis-
solution of TiO2 in the spinel lattice was
probably the reason for improvement.
Sarkar et al. [25] studied reaction sintering
of spinels with MgO:Al2O3 molar ratios of
Table 2 • Hot strength (in MPa) values of different spinel c­ ompositions without and
with TiO2
Amount of TiO2 / mass-% Sintering temperature / °C
1550
Stoichiometric spinel
Without additive 162
0.5 151
1 118
2 102
Magnesia-rich spinel
Without additive 189
0.5 182
1 183
2 157
Alumina-rich spinel
Without additive 142
0.5 134
1 124
2 120
28-32_RP_Sarkar.indd 30
Refractories Manual 2011
Review Papers
2:1, 1:1 and 1:2 with TiO2 as additive up to 2
mass-%. They reported that TiO2 was bene-
ficial for densification of alumina rich and
stoichiometric spinels at 1550 oC, but at
higher temperatures higher amounts of
­additive showed a deteriorating effect due to
grain growth. TiO2 showed a deteriorating
effect on hot strength due to an increased
roundedness of the grains and the presence
of higher amounts of impurities and TiO2 at
the grain boundaries. Details of the varia-
tion of hot strength against temperature and
amount of TiO2 are given in Table 2 for all
the stoichiometric, magnesia rich and alu-
mina rich compositions [26]. Retained
strength after thermal shock was also re-
ported to decrease in presence of TiO2 due
to the formation of low melting compounds
at grain boundaries (presence of impurities
and TiO2).
The effect of addition of TiO2 and MnO2
was studied by Baik [27] who reported that
TiO2 was more effective in promoting the
densification of spinel than that of MnO2.
Bin and others [28] studied the effect of ad-
dition of 1.5 mass-% of mixed ZrSiO4 and
TiO2 to magnesium aluminate spinel and
obtained improved sintered density and
better hot strength due to the formation
of high viscous ZrO2 and SiO2 containing
glassy phase.
Baranova et al. [29] studied the sintering of
high purity magnesium aluminate and
1600 1650
170 168
174 156
156 131
139 111
183 183
173 161
178 131
155 128
135 137
137 134
131 138
129 131
found increased sinterability with 5 mass-% 1
Y2O3. Posarac et al. [30] reported that an in-
crease in the amount of Y2O3 significantly
improved the densities as well as the thermal
shock resistance. Yttria reacts with spinel
forming YAlO3 having a lower thermal ex-
pansion compared to spinel and causes the
residual stresses, which is beneficial for the
thermal cycling. The effect of the addition of
Y2O3 up to 4 mass-% on reaction sintering of
spinels (MgO:Al2O3 molar ratio 1:1 and 2:1)
was studied by Sarkar et al. [31] in the tem-
perature range of 1550–1650 °C. They re-
ported that presence of Y2O3 enhances the
densification of both the batches but is more
effective for the 1:1 batch, which is otherwise
difficult to sinter. The Y3+ ion of Y2O3 substi-
tutes the Al3+ ion of the spinel structure,
which generates lattice strain and improves
the mass transfer and densification.
Ju and co-workers [32] found improved
thermal shock resistance for periclase spinel
refractories by adding a small amount of
Cr2O3 as chrome concentrate. Cr2O3 was re-
ported to form a spinel solid solution and
exhibit increased melting loss resistance with
increasing Cr2O3/Al2O3 and Cr2O3/Fe2O3 ra-
tios. The effect of the addition of Cr2O3 up to
4 mass-% was studied Sarkar et al. [33] on
spinel compositions with MgO:Al2O3 molar
ratios of 2:1, 1:1 and 1:2. They reported that Fig. 1
Cr2O3 showed the greatest effect on densifi-
cation for alumina rich spinel. Cr2O3 was
found to decrease the temperature of com-
plete solid solubility of excess alumina in
spinel for the alumina rich composition but
no Cr-bearing phase was reported. It was
Tabl
found that the cold and hot strength deterio-
rated for all the compositions and the delete- Batc
rious effect was more pronounced for batch-
es containing higher amounts of additive.
Cr2O3 was also found to be effective for grain
growth, especially for the alumina rich com- Stoi
position. The effect of Cr2O3 on the micro-
structure of three different spinel composi-
tions is shown in Fig. 1 [25].
Skomorovskaya [34] studied the effect of
oxides of yttrium, ytterbium, holmium, dys-
prosium and cerium up to 4 mass-% on spi-
nel ceramics and reported comparatively Mag
better and more stable properties for the
spinels containing dysprosium oxide and
­ytterbium oxide. The microstructure also
showed fine crystalline spinel grains with
clear contour for these additions.
Ganesh et al. reported [35] that formation
of the spinel phase is a strong function of Alum
moisture and CaO content of the precursor
oxides. The authors have concluded that raw
mixtures having >0.9 mass-% CaO exhibit-
ed higher sintered properties compared
with others.
10.05.11 15:04
 Refractories Manual 2011 31

Review Papers

ass-% 1 Aguilar [36] studied the effect of the addi-

an in- tion of CaCO3 (up to 30 mol-%) in mix-
cantly tures of MgO and Al2O3 (molar ratio 1:1)
ermal on the formation of MgAl2O4 at 1400 °C.
spinel They reported that fired products con-
al ex- tained mainly the spinel phase with a small
es the amount of calcium aluminates (CaAl2O4
or the and Ca12Al14O33) and calcium compounds.
ion of Zografou and others [37] found that addi-
ing of tion of SiO2 in magnesia rich spinel dete-
d 2:1) riorated densification, since the formation
e tem- of forsterite phase consumes a certain
ey re- amount of free magnesia and thus the for-
es the mation of anion vacancy is reduced. How-
more ever, the alumna rich composition densi-
erwise fied much faster in the presence of SiO2
ubsti- due to the formation of a liquid phase
cture, above 1370 °C (in the MgO–Al2O3–SiO2
proves system), which remarkably enhanced the
grain boundary diffusion. Again Yi et al.
roved [38] reported that the addition of SiO2 re-
spinel tarded the formation of spinel due to the
unt of formation of some intermediate com-
as re- pounds, decreased the linear expansion of
n and the powder compacts on heating and pro-
e with moted the densification of the compacts at
O3 ra- higher temperatures.
up to Using ZnO in stoichiometric spinel, Ghosh
3] on et al. [39] achieved 99 % densification at
molar 1550 °C. They reported the highest bending
d that Fig. 1 • Effect of Cr2O3 on the microstructure of different spinel compositions strength and retained cold strength after
ensifi-
3 was
com-
na in
on but
t was
Table 3 • Phase analysis of different spinels containing MgSO4 sintered at various temperatures
terio-
delete- Batch MgSO4 / mass-% Phases present
batch- 1550 °C 1600 °C 1650 °C
ditive.
grain
com- Stoichiometric 0 Spinel Spinel Spinel
micro-
0.5 Spinel Spinel Spinel
mposi-
1.0 Spinel Spinel Spinel
ect of 2.0 Spinel Spinel Spinel
m, dys-
n spi-
atively Magnesia-rich 0 Spinel + Periclase Spinel + Periclase Spinel + Periclase
or the
e and 0.5 Spinel + Periclase Spinel + Periclase Spinel + Periclase
e also 1.0 Spinel + Periclase Spinel + Periclase Spinel + Periclase
with
2.0 Spinel + Periclase Spinel + Periclase Spinel + Periclase

mation
on of Alumina-rich 0 Spinel + Corundum Spinel + Corundum Spinel
cursor
at raw 0.5 Spinel + Corundum Spinel Spinel
hibit- 1.0 Spinel + Corundum Spinel Spinel
pared
2.0 Spinel + Corundum Spinel Spinel

28-32_RP_Sarkar.indd 31 10.05.11 15:04

 32
thermal shock with 1 mass-% ZnO. They al-
so suggested that ZnO enters in the spinel
structure, causing an anion vacancy and re-
sulting in higher densification and strength.
They also reported a reduced grain size due
to restricted grain boundary movement in
the presence of an additive.
Fujita and coworkers [40] reported that
dispersion of fine and homogeneous te-
tragonal zirconia grains in sintered spinel
bodies improves the bending strength and
fracture toughness. In a separate work the
same group [41] reported that a ZrO2 con-
tent above 1.4 vol-% improved the densi­
fication, above 6.6 vol-% improved the
bending strength and between 12.5 to 15.1
vol-% improved the fracture toughness of
the sintered spinel products. They also
found enhanced densification below
1400 °C for the ZrO2 containing bodies, re-
ported greater strength on a higher extent
of ZrO2 transformation from the tetrago-
nal phase to the monoclinic one and im-
proved fracture toughness with an increas-
ing amount of tetragonal zirconia content.
Tsuboi et al. [42] worked on the same sys-
tem with various MgO:Al2O3 ratios. They
reported higher fracture toughness for all
ZrO2 containing bodies, higher densifica-
tion for 50–62.5 mol-% Al2O3 containing
bodies with 10 vol-% ZrO2 and greater
strength with increasing amount alumina
for compositions containing more than
50 mol-% alumina where ZrO2 was present
in tetragonal form.
Adylov [43] studied the effect of Y2O3, SiO2
and MgO on MgO∙nAl2O3 (n varies from
1–2.5) spinel in a solar furnace. He found
that additives reduce the porosity level from
15 % to 0.15–1.5 % and also reported an in-
creased erosion resistance of the resultant
body against optical glass.
The addition of MgSO4 in spinels was stud-
ied by Sarkar and et al. [44] who reported a
desintering effect at lower sintering temper-
atures, mainly for Al2O3-rich and stoichio-
metric spinels. MgSO4 was reported to en-
hance the solid solubility of the excess co-
rundum phase in spinel and make complete
solubility of free corundum at lower tem-
peratures for the Al2O3-rich composition.
Details of the phases present in presence of
MgSO4 for three different spinel composi-
tions are given in Table 3 [25]. MgSO4 also
0showed its beneficial effect on ambient and
high temperature strength for all the com-
positions may be due to solid-state sintering
and absence of any liquid phase. However,
the retained strength after thermal shock
was reported to deteriorate in the presence
of MgSO4.
28-32_RP_Sarkar.indd 32
Refractories Manual 2011
Review Papers
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Received: 08.12.2010
(final version)
10.05.11 15:04