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A review on magnesium aluminate (MgAl2O4)

spinel: synthesis, processing and applications

I. Ganesh

To cite this article: I. Ganesh (2013) A review on magnesium aluminate (MgAl2O4) spinel:
synthesis, processing and applications, International Materials Reviews, 58:2, 63-112, DOI:
10.1179/1743280412Y.0000000001

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Published online: 12 Nov 2013.

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A review on magnesium aluminate (MgAl2O4)
spinel: synthesis, processing and applications
I. Ganesh*
Magnesium aluminate (MgAl2O4) spinel (MAS) is a synthetic material with cubic crystal structure
and excellent chemical, thermal, dielectric, mechanical and optical properties. These properties
made MAS an indispensable material for optically transparent windows, domes and armours, and
for certain refractory applications. High processing cost of dense MAS ceramics is in the main
responsible for its limited usage in certain important applications despite its excellent
performance in them. The volume expansion (y8%) associated with MAS phase formation from
alumina and magnesia does not allow obtaining dense MAS bodies in a single-stage reaction
sintering process. Therefore, dense MAS bodies are made by following a double stage firing
process, which is expensive. The existing literature suggests that the processing cost of dense
MAS ceramics could be reduced to a great extent by decisive selection of starting raw materials,
powder processing and densification conditions, and by understanding the underlying
mechanisms of MAS formation and densification. Since there is no review article covering the
complete comprehensive information of MAS, an attempt is made to write this review article with a
main perspective of synthesis, processing and important applications of MAS and its utility for
certain future emerging novel and innovative applications.
Keywords: Magnesium aluminate spinel, Optically transparent ceramics, Infrared domes/windows, Hot pressing, Hot isostatic pressing, LiF, Y2O3, Net
shape consolidation, Humidity sensors, Refractory material, Catalyst, Catalyst support

00
List of symbols VMg magnesium vacancy with double negative
charge
a0 lattice parameter VO.. oxygen vacancy with double positive charge
Al| Al aluminium ion sitting on aluminium site with e9 dielectric constant
neutral charge f zeta potential
Al...
i aluminium interstitial ion with triple positive W Schottky defect
charge C centre of Brilliun zone
Al.Mg aluminium ion sitting on magnesium lattice DGfo standard molar Gibbs energy of formation
site with single positive charge
DGr Gibbs energy of reaction
i antisite defect
0 DHf enthalpy of formation
MgAl magnesium ion sitting on aluminium site
DSf entropy of formation
with single negative charge
Mg.. i magnesium interstitial ion with double posi-
tive charge Introduction
Mg|Mg magnesium ion sitting on magnesium site Recently, magnesium aluminate (MgAl2O4) spinel
with neutral charge (MAS) has received a great deal of attention from
00
Oi oxygen interstitial ion with double negative academia and the industry sector on account of its best
charge combination of several important properties, such as
O| O oxygen ion sitting on oxygen site with neutral high melting point (2135uC), high hardness (16 GPa),
charge relatively low density (3?58 g cm23), high mechanical
Ra roughness strength both at room (135–216 MPa) and elevated
tan d dielectric loss temperatures (120–205 MPa at 1300uC), high resistance
000
VAl aluminium vacancy with triple negative against chemical attack, wide energy band gap, high
charge electrical resistivity, relatively low thermal expansion
coefficient (961026uC21 between 30 and 1400uC), high
Centre for Advanced Ceramics, International Advanced Research Centre thermal shock resistance, etc.1–6 Furthermore, MAS
for Powder Metallurgy and New Materials (ARCI), Hyderabad 500 005, does not react with SiO2 until 1735uC, with MgO or
AP, India CaO until 2000uC, with Al2O3 until 1925uC and,
*Corresponding author, email ibramganesh@arci.res.in excepting alkaline earth metals, it can be in contact

ß 2013 Institute of Materials, Minerals and Mining and ASM Internationa

Published by Maney for the Institute and ASM International
DOI 10.1179/1743280412Y.0000000001 International Materials Reviews 2013 VOL 58 NO 2 63
Ganesh A review on MAS: synthesis, processing and applications

with all other metals.1 The typical properties of
polycrystalline MAS are presented in Table 1.1–7 Fully
dense, polycrystalline MAS is transparent optically, as
well as in the 3–5 mm IR regions, given the grain size is
much less than the wavelength of incident light.2–5 As it
allows larger wall thickness than alumina without
loosing its transparent properties, it has been used for
optical engineering applications, such as armoured
window systems, high energy laser windows and light-
weight armour.7–16 Now, MAS has replaced the tradi-
tional alumina, sapphire, AlON, ZnS and lanthanum
niobate ceramics in applications requiring light trans-
mission in the wavelength range of 2–5?5 mm. Good
resistance to radiation induced swelling and strength
degradation made MAS a potential fusion reactor
power core insulating material.6 Because of its basic
nature, porous MAS both in bulk and thin film form
showed potential as an electronic humidity sensor.17–22
Its low dielectric constant (e57?5) and low loss tangent
(tan d5461024) properties, as well as the close match
of its oxygen ion lattice structure with Si and with a
number of other important oxide systems, made MAS
an attractive material for integrated electronic devices.23
Given its high melting point and high chemical inertness,
MAS has been employed to replace traditional chromite
based refractories in cement rotary kilns and steel ladles,
since the latter refractories contain Cr(VI) species, which
create both environmental and health hazards.1,24 Thin
films of MAS exhibited potential utility in thermal
barrier coatings (TBCs) for the blades and vanes in the
hot section components of gas turbines.25 Furthermore,
MAS has also been employed as an alternative material
to replace the conventional carbon anode in aluminium
electrolytic cells.26 Its low acidity and good thermal
stability made MAS an excellent catalyst for oxidation
of SO2 to SO3 and in the fields of environmental,
petroleum processing and fine chemical production.27,28
Owing to the above mentioned properties, MAS was
also employed as a catalyst support for a great variety
of reactions including De–SOx,29,30 selective cataly-
tic reduction (SCR) of NO,31 ammonia synthesis,32,33
n-butane dehydrogenation,34,35 dry reforming of
methane,36,37 chemical looping combustion (CLC),38
water–gas shift reaction,39 catalytic steam reforming of
methane40 and propane dehydrogenation.41
Although, a great number of papers deal with MAS in
the literature, none of them present together the
complete information pertaining to the fundamentals
(properties, crystal structure and phase diagram), the
problems of volume expansion associated with MAS
phase formation from alumina and magnesia, the utility
of single or double stage sintering processes, the
methods available to reduce the processing cost of
MAS products, the various routes employed for the
preparation of MAS powders, single crystals, whiskers
and thin films, the available powder consolidation (i.e.
processing) techniques, the effects of starting raw
materials, chemical composition (i.e. non-stoichiome-
try), defect reactions, impurities/sintering aids, proces-
sing routes, etc., on densification behaviour of the
powder, the advanced spectral characteristics of the
powders, the optical, mechanical, dielectric, thermal and
magnetic properties of sintered materials, the applica-
tions, etc.42–47 This review article is an attempt to fill this
gap.
Crystal structure and phase diagram
The crystal structure of MAS has been reported by
Bragg48 and Nishikawa49 independently (Fig. 1). The
spinel structure (sometimes called garnet structure) is
named after the mineral spinel (MgAl2O4); the general
composition is AB2O4. The structure of MAS is based
on the structure of diamond. The positions of the A ions
are nearly identical to the positions occupied by carbon
atoms in the diamond structure. This could explain the
relatively high hardness and high density typical of this
group. The arrangements of the other ions in the
structure conform to the symmetry of the diamond
structure. However, they disrupt the cleavage as there
are no cleavage directions in any member of this group.
The unit cell of the 2–3 MAS can be expressed as
Mg8Al16O32, in which 32 oxygen anions are face centred

Table 1 Typical physical properties of polycrystalline MAS1–7

Property Value

Density/g cm 23
3.58
Hardness, Knoop 1398
(100 gm)/kg mm22
Specific heat 0.21
(at 20uC)/cal g21 K21
Poisson’s ration 0.26
Melting point 2135uC
Strength at 25uC 4-point bending Biaxial Tension Compression Elastic modulus Bulk modulus Shear modulus
103 MPa 172 MPa 110 MPa 2.69 GPa 273 GPa 192 GPa 110 GPa
Coefficient of thermal At 25–200uC At 25–500uC At 25–1000uC
expansion/61026 K21 5.6 7.3 7.9
Dielectric 1.27 mm thick 0.25 mm thick
strength/kV mm21 490 580
Resistivity/V cm At 25uC At 300uC At 500uC At 700uC
.1014 561014 261014 461014
Thermal At 25uC At 100uC At 1200uC
conductivity/W m21 K21 24.7 14.8 5.4
Dielectric properties 1 kHz 1 MHz 9.3 GHz
Dielectric constant 8.2 8.2 8.3
Dielectric loss 0.00025 0.0002 0.0001
Refractive index at 0.49 mm 0.59 mm 0.66 mm 1.0 mm 2.0 mm 3.0 mm 4.0 mm 5.0 mm
different wavelengths l 1.736 1.727 1.724 1.704 1.702 1.698 1.685 1.659

64 International Materials Reviews 2013 VOL 58 NO 2


1 Structure of MAS: Mg ions sit at tetrahedral sites while
Al ions occupy octahedral sites; unoccupied tetrahe-
dral sites are represented by (blue) triangles and octa-
hedral sites are shown by (green) cubes48,49
cubic (fcc) close packed with a space group Fd3m
(number 227), with eight MgAl2O4 units per cubic
cell.50,51 Such close packing provides 64 divalent
tetrahedrally (IV) coordinated cation sites and 32
octahedrally (VI) coordinated trivalent cation sites, of
which only 24 are filled. The cations (usually metals)
occupy one-eighth of the tetrahedral sites and a half of
the octahedral sites, and there are 32 oxygen ions in
the unit cell. The anion sublattice is arranged in a
pseudocubic close packed spatial arrangement. This
structure is composed of edge sharing AlO6 octahedral
chains. In one unit cell, along c axis, there are four layers
of AlO6 octahedral chains. Neighbouring layers are
perpendicular to each other. One tetrahedral site in eight
is occupied by divalent cation, and trivalent cations
occupy half of the octahedral sites. The divalent
magnesium (Mg2z) ions are located at eight of the 64
tetrahedral interstices. The remaining interstices are
unoccupied, but have the capability to accommodate
cation species within a stable structure even at high
temperatures and pressure.50 The Mg2z and Al3z are
bonded to oxygen ions, which in this complex structure
are dilated away from their ideal lattice positions. The
physical and structural properties of MAS vary accord-
ing to the following factors: the lattice parameter a0, the
anion parameter u (which is a measure of the oxygen
dilation) and the cation inversion parameter i (which is a
measure of the antisite defects on the cation sublattice).
These factors are detailed by Sickafus et al.51 Owing to
the availability of a large number of empty tetrahedral
and octahedral sites, the unit cell of MAS is considered
as a host cell capable of holding a large number of
divalent and trivalent cations in solid solution. The
permissible range of radii for these cations to be
accommodated in the tetrahedral and octahedral sites
is 0?044–0?100 nm. Accordingly, the lattice parameter of
MAS ranges from 0?80 to 0?84 nm, depending on the
radii of the foreign cations occupying the vacant sites.
MgAl2O4 spinel can be distinguished as normal and
inverse. In the normal spinel, all Al3z ions are in
octahedral coordination with local symmetry D3d, and
all Mg2z ions are in tetrahedral coordination with point
group symmetry Td. Thus, the general formula may be
Ganesh A review on MAS: synthesis, processing and applications
2 MgO–Al2O3 phase diagram53
written as (Mg)[Al2]O4 or (Mg8)[Al16]O32 for the cubic
cell, where ( ) and [ ] denote tetrahedral and octahedral
sites respectively. The Mg–O and Al–O bond lengths in
the normal spinel are 1?967 and 1?855 Å respectively.52
The MgO–Al2O3 phase diagram is shown in Fig. 2.53
The stoichiometric MAS contains 28?2%MgO and
71?8%Al2O3 and melts congruently at 2135uC. A small
quantity of MgO in Al2O3 lowers its melting point
appreciably, even though MgO has a very high melting
point. Further, there are two eutectic reactions and an
intermediate phase, MgO.Al2O3. There are very little
terminal solubilities, i.e. Al2O3 dissolves only a negli-
gible amount of MgO and vice versa. So, the pure end
phases are the same as components for all practical
purposes. The MgO–Al2O3 system can also be consid-
ered as two separate phase diagrams, the components
for one being MgO and MgO.Al2O3 and for the other
being MgO.Al2O3 and Al2O3. MgAl2O4 spinel possesses
a very wide range of stoichiometry and is the only phase
that forms at temperatures up to 1600uC.54,55 At this
temperature, the solid solubility of MgO and Al2O3 in
MAS is estimated to be 2 and 6% respectively. On
increasing the firing temperature to 1700uC, the solubi-
lity of these two oxides in spinel increases to 3?0 and
10?0% respectively. At 2000uC, the solid solution ranges
from 40 to .80%. In terms of the values of n in
MgO.nAl2O3, n ranges from ,0?6 to .7 at y1990uC.
However, the high temperature stability of MAS has
been found to be highly influenced by the pressure acting
upon it.56,57
In separate studies, Akaogi et al.58 and Funamori
et al.59 found that MAS decomposes into a mixture of
MgO and Al2O3 at a temperature in the range of 1200–
1600uC under the pressure of 15–16 GPa. The resultant
MgO and Al2O3 again reacts to form MAS phase with
calcium ferrite structure at 25–27 GPa.59 This calcium
ferrite phase further transforms to CaTi2O4 type
structure at y40 GPa and 2000–3000uC.59 In another
study, a very dense phase, e-MgAl2O4, was formed at
y1000uC and pressures above y25 GPa.60 This latter
International Materials Reviews 2013 VOL 58 NO 2 65
Ganesh A review on MAS: synthesis, processing and applications
3 Phase relations in MAS at high pressures and high
temperatures. Closed and open circles represent MAS
calcium ferrite and the assemblage of MgO periclase
and Al2O3 corundum respectively. Open squares indi-
cate the mixture of the new Mg2Al2O5 phase and Al2O3
corundum. An open double square shows the mixture
of the new Mg2Al2O5 phase, Al2O3 corundum and MgO
periclase. Closed squares indicate the new MAS phase.
Per: periclase, Cor: corundum, Cf: calcium ferrite, Np:
new phase62
phase was further transformed to CaTi2O4 type struc-
ture with further increasing of pressure (45–50 GPa) and
temperature (1100–2500uC).61 Using a multi-anvil appa-
ratus, Enomoto et al.62 observed the phase transition
of MAS under 21–27 GPa pressure and within the
temperature range of 1400–2500uC (Fig. 3). The mixture
of MgO and Al2O3 is stable up to about 26–27 GPa
within the temperature range of 1400–2000uC and under
higher pressures, calcium ferrite type MgAl2O4 becomes
stable. The transition boundary between the two fields
has a negative slope. At a temperature above 2000uC
and pressure below 25?5 GPa, a mixture of Al2O3 and
a new phase with Mg2Al2O5 composition coexists.
The transition boundary between the two fields has a
strongly negative pressure–temperature slope. Enomoto
et al.62 further observed that Mg2Al2O5 phase represents
a new structure type with orthorhombic symmetry
(Pbam), and possesses the lattice parameter values of
a59?3710(6) Å, b512?1952(6) Å, c52?7916(2) Å, V5
319?03(3) Å3 and Z54. This structure was also found to
consist edge sharing and corner sharing (Mg,Al)O6
octahedra, and chains of edge sharing octahedra
running along the c axis. A part of Mg atoms were
found to be accommodated in six coordinated trigonal
prism sites in tunnels surrounded by the chains of edge
sharing (Mg,Al)O6 octahedra.62 This structure is similar
to ludwigite (Mg,Fe2z)2(Fe3z,Al)(BO3)O2. The molar
volume of the Mg2Al2O5 phase is smaller by 0?18% than
the sum of molar volumes of 2MgO and Al2O3. High
pressure dissociation to the mixture of corundum type
phase and the phase with ludwigite related structure is
noted only for MAS phase among various A2zB23zO4
compounds. In line to the data in phase diagram shown
in Fig. 3, Irifune et al,56 also observed the phase
transformation of MAS into a new high pressure form
at pressures above 25 GPa in a multi-anvil high pressure
apparatus that had a structure similar to that of
66 International Materials Reviews 2013 VOL 58 NO
CaFe2O4 (calcium ferrite). The zero pressure density of
this new high pressure form was determined to be
3?937(3) g cm23, which is 2% denser than the lower
pressure assemblage of periclasezcorundum. This high
pressure form of MgAl2O4 could be an important host
of aluminium in the Earth’s lower mantle.58 Further,
this MAS is the common constituent of low pressure
peridotite xenoliths, and an important host mineral for
aluminium and other trivalent cations in the shallow
upper mantle.58,59
Synthesis routes of MAS
Solid state reaction
Since natural occurrence is little, MAS is synthesised
artificially.24 There are several soft solution chemistry
routes, such as coprecipitation, spray drying, freeze
drying and spray pyrolysis by which MAS can be
synthesised at par low temperatures. However, none of
these processes is suitable for manufacturing of MAS in
bulk quantity for applications such as refractories. Thus,
solid oxide sintering is the feasible route for manufactur-
ing of MAS aggregates for refractory applications. The
most popular method in commercial production is the
conventional solid state reaction of Mg and Al bearing
precursors, such as oxides, hydroxides and carbonates.
The formation of MAS from a mixture of periclase and
corundum is associated with a volume expansion of
y8?0%, which can be simply calculated from their density
differences (MgO: 3?58 g cm23; Al2O3: 3?99 g cm23;
MgAl2O4: 3?58 g cm23). This expansion is equivalent to
a linear expansion of 2?6%. Owing to this volume
expansion, normally, the double stage firing process is
employed to make dense MAS grains for refractory
applications. Owing to the involvement of two consecu-
tive firing cycles, the cost of MAS grain has been
increased. A lot of studies have been devoted to under-
stand the volume expansion behaviour of MAS phase
formation and to reduce the processing cost of dense
MAS grains for refractory applications.63–90
In a study, Kanai et al.63 studied the linear thermal
expansion behaviour of various MgO/Al2O3 powder
(y0?5 mm) mixtures compacts as a function of tempera-
ture and noted expansion of compositions above 900uC,
which was ascribed to the formation of MAS phase.
However, some shrinkage was noted above 1300uC due
to sintering. A largest linear expansion (y5%) was
noted for the stoichiometric MAS composition. Such a
large expansion reflects the difficulty in obtaining dense
MAS ceramics in a single stage reaction sintering
process. Apart from this, MAS also possesses a wide
solid solution range on the alumina side at high
temperatures.64 The molar volume of MAS decreases
slightly with the solid solubility of alumina. The
theoretical value is 39?77 cm3 mol21 for MgAl2O4 and
39?24 cm3 mol21 for MgO.2Al2O3. The latter one is the
composition at the boundary in contact with Al2O3 at
y1600uC (Fig. 2).
Wagner65 gave the underlying mechanism in the
formation of MAS phase from corundum and periclase
upon the solid state reaction at elevated temperatures
(Fig. 4).66 He suggests that the reaction proceeds by
counter diffusion of the cations through the product
layer, where oxygen ions remain at the initial sites. To
keep the electroneutrality, 3Mg2z diffuse toward the
2

66
4 Wagner mechanism
alumina side and 2Al3z diffuse toward the magnesia
side. At the MgO/spinel boundary, diffused 2Al3z react
with MgO to form MgAl2O4, while diffused 3Mg2z
react with 3Al2O3 to form 3MgAl2O4 at the Al2O3/spinel
boundary. As a consequence, the thickness ratio of two
MAS layers formed at alumina side and magnesia side is
3 : 1. If the Wagner mechanism is absolute, the thickness
ratio of two MAS layers formed at Al2O3 side and MgO
side, denoted as R, always equals to 3. However, this R
value was found to be increased in real experiments,
owing to changes in composition and sintering tempera-
ture. The R value for the composition MgO.nAl2O3 was
formulated as R53(7nz1)/(3nz5). Yamaguchi et al.67
found that R values varies from 4?1 to 4?6 within 1495–
1595uC temperature range, being independent of
whether single or polycrystalline specimens form. The
other factor is the vapour transportation of MgO. The
saturated vapour pressure of MgO gas coexisting with
periclase and MAS at 1527uC are 2?561025 and
6?261027 Pa respectively. These data imply that MgO
molecules vapourised from periclase may sink on
corundum to form MAS. If the contact between
magnesia and alumina is rough, the diffusion of MgO
vapour occurs through the gap and then MAS forms at
the alumina side only, which also results in an increase
of the R value. A value of R55?6 at 1535uC was reported
for a diffusion couple in rough contact.66 According to
Wagner,65 if MgO diffuses to alumina side only in one
direction, R becomes infinite. In fact, there are three
kinds of particles’ contacts in a powder compact,
namely, Al2O3–MgO, Al2O3–Al2O3 and MgO–MgO
pairs. For convenient purposes, an expansion of one
alumina particle in contact with one magnesia particle is
shown in Fig. 5.66 If the molar ratio of alumina and
magnesia is 1 : 1, a stoichiometric MAS is formed
without overs and shorts of Al2O3 and MgO. In the
MAS formation based on Wagner mechanism, four
MgO change to one MgAl2O4 at the MgO side. The
volume change of this portion is 0?884 (the molar
volume of MgO, 11?26 cm3). At the Al2O3 side, four
Al2O3 change to three MgAl2O4 and the volume change
of this portion is 1?167 (the molar volume of Al2O3,
25?56 cm3). That is, MgO side shrinks and Al2O3 side
expands as the MAS formation proceeds. The molar
volume ratio of alumina to magnesia is 0?694 : 0?306.
After MAS formation, magnesia portion shrinks to
0?271 (0?30660?884) and this shrinkage is assumed to
occur to the X direction (Fig. 5).66 Alumina portion
Ganesh A review on MAS: synthesis, processing and applications
5 Expansion model of two particles system of alumina
and magnesia66
expands to 0?731 (0?69461?053) along the same direc-
tion. The total is 1?002; i.e. a linear expansion of 0?2%.
As alumina portion expands isotropically, the Y and the
Z expansions are 5?3% and an increase of R increases the
expansion of the Al2O3 side.66 The calculated expansions
for different R values could be seen from Table 2.66 For
R56, a linear expansion of alumina portion is over 10%.
Concerning R5‘, Navias68 performed a curious experi-
ment in which a piece of sapphire was separately located
from MgO and was heated in a hydrogen atmosphere at
1900uC. This led to the formation of MAS, indicating
that the original alumina gains a volume increase of
47%. This is slightly less than the expected one (55?6%)
due to the deficiency of MgO, in other words, the solid
solubility of alumina. In Fig. 5, the average linear
expansion of the Al2O3–MgO pair after MAS formation
is 3?6%. When R is infinite, the average expansion is
found to be 4?1% from the same consideration.66
Normally, MAS formed at the interface of MgO and
Al2O3 grains separates the reacting species increasing the
diffusion path, and thus slowing down the reaction.69
This reaction is accelerated industrially by carrying it
out in two stages.1,70–72 In the first stage, the reactants
are fired at a low temperature of around 1200–1400uC
for partial spinelisation, followed by regrinding, recom-
paction and second firing at y1700uC. Regrinding was
found to be effective in bringing the fresh reacting
surfaces together, essential for a faster reaction. The
MAS phase formation was also found to be highly
influenced by the raw materials characteristics, such as
moisture (both adsorbed/chemisorbed and hydroxyl
groups), impurities (CaO, Na2O, etc.), average particle
size, particle size distribution, and by the compact green
density (GD), calcination temperature, rates of heating
and cooling, holding time at final calcination tempera-
ture, etc.70–72 The compacted mixture of aluminium and
magnesium hydroxides reacted to form y90% MAS
Table 2 Expansion value of alumina side in diffusion
couple versus thickness ratio R (Ref. 66)
Expansion
R Volume/% Linear/%
3 16.7 5.3
4 24.4 7.6
5 29.7 9.0
6 33.4 10.1
‘ 55.6 15.9
International Materials Reviews 2013 VOL 58 NO 2 67
Ganesh A review on MAS: synthesis, processing and applications
phase at 1300uC for 1 h, whereas the similarly com-
pacted mixture of aluminium and magnesium oxides to
reach about the same amount of MAS phase took y4 h
holding time at 1300uC. These studies suggest that the
oxide precursors react at a slower rate in comparison to
their corresponding hydroxide precursors mixtures.
Further, it is generally agreed that the MAS phase
formation temperature should be kept as low as possible
to avoid the formation of large agglomerates, which
inhibit otherwise the sintering activity upon subsequent
densification operation.72
In order to bring down the processing temperature
and the cost of dense MAS grains for refractory
applications, the effect of raw materials type and their
composition on formation and densification behaviour
of MAS in a single stage firing process was also
investigated.45,46 In a study, Tripathi et al.45 studied
the effect of MgO raw material reactivity on formation
and densification behaviour of MAS in a single step
reaction sintering (firing) process at 1650–1750uC for
2 h. The mixture of calcined alumina and lightly
calcined (1100uC) reactive caustic MgO or inert sintered
MgO was used in this study. The volumetric expansion
data associated with MAS phase formation was utilised
to identify the initial MAS formation temperature by
dilatometry. The phase formation from a mixture of
reactive caustic MgO and alumina mixture was found to
be higher than that of the other. This is due to the fact
that the reactive caustic MgO had a higher surface area
and lower crystallite size. It is interesting to note that,
although the mixture of caustic MgO and alumina
exhibited faster phase formation, their densification rate
was found to be lower in comparison to the other one.
The higher volume expansion and grain growth asso-
ciated with the enhanced phase formation was found to
be responsible for the noted inferior sintering behaviour.
In another study, Sarkar et al.46 studied the effect of
alumina raw material content (i.e. non-stoichiometry)
on densification behaviour of reaction sintered MAS at
1600–1700uC for 2 h. The alumina rich MAS exhibited
an inferior sintered properties in comparison to those
exhibited by magnesia rich MAS. In this case, the grain
growth suppression was noted due to excess MgO at
grain boundaries. Further, the alumina rich composi-
tions exhibited relatively large size grains. Nevertheless,
the degree of densification levels achieved for these MAS
grains formed in a single stage reaction sintering route
are not enough for many refractory applications.
Certain mineralisers are also employed to accelerate
the phase formation and densification of MAS.72–74
These mineralisers are of two types. One type of
mineralisers reduces the spinel forming temperature
and the other type reduces the sintering temperature.
The AlF3, V2O3 and MgCl2 fall in the first category,
whereas TiO2, Y2O3, LiF, B2O3, ZnO, Fe2O3 and CaO
belong to the second category. The boron containing
compounds have also been found to be successful
as mineralisers for MAS formation,73,74 which form
an MgO modified boroaluminate liquid.74 However,
>2 wt-%B2O3 caused the formation of Mg3B2O6 cry-
stals, which have reduced the required mineralising
effect during MAS phase formation. Because of its high
viscosity, this MgO modified boroaluminate liquid
exhibited very little fluxing effect. Further, its wett-
ability was found to be very low towards alumina and
68 International Materials Reviews 2013 VOL 58 NO
magnesia grains. On the other hand, Li2B4O7 and
Na2B4O7 were found to be very effective fluxing agents
and enhanced the reaction rate of MAS phase forma-
tion by reducing the viscosity of the melt and also by
increasing the wettability. In another study, Zhang
et al.74 synthesised MAS powder by heating an equi-
molar composition of MgO and Al2O3 in LiCl, KCl or
NaCl. A decrease in the MAS phase formation tem-
perature was noted from .1300 to y1100uC in LiCl,
and to y1150uC in KCl or NaCl. The MAS powder
formed in this process was found to be in pseudo-
morphic and retained, to a large extent, the size and
morphology of the original Al2O3 raw material. This
indicates that a template formation mechanism played
an important role in this process. However, other than
Mg and Al based salts, all other mineralisers certainly
contaminate the MAS product and restrict its applica-
tions to lower temperatures only.72
Alternatively, a single stage firing process called
electrofusion technique is also employed to prepare high
purity MAS.24,63 In this process, the mixture of calcined
alumina and natural magnesite is melted in an electric
arc furnace. High temperature generated in this process
volatilises impurities. Nevertheless, this process is quite
energy intensive and not viable to practice by many of
the countries where electricity is expensive for many of
the refractory applications.24 In another alternative
single stage firing process, Sarkar et al.47 prepared dense
MAS grains with a theoretical density (TD) of 99?5% at
1600uC. In this process, an attritor milling was utilised
for 6 h to reduce the particle size of starting raw
materials mixtures. However, in this process, there is a
possibility that grinding media used for attrition milling
contaminate the resultant MAS grains.
In a quest to identify more economic routes for
synthesis of MAS powders via solid state reaction for
certain refractory applications, the microwave (MW)
energy was also considered. In a recent study, Ganesh
et al.75 prepared MAS powders using aluminium and
magnesium oxides as starting materials in a domestic
MW oven (operated at 2?45 GHz frequency with
700 W power) using elemental carbon as the MW
susceptor. For comparison purposes, the same raw
materials mixture compact was also calcined in a
conventional electrically heated furnace at 1350uC for
1 h to obtain MAS powder with y93% spinel phase.75
The total time consumed in this latter conventional
process was .24 h. On the other hand, when the same
raw materials mixture compact was treated in an MW
oven with the help of about 20–50 wt-% elemental
carbon, a considerable amount of MAS phase forma-
tion was noted within 60 min. Figure 6 shows the
XRD spectra of MAS powders formed in an MW oven
with the help of different amounts of C.75 It can be
seen that even 20 wt-%C is sufficient to convert raw
materials mixture into y82% MAS phase. The MAS
phase content reaches 93% with 50 wt-%C within
60 min. These XRD results clearly reveal that the
MAS powder can be synthesised at much lower time
intervals and with much less electrical energy input in a
MW oven by utilising the chemical potentials of raw
materials when compared with the conventional cal-
cination route in an electric furnace. Nevertheless, the
carbon source is a limitation here to practice this
process commercially.
2

6 X-ray diffraction patterns of MW treated stoichiometric
mixture of aluminium trihydroxide and caustic MgO in
presence of different amounts of carbon69
Mechanochemical synthesis (MS)/mechanical alloying
(MA) is also tried to synthesise MAS powder via solid
state reaction to bring down the powder synthesis costs.
In a study, Mackenzie et al.76 synthesised MAS pre-
cursors by MS/MA using Al(OH)3 and Mg(OH)2 or
basic magnesium carbonate as starting raw materials.
Upon heating of resultant precursors at 850uC yielded
MAS powders. The MAS powder derived from the
hydromagnesite containing precursor showed superior
sintering ability at 1400–1600uC under pressureless
sintering conditions, producing a sintered body of 97%
TD at 1600uC. Under the same conditions, the brucite
derived MAS achieved only 72% TD and showed a
morphology consisting of widely disparate grain sizes. In
a similar way, Kim and Saito77 prepared MAS powder
by milling a mixture of Mg(OH)2 and gibbsite followed
by calcining at y800uC. Although MS/MA could ac-
tivate the solid state reaction at room temperature (RT),
the heat treatment at y800uC was needed. In another
study, Kong et al.78 synthesised MAS powder with an
average grain size (AGS) of y100 nm at 900uC from a
mixture of MgO and Al2O3 high energy milled for 12 h.
The milling operation was carried out in a planetary ball
mill in air at RT. These powders led to dense MAS
ceramics with 98% TD and an AGS of 2–5 mm upon
sintering at 1550uC for 2 h. Yet in another study,
Domanski et al.79 synthesised MAS powders from c-
Al2O3–MgO, AlO(OH)–MgO and a-Al2O3–MgO mix-
tures at RT under air atmosphere following MS/MA
route. The formation of MAS occurred faster with
Ganesh A review on MAS: synthesis, processing and applications
c-Al2O3 than with AlO(OH) or a-Al2O3. After 140 h, in
MS/MA process, the mixture of c-Al2O3–MgO led to the
formation of MAS with 99% phase.
In another study, Kuntz et al.80 described the reaction
bonding method for MAS ceramics that undergo neg-
ligible shrinkage during sintering and possess high gas
tightness in spite of significant residual porosity. In
contrast to conventional fabrication routes, this method
utilises aluminium metal and magnesium oxide as
precursors (MgOz2Alz# 3/2 O2RMgAl2O4). Al or
AlMg alloys used for this purpose had low melting
points close to 660uC and compensated the sintering
shrinkage due to in situ oxidation. The precursor
mixture formed upon milling of reaction mixture was
converted into MAS phase at 1400uC. The MAS yield
was found to be depended on the initial particle size of
raw materials and the diffusion lengths between reacting
species. Yet, in another different study, Henkel et al.81
also synthesised MAS powder by high energy ball
milling of MgO and metallic Al–3 wt-%Mg followed by
calcination at 1400uC. Results noted in this study were
similar to those noted by Kuntz et al.80 Yet in another
study, Ye and Troczynski82 studied the effect of high
energy milling on the decomposition behaviour of
precursors formed by the sol–gel route and on the
formation behaviour of MAS phase. The milling
operation decreased the dehydroxylation temperature
of Al(OH)3 from 190 to y130uC. The activation energy
for MAS formation was decreased from 688 kJ mol21
for the as prepared precursors to 468 kJ mol21 for the
precursors milled for 5 h. Milling of the precursor
mixture lowered the incipient temperature of MAS
formation from 900 to 800uC, and the temperature of
complete MAS spinel formation from .1280 to
y900uC. The activation energy of these reactions has
been calculated following the method developed by
Kissinger.83 Krilova and Stevulova84 studied the kinetics
of solid state reaction of MAS formation during MS/
MA and confirmed it as the first order reaction.
In another study, Kumar and Sandhage85 described
the fabrication of near net shaped MAS bodies in the
form of discs and bars by infiltration of molten
magnesium into porous alumina preforms. A bulk
density (BD) of 3?34 g cm23 (y92?7% TD) with a
minimal dimensional variation after sintering at 1700uC
for 6 h was reported. Since, metallic magnesium is
costlier ($1?53 versus $0?75 per pound) and much lighter
(1?74 g cm23 versus 2?70 g cm23) than aluminium, this
process has been found to be not viable to practice
commercially. Also, the enthalpy of fusion of Mg
(2?14 kcal mol21) is slightly lower than that of Al
(2?58 kcal mol21). Hence, for enhanced penetration of
the liquid metal into an oxide matrix, and for favourable
thermodynamic and kinetic aspects together with the
economy of the process, a combination of Al (l)zMgO
(s) has been suggested. Considering these benefits, Ping
et al.86 used metallic aluminium instead of magnesium
together with MgO to synthesise MAS powder via self-
heat sustained (SHS) route under relatively mild
reaction conditions. Low temperature melting of alumi-
nium and subsequent exothermic reaction between
molten aluminium and magnesia appeared to have led
to a powder with a very high fraction of the MAS phase
with small particle size and narrow particle size
distribution. This powder upon sintering for 4 h at
International Materials Reviews 2013 VOL 58 NO 2 69
Ganesh A review on MAS: synthesis, processing and applications
7 Image (SEM) of MAS whisker grown by heating at
1500uC for 4 h (Ref. 87)
1600uC led to compacts with density as high as y92%
TD.
In another study, Hashimoto and Yamaguchi87
obtained MAS whiskers with a diameter of y3?1 mm
and a length of y4 mm from a mixture of MgO, C and
Al heat treated at 1500uC for 8 h in an atmosphere of
CO and CO2 (Fig. 7). This reaction was believed to
occur via oxidation reduction of reactants. The whiskers
were grown along (111) direction. The oxygen partial
pressure suitable for MAS whisker growth was found to
be in the range of 10212?1–10211?5 MPa. Normally, MAS
whiskers are made by a vapour phase reaction.88,89 In
another study, Wolf and Coskren88 obtained MAS
whiskers by heating a powder mixture of MgO and C in
an Al2O3 tube with a low argon flow at .1550uC. Yet in
another study, Suvorov et al.89 examined the growth of
MAS whiskers by firing rods of MgO and Al2S3 in a 5 : 1
ratio at 1300u and 1800uC in an Al2O3 tube capped with
a graphite lid.
Yet in another study, Xanthopoulou90 synthesised a
MAS powder by self-propagating high temperature
synthesis (SHS) route. The initial charges consisted of
powder mixtures of MgO, Al and Co3O4 (as a dopant to
enhance the catalytic function of the resulting product),
and in some cases, Al2O3, MgO or SiO2. After mixing
the initial components in air, cylindrical samples were
formed by uniaxial compaction at a pressure of up to
20 MPa. These compacts were pretreated at T05770–
920uC in a furnace. Initiation of SHS combustion was
carried out by a small amount of thermite mixture
(85%Fe3O4 and 15%Al).90 The powder obtained in this
process displayed good compressive strength (5–
65 MPa) and low surface area, owing to the high
combustion temperatures achieved by SHS (1?2–
1?8 m2 g21). Nevertheless, the MAS powders prepared
by following the above described solid state reaction
synthesis routes are not suitable for fabricating optically
transparent ceramic windows/domes/armours plates but
for refractory applications.
Soft solution chemistry routes
For certain applications, such as optically transparent
windows/domes/armours, catalysts and catalyst sup-
ports, humidity sensors, etc., the powders formed in
soft solution chemistry routes are preferred because of
their better powder characteristics when compared with
those formed in the solid state reaction routes described
in the previous sections. Soft solution chemistry routes
offer many advantages, such as the potential to control
70 International Materials Reviews 2013 VOL 58 NO
product homogeneity and purity, the size, shape, and
distribution of the resulting ceramic particles and
processing temperatures, which are increasingly neces-
sary for producing advanced ceramic products.91,92
In a study, Bratton93–95 prepared MAS powder by
calcining a compacted stoichiometric mixture of alumi-
nium hydroxide and magnesium hydroxide. This powder
upon compaction and sintering at 1600uC for 6 h
revealed a density equivalent to 96% TD. It has been
reported that the sinterability of wet chemically derived
oxide powders possess close relationship with the pro-
perties of its precursors. In another study, Hokazono
et al.96 hydrolysed a mixture solution of magnesium and
aluminium nitrates using urea as a hydrolysing agent at
90uC to obtain a mixture of gel-like amorphous alumina
hydrate and Mg4Al2(OH)14.3H2O phases. This mixture
led to a dense MAS body with 99% TD upon sintering at
1600uC for 4 h. In another study, an aqueous solution of
magnesium and aluminium nitrates was hydrolysed by
using ammonium bicarbonate as an hydrolysing agent to
obtain a MAS precursor mixture consisting crystalline
ammonium dawsonite hydrate (NH4Al(OH)2CO3.H2O)
and hydrotalcite (Mg6Al2(CO3)(OH)16.4H2O) phases.97
This precursor upon calcination at 1100uC for 2 h
followed by regrinding, recompaction and second firing
under vacuum at 1750uC in 2 h without any sintering
additives led to the formation of translucent MAS
body. Yet in another study, Zawrah et al.98 prepared a
crystalline MAS powder using magnesium and alumi-
nium chlorides as precursors at 1000uC. The die pressed
compacts of this powder upon sintering at 1550uC with
2 wt-%ZnO or 3 wt-%MnO2 as sintering aids exhibited
.94 and 96% TD respectively. These doped samples
exhibited improved mechanical properties when com-
pared with the undoped ones. In another study, Wajler
et al.99 precipitated Mg and Al nitrate precursors using
ammonium carbonate as a precipitating agent leading to
the formation of NH4Al(OH)2CO3.H2O (ammonium
dawsonite). Upon aging, this ammonium dawsonite was
converted into hydrotalcite, Mg6Al2(CO3)(OH)16.4H2O.
The coexistence of both of these phases in very close
contact resulted in their easier decomposition into
crystalline MAS powder. These powders were found to
be highly suitable for fabricating transparent MAS
components. In another study, Rashad et al.100 synthe-
sised a single phase nanocrystalline MAS powder from
anhydrous chlorides of aluminium and magnesium using
either tetraethylammonium hydroxide as a precipitant or
8-hydroxylquinoline as a complexing agent. The MAS
powder formed utilising 8-hydroxylquinoline exhibited a
specific surface area of y182 m2 g21 after calcination at
600uC with small rodlike structures, whereas the one
formed by using tetraethylammonium hydroxide had
spherical shaped particles after annealing at 1000uC. In
another study, Schreyeck et al.101 synthesised MAS
powder by heating the mixture of sulphates of Mg and
Al at 1200–1600uC for 2–14 h. The MAS powder formed
at 1600uC for 14 h exhibited a dielectric constant of 5?5.
Nevertheless, the powders formed in coprecipitation routes
utilising metal chlorides, sulphates, nitrates, carbonates,
etc., as precurors always contain some amounts of leftover
anions as impurities, which are difficult to remove off.
These anion impurities stay at grain boundaries after
sintering and cause scattering of transmitting light, hence
render transulucency to the sintered bodies.
2

8 Image of SEM microstructure of MAS sintered at
1500uC for 3 h (Ref. 105)
The MAS powders without any such anion impurities
could be prepared by following sol–gel route where high
purity alkoxides are utilised as precursors. In a study,
Pacurariu et al.102 synthesised a high purity stoichio-
metric MAS powder using aluminium isopropoxide and
magnesium nitrate as precursors following a sol–gel
route. In another study, Yuan et al.103 prepared MAS
powder via a modified sol–gel route using nitrates as
precursors instead of alkoxides and Xanthan gum and
locust bean gum as gel forming agents. The gels formed
in this process led to a nanometre sized MAS powder
with an average crystallite size of 20 nm upon calcina-
tion at 800uC. In another study, Ye et al.104 prepared
MAS powder following a sol–gel cum precipitation
route, in which aluminium isopropoxide and magnesium
acetate were utilised as the starting materials. The gel
formed in this process led to a fully crystalline
stoichiometric MAS powder upon calcination at
900uC. In another study, Shiono et al.105 synthesised
very fine, chemically stoichiometric, high purity and
highly reactive MAS powder via sol–gel route using a
heterogeneous alkoxide solution that contained very fine
MgO powders. The powder obtained at 1200uC for 1 h
led to a fully dense microstructure upon compaction
under hydrostatic pressure of 350 MPa followed by
sintering at 1500uC for 3 h without the use of any
sintering additive (Fig. 8). Although the sol–gel process
produces single/composite oxide powders with con-
trolled textural and surface properties, atomic homo-
geneity of the powders obtained by this process is rather
poor. The problems associated with the preparation of
atomically homogenous binary oxide materials by the
sol–gel process due to the different hydrolysis and
condensation rates of different metal cations can be
resolved by choosing alternate alkoxide precursor
materials. A less reactive precursor can be given a head
start by allowing prereaction with water. This technique,
known as ‘prehydrolysis’, and is the most commonly
used reactivity matching scheme in the sol–gel synthesis.
On the other hand, a highly reactive precursor can be
slowed down by replacing some of its alkoxy groups
Ganesh A review on MAS: synthesis, processing and applications
with different ligands in a process known as ‘chemical
modification’. The most commonly employed chemical
modifiers include acetic acid and acetylacetone. Owing
to the involvement of expensive alkoxide precursors, the
MAS powders obtained in sol–gel routes are always
expensive, hence are suitable mainly for fabricating high
end products such as optically transparent aromours/
windows/domes only.
Recently, the so called combustion synthesis has
emerged as an effective powder synthesis route which
is simple and economic.106 This process does not require
any acids and bases to hydrolyse the corresponding
salts, and washing, filtration, drying and calcination
steps can be eliminated, which in turn saves a consider-
able amount of energy and time. However, these
powders are rather less sinterable, because of their
lower surface areas and plate-like powder morphology.
It is a well established fact that the morphology, particle
size and surface area of these powders are a direct
consequence of the amount of gases that escape during
combustion. The amount of gases that escape during
combustion mainly depends on the nature and amount
of fuel that is used (i.e. the higher the molecular size and
weight of the fuel the larger the gas generation). As the
distance between the two adjacent metal ions in the
solution increases by the separation of the fuel molecule,
the interaction of the hydrolysed metal ions will
decrease, which in turn results in the powders with fine
particle sizes, higher specific surface areas and a lower
degree of agglomeration. Owing to these advantages, the
solution combustion synthesis is also employed to
prepare MAS powders using different types of organic
fuels either in a conventional electrical oven or in a MW
oven.107–111
In a study, Bhaduri et al.107,112 synthesised nanocrys-
talline stoichiometric MAS powder using metal nitrates
as oxidisers and urea as a fuel. The powder obtained in
this process was consolidated by slip casting route
followed by cold isostatic pressing (cipping) at 275 MPa
for 10 min. Thus, obtained compact was hot isostatic
pressed (hipped) at 1300uC for 4 h to obtain dense MAS
body with a hardness of 779 kg mm22. In another
study, Ganesh et al.109,110 synthesised MAS powders
using sucrose and urea as fuels. The urea derived powder
had an average particle size that is several times larger
than that of the one formed in a sucrose combustion
route. Because of its fine particle size, the sucrose
derived powder had a Breunauer, Emmett and Teller
(BET) surface area of 65?8 m2 g21, whereas the urea
derived one had only y8?06 m2 g21. Furthermore, the
sucrose derived powder was densified to BD of
3?44 g cm23, an apparent porosity (AP) of 1?76% and
a water absorption capacity (WA) of 0?52% upon
sintering at 1625uC for 2 h, whereas the urea derived
powder upon sintering under identical conditions had a
much lower BD (3?24 g cm23). Since urea combustion
derived powders show poor sintering ability, Bhaduri
et al.107,108 employed hipping technique to densify urea
combustion derived MAS powders. In another alter-
native route, to reduce the particle size of urea
combustion derived MAS powders, Ganesh et al.112
performed combustion synthesis experiments in a
commercially available domestic MW oven operated at
2?45 GHz frequency. The batch size had a greater
influence on the characteristics of combustion derived
International Materials Reviews 2013 VOL 58 NO 2 71
Ganesh A review on MAS: synthesis, processing and applications
powders in a MW oven. The surface areas of powders
decreased from 36?8 to 0?1 m2 g21 for MW synthesised
powders and from 126 to 8?1 m2 g21 for conventional
electric oven synthesised powders respectively, when the
batch size was increased from 2 to 100 g. This could be
attributed to the sintering of the sample due to high
adiabatic temperature generated as a result of increased
heat accumulation with bigger batch quantities. The
MW and conventional electric oven derived powders
exhibited grains/crystals with average sizes in the range
of 20–50 nm and 100–250 nm respectively. Yet in
another study, Ianos et al.113 synthesised MAS powder
by following combustion route using metal nitrates as
oxidisers and urea, glycine and b-alanine as fuels. Urea
proved to be the most adequate fuel for aluminium
nitrate, while b-alanine proved to be the proper one for
magnesium nitrate. In the case of MAS, the best results
were achieved only when the mixture of fuels (urea and
b-alanine, urea and glycine) were employed. The use of
fuel mixtures allowed the formation of pure, nanocrys-
talline MAS directly from the combustion reaction,
without any subsequent annealing step. The use of a
single fuel (urea, glycine or b-alanine) led to the
formation of an amorphous powder, which required
further annealing in order to achieve the crystalline
MAS. In a separate study, Pacurariu et al.102 synthe-
sised MAS powder via solution combustion route using
the same set of organic fuels (i.e. urea, glycine and b-
alanine) and compared the properties of the resultant
powders with those of powders obtained in a sol–gel
route from organic precursors. The crystallite size was
strongly influenced by the type of fuel employed. An
average crystallite size of 3?45 nm was noted for urea
combustion derived powder, of 8?34 nm for powder
formed upon calcination of aluminium and magnesium
glyoxylate mixture, and of 10?36 nm for the powder
formed in a b-alanine combustion at 700uC. In another
study, Alinejad et al.114 synthesised nanocrystalline
MAS powder using metal nitrates and a polymer
matrix precursor composed of sucrose and polyvinyl
alcohol. The XRD study of these powders revealed that
the MAS phase formation temperature was between
600 and 700uC for this route. The powder formed at
800uC for 2 h had faceted shaped morphology and its
crystallite size was varied in the range of 8–12 nm.
Further, the ratio of polymeric matrix to metal ions
had a significant influence on the crystallite size of the
MAS powder formed. In another study, Adak et al.115
used polyvinyl alcohol along with stoichiometric mixed
metal nitrate solution to obtain a MAS precursor
mixture. The resultant precursor was transformed into
a fully crystalline MAS powder upon calcination at
800uC. Yet, in another study, Li et al.116 used rather a
new combination of gel forming organic monomers (i.e.
acrylamide, 5 wt-%, and N,N9-methylene bisacryla-
mide, 1 wt-%) to avoid the segregation of metal ions
hydrolysed from magnesium and aluminium nitrates.
An aqueous solution containing these organic mono-
mers, metal nitrates and urea was converted into a
gel with the help of a polymerisation initiator (i.e.
ammonium persulphate at 60uC). The three-dimen-
sional space network formed in the gel held the mixed
Mg–Al hydroxide precipitates in a microarea, which led
to fine nanometre sized MAS particles upon drying and
calcination at y700uC.
72 International Materials Reviews 2013 VOL 58 NO
This solution combustion synthesis route has been
found to be highly beneficial, particularly for composite
oxide powders than the single oxide powders when
compared with the expensive sol–gel route. The combus-
tion synthesised ZrO2–MgAl2O4 composite powders
exhibited much improved sintered properties and
microstructure, when compared with similar composite
powders formed in a conventional solid state reaction
route and with stoichiometric MAS powder formed in
combustion route.110
Recently, hydrothermal synthesis has also received a
great importance for synthesising oxide powders.117,118
Hydrothermal synthesis is a process that utilises single
or heterogeneous phase reactions in aqueous media at
an elevated temperature (T.25uC) and pressure
(P.100 kPa) to crystallise ceramic materials directly
from solution. This method offers many advantages
over conventional and non-conventional ceramic pow-
der synthesis routes. All forms of ceramics can be
prepared with hydrothermal synthesis, namely, powders,
fibres and single crystals, monolithic ceramic bodies,
and coatings on metals, polymers and ceramics. From
the standpoint of ceramic powder production, there are
far fewer time and energy consuming processing steps,
since high temperature calcination, mixing and milling
steps are either not necessary or minimised. Moreover,
the ability to precipitate already crystallised powders
directly from solution regulates the rate and unifor-
mity of nucleation, growth and aging, which results in
improved control of size and morphology of crystallites
and significantly reduces aggregation levels that is
not possible with many other synthesis processes.
The elimination/reduction of aggregates combined with
narrow particle size distributions in the starting
powders leads to optimised and reproducible properties
of ceramics because of better microstructure control.
Considering these advantages, in a study, Chen et al.117
employed hydrothermal route to synthesise MAS
powders. The platelets of MAS with 100–200 nm width
and 25 nm thickness are formed upon hydrothermal
treatment of c-AlO(OH) in a magnesium nitrate
aqueous solution at 400uC. In another study, Amini
et al.118 prepared MAS powder by hydrothermal
assisted sol–gel route using MgAl2(OCH2–CH2OR)8,
where R5CH3, CH2CH2OCH3, MgAl2[OCH(CH3)2]8
and MgAl2(O–sBu)8 as precursors dissolved in toluene.
The gels obtained from Mg–Al alkoxides contained six
coordinated aluminium atoms in solution (reagents 1
and 2), which led to the formation of pure MAS phase
upon calcination at 700uC, whereas under similar
hydrolysis and calcination processes, the precursors of
reagents 3 and 4 contained four coordinated aluminium
and led to the formation of MAS phase along with
some Al2O3 and MgO. Upon processing in hydro-
phobic solvents, spherical particles are formed, while in
the parent alcohol, non-spherical powders are formed.
Recently, freeze drying method has been considered to
be a superior one over spray drying method with respect
to the loose BD of the obtained powders. The skeleton
of the spray dried powder is normally a thin wall hollow
sphere, which leads to the formation of pores in the
sintered samples resulting in low BD. In another study,
Wang et al.119 synthesised highly sinterable MAS
powder using alkoxide precursors via a freeze drying
method. The powder formed in this route upon cipping
2

under 206?8 MPa followed by sintering for 3?5 h at
1500uC exhibited a sintered density of .95% TD. These
sintered MAS samples upon hipping at 1500uC under
200 MPa in Ar atmosphere for 2 h led to a reasonably
good transparency. In another study, metal sulphates
were employed as the starting materials in the same
freeze drying method to prepare MAS powder.120
In a study, Vestal et al.121 synthesised MAS nano-
particles following normal micelle synthesis route. In
this process, initially a normal micelle solution was
prepared by adding an aqueous solution of sodium
dodecyl sulphate to an aqueous solution containing
requisite amounts of magnesium nitrate and aluminium
nitrate. In this micelle solution, the metal nitrates were
hydrolysed by drop wise addition of diluted ammonium
hydroxide solution at pH y10?3. Ethanol was then
introduced into the suspension and the flocculated
particles were collected by centrifugation. After drying
at 100uC, the resultant material was treated at 800uC for
20 h to form fully crystalline MAS powder. Based on the
obtained results, it was concluded that the particle size
could be tuned over the range of 4–20 nm by controlling
the reactant concentration in the micelle solution. In
another study, Meyer et al.122 synthesised nanosized
MAS particles by a sol–gel type hydrolysis of alkoxides
in the inverse micelles of water/oil microemulsions. In
this study, Mg[Al(OPri)4]2, an heterobimetallic alkoxide
was employed as a source of MAS. In this study, the
hydrophilic chain length of the detergent was found to
change with the water droplet size, which had a strong
influence on the resultant MAS powder particle size.
Further, it was noted that the single bimetallic precursor
was found to be superior to produce stoichiometric MAS
powder at relatively lower temperatures when compared
to mixtures of two separate metal alkoxide precursors.
In comparison to powders formed in solid state
reaction synthesis routes, those formed in soft solution
chemistry routes exhibited strong promising for proces-
sing of advanced ceramic products such as optical
transparent domes/windows/armours and have the
tendency to show better performance, as catalysts and
catalyst supports on account of their higher specific
surface areas, smaller particle sizes, controlled crystal
structures and higher purities.
Preparation of thick/thin films
Thin/thick films of MAS have been employed for various
purposes including TBCs, for the blades and vanes in the
hot section components of gas turbines, buffer layers for
the growth of oxide superconductors, ferroelectric ran-
dom access memory applications, humidity sensors
and electroluminescent phosphors.123,124 Initially, MAS
films125 used to be prepared by following physical vapour
deposition methods, such as sputtering, electron beam
evaporation, etc., with relatively inferior characteristics.
However, recently, several advanced techniques, which
rely mainly on chemical reactions, such as chemical
vapour deposition (CVD), metal organic chemical vapour
deposition (MOCVD), atomic layer deposition, plasma
spray techniques, etc., have been developed to produce
thick, as well as thin films, with much improved
characteristics.
In a study, Ihara et al.126 conventionally grown MAS
films from a reaction mixture of Al–HCl–MgCl2–CO2–
H2 at .1000uC, which led to the formation of CO and
HCl as byproducts. The electron Hall mobility and the
Ganesh A review on MAS: synthesis, processing and applications
defect density of the Si active layer on epitaxially grown
MAS were found to be mn51400 cm2 V21 s21 and
16104 cm22, respectively, when the Si thickness was
8 mm and the doping concentration n5261014 cm23.
However, the main shortcoming of this process was the
high reaction temperature. The corrosive and toxic by-
products formed in this process are also strong deterrents
for scaling up of this process. To avoid these problems,
metal organic chemical vapour deposition (MOCVD) has
been introduced for same purposes.127–133 In a study,
MAS thin films were deposited by volatile surfactant
assisted MOCVD at 850–950uC using Mg(thd)2(phen),
Al(acac)3 and O2 as precursors.127 In another study,
Stollberg et al.128 deposited MAS thin film onto silica
substrates following combustion CVD and studied their
performance as over layer on TBCs used in the hot
sections of gas turbines at temperatures in the range of
850–1150uC. In this study, magnesium naphthenate,
bis(2,2,6,6-tetramethyl-3,5-heptanedionato) magnesium
dihydrate (Mg(C11H19O2)2.2H2O and aluminium acet-
ylacetonate were used as precursors. However, the use of
separate sources for the growth of MAS films resulted in
some deviations from stoichiometry in the films, leading
to point defects and precipitates. Moreover, high growth
temperature was also resulted in high tensile stress
and lattice defects in the MAS films, because of the
differences in lattice constants and thermal expansion
coefficients between MAS and silicon. In addition to this
temperature problem, synthesis of MAS device structures
by CVD also require the precise control of the
magnesium to aluminium ratio together with oxygen
content. To avoid these shortcomings, single bimetallic
precursors have been introduced to grown MAS films.128
More recently, stoichiometric MAS films have been
grown at temperatures from 500 to 1000uC, using
magnesium dialuminum isopropoxide, Mg[Al(OiPr)4]2,
a bimetallic precursor with the same 1 : 2 Mg/Al ratio.
The thick MAS films formed have been used as protective
layers for zirconia electrolytes in solid oxide gas sensors.
In another study, Zhang et al.129 used Mg[Al(OiPr)4]2, a
commercially available single bimettalic precursor, to
grow polycrystalline crack free stoichiometric MAS film
on the surfaces of Si(100) and MgO(l00) substrates at the
deposition temperature of 400–600uC, following both
thermal and plasma enhanced MOCVD. The resultant
films had the same composition of Mg/Al ratio as in the
starting compound (Mg/Al51 : 2) over a wide range of
deposition conditions. Further, the deposition tempera-
ture required for the formation of crystalline MAS was
found to be significantly reduced and crystallinity was
much improved on Si substrate when a remote plasma
enhanced MOCVD process was employed. The MAS
films deposited on Si(100) by plasma enhanced MOCVD
at 700uC were epitaxial with a breakdown voltage greater
than 106 V cm21 for films which were 3 mm thick,
suggesting that the MOCVD deposited MAS thin films
are useful for many electronic applications.130
In a separate study, Mathur et al.131 investigated the
chemical and material aspects of MAS thin films formed
from three single molecular bimetallic precursors,
[MgAl2(OPri)8], [MgAl2(OBut)8] and [MgAl2(OBut)4H4],
in the gas phase. These precursors are termed as MA1,
MA2 and MA3 respectively. The properties of the MAS
films formed from these precursors are a strong function
of the composition of the precursor molecule. The
International Materials Reviews 2013 VOL 58 NO 2 73
Ganesh A review on MAS: synthesis, processing and applications

9 Image (SEM) of MAS films deposited on Fe at 550uC using a MA1, b MA2 and c MA3 respectively131

formation of these single molecular precursors can be Plasma spraying is a rapid heating, cooling and
shown with the following reactions solidification process that often results in the formation
of deposits characterised by a coarse grain structure,
MgCl2z2LiAlH2 (OBut )2?½MgAl2 (OBut )4 H4 z2LiCl (1) significant porosity (generally in the range 8–15 vol.-%)
and a lamellar morphology. Usually, coarse structures
½MgAl2 (OBut )4 H4 z(excess)Pri OH? are produced because spraying processes use coarse
powders (20–90 mm) as feedstock materials. In a
½MgAl2 (OPri )8 (Pri OH)2 z2H2 (2)
process, Bertrand et al.134 studied the morphology and
crystalline structures of MAS thin films resulted via the
½MgAl2 (OPri )8 (Pri OH)2 zD, vacuum? dried particle plasma spray technique in which non-
sintered spray dried particles were directly introduced in
½MgAl2 (OPri )8 {2Pri OH
the plasma spray torch. Indeed, the dried particle plasma
½MgAl2 (OBut )4 H4 z(excess)But OH?
½MgAl2 (OBut )8 z2H2 (3)
The SEM micrographs of MAS thin films deposited on
Fe at 550uC using MA1, MA2 and MA3 respectively, are
presented in Fig. 9, and the cross-sectional SEM images
of MAS films formed on silicon substrate from MA1,
MA2 and MA3 are presented in Fig. 10.131 The features
of these micrographs reveal that the MAS thin films
formed from single molecular precursors are quite
comparable with those formed in the physical vapour
deposition routes.131
In another study, Rocheleau et al.132 deposited
amorphous thin films of MAS onto crystalline silicon
and glass substrates from the metal alkoxide source,
Mg[Al(OPri)4]2, at temperatures between 250 and 500uC.
The growth rate was found to be negligible at 250uC, but
increased with substrate temperature between 300 and
425uC, consistent with a surface reaction limited process.
Above 425uC, the growth was limited by the availability
of reactant, and no further increase in the conversion
efficiency or the growth rate was observed. The volatility
of the alkoxide source allowed vapourisation at modest
source temperatures, between 120 and 170uC. In fact,
the liquidity of the alkoxide at temperatures below
100uC offers the possibility of low cost, high rate spray
pyrolysis as a means of film deposition.
Yet, in another study, Putkonen et al.133 prepared
MAS films by atomic layer deposition at 100–400uC onto
soda lime glass and Si(100) substrates using (C5H5)2Mg,
(CH3)3Al and H2O as precursors. As deposited films were
amorphous while films annealed at 800uC exhibited a
strongly (111) oriented MAS structure. Film rough-
ness was found to depend on the pulsing ratio of the 10 Cross-sectional SEM images of MAS films on silicon
precursors. obtained from a MA1, b MA2 and c MA3131

74 International Materials Reviews 2013 VOL 58 NO 2


11 Apparatus for growing MAS single crystals136
spray process makes it possible at the same time to
achieve thin structures with competitive deposition
efficiencies, since it is based on solid precursors and to
complete in-flight chemical reactions, as the initial
components are of small size and are intimately mixed.
It was demonstrated that the morphology and chemical
composition of the splats produced were heavily
dependent on both the plasma characteristics (nature
and power) and the powder injection parameters (carrier
gas flowrate and injector angle). Owing to very fine
mixing of the elementary powders, the starting oxides
(MgO and Al2O3) react together to form MAS phase. By
reducing the size of the starting aggregates, a roughness
Ra as low as 3?8 mm was achieved for a 200 mm thick
coating. Two different types of splats were identified.
The first one consisting of individual well melted
droplets and in the case of second one, the starting
aggregates melted at their outer parts and just strength-
ened in their cores. The former was dominant in an Ar/
H2/70uC plasma that led to dense coatings built of 1 mm
thick splats, whereas, the latter was dominated in an
Ar/He/90uC plasma, which led to porous coatings. It
can be concluded from these discussions that MOCVD
of bimettalic single precursors could be better op-
tions to fabricate reliable MAS thin films for various
applications.
Fibres and single crystals synthesis
Apart from thin films, MAS fibres135 and single
crystals136 are also required for certain applications.
MgAl2O4 spinel single crystals are widely used for bulk
acoustic wave and MW devices and fast IC epitaxial
substrates. It is also found that MAS is a good substrate
for III–V nitride devices. In a study, Liu and Laine135
synthesised MAS fibres by the pyrolysis of extrudates
formed from a precursor that was recovered by vacuum
evaporation of the solvent from a stoichiometric mixture
of magnesium acetate and aluminium formate dissolved
in H2O with stabilising additives. The MAS precursor
Ganesh A review on MAS: synthesis, processing and applications
12 Single crystal boule of stoichiometric MAS grown by
flame fusion with in situ annealing137
behaved like a separate compound and decomposed
to crystalline MAS directly at y600uC, without any
conclusive evidence of phase separation. Furthermore,
this MAS precursor could be easily extruded or hand
drawn to form well defined green fibres. The 20 mm
diameter extruded fibres could be pyrolysed at 300uC for
2 h in air to remove carboxylate ligands, and could be
sintered at the rate of 15uC min21 to 1500uC for 2 h in
air to obtain final fibres with a diameter of y10 mm,
1?2¡0?4 mm grain size and average bend strength of
1?0¡0?4 GPa.
In another study, Bratton and Ho136 grown MAS
spinel single crystals and fibres on alumina substrates
using a custom built furnace (Fig. 11). This furnace was
heated with a 40 kW Ajax-Northrup spark gap gen-
erator. The single crystals were grown on the outer wall
of the MgO crucible at 1800uC for 6 h in argon
atmosphere. The MAS crystals are formed on the
surfaces of sintered Al2O3 substrate and grew toward
the MgO cover. Fibres grew up to 25 mm long with
diameters between 7 and 80 mm. Representative platelet
dimensions noted are: up to 5 mm long, 0?2–1?2 mm
wide and 0?014–0?05 mm thick. Several very thin
platelets suitable for electron transmission studies are
also formed. A single crystal boule (7/8 inches long and
5/16 inches diameter) of stoichiometric MAS (Fig. 12)
was also grown by flame fusion method (Verneuil
process) at 1910uC and then annealed in situ from
1450 to 400uC at y10uC h21 by Arlett and Robbins.137
In this process, a mixture of 33?3 mol.-% MgSO4–7H2O
and 66?7 mol.-% AlNH4–(SO4)2.12H2O was heated in
an alumina tray to 400uC to form a porous cake. This
cake was crushed and calcined at 1200uC in a Globar
furnace for 16 h. The resultant powder was then
screened into the mesh fraction of 2120 to z200 and
then used as feed powder in the flame fusion furnace. A
MAS single crystal boule is grown out of this powder
with and without seeds, using a multiple tube flame
fusion burner and a Pt10Rh wound after heater for in
situ annealing of the boule. Crystals are grown, while the
heater was set at 1450uC. Following the growth of the
MAS crystal, the boule was lowered into the hot zone of
the heater. At this point, the gases are slowly turned off
and the boule was cooled at 10uC h21 to 400uC.
Spectral characterisation of MAS
powders
A thorough characterisation of pure and various metals
doped MAS powders with respect to crystal structure
and its effect on electrical, magnetic, dielectric, optical
and mechanical properties is very much necessary to
evaluate their functions, full potential and suitability for
International Materials Reviews 2013 VOL 58 NO 2 75
Ganesh A review on MAS: synthesis, processing and applications
13 Fourier transform infrared spectra of A-MAS and T-
MAS powders138,139
various new upcoming applications in the different
branches of industry and society, and to understand the
diffusion mechanisms of metal ions during densification
of these ceramics under different sintering conditions.
The following sections present the various spectral
characteristics of MAS and doped MAS powders.
Figure 13 shows the Fourier transform infrared spec-
tra of two different MAS powders recorded between
400 and 4000 cm21.138,139 A-MAS is a as synthesised
powder, whereas the T-MAS is a powder surface treated
against hydrolysis in an ethanolic solution of phosphoric
acid at 80uC for 24 h.138,139 Both powders exhibit two
major transmittance bands at 509 and 698?85 cm21, a
medium size transmittance band at y3450?6 cm21 and a
minor transmittance band at 1625?2 cm21. The A-MAS
powder exhibits two additional minor transmittance
bands at 2334?6 and 2893?2 cm21, whereas the T-MAS
exhibits a new band at y1092?5 cm21. The common
transmittance bands shown by both the powders at
y3450 cm21, and at y1625 cm21 correspond to broad
–OH stretching and H–O–H bending vibrations respec-
tively. The transmittance bands noted at y698?85 cm21
and at 509 cm21 correspond to the AlO6 groups, which
built up the MAS and indicate the formation of MAS
powders. Pure H3PO4 normally reveals a small trans-
mittance band at 500–550 cm21, a large transmittance
band at 1500–1800 cm21 and a low intense band at
2000–3200 cm21, due to different vibrations of phos-
phate molecule.139 The absence of two transmittance
bands, around 2334?6 and 2893?2 cm21 and the presence
of a new transmittance band at 1092?5 cm21 in T-MAS
powder indirectly suggests that the phosphate coating
on the surface of the treated powder is restricting the
vibrations of some of the functional groups, which
might have been blocked by H2 PO{ 4 groups. The
76 International Materials Reviews 2013 VOL 58 NO
14 Raman spectra of natural MAS of Mongaragàla District,
Sri Lanka (Harvard Mineralogical Museum no. 126100)
containing 27?33%MgO, 71?45%Al2O3 and 1?08%FeO
along with some small impurities140
presence of band at 1092?5 cm21 in the T-MAS can be
attributed to the phosphate coating formed on the
surface of the powder.
In a study, Slotznick and Shim140 investigated a
high purity naturally occurred MAS having a chemi-
cal composition of 27?33%MgO, 71?45%Al2O3 and
1?08%FeO along with some small other metal impurities
by gated Raman spectroscopy (Fig. 14) to know the
cation exchange in tetrahedral and octahedral holes (i.e.
to find out whether it is a normal or inverse spinel) as a
function of temperature between ambient to 1400uC. In
the normal MAS, Mg and Al atoms are normally in the
tetrahedral and the octahedral sites respectively. Some
Al atoms enter into the tetrahedral sites through an
order disorder transition at high temperatures
IV
MgVI Al2 O4 'IV (Mg1{x Alx )VI (Al2{x Mgx )O4 (4)
where the superscripts represent the coordination
numbers of the cations and x is the fraction of Al
atoms in the tetrahedral sites, known as the inversion
parameter. Spinels with x50 and x51 are called
‘normal’ and ‘inverse’ respectively. Since MAS belongs
2

15 First Brillouin zone of fcc MAS (MgAl2O4) structure (C:
centre of Brilliun zone; M: centre of edge; K: middle
of edge joining two hexagonal faces; L: centre of hex-
agonal face; U: middle of edge joining hexagonal and
square face; W: corner point; X: centre of square
face)142
to Fd3m space group, it is expected to reveal five Raman
active modes.141 The first Brillouin zone of face centre
cubic spinel MAS structure can be seen from Fig. 15.142
In some MAS powders, more Raman modes can be
observed than predicted by group theory. It has been
suggested that most of these extra features are related to
cation disorder. An extra mode noted at 727 cm21 in
synthetic and heat treated natural MAS is attributed to
the partially inverted MAS. In addition, an asymmetric
broadening of the most intense mode at 410 cm21, e.g. is
related to cation disorder, as it is observed only in
synthetic or heat treated natural MAS. This Raman
spectrum also reveals that there is an irreversible cation
disordering in the MAS at 1100–1200uC, as there is a
rapid broadening in the mode at 409 cm21 and the
appearance of two weak modes at 210 and 520 cm21 at
16 Spectrum (EPR) of MAS/Cr (equivalent to 0?01 mol.-%Al)
at RT143
Ganesh A review on MAS: synthesis, processing and applications
17 UV visible diffuse reflectance spectrum of MAS/Cr
(equivalent to 0?01 mol.-%Al)143
the transition temperature (1100–1200uC). Furthermore,
there is a change in the frequencies of modes at 313 and
666 cm21 at the transition temperature. The discontin-
uous frequency decrease of the mode at 313 cm21 and
the increase in the frequency of the mode at 666 cm21
have been explained by the entrance of heavier Al atoms
into the tetrahedral sites and the entrance of lighter Mg
atoms into the octahedral sites respectively.
In another study, Singh el al.143 investigated the in-
fluence of chromium impurity equivalent to 0?01 mol.-%
of Al3z on the optical properties of MAS host by elec-
tron paramagnetic resonance (EPR) and diffuse reflec-
tance UV visible spectroscopy techniques. Figure 16
shows the EPR spectrum of MgAl2O4/Cr3z powder
recorded at RT.143 It can be seen that in the low field
region, an intense broad resonance signal is present at
g53?82, along with a few weak resonance signals at
g55?37 and 4?53. In another study, Bray144 reported
that in strong crystal fields, where the zero field splitting
exceeds the energy of MW, the EPR spectra of Cr3z is
dominated by a peak at geff53?8 in the case of uniaxial
crystal field symmetry, and by a signal at geff55?4 for an
ortho rhombic field. As the Cr3z ions belong to d3
configuration with 4A2g as ground state, the four fold
spin degeneracy of the ground state 4A2g is removed by a
subsequent low symmetric field and splits into two
Kramers doublets, MS5¡3/2 and ¡1/2. If there is a
large separation between these two doublets then the
resonance at g52?6.145 The signals at low field region are
normally attributed to isolated Cr3z ions, where as the
signal in the high field region near g<2 is an indication
of Cr3z ions that may occur in pairs.146 In the study of
Singh el al.,143 the signal at g51?96 could be assigned to
exchange coupled Cr3z ions, whereas the resonance
signals at g55?37, 4?53 and 3?82 are due to isolated ions.
Figure 17 shows the optical spectrum of MgAl2O4/
Cr3z phosphor recorded at RT.143 The spectrum is a
characteristic of Cr3z ions in octahedral symmetry. For
Cr3z ions in octahedral symmetry, three spin allowed
transitions 4A2g(F)R4T1g(F), 4A2g(F)R4T2g(F) and
International Materials Reviews 2013 VOL 58 NO 2 77
Ganesh A review on MAS: synthesis, processing and applications
a excitation spectrum at lem5686 nm; b emission
spectrum at lex5551 nm (Ref. 143)
18 Typical photoluminescence spectra of Cr3z (equiva-
lent to 0?01 mol.-%Al) doped MAS
4
A2g(F)R4T1g(P) are expected. The two broad bands
observed at 371 nm (26 945 cm21) and 551 nm
(18 145 cm21) are assigned to the transitions 4A2g(F)R
4
T1g(F) and 4A2g(F)R4T2g(F) respectively. The band in
the UV region at 262 nm was assigned to charge transfer
band of Cr6z–O22.
Figure 18 shows photoluminescence excitation and
emission of MgAl2O4/Cr3z phosphor at RT.143 The
photoluminescence spectrum of MgAl2O4/Cr3z phos-
phor has been characterised by the transitions of 3d3 of
Cr3z ions acting as an activating centre. The excitation
spectrum mainly consists of two intense broad bands
observed at 420 nm (23 803 cm21) and 551 nm
(18 145 cm21) and were assigned to the transitions
4
A2g(F)R4T1g(F) and 4A2g(F)R4T2g(F) of Cr3z ion
respectively. The emission spectrum is typical for Cr3z
ions in octahedral site. The intense sharp peak around
686 nm (14 573 cm21) is the well known R line, which is
assigned to the 2EgR4A2g transition of Cr3z ions. The
weaker lines at 674 nm (14 833 cm21) and 706 nm
(14 160 cm21) are vibronic side bands. Further, it can
be seen from the expanded R line region that the R
lines are slightly resolved as two lines at 686 nm
(14 573 cm21) and 689 nm (14 510 cm21). From the
data of Figs. 16218, it could be concluded that the
Cr3z ions in this phosphor are in distorted octahedral
symmetry. The number of spins N participating in
resonance at g51?96 increase with decreasing tempera-
ture obeying the Boltzmann law. The red emission is
around 686 nm in MAS lattice, which has been
attributed to the Cr3z substitution in Oh sites of
Al3z ions and is assigned to 2EgR4A2g transition from
Cr3z ions.
The emission spectra of MAS doped with 0?005, 0?01,
0?015 mol.-%Tb3z are presented in Fig. 19.147 Each of
these spectra could be divided into two parts. The
emission between 400 and 450 nm is due to transitions
from the 5D3 excited state. Above 480 nm, the emission
peaks are originated from 5D4 excited state. The
5
D4R7FJ (J56, 5, 4, 3) characteristic emissions of
Tb3z, at 415, 438, 488, 543, 586 and 623 nm, are
assigned to the transitions of 5D3 to 7F5, 7F4 and 5D4 to
7
F6, 7F5, 7F4 and 7F3 respectively. Under an UV lamp, a
78 International Materials Reviews 2013 VOL 58 NO
19 Emission spectra of MgAl2O4/Tb3z powder phosphors
with lexci5350 nm (Ref. 147)
strong green luminescence could be observed. The
corresponding emission spectra of MgAl2O4/Tb3z
indicate narrow emissions which are attributed to
4
fR4f transitions within Tb3z ions. Among the mea-
sured emission transitions, the green emission transition
5
D4R7F5 at 543 nm shows higher intensity due to the
nature of Tb3z dopant ion in the host matrix. The other
three peaks seen at 488 nm (5D4R7F6), 586 nm
(5D4R7F4) and 623 nm (5D4R7F3) are attributed to an
excitation at 350 nm. Emission intensities from 5D3
excited state decrease with the increase in the terbium
concentration and shows a maximum intensity at
543 nm. This phenomenon is attributed to the energy
transfer from 5D3 excited state to 5D4 excited state.148
Comparing the emission intensities of the different
doping concentrations of Tb3z, it could be observed
that in the range of 0?005–0?015 mol.-% doping con-
centrations, the luminescent intensities originating from
the Tb3z, 5D4R7FJ (J56, 5, 4, 3) transitions increased
with an increase in concentration; as a result, the
luminescent intensity reached a maximum at 0?01
mol.-%Tb3z.
Figure 20 shows the TEM and high resolution TEM
(HRTEM) of nanosized MAS powder formed at 1150uC
for 4 h by the molten salt baking of aqueous solution
containing high purity NH4Al(SO4)2.12H2O and
MgSO4.7H2O in 2 : 1 molar ratio.149 The average size
of crystals in these micrographs is y35 nm. Some larger
particles could be 40 nm and some smaller particles
could reach up to 25 nm relatively homogeneously. The
TEM and HRTEM analyses show that the formed
powder in this method is well crystallined with few
defects. The highly transparent nanoceramics were
formed from this powder exhibited a transmittance
T<80%.149 These results suggest that the well dispersed
nanosized powders could be prepared following a low
cost melted salt method at 1150uC for 4 h.
Figure 21 shows the electron spin resonance (ESR)
spectra of MgAl2O4/V single crystal recorded at
2223uC.150 This colourless transparent MAS single
crystal was synthesised by Fujimoto et al.150 from a
melt of MgO (99?99%) and Al2O3 (99?999%) in an
oxidising atmosphere, following the floating zone
method in which a Xe lamp was used as a heating
source. A hyperfine structure with eight components
came from vanadium nuclei (I57/2), but intensities of
2

20 a TEM and b HRTEM of nanosize MAS powder calcined at 1150uC for 4 h (Ref. 149)
these signals are by two orders of magnitude weaker,
compared with the total number of doped vanadium
ions. They have estimated the number of spins by
comparing the signal intensity with a known concentra-
tion of standard sample under non-saturating condition
with due consideration for temperature, g values, spin
quantum number and sensitivity of the spectrometer.
This ESR study indicates that the doped vanadium ion
exist as V5z (S50, 3d0) in the electronic ground state
mainly at B sites and as a small density of V5z at A site.
In another study, Izumi et al.151 examined the valence
band photoemission spectra (XPS) of single crystals of
pure MAS and Zn doped MAS obtained by the same
above mentioned floating zone method (Fig. 22). Since
the photo-ionisation cross-section of the Zn 3d subshell
is larger, when compared with that of O 2p subshell at
photon energy of 1486?6 eV, the Zn 3d band could be
seen at y14 eV in the valence band spectra. In the case
of pure MAS, the broad spectral feature is seen above
the O 2p band and below the Fermi level, as indicated by
an arrow in Fig. 22. This broad spectral feature is
probably derived from the Al–Mg antisite defects. In Zn
doped MAS, the broad spectral feature disappears and
the relatively sharp edge structure appears just above the
O 2p band (also indicated by the arrow in Fig. 22).
In a study, Hosseini152 calculated the structure, band
structure, total density of states, dielectric function,
reflectivity, refractive index and loss function for MAS
using density functional theory. The full potential
linearised augmented plane wave method was used with
the generalised gradient approximation. Calculations of
21 Spectrum (ESR) of 1?0%V doped MAS single crystal
at 2223uC (Ref. 150)
Ganesh A review on MAS: synthesis, processing and applications
the optical spectra have been performed for the energy
range 0–40 eV. It was shown that the material is
transparent at visible wavelengths and the dispersion
curve of the refractive index is fairly flat in the long-
wavelength region and rises rapidly towards shorter
wavelengths. The refractive index is 1?774 at 800 nm
near the visible region.
The calculated electronic band structure for MAS
along the high symmetry directions is shown in
Fig. 23.152 The calculations were performed using
generalised gradient approximation with the relaxed
atomic positions. The overall band profiles calculated in
this work are consistent with other first-principles
calculation results reported previously.152 The scale of
energy in all figures is in eV and the top of the valence
band is set to zero (Fermi level) on the energy scale. The
valence bands are separated by a 5?2 eV direct gap at C
point from the conduction band states (Fig. 15).
Experimentally, the optical reflectivity measurements
reported the minimum band gap of MAS to be direct at
C with a value of 7?8 eV (Fig. 15).152 Hossini calculated
band gap is smaller than the experimental values. This
discrepancy could be arisen from the generalised
22 Valence band photoemission spectra of pure MAS
and Zn doped MAS151
International Materials Reviews 2013 VOL 58 NO 2 79
Ganesh A review on MAS: synthesis, processing and applications

gradient approximation, which is known to under-

estimate the energy band gap of insulators. There are
two indirect band gaps in the [111] and [101] directions,
along C–L and C–X (Fig. 15), with values of 7?5 and
8?2 eV respectively.
Figure 24 shows the calculated total density of states
for MAS structure.152 The lower O 2s band splits into
two: a very sharp peak at 216?0 eV and a lower part
2?0 eV wide with double peaks. The sharp structures in
the energy range 218?2 to 215?5 eV are mainly due to O
2s states. The upper valence band is composed mostly of
O 2p states and hybridised with Mg 3s and Al 3p
orbitals. The conduction band has compounds from
both Mg 3s and Al 3p states. The electron density of
MAS in the (100) plane for two and three dimensions is
plotted in Fig. 25.152 This plane does not contain any
magnesium ions and shows the oxygen ions (large
circles) and aluminium ions (small circles) which are
arranged diagonally between each other. In Fig. 26, the
electron density in the (110) plane for two and three
dimensions is shown.152 This plane contains all three
types of ions. Between two rows of magnesium ions of
this plane there is an empty channel with almost no or
little charge.
Hossini also recorded the electron energy loss spec-
trum of MAS (Fig. 27).152 Normally, plasmon losses
correspond to a collective oscillation of the valence
23 Band structure of MAS152 electrons and their energy is related to the density of

24 Total density of states of MAS structure and total Mg, Al and O atoms152

80 International Materials Reviews 2013 VOL 58 NO 2


25 Electron densities of MAS in (100) plane in a two and b three dimensions152
26 Electron densities of MAS in (110) plane in a two and b three dimensions152
valence electrons. In the case of interband transitions,
which consist mostly of plasmon excitations, the
scattering probability for volume losses is directly
connected to the electron energy loss function.
Figure 27 also shows other peaks and features in
addition to the plasmon peak, associated with interband
transitions. The plasmon peak is usually the most
intense feature in the spectrum and this is at an energy,
where the real part of the frequency dependant dielectric
function goes to zero, after the zero loss peak; the zero
loss peak is absent in this spectrum. Hosseini152 also
recorded the dispersion curve of the refractive index of
MAS (Fig. 28). The curve is fairly flat in the long
wavelength region and rises rapidly towards shorter
wavelengths, showing the typical shape of a dispersion
curve near an electronic interband transition. The strong
increase in the refractive index is associated with the
27 Electron energy loss spectrum of MAS152
Ganesh A review on MAS: synthesis, processing and applications
fundamental band gap absorption. The refractive index
is 1?774 at 800 nm near the visible region; the
wavelengths of visible light are shaded.
The CT lines in the 27Al MAS NMR spectra of the
untreated and heat treated (at 1450uC for 9 h) MAS
samples are shown in Fig. 29.153 The two spectra show
the same trend: a prominent line in the range 220–
10 ppm corresponding to AlO6 octahedra and a less
intense line in the range 50–80 ppm, which is character-
istic of Al atoms in a tetrahedral environment. The
characteristic quadrupolar second order contribution
line shapes are broadened due to the statistical distribu-
tion of Mg and Al atoms on O (octahedral) and T
(tetrahedral) sites. These spectra are consistent with
those reported previously in the literature.50 The
intensity of the [Al] T peak obviously decreases with
the heat treatment. Proportions of different aluminium
28 Wavelength dispersion curve of refractive index for
MAS152
International Materials Reviews 2013 VOL 58 NO 2 81
Ganesh A review on MAS: synthesis, processing and applications

a as received; b heat treated at 1450uC/9 h/N2

29 High resolution 27Al CT MAS NMR spectra of synthetic MAS: lines labelled as * are spinning side bands of satellite
transitions153

sites are obtained upon performing a numerical integra-

tion of the experimental lines. Aluminium proportions
in the O and T sites for synthetic MAS are summarised
in Table 3.50 This suggests that cation disorder in the
MAS is partially reduced after annealing. One can
remark that the natural MAS is normal, but becomes
inverse upon heating.
Properties of MAS powders
A thorough study and understanding of various proper-
ties, such as thermodynamic, thermal, dielectric, mag-
netic, mechanical and optical are very much important
to find out the suitability of MAS ceramics in several
other new fields and applications. The following sections
discuss about various properties of MAS ceramics.
Thermodynamic properties
In a study, Jacob et al.154,155 measured Gibbs energy,
enthalpy and entropy of reaction (MgOzAl2O3R
MgAl2O4) in a solid state cell using single crystal CaF2
as the solid electrolyte in the temperature range of 627 to
977uC. The oxidation and reduction half cell reactions of
this cell can be represented as
Pt,O2 ,MgOzMgF2 jCaF2 jMgF2 zMgAl2 O4 zaAl2 O3 ,
O2 ,Pt
1 electrode is a measure of the Gibbs energy of formation
MgF2 z O2 za-Al2 O3 z2e{ ?MgAl2 O4 z2F{
2 DGf of nanocrystalline MAS from its component oxides in
MgOz2F{ ?MgF2 zO2 z2e{
Since oxygen partial pressure is same over both the
electrodes, the net cell reaction can be represented as
Table 3 Al atoms repartition rates in MgAl2O4 samples50
MgAl2O4 sample [Al]O d/ppm [Al]T d/ppm
As received 78 13.7 22 68.5
Annealed 88 13.4 12 72.1
MgOza-Al2 O3 ?MgAl2 O4 (8)
Hence, the standard Gibbs energy change for this
reaction (8) is directly related to the emf of the cell E
by the Nernst equation (9)
DG8o ~{2FE
~{23600{5:91T(+150) J mol{1 (9)
where DG6 is the standard Gibbs energy change for
reaction (8) and F is the Faraday constant. The tem-
perature independent term on the right hand side of
equation (9) gives a ‘second law’ enthalpy of formation of
MAS from component oxides at a mean temperature
of 800uC. The derived value (223?6¡1 kJ mol21) is
in good agreement with calorimetric values of 224?8
kJ mol21 at 692uC and 222?3 kJ mol21 at 900uC re-
ported by Shearer and Kleppa,156 of 222?5 kJ mol21 at
700uC by Charlu et al.157 and of 223?8 kJ mol21 at 700uC
by Navrotsky et al.158 The ‘second law’ entropy of
formation of MAS from oxides derived from the study
of Jacob et al.155 (5?91¡1?0 J (mol21 K21) at an average
temperature of 800uC is smaller than the evaluated value
(8?7¡4?2 J (mol21 K21)) in JANAF tables.155 If the
particle size of MAS is 3 mm, then emf of the cell E gives
essentially the standard molar Gibbs energy of formation
(5) of MAS DGfo from its component oxides.154 The emf of the
cell with nanocrystalline aluminate material at the working
(6)
their normal thermodynamic reference states
(7)
DGf ~{2FE (10)
where F is the Faraday constant. The corresponding
enthalpy and entropy of formation of MAS for each
particle size can be obtained from the temperature
coefficient of emf
i/%
DHf ~{2FEz2FT(dE=dT) (11)
44
24
DSf ~2F (dE=dT) (12)

82 International Materials Reviews 2013 VOL 58 NO 2


30 Plot of resistivity versus temperature for a MAS synthesised at pH 5–10 and b MAS and MgAl1?8M0?2O4 (where
M5Cr3z, Mn3z and Fe3z)23
The enthalpy and entropy of formation of MAS are
average values in the temperature range of measurement.
These thermodynamic property values increased linearly
with surface area
DGf (9270 C)~{30 740z0:7514A(+300) J mol{1 (13)
DHf ~{23 690z1:299A(+1300) J mol{1 (14)
DSf ~5:878z4:565|10{4 A(+1:1) J mol{1 K{1
These results indicate that nanocrystalline MAS with
13 nm (A518, 237 m2 mol21) average particles has a
higher enthalpy relative to its component oxides (MgO and
a-Al2O3) in the microcrystalline form. With particles below
5?8 nm (A540, 910 m2 mol21) at 927uC, the Gibbs energy
of the MAS was found to be higher than that of an
equimolar mixture of microcrystalline component oxides
of alumina and magnesia.
Electric, dielectric and magnetic properties
In a study, Iqbal and Ismail23 studied electrical,
dielectric and magnetic properties of transition metals
doped MAS powders. The resistivity of MAS is slightly
influenced by the pH of the starting precursor solution
utilised for powder synthesis (Fig. 30a). The metal–
semiconductor transitions are clearly evident at a
temperature TMS depending upon the nature of the
dopant in MAS and MgAl1?8M0?2O4 (where M5Cr3z,
Mn3z, Fe3z) in the temperature range of 25–400uC
(Fig. 30b).23 TMS is the metal–semiconductor transition
temperature at which resistivity of the sample reaches a
maximum; a semiconducting behaviour (negative Dr/
DT) above TMS (T.TMS) and metallic behaviour
(positive Dr/DT) below this temperature (T,TMS).
31 Plot of dielectric constant against frequency for a MAS synthesised at pH 5–10 and b magnesium aluminate synthe-
sised at pH 5–10 (Ref. 23)
Ganesh A review on MAS: synthesis, processing and applications
Resistivity values initially decrease up to a temperature
T of about 65–87uC, which is attributed to the moisture
absorbed by the samples and other impurities like CO2
gas trapped from air, etc. These trapped impurities
escape at T of about 65–87uC and causes an increase in
the resistivity values up to a temperature T5TMS, at
which sufficient activation energy is available to
thermally activate the charge carriers followed by the
decrease in resistivity throughout the remaining tem-
perature range as a result of liberation of the trapped
charges. This trend is a normal behaviour of semicon-
ductors. This kind of changes in resistivity values is
attributed to the migration of excess Al3z cations from
octahedral sites to the tetrahedral sites in alumina rich
non-stoichiometric aluminates.
The dielectric constant e9 and the dielectric loss tan d
of MAS formed under different pH conditions show
similar trends (Fig. 31).23 Polarisation in the samples is
normally induced due to the applied electric field at the
expense of electronic exchange between Al3z and Al2z.
The dielectric constant decreases with the increase in the
frequency eventually becoming constant at higher
frequencies. The dielectric constant and dielectric loss
reveal higher values at lower frequencies. Polarisation
decreases at higher frequencies as the dipoles do not
have enough time to follow the reversal of the electric
field at higher frequencies. Owing to space charge
polarisation, cations can migrate to vacancies, forming
an electric double layer so that the material can behave
as a conductor as has been seen in the resistivity curves
below TMS, or it is due to a change in volume or
structure at the transition point. These samples show
low range dielectric constant values from 8?26 to 10?21
at various pH values and the one at pH 9 exhibits the
lowest value.
International Materials Reviews 2013 VOL 58 NO 2 83
Ganesh A review on MAS: synthesis, processing and applications
32 Fracture toughness versus temperature for MAS com-
paring three test methods161
The pure MAS exhibited a negative magnetisation M
and the both Mn and Cr doped MAS derivatives, a
diamagnetic behaviour at RT with the increase in
applied magnetic field H.23 Nevertheless, a paramagnetic
behaviour, i.e. positive magnetisation with the applied
field for MAS doped with Fe is noted. Magnetic
properties of solid solutions comprising tetragonal
MgMn2O4 and cubic MAS have been measured by
Keer et al.,159 but the effects of the substitution of
transition metals on the spin orientations of doped MAS
samples have not been given much attention. The results
of Iqbal and Ismail23 study reveal that by the substitu-
tion of various cations into the MAS lattice the magnetic
ordering of the spins could be altered.
Mechanical properties
In a study, Stewart and Bradt160 investigated the
temperature dependent fracture toughness of single
and polycrystalline MAS for different grain sizes. The
comparable RT fracture toughness values were noted
for both single crystal and polycrsytalline MAS cera-
mics. The fracture toughness of polycrystalline MAS
34 Hardness and fracture toughness values of different nanocrystalline MAS compositions107
84 International Materials Reviews 2013 VOL 58 NO
33 Modulus of rupture versus temperature for MAS161
was least affected by the change in grain size. In another
study, Ghosh et al.161 measured fracture resistance of
fully dense, transparent, polycrystalline MAS from RT
to 1400uC by following the chevron notched beam and
the straight notched beam macroflaw techniques, as well
as by the indentation induced controlled microflaw test
method using the three point bending test. The fracture
toughness values (Fig. 32) obtained by the chevron
notched specimen and the controlled microflaw test
technique are very similar from RT through 800uC.161
The temperature dependant flexural strength values
(Fig. 33) have shown a similar trend that was observed
in fracture toughness change of MAS with temperature.161
The dense MAS ceramics undergo deformation at mo-
derate temperatures and those with nanocrystalline
grain size undergo extended deformation at relatively
lower temperatures.107,108 In a study, Bhaduri and
Bhaduri107,108 densified nanocrystalline MAS and its
composites by following hipping technique. The hard-
ness and fracture toughness values measured for
nanocrystalline MAS composites varied between 2?89
and 7?79 GPa, and between 2?5 and 5?82 MPa m1/2
respectively (Fig. 34).107 The hardness of these MAS
ceramics is dependant on composition at 1000uC. In
another study, Laag et al.162 investigated the influence
2

35 Schematic representation of phosphate layer chemi-
sorbed onto surface of MAS powder particle187
of water on fracture toughness of two types of poly-
crystalline (A and B) and the single crystal MAS in order
to determine whether water adsorption play any role
during subcritical crack growth as it does for MnZn
ferrites, a compound with the same spinel structure.163
Type A MAS had a relative density of 87% and type B
with 98%, with the AGSs of 10 and 2 mm respectively.
Type A showed low elastic properties, which are
attributed to the large fraction of pores in it. Further,
the fracture toughness decreased with increasing humid-
ity for dense ceramics, indicating that adsorption plays an
important role. However, porous ceramics only showed a
sharp decrease between 0 and 10%, and there was hardly
any decrease afterwards. This implies that the pores
inhibit in some way during fracture. The exact mechanism
behind this behaviour still remains unclear.
Net shape forming of MAS components
Considering the importance of net shaped consolidation
of MAS ceramics for certain applications like radomes,
IR domes and windows for certain important strategic
36 a zeta potential versus pH of A-MAS and T-MAS powders and b zeta potential of T-MAS powder as function of added
amounts of dispersants138,139
Ganesh A review on MAS: synthesis, processing and applications
applications,164–184 Ganesh et al.138,139,185,186 developed
a surface passivation technique for passivating MAS
powder against hydrolysis, so that it can be processed
into net shaped components by following aqueous
colloidal processing routes. To avoid the strong reacting
tendency of MAS powder with water owing to its highly
basic character, the surface passivation of MAS powder
was accomplished by treating the as synthesised
MAS powder in an ethanolic solution of H3PO4 and
Al(H2PO4)3 at 80uC for 24 h. A schematic diagram of
phosphate coating on MAS is shown in Fig. 35.187
The change of zeta potentials f of the A-MAS and T-
MAS powders as a function of pH is shown in
Fig. 36a.138,139 The A-MAS powder exhibits a pHiep
in the range of 9–10 (between those of alumina and
magnesia), whereas the T-MAS exhibits a pHiep at y3.
The T-MAS powder exhibits negative and relatively
small f values (|f|(7) along almost the entire pH range
tested. Figure 36b shows the influence of added amounts
of different dispersing agents, either separately or com-
bined, on f of the T-MAS powder. It can be seen that f
decreases gradually with increasing added amounts
of dispersants reaching minimum values of 234 and
235 mV in the presence of 20 mL g21 Duramax D-3005
and 35 mL g21 TMAH respectively.138,139 However, the
combination of a fixed amount of TMAH (35 mL g21)
and varying amounts of Duramax D-3005 revealed
a synergetic effect, enabling to achieve higher absolute
values of f that are more suitable to promote electrostatic
stabilisation of the powder particles in concentrated
aqueous slurries.188,189 The treated powder dispersed with
35 mL g21 TMAH and 30 mL g21 Duramax D-3005
exhibited negative f values in the range of 40–50 mV,
enabling the preparation of stable and concentrated
aqueous slurries.
Table 4 presents the values of various properties of
MAS ceramics consolidated by six different types of
colloidal processing routes using T-MAS powder and
sintered for 1 h at 1650uC.190–194 This table also
summarises the green [density, strength and linear
shrinkage (LS)] properties of MAS consolidates. The
relative density values of greens varied from 45?16 to
46?50%. Bodies consolidated by non-liquid removal
International Materials Reviews 2013 VOL 58 NO 2 85
Ganesh A review on MAS: synthesis, processing and applications

colloidal processes (the HAS-5-45, GCHAS-5-45, GC-
45 and TIG-45; Table 4) are found to be comparable
with the one consolidated by slip casting (SC-45)
route.190 The presence of 4?1 wt-%AlN, a component
less dense (3?26 g cm23) than MAS (3?58 g cm23), did
not negatively affect the GD of GCHAS-5-45 in
comparison to GC-45. Therefore, the lower GD of
HAS-5-45 can be attributed to the absence of a fine
three-dimensional network formed by the in situ
polymerisation of monomers that creates a higher
driving force for shrinkage, which is expected to
strengthen the consolidates, as observed. All LS values
are in the safety range (,4%) for a successful fabrication
of complex shaped components by near net shaping
routes.171,190 The sample, GCHAS-5-45 is benefited
from both strengthening mechanisms offered by gelcast-
ing and HAS processes being the strongest one. Based
on green strength, the MAS consolidates can be ordered
as: GCHAS-5-45 (21?23¡0?42 MPa).GC-45 (15?64¡
2?38 MPa).HAS-5-45 (11?849¡1?76 MPa).SC-45
(7?832¡2?16 MPa).DP (0?245¡0?3 MPa). These re-
sults clearly suggest GCHAS is the most interesting
process for fabricating thin wall MAS components like
radomes and domes, as it confers a very high strength
to the greens permitting green machining to obtain the
desired shape.
Based on sintered density, the MAS ceramics can be
arranged as: GC-45 (98?43%).DP (97?93%).GCHAS-
5-45 (96?92%).SC-45 (94?89%).HAS-5-45 (94?07%).
TIG-45 (93?74%). Though having theoretical pore
volume fractions in the range of 1?57–6?26%, the values
of AP and WA are lower than 1?5 and 1% respectively,
indicating the presence of significant fractions of closed
porosity.190 Table 4 reveals that DP, GC-45 and
GCHAS-5-45 samples with relatively higher green
densities show superior sintered properties. Although
the green SC-45 and GC-45 samples exhibit similar
degrees of packing, the sintered density of SC-45 is
y3?5% lower.191 The poor densification ability of TIG-
45 could be ascribed to its low GD and weak adhesion
among the particles reflected in the poor green strength.
MgAl2O4 spinel ceramics with y95% of the TD were
considered to be suitable for certain applications,
qualifying DP, GD and GCHAS as promising powder
processing routes for MAS ceramics.24 Table 4 confirms
that the MAS ceramics consolidated by the present
colloidal processing routes exhibit better mechanical
properties (hardness and three point bend strength) in
comparison to those prepared by the other shaping
techniques.194 The LS upon sintering of these MAS
ceramics did not exceed 18?5%, being within the safety
range for net shaped fabrication of thin wall compo-
nents devoid of any defect.171,190
The SEM micrographs of DP, TIG-45, SC-45, GC-
45, HAS-5-45 and GCHAS-5-45 samples sintered for
1 h at 1650uC are presented in Fig. 37 respectively, and
their corresponding grain size histograms and the AGS
in Fig. 38.190 The lines in the grain size distribution
plots are the fitting curves according to a Poisson
distribution function. It can be seen from Fig. 37 that
all the samples consist of equiaxed grains (in the size
range of 3?01–18?27 mm; Table 4) packed with varied
closeness. In general, these microstructures reveal the
presence of both intra and intergrain porosities. In
accordance with the findings of Archimedes’ principle,
the microstructures reveal considerable amount of
closed porosity (intragrain porosity), what can be seen
very clearly from the microstructures of HAS-5-45
(Fig. 33e) and GCHAS-5-45 (Fig. 33f), which had AlN
(4?1 wt-%) in their starting slurries. Furthermore, the
sintered GC-45, DP and GCHAS-5-45 samples seem to
possess more densely packed grains then the others.
Among the six samples, the HAS-5-45 and GCHAS-5-
45 consist of an apparent higher fraction of larger
grains, which could be responsible for their measured
higher hardness.190–194
The grain size histograms reveal that the DP (3?43–
12?8 mm and 6?48 mm) and SC-45 (3?01–12?92 mm and
5?73 mm) possess narrow grain size distributions and
lower AGSs, whereas the HAS-5-45 (3?73–17?17 mm
and 8?40 mm) and GCHAS-5-45 (3?45–18?27 mm and
8?33 mm) contain relatively wide grain size distributions
and large AGSs.190 The GC-45 and TIG-45 contain
intermediate grain size distributions and AGSs (Table 4
and Fig. 38). The flexural strength of these ceramics
appears to be depended more on the degree of the
densification achieved upon sintering in comparison to
the average size of grains and their distribution.190–194

Table 4 Properties of green and sintered (1650uC for 1 h) MAS ceramics*190

Green properties Sintered properties

Grain size/mm

LS upon Flexural Flexural

GD/ RD/ drying/ strength/ BD/ RD/ AP/ WA/ Hardness/ strength/
Sample{ g cm23 % % MPa g cm23 % % % LS/% Min. Max. Ave. kg mm22 MPa

GC-45 1.635 45.67 2.878 15¡2.4 3.52¡0.04 98.43 0.27 0.08 18.25 3.21 15.82 7.08 800¡13 183¡8
SC-45 1.623 45.33 … 7¡2.4 3.39¡0.07 94.89 1.03 0.78 17.68 3.01 12.92 5.73 656¡19 153¡11
HAS-5-45 1.617 45.16 2.936 11¡1.7 3.36¡0.08 94.07 0.13 0.05 17.83 3.73 17.17 8.40 1192¡16 112¡9
GCHAS-5-45 1.638 45.75 3.156 21¡0.4 3.47¡0.05 96.92 0.25 0.07 17.83 3.45 18.27 8.33 1197¡19 169¡11
TIG-45 1.627 45.44 3.046 … 3.35¡0.06 93.74 1.49 0.43 17.65 3.56 13.94 6.91 1092¡34 …
DP 1.665 46.50 … 0.25¡0.3 3.50¡0.03 97.93 0.06 0.02 17.53 3.43 12.8 6.48 811¡18 173¡5
*GD: green density; RD: relative density; LS: linear shrinkage; BD: bulk density; AP: apparent porosity; WA: water absorption capacity;
GC: aqueous gelcasting; SC: aqueous slip casting; HAS: hydrolysis assisted solidification; GCHAS: hydrolysis induced aqueous
gelcasting; TIG: temperature induced gelation; DP: dry pressing of freeze dried granules.
{The numbers 5 and 45 in the sample codes stand for the 5 wt-% alumina deficient composition, which is compensated with equivalent
amounts of as purchase AlN that undergoes hydrolysis during aqueous processing leading to the formation of alumina upon eventual
sintering, and the volume fraction of solids in the slurries respectively.

86 International Materials Reviews 2013 VOL 58 NO 2


37 Images (SEM) of sintered (1650uC, 1 h) ceramics consolidated by a DP, b TIG-45, c SC-45, d GC-45, e HAS-5-45 and f
GCHAS-5-45 (please refer to Table 4 for more details of these materials)190
Processing of dense MAS bodies
Processing of MAS grains for refractory
applications
As mentioned earlier, dense MAS bodies cannot be
prepared following a single stage reaction sintering
process, as there is a considerable amount of volume
expansion (y8%) associated with the formation of
MAS phase from Al2O3 and MgO.1,24,66 To avoid this
problem, alternatively, a double stage firing process is
employed. In this latter process, alumina and magnesia
precursors are initially calcined at .1500uC to produce
MAS powder with the desired spinel phase (.80%), and
then the MAS powder is ground, compacted and
sintered at .1900uC.1,24,66,70–72 Owing to the involve-
ment of two consecutive firing cycles, the cost of dense
MAS bodies is usually high. Alternatively, fused MAS
bodies are also produced following a very expensive
single stage firing process, in which alumina and
magnesia raw materials mixtures are electrofused in an
Ganesh A review on MAS: synthesis, processing and applications
electrical furnace at .2000uC.24 But this latter process is
not viable for many of the countries, as electricity is very
expensive in those countries. Therefore, the affordable
and practically viable process for producing dense and
high purity MAS grains for refractory applications has
been double stage firing process, in which the cost of
production could be reduced considerably by reducing
both firing temperatures with the help of optimised
processing parameters. In a study, Ganesh et al.70,71
investigated the influence of various processing para-
maters, such as:
(i) MAS phase content
(ii) mass and GD of powder compact
(iii) average particle size
(iv) chemical composition
(v) sintering temperature
(vi) holding time at final sintering temperature on
densification ability of MAS grains formed in a
double stage firing process.
The following conclusions are made.
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Ganesh A review on MAS: synthesis, processing and applications

38 Grain size histogram and AGS of DP, TIG-45, SC-45, GC-45, HAS-5-45 and GCHAS-5-45 ceramics sintered for 1 h at
1650uC measured from SEM micrographs shown in Fig. 37 using image analyser: lines in grain size distribution
plots are fitting curves according to Poisson distribution function (please refer to Table 4 for more details of these
materials)190

1. The formation of MAS phase is strongly influenced
by the moisture and CaO contents of the raw
materials.
2. Magnesia rich MAS composition exhibits higher
densification ability that that of alumina rich MAS
composition.
3. Stoichiometric MAS grains with a BD of
.3?35 g mL21, AP of ,2?0% and WA of ,0?5%
could be prepared at 1650uC for 1 h using MAS
powder with a median particle size of ,2 mm, the
CaO content of .0?9%, the compact (green) density
of .1?95 g mL21 and the spinel content of .90%.
4. Stoichiometric MAS grains possess an AGS of
y10 mm, whereas the alumina rich MAS with 90%
alumina upon sintering at 1650uC for 1 h possess
average grains of y20 mm, which are important
from the refractory applications point of view.
Influence of sintering aids on densification
behaviour
There is hardly any method in which the MAS powder
either commercially obtained or synthesised by follow-
ing most of the commonly employed synthetic routes is
fully densified into components without the help of
sintering aids, such as Na3AlF6, AlCl3, CaCO3, LiF,
CaB4O7, B2O3, NaF, CaF2, ZnF2, BaF2, CaCl2, TiO2,
etc.24,41–47 In a study, Villalobos et al.16 hot pressed
MAS powder (Ceralox, Tucson, AZ, USA) with 0?5, 2
and 10 wt-%LiF at 1600uC for 2 h under vacuum by
ramping at a rate of 10uC min21 in a graphite die press.
There were two holds each for 30 min at 950 and
1200uC. Pressure schedule consisted of maintaining
200 psi until the end of the 1200uC hold. The pressure
was then slowly increased to 4000 psi and held until the
end of the 1600uC treatment. The densification of MAS
into transparency was highly influenced by the concen-
tration of LiF and its distribution in the powder
compact.16 In another study, Rozenburg et al.12,13
examined the detailed mechanism involved in the
reactions between LiF and MAS at temperatures up to
1500uC using various analytical techniques. A wet
chemical impregnation technique was employed to coat
the surface of MAS powder particles uniformly with LiF
sintering aid.11 The formation of LiAlO2 and MgF2 as
active reaction products was noted. The formation of a
transient liquid phase comprising MgF2 and LiF was

88 International Materials Reviews 2013 VOL 58 NO 2


39 Image (SEM) of 40 wt-% LiF–MAS sample quenched
from 1000uC in air: arrows indicate highly faceted spi-
nel grains growing from fluoride rich melt12,13
also noted at intermediate temperatures, which is
subsequently consumed at higher temperatures to form
MAS. A highly faceted grains grown out of fluoride
rich melt are also noted (Fig. 39).12,13 These grains are
identified as MAS and the melt consisting of fluorine
and magnesium with some oxygen and aluminium. The
MAS formed at 1500uC did not contain any LiF. All of
the initial LiF in the system evaporated at temperatures
exceeding 1300uC, when the powder mixture was not
compacted. Just before the melting point of LiF, it
reacted with MAS, leading to the formation of LiAlO2/
LiAl4FO6 along with MgF2. The following series
(equations (16)–(18)) of interactions between MAS and
LiF are proposed to occur above the melting point of
LiF by Rozenburg et al.12,13
3LiF (1)zMgAl2 O4 (s)?LiF=MgF2 (1)z2LiAlO2 (s) (16)
LiF=MgF2 (1)?LiF(g)zMgF2 (g) (17)
2LiAlO2 (s)zMgF2 (g)?2LiF(g)zMgAl2 O4 (s) (18)
This reaction sequence also explains why large amounts
of LiF act corrosively against the MAS and why the
40 Image (SEM) showing a the fracture surface of a trilayer specimen created by HP pure LiF powder between pure spi-
nel powder. The HP direction is vertical in the figure. The central region where LiF was placed led to coarse grains
of spinel. Upon chemically etching a polished surface, b it is apparent that the large grain spinel reacts differently to
the chemical etch than the finer grain material adjacent, likely because the large grain material contains defects11
Ganesh A review on MAS: synthesis, processing and applications
yield of MAS can increase in the reactive sintering of
MgO and Al2O3.
Reimanis and Kleebe performed a model experiment
to understand the exact influence of LiF on micro-
structure evolution during hot pressing (HP) of MAS
ceramics under 35 MPa pressure at 1500uC for 2 h.11
The experiment was performed by fabricating a trilayer
specimen, comprising of MAS powder, LiF powder and
MAS powder. The LiF powder was added in a quanity
corresponding to a theoretical dense LiF thickness of
100 mm after sintering. Observation of the cross-
sectional fracture surface (Fig. 40a) reveals large grains
that were determined by XRD to be MAS.11 However,
EDS within the SEM showed that the Mg/Al ratio
varied substantially in this region of large grains. When
the specimen was polished and then etched with HF, the
etch preferentially attacked the large grains (Fig. 40b).11
A likely explanation is that the large grains are highly
defected and hence more sensitive to the chemical etch,
which is seen as indirect evidence that Li and F ions
incorporated into the lattice of the large grains as shown
in equation (19)
MgAl2 O4 0 00
3LiF LiMg z2LiAl z3F.O zVO.. (19)
Based on their study, Reimanis and Kleebe concluded
that the densifcation of LiF doped transparent spinel
proceeds as follows:
(i) at the early stage of sintering, a homogeneous
liquid is formed that wets the MAS grains and
promotes the rearrangement of grains and grain
boundary mobility Mb
(ii) MAS continues to dissolve in the transient
liquid phase, leading to the precipitation of
MAS particles (with incorporation of Li and F);
those grains are prone to coarsening due to a
high concentration of oxygen vacancies (equa-
tions (18) and (19))
(iii) at higher sintering temperatures, the LiF vapour
pressure is sufficiently high for evaporation
(iv) upon cooling to RT, no LiF remains in the
component, with the exception of Liz and F2
ions incorporated into the MAS host lattice.
Figure 41 shows the HRTEM images of MAS samples
doped with 5 wt-%LiF cooled from intermediate tem-
peratures: 900 and 1000uC. Note that in both cases, no
International Materials Reviews 2013 VOL 58 NO 2 89
Ganesh A review on MAS: synthesis, processing and applications
41 Images (HRTEM) from spinel samples doped with 5 wt-% fraction LiF cooled from intermediate temperatures a 900uC
and b 1000uC
continuous intergranular amorphous film was ob-
served, which led to the hypothesis that a wetting
dewetting mechanism is acting in this system, which,
however, could only be verified via additional quench
experiments.11 The insets at the right upper corner
represent the corresponding Fourier filtered images of
the boxed areas.
It is suggested that the appearance and growth of
pores arising from an elevated temperature heat treat-
ment are caused by the formation of gaseous species
from small amounts of impurities present in the MAS.
Specifically, C and S, present in small quantities (tens of
parts per million), would form gaseous oxides in the
presence of oxygen, and under elevated temperatures
and extended times, these gaseous oxides would form
pores at MAS grain boundaries. This mechanism of
pore growth has previously been reported for hot
pressed Al2O3 heat treated at 1600uC.195 For the case
of MAS, powders synthesised by Baikowski Incor-
porated are known to contain sulphur, as they are
synthesised from sulphates;196 carbon is ubiquitous in
oxide processing. The issue of swelling is not only
relevant to heat treatment studies, but also to proces-
sing, because it is clear that the same pore growth
process counters the effects of sintering. Meir et al.197
a as fabricated; b heat treated for 50 h at 1550uC in air11
42 Images of SEM showing fracture surfaces of 1 wt-%LiF specimen corresponding to Fig. 36
90 International Materials Reviews 2013 VOL 58 NO
pointed out that C present due to field assisted HP
[(spark plasma sintering (SPS)] inhibits sintering; indeed,
they showed a microstructure of a pressureless spark
plasma sintered MAS that exhibits the classic character-
istics of the formation of gaseous species (substantial
porosity located along grain boundaries), similar to the
one shown in Fig. 42.11 They conclude that one of the
roles of LiF is that it may react with C and ameliorate
this problem. Experiments to confirm the above des-
cription include an extensive heat treatment of the
powders before HP, similar to what Bennison and
Harmer discuss for hot pressed Al2O3. It is worth noting
that prolonged heat treatment times can lead to pore
coalescence along MAS grain boundaries, as illustrated
in Fig. 43, strongly diminishing transparency.11 On the
other hand, using an ultra pure starting powder in
addition to a powder heat treatment to eliminate even
small amounts of impurities, before densification will
ultimately suppress swelling, as depicted in Fig. 44, and
result in a highly transparent MAS body.11
Rare earth oxides, such as 4 wt-%Yb2O3, 4 wt-%
Dy2O3, etc., were also identified as better sintering
aids to improve the densification behaviour of MAS
powders.198 In another study, Sarkar et al.199 noted
Cr2O3 (up to 4 wt-%) as an effective sintering aid for
2
 Ganesh A review on MAS: synthesis, processing and applications

43 Images (SEM) of fracture surfaces of undoped spinel hot pressed and post-annealed for 50 h at 1550uC in air: note
pronounced coalescence of pores located at spinel interfaces upon long term annealing11

MAS. Cr2O3 decreased the temperature of complete
solid solubility of excess alumina in MAS for the
alumina rich composition and no effect of Cr2O3 was
found on flexural strength of the sintered product when
its concentration was ,4 wt-%. However, .4 wt-
%Cr2O3 had a detrimental effect on MAS sintered at
1650uC, irrespective of the starting chemical composi-
tion. Deleterious effect was much pronounced for the
hot strength values, particularly for the magnesia rich
composition. In another study, Ganesh et al.72 utilised
AlCl3 as a sintering aid for promoting the densification
ability of stoichiometric MAS in a conventional double
stage firing process, in which aluminium trihydroxide
and calcined caustic magnesia were used as starting raw
materials. The MAS bodies sintered at 1550uC with
0?057 mol-%AlCl3 exhibited a BD of 3?40 g cm23, AP
of 0?193% and WA of 0?01%. AlCl3 was also found to be
effective in enhancing MAS phase formation. AlCl3
exhibited best performance on densification of MAS
powder, which had some small amounts of unreacted
MgO and Al2O3 in it. The positive affect of AlCl3 was
attributed to its hygroscopic nature.72
Based on two separate studies, Sarker et al.200 and
Posarac et al.201 suggested that Y2O3 could be an
effective sintering additive for MAS. In another study,
Mroz et al.42 prepared nanostructured MAS (referred to
as nano-MAS) by following a proprietary method in
which Y2O3 was used as a sintering additive. The
properties of this nano-MAS sintered with Y2O3 was
compared with those estimated for a production quality
IR transparent MAS (Surmet, Burlington, MA, USA)
(referred to as fine MAS) as summarised in Table 5. It
can be seen from this table that the AGSs of nano-MAS
and fine MAS ceramics are 345 nm and 2?1 mm
respectively. The sizes of the largest grains of these
ceramics can be seen from Fig. 45 as 970 nm and
25?7 mm respectively.42 Figure 46 shows a SEM micro-
graph of the largest grain found in fine MAS.42 The
Hillert202 ratio (dMax/dAve) for nano-MAS is 2?8, which
is close to the ratio 2?0 for ‘normal’ grain growth. In

44 Images of SEM showing fracture surfaces of 1 wt-%LiF specimen hot pressed for 2 h at 1550uC in air: elimination of
pores at spinel interfaces was achieved by using ultra pure starting powder in addition to powder heat treatment
before densification, resulting in high transparency11

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Ganesh A review on MAS: synthesis, processing and applications

45 Image (SEM) of etched cross-sections of a nano-MAS and b fine MAS42

contrast, that ratio for fine MAS is 12?2, indicating

‘abnormal’ grain growth. Figure 47a shows a bright filed
TEM micrograph of nano-MAS, which confirms the
uniform grain size distribution in that MAS. Figure 47b
is a higher magnification bright field TEM micrograph
showing near ideal (y120u) dihedral angles at triple
points, typical of solid state sintered, equiaxed grain
structure with grain boundaries free of glassy phase.42
Figure 48 shows in-line transmission data for nano-
MAS and fine MAS ceramics (1 mm thickness) in the
wavelength range 2–7 mm.42 Theoretically, calculated
transmission curve for MAS is also plotted in Fig. 48 as
reference.42 This was calculated using the FilmStar
software program (FTG Software, Princeton, NJ, USA)
from tabulated and measured refractive index values as
a function of wavelength and sample thickness. The data
for the two MAS ceramics are virtually indistinguishable
in Fig. 48.42 The inset in Fig. 48 shows transmission
data in the more important wavelength range of 3–5 mm
for IR window/dome applications.42 At longer wave-
lengths (4–5 mm) the in-line transmission in nano-MAS
is higher than in fine MAS, and it reaches the theoretical
limit. At shorter wavelengths (3–4 mm), nano-MAS has
somewhat lower transmission than the theoretical limit.
Overall, transmission in nano-MAS is on par or better
than fine MAS. The optical scatter was found to be
,0?2 cm21 for both MAS ceramics (Table 5).42 It can
be seen from Table 5 that nano-MAS is some what
harder (16?8 GPa) than fine MAS (15?2 GPa).
Figure 49 shows strength data for nano-MAS and fine
MAS ceramics, represented as Weibull plots.42 The
average strength sC of nano-MAS is 470 MPa, while
that of fine MAS is 364 MPa. Also, the Weibull
modulus m of nano-MAS is higher (6?2) than that of
fine MAS (5?3). In comparison, coarse MAS is
significantly weaker (sC5160 MPa), but it has a higher
Weibull modulus (m59?6). The fracture toughness of
nano-MAS and fine MAS ceramics is found to be
46 Image (SEM) of etched cross-section of fine MAS
showing largest grain found42
identical at KIC51?4 MPa m1/2 (Table 5), and both are
found to fracture transgranularly. The surface reflec-
tance of nano-MAS was found to decrease by only 0?4%,
to 10?6%, while that in fine MAS decreased by 3?0%, to
8?0% (Table 5).42 These results show that the sand
eroded surface of nano-MAS is less roughened com-
pared with fine MAS surface, indicating relatively higher
sand erosion resistance in nano-MAS.
Figure 50 shows thermal conductivity data for both
nano-MAS and fine MAS ceramics.42 The conductivity
of nano-MAS is y14% lower than that of fine MAS at
RT. With increasing temperature, the conductivities of
both MAS ceramics decreased as expected, and the
difference disappears. Table 5 lists values of the thermal
shock figure of merit (mild shock case), R9, as defined by
Hasselman,203,204 for the two MAS ceramics
sC (1{n)k
R’~ (20)
aE
where values of elastic modulus E5295 GPa,205 Poisson’s
ratio n50?26,14 and thermal expansion coefficient

Table 5 Optical and mechanical properties of spinel materials42

Average Size of Thermal

grain largest Optical Average Weibull’s Fracture shock merit Reflectance
Relative size grain scatter*/ strength modulus/ toughness Hardness figure{ after sand
Spinel density dAve dMax cm21 sC/MPa m KIC/MPa m1/2 H/GPa R9/kW m21 erosion{/%

Nano-MAS 100% 345 nm 970 nm ,0.2 470 6.2 1.4 16.8 2.1 10.6
Fine MAS 100% 2.1 mm 25.7 mm ,0.2 364 5.3 1.4 15.2 1.9 8.0
*At l53?39 mm.
{Using equation (20).
{At l50?2 mm; initial surface reflectance 11% before erosion for both samples.

92 International Materials Reviews 2013 VOL 58 NO 2


47 Bright field TEM images of nano-MAS at a low and b high magnifications42
48 Measured in-line optical transmission of nano-MAS
and fine MAS ceramics (1 mm thickness specimens)
in wavelength range 2–7 mm: theoretically calculated
curve for MAS is included for comparison; inset
shows data for wavelength range 3–5 mm, with
expanded transmission (%) axis42
49 Weibull type plots of failure probability F and strength
sC of nano-MAS, fine MAS and coarse MAS ceramics:
data for fine MAS and coarse MAS ceramics are from
previous unpublished study (Surmet Corp.)42
Ganesh A review on MAS: synthesis, processing and applications
a58?061026uC21 for MAS ceramics are considered.
Values of room temperature thermal conductivity k
of 14?2 and 16?6 W m21 K21 for nano-MAS and fine
MAS ceramics respectively, are used.14 The higher
average strength of nano-MAS, relative to fine MAS
has been attributed to the significantly smaller size of
the largest grains in nano-MAS. This effect could be
analysed as follows. The strength sC of a brittle
ceramic is given by206
KIC
sC ~ 1=2
(21)
Y CR
where Y is a geometrical constant, KIC is the fracture
toughness and CR is the critical flaw size. Taking
KIC 51?4 MPa.m0?5 and sC5364 MPa for the fine
MAS (Table 5), and assuming Y51?26 for a half
penny surface crack,206 CR59?3 mm is calculated.42
Thus, these results clearly indicate that Y2O3 is a very
effective sintering aid for densifying MAS ceramics
with controlled grain size and improved sintered
properties.
Defects reactions and non-stoichiometry versus
densification
Ting and Lu44 constructed the Brouwer defect equili-
brium diagram based on intrinsic Schottky defects
(Fig. 51) to explain the influence of defects and non-
stoichiometry on densification behaviour of MAS. The
50 Thermal conductivity as function of temperature of
nano-MAS and fine-MAS42
International Materials Reviews 2013 VOL 58 NO 2 93
Ganesh A review on MAS: synthesis, processing and applications

000 0 00
Mg|
Mg zVAl ?MgAl zVMg (27)

00 000
Al| .
Al zVMg ?AlMg zVAl (28)

Possible defects in alumina rich MAS

The excess Al2O3 (i.e. hyperstoichiometry) can be
accommodated in MAS by placing the aluminium ions
at the initially vacant tetrahedral magnesium sites then
creating the substitutional defect of Al.Mg . Charge
000
compensating defects of either aluminium (VAl ) or
00
magnesium (VMg ) vacancies are generated to maintain
the overall neutrality in the host lattice. Ionic conduc-
tion in excess Al2O3–MAS is attributed to cation
vacancy migration, which supports the theory of Al3z
000
cation vacancies VAl as the principal charge compensat-
ing mechanism. Extrinsic behaviour could be described
by the following reactions, where both cation vacancies
located on either the tetrahedral or octahedral site are
considered to be the principal charge compensating
defects
000
51 Brouwer diagram for MAS compositions consisting 4Al2 O3 ?5Al| | .
Al z12 OO z3AlMg zVAl (29)
intrinsic Schottky defects44
00
4Al2 O3 ?6Al| | .
Al z12OO z2AlMg zVMg (30)
electronic disorder and anionic Frenkel disorder were
000
neglected while constructing the Brouwer diagram. Five The overall charge neutrality is maintained by VAl or
0 00 000
ionic defects were considered: Al.Mg , MgAl , VMg , VAl , 00
VMg . If the distribution of cation vacancies in the crystal
..
VO . Because it is the variation of defect concentrations
lattices is assumed to be completely random, the defect
with the degree of non-stoichiometry that is most reaction equation incorporating both cation vacancies
relevant to the sintering process, the Brouwer diagram for charge compensation could be expressed as
is the basis for the dependence of equilibrium concen-
00 000
trations of these five defects upon the activity of either 12Al2 O3 ?16Al| | .
Al z36OO z8AlMg zVMg z2VAl (31)
MgO or Al2O3 at constant temperature T, pressure P,
and oxygen partial pressure pO2 . According to Kroger–
Vink notations, three types of intrinsic defects: mis-
Possible defects in magnesia rich MAS
placed atoms, Schottky and Frenkel defects could be
expected for MAS. The calculated formation energies of Non-stoichiometric compositions on the excess MgO
cation defects of the Fremkel type (y7 eV) are higher (i.e. hypostoichiometry) side exhibit a rather limited
than those of the Schottky type (y4?5 eV). Note that solubility, in contrast to the excess Al2O3 hyperstoichio-
these figures show a large deviation from the 2?0–3?2 eV metry. The defect reaction equations written below take
derived from diffusion data for Frenkel defects. into account both charge compensating defects of
Further, according to Kroger–Vink, the arrangement Frenkel cation interstitials and Schottky anion vacan-
of cations and anions, and the formation of different cies. When Frenkel cation defects predominate in the
kinds of defects for MAS can be shown with equa- intrinsic region, the defect reactions for the extrinsic
region could be
tions (22)–(28)
0
|
| . 0 4MgO?2MgAl zMg| ..
Mg z4OO zMgi (32)
½Mg|
Mg z½AlAl ~½AlMg z½MgAl  (22)
0
Overall charge neutrality in the crystal lattices requires 4MgOzAl| | | ...
0 Al ?3MgAl zMgMg z4OO zAli (33)
that [Al.Mg ]5[MgAl ]
Defect reaction equations for cation Frenkel pairs and If Schottky defects, being energetically more favourable,
predominate in the intrinsic region, the defect reaction
for oxygen interstitial and vacancy pairs are as follows
becomes
00
Mg| ..
Mg ?Mgi zVMg (23) 0
|
3MgO?2MgAl zMg| ..
Mg z3OO zVO (34)
000
Al| ...
Al ?Ali zVAl (24) Sintering studies on MAS by Ting and Lu44 showed that
the densification rate increases with the amount of
O| .. 00 excess MgO. Based on the argument of solid state
O ?Oi zVO (25)
diffusion, oxygen vacancies are proposed to be the rate
Defect reaction equations for the Schottky defects are as determining species for densification. Based on equa-
follows tion (28), the intrinsic Schottky type defect reaction and
00 000
its corresponding equilibrium constants can be ex-
w?VMg z2VAl z4VO.. (26) pressed as follows

94 International Materials Reviews 2013 VOL 58 NO 2

 Ganesh A review on MAS: synthesis, processing and applications

00 000
w?VMg z2VAl z4VO.. (26)

00 000
Ks ~½VMg ½VAl 2 ½VO.. 4 (35)
The equilibrium constants for the cation inversion
reactions described previously by equations (27) and
(28) could be written as follows
000 0 00
Mg|
Mg zVAl ?MgAl zVMg (27)


0 
h 00 i
MgAl VMg
K1 ~ h i
000
 (36)
Mg|
Mg VAl

00 000
Al| .
Al zVMg ?AlMg zVAl (28)
h i 000  52 Pressureless sintering kinetics for compositions ran-
Al.Mg VAl ging from x50?80 to x51?50 (Ref. 44)
K2 ~  h 00 i (37)
Al|
Al VMg

The following two reactions, when combined, allows one

to correlate defect concentrations with the activity of
Al2O3 aAl2O3. The formation of MAS by the reaction of
MgO with Al2O3 in the binary system of MgO–Al2O3
can be shown as follows
MgO(s)zAl2 O3 (s)'MgAl2 O4 (ss)
KR ~aMgO aAl2 O 3 ~exp DG o =RT)
where DGo denotes the standard free energy of
formation.
In order to derive a functional relation between aAl2 O 3
and the concentration of point defects under a set of
experimental conditions of pO2 , P and T, the MAS solid
is assumed to be in equilibrium with its surroundings as
follows
0 dependant on the degree of non-stoichiometry in MAS
2MgOz2Al| | ..
Al zOO ?2MgAl zAl2 O3 zVO
 oxygen vacancies, which compensate for the formation
0 2  
MgAl aAl2 O3 VO..
K3 ~  2  | 
a2MgO Al|Al OO
h 0 i2   {2  | {1 {1
K3 ~a3Al2 O2 MgAl VO.. Al|
Al OO KR
Overall charge neutrality in the crystal is described by
00 000 0 e.g. densification rate dependence on the degree of non-
2½VMg z3½VAl z½MgAl ~½Al.Mg z2½VO.. 
Regions in the Brouwer diagram are assigned to specific
neutrality approximations; vertical dotted lines drawn
arbitrarily do not represent the true width of the
corresponding region. The dependence of defect con-
centration on impurity content (i.e. Al2O3 for the
present case of hyperstoichiometry) is only valid for
compositions located in the solid solution range. The
intrinsic region in oxide ceramics, e.g. Al2O3, is almost
impossible to observe experimentally. For MAS, the
intrinsic region where misplaced atoms are the pre-
dominant defects would be extremely narrow.
For compositions near stoichiometry, the cation
inversion produces the highest concentration of defects
(i.e. equations (36) and (37)), in which the neutrality
0
approximation is assigned to [Al.Mg ]>[MgAl ]. The
concentration of oxygen vacancies in regions I, II and
III decreases monotonously with increasing excess
Al2O3, although at different rates for the individual
extrinsic regions. Cation vacancies increase with increas-
000
ing degree of excess Al2O3, and [VAl ] levels off at high
(38) hyperstoichiometric compositions (region III). The
00
increase in magnesium vacancy concentration [VMg ]
(39) toward a higher degree of hyperstoichiometry (region II)
000
yields a larger slope than that of [VAl ]. The neutrality
000
.
approximation of [AlMg ]53[VAl ] has moved to
00
[Al.Mg ]52[VMg ] at highly excess Al2O3 compositions. It
is important to realise that oxygen vacancies, being the
predominant species in excess MgO compositions,
clearly decrease in concentration with the degree of
excess Al2O3. From the Brouwer diagram constructed
here, the concentration of oxygen vacancies is strongly
(40) compositions. Excess MgO leads to a steady increase of
0
of a substitutional defect, MgAl , generated by hypos-
(41) toichiometry. The dependence of defect concentrations
on the degree of non-stoichiometry is illustrated here in
the Brouwer diagram by the activity of Al2O3. Because
(42) the activity in solid solution is a strong function of the
degree of non-stoichiometry, a translation from aAl2O3 to
[Al2O3] becomes necessary so that experimental results,
(43) stoichiometry, could be compared with the Brouwer
diagram constructed theoretically.
Effect of non-stoichiometry on pressureless sintering
kinetics of MAS is shown in Fig. 52 for compositions of
x50?8 to x51?5 (where x51 for stoichiometric MAS)
with increasing Al2O3 content.44 It can be clearly seen
that the magnesia rich compositions underwent densifi-
cation with much faster rate than those of alumina rich
compositions. Furthermore, for excess MgO composi-
tions, sintered density increased very rapidly to 95%
within 1 h and levelled off without significant densifica-
tion afterward. The stoichiometric and excess Al2O3
compositions have significantly lower densities. Sintered
density with increasing Al2O3 content also experienced a
steady decline, as seen from x51?0 to x51?5. These
results strongly support the predictions made from

International Materials Reviews 2013 VOL 58 NO 2 95

Ganesh A review on MAS: synthesis, processing and applications
53 Dependence of densification rate on degree of hyper-
stoichiometriy (i.e. excess Al2O3) at 1600uC (Ref. 44)
Brouwer diagram constructed for MAS as discussed in
the above section.
The densification rates of MAS having different
stoichiometric compositions at rrel590% are presented
in Fig. 53.44 The excess MgO composition of x50?8 has
a five times higher densification rate than the stoichio-
metric (x51?0) composition. Sintering of the excess
MgO (x50?8) composition, where second phase pre-
cipitates are observed, produces the highest densification
rate (y1024 s21) of all (Fig. 53). The densification rate
is reduced abruptly as the composition moves from
excess MgO (x50?95) to stoichiometric (x51?0). The
log–log plot of densification rate versus Al2O3 content
(in mol.-%) of the powder composition shows that
excess MgO compositions within the solid solution
range give a slope y3 times higher than the excess
Al2O3–MAS (223?7 versus 27?7, as shown in Fig. 53).
This indicates that densification rate decreases three
times more rapidly when composition reaches stoichio-
metry from hypostoichiometry. It is intriguing that the
concentration of oxygen vacancies V.. O also decreases by
the same ratio of 3 : 1 in the range from excess MgO to
54 Arrhenius plot of densification rate versus tempera-
ture for pressureless sintering at rrel575%, from
which activation enthalpies were estimated44
96 International Materials Reviews 2013 VOL 58 NO
55 Grain size exponents p determined for pressureless
sintered x50?91 and 1?00 at 1600uC (Ref. 44)
excess Al2O3 compositions (Fig. 54). These results
indicate that densification appears to have been con-
trolled by oxygen vacancy diffusion in these composi-
tions and excess MgO has definitely contributed to the
enhancement of densification.
Activation enthalpy DH determined from the log
[(drrel/dt)/T] versus (1/T) plot represents that of the
diffusion mechanism responsible for the rate controlling
step. The rate controlling mechanism can then be
understood on the basis of activation enthalpy. The
Arrhenius plots for pressureless sintered three composi-
tions are presented in Fig. 54.44 Densification rates at
rrel575% are used to deduce the activation enthalpy
based on two premises. First, particle rearrangement
accounting for densification up to rrel(70% could be
excluded. Second, grain size at this stage was found to be
very similar to the initial particle size, where no
appreciable grain growth has taken place. The value
obtained is, therefore, the activation enthalpy for the
densification mechanism in the initial sintering stage.
For pressureless sintering, the activation energies
estimated for x50?92, 1?0 and 1?50 are DH5489, 499
and 505 kJ mol21 respectively. These values indicate
that an identical mechanism of densification may have
been responsible for the rate determining step of
sintering in the initial stage for the three different
compositions sintered.
Determination of the grain size exponent p is
necessary, so that the actual densification mechanism
could be identified unambiguously with confirmation
from the DH value. Figure 55 shows the p values as
estimated by Ting and Lu44 from the densification
versus grain size plot. Fitting the data of this figure in a
single slope yields p52?35 and 2?47 for x50?92 and 1?0
respectively. The discrepancy between p and lattice
diffusion controlled densification (p53) derived from the
ideal two sphere model could be attributed to the
concurrent mechanisms during sintering. Thus, these
results clearly indicate that oxygen vacancies are the rate
determining steps during densification of MAS ceramics
and the oxygen vacancies can be created by doping some
amounts of excess MgO into MAS.44
Sintering atmosphere versus densification
Thermodynamic calculations have shown that MAS at
low oxygen partial pressures (e.g. reducing environments),
2

above 1650uC will lead to a decomposition reaction in
which elemental Mg gas is formed,207 and which is also
accompanied by the creation of oxygen vacancies. Indeed,
experimental studies have indicated that the removal of
MgO during densification has a profound influence on
the resulting microstructure.203,208,209 Ting and Lu210
also investigated the effect of low oxygen partial
pressure on the sintering of MgOnAl2O3, where n varies
between about 0?9 and 1?2. They observed enhanced
densification at sample surfaces due to the evaporation
of MgO during densification, and they inferred that
predominantly the oxygen vacancies, which would be
created in addition to the Al vacancies, enhance diffu-
sion. A similar mechanism was suggested by Bratton208
earlier, although grain boundary diffusion could not be
ruled out completely. Ting and Lu’s results showed
that sintering under vacuum (or reducing atmosphere)
creates a sandwich-like microstructure with three re-
gions of different grain size.210 In their study, the sam-
ple interior exhibited grains containing voids, charac-
teristic for high stresses arising during differential
sintering. A large grain area was observed in the near
surface region. Similar abnormal grain growth beha-
viour was observed by Matsui et al.,211 who sintered
MAS with n51?07 at 1800uC under hydrogen. The
exterior of Ting and Lu’s samples consisted of excess
Al2O3–MAS, and the [Al2O3/MgO] ratio decreased to
the interior of the samples considerably. A similar
result has been reported for the grain boundary che-
mistry of MAS with varying overall stoichiometry: for
all compositions, a strong local stoichiometry deviation
exists at the grain boundary, with the Al/Mg ratio
increasing sharply across the boundary; Chiang and
Kingery209 deduced that such a deviation governs grain
boundary mobility Mb.
Spark plasma sintering
In another study by Morita et al.,212 densified poly-
crystalline transparent MAS in an SPS furnace using a
commercially available high purity MAS powder (TSP
15, Taimei Chemical Co., Ltd, Japan) having an average
particle size y360 nm and purity .99?97%. The powder
was placed in a graphite die with inner diameter of
30 mm and applied uniaxial pressure of y80 MPa.
Under vacuum, the powder was heated to 1300uC at a
heating rate ranging from 2 to 100uC min21. The
powder was held at the final sintering temperature for
20 min under the compressive load and subsequently
annealed at 1150uC for 10 min in order to relieve any
residual strain. Before annealing, the applied pressure
was reduced to ,5 MPa. By this procedure, a circular
disc of 30 mm diameter and 3 mm thickness was
formed. These SPS sintered MAS discs exhibited an
in-line transmission of y47% for a visible wavelength of
550 nm and a residual porosity of ,0?5% when sintered
at 1300uC for 20 min by SPS by employing a heating
rate of ,10uC min21 without employing any sintering
aid. Yet, in another study, Frage et al.213 observed a
light transmission of y70% for a high purity and LiF
doped MAS material sintered at 1600uC by SPS using
relatively low heating rate of y10uC min21. The SPS
sintered MAS bodies had a grain size of .10 mm.212,213
In some other study, Meir et al.197 fabricated transpar-
ent MAS following SPS with the help of LiF (1 wt-%).
The maximum transparency of the product in the visual
wavelength range noted was y75%. However, the size
Ganesh A review on MAS: synthesis, processing and applications
of the MAS component is limited by the die size of the
SPS furnace. Furthermore, C is abundantly present in
SPS, because high electrical currents lead to sputtering
of C from the chamber fixtures. If C were left at the
grain boundaries in MAS, it would tend to prohibit
sintering between grains, likely by a swelling type
mechanism. However, the removal of the impurities
including C by LiF during HP has been reported.11
Microwave sintering
Susceptor assisted (MW) heating (SAMH) has also been
employed for densifying MAS ceramics.214–216 In a
study, Goldstein et al.214 densified MAS ceramics
following SAMH from a near stoichiometric pure
MAS powder. This powder had agglomerated particles
having a mean size of 30 nm and a specific surface area
of 29 m2 g21. This powder was cipped at 240–260 MPa
to obtain green compacts with a density of 1?80 g cm23
and placed in a refractory casket exhibiting suitable MW
transparency and then treated in an MW furnace
operated at 2?45 GHz using multimode peak power of
2 kW. The temperature noted on external surface of
casket was 600–750uC. A cylindrical layer of SiC grit
(100–500 mm grains; grade Carborex of Orkla Exollon,
Norway), having a thickness of y3 mm, was also
inserted as the susceptor in the casket during sintering
experiments.215 Like alumina, MAS also do not possess
suitable electrical properties (er58?5, tan d5361024 at
9?54 GHz, re51012 Vm) at RT; hence, it cannot be
directly sintered in an MW oven at 2?45 GHz operating
with power levels of 2 kW. This is the reason why
SAMH is required to densify MAS. In this case, the
main heat source is the thermal radiation from the
susceptor. The absorption of MW power by the sus-
ceptor decreases at high temperatures, owing to the
dramatic reduction of the MW radiation penetration
depth over 700uC.214 On the other hand, the amount of
MW radiation absorbed by the specimens increases with
temperature due to the increase in MAS dielectric loss
and the reduction of the fraction absorbed by SiC. At
1400uC, MAS do not need any susceptor for undergoing
densification, as it possesses desired dielectric loss at this
temperature.216 The MAS ceramics sintered in an MW
oven had a very similar microstructure to that of the
specimens conventionally rapid fired. This means that
no microstructure refinement is brought about by the
use of MW heating in the case of MAS. High density
(BD599?8% TD) translucent specimens were obtained
after hipping (1550uC/Ar/200 MPa) of SAMH sintered
MAS discs. However, optically transparent MAS com-
ponents for any commercial purpose are yet to be made
by following SAMH technique.
Processing of optically transparent MAS
ceramics
Transparency for MAS was first demonstrated in 1961
by the General Electric Company, and since that time,
there has been an intermittent effort to develop optical
quality MAS for a range of IR windows, dome and
armour applications. A good summary of the early
development efforts can be found in the literature.217,218
Processing of MAS powder to produce a transparent
component has been proved to be challenging over the
past 40 years.5–16 The existing literature on MAS also
indicates that attempts to make high quality MAS
International Materials Reviews 2013 VOL 58 NO 2 97
Ganesh A review on MAS: synthesis, processing and applications
transparent ceramics have failed todate, because the
densification dynamics of MAS are also poorly under-
stood.8–16 Early commercial production of transparent
MAS domes for missile dome applications for the
Stinger–Post missile were carried out in the early 1990s
by Alpha Optical and its parent company Coors
Ceramics.8–16 Unfortunately, Coors Ceramics stopped
commercial production of hot pressed MAS in 1993,
because poor yields and low throughput made the
process unprofitable. Poor yields of MAS parts were in
part, due to the inconsistent quality of the starting
materials. Internal scattering of light in an inherently
transparent material may render a material translucent
or opaque. Such scattering occurs at density fluctua-
tions, grain boundaries, phase boundaries and pores. In
order to avoid these difficulties, currently, two
approaches are being followed:
(i) HP to transparency followed by HIP
(ii) the pressureless sintering to produce an opaque
product which can be hipped to transparency.
Using HP/HIP processing, excellent optical performance
was achieved previously with MAS in small sizes and
thin wall thickness by Coors Ceramics and Alpha
Optical Systems. An effort to fabricate transparent
MAS by RCS Technologies Inc., using rate controlled
pressureless sintering followed by HIP processing in the
early 1990s also showed considerable promise. It is also
known that the quality of transparent MAS windows is
very sensitive to the quality of the raw material (both
purity and morphology).42–44 Previously (for example at
Coors Ceramics), the commercial production of MAS
domes started with alumina and magnesia oxides
produced from sulphate or a chloride based processes.
Unfortunately, residual anions impurities (.500 ppm)
remain after the precursors are calcined. These anions
can later become trapped in the grain boundaries of the
hot pressed MAS, which leads to light scattering and
gives the domes a foggy appearance. The most com-
monly used commercial powder, made by Baikowski
Incorporated, is synthesised through the coprecipitation
of Mg and Al salts.11 This is followed by desulphurisa-
tion, further calcining, and finally, jet milling to adjust
the particle size and surface area. Typically, small
amounts of sulphur remain in this powder. Other tech-
niques used to synthesise MAS powders include mo-
dified Bayer type processes, metal alkoxide hydrolysis,
various sol–gel type procedures, and a chemical techni-
que that was shown to have tremendous versatility in
terms of controlling stoichiometry, particle size, size
distribution, morphology and high levels of purity. The
poor optical quality in transparent MAS ceramics is
particularly prevalent when multiple parts are simulta-
neously hot pressed (as one does to reduce manufactur-
ing costs).11
However important, the development and application
of an optimised sintering approach is not the key to a
high transparency, even the most advanced HIP regime
will not provide transparent components withoutselec-
tion of the right raw powder together with application
of a very special, defect avoiding processing.11,42–44
Therefore, the in-depth knowledge of the processing of
synthetic MAS is highly essential for realising its full
potential, not only for transparent armour and dome
applications, but also others. The understanding of
following processing variables has been suggested to be
98 International Materials Reviews 2013 VOL 58 NO
also very important in the fabrication of transparent
MAS bodies:
(i) rates of heating and cooling
(ii) rates of pressure application and removal
(iii) hold times
(iv) the maximum temperatures and pressures.
The homogenous distribution of LiF within the powder
compact before sintering is essential in fully utilising
its effectiveness. The removal of LiF before complete
densification is also found to be a necessary, as it has
been found to be responsible for scattering of light. On
the other hand, optical transparency of MAS across the
visible and/or IR electromagnetic radiation spectrum
implies that a residual porosity of less than y0?1% and
pore dimensions not greater than about a tenth of the
wavelength of the light of interest are required. For IR
applications, this means that pore diameters should not
exceed y20 nm. This stringent requirement on the
allowable level of porosity has provided considerable
challenges for reliable manufacturing, and has driven up
the cost by mandating that parts be hot isostatically
pressed. The fabrication of large parts has been par-
ticularly difficult by following HIP.11
In a study, Ting and Lu15 investigated HP kinetics of
MAS with MgO excess, near stoichiometric and Al2O3
excess composition by HP MAS powders at 1450 to
1550uC, under the Ar pressure of 5–38?3 MPa. Based on
the obtained results it was concluded that:
(i) HP of MAS is rate determined by lattice
diffusion of oxygen in a low stress regime and
by climb controlled dislocation creep in a high
applied stress regime
(ii) the transition stress for the densification mechan-
ism changing from dislocation to diffusion
decreases with the content of Al2O3 in the initial
powder composition and is consistent with the
prediction of the variation of oxygen vacancy
concentration
(iii) the zero densification rate period represents an
incubation time when recovery by dislocation
climb takes place before densification recom-
mences as the internal stress is exceeded by the
decreasing effective stress.
In another study, Goldstein et al.219 synthesised MAS
powder by flame spray pyrolysis and compacted by
cipping followed by sintering for 2 h at 1650uC in air to
obtain dense spinel with 99?9% TD. Another green
powder compact was treated for 80 h at 1400uC. These
two differently sintered MAS parts were hipped for 3 h
at 1500uC under 200 MPa pressure of Ar. Between the
two hipped MAS parts, the one sintered at 1400uC
exhibited superior real in-line transmission (RIT) of 63%
(635 nm), an AGS of 2?2 mm, and a hardness of
13?2 GPa. When hipped at 1700uC, the RIT attained a
value of 77%, while the average grain increased to 17 mm
and the Vickers hardness slightly decreased to 12?8 GPa.
However, the product yields of these processes were
found to be not encouraging and the mechanical
strength of the green consolidates was poor. Yet in
another study, Krell et al.9,10 prepared fine grained,
highly transparent hard tiles of MAS following a double
stage densification mechanism without using any sinter-
ing aid. In the first stage, the powder compacts of three
different types of MAS (one had a BET surface area of
28 m2 g21 and particle size in the range of 50–100 nm;
2
 Ganesh A review on MAS: synthesis, processing and applications

a specific surface 28 m2 g21 (European manufacture); b 15 m2 g21 (American manufacturer); c one prepared in their
laboratory
56 Hot isostatic pressing temperatures, AGSs, RIT values and macrohardness (HV10) of sintered transparent spinel man-
ufactured starting from different commercial powders: RTI data for thickness 0?8 mm and l5640 nm9,10

another one had BET surface area of 15 m2 g21 and
particle size slightly higher than the previous one; and
the third one was prepared in their lab following an
undisclosed route) were sintered in open air atmosphere
to achieve densification of y96% TD. For comparison
purposes, a stoichiometric mixture of alumina and
magnesia was also compacted and sintered in open air
atmosphere to achieve the densification of y96% TD.
The four presintered MAS bodies made from four
different starting powders were hipped under 200 MPa
argon pressure at temperatures ranging from 1360 to
1650uC for different time intervals. The sintered micro-
graphs together with HIP temperature, AGS and RIT
transmission (referred to 0?8 mm thickness, l5640 nm;
absolute RIT of the 1?6 mm thick disc is 80%) of three
different transparent MAS tiles made from MAS
powders are presented in Fig. 56.9,10 Two commercial
powders led to the formation of fine grained, highly
transparent and hard MAS tiles in spite of their different
technological performance. The powder synthesised in
their laboratory exhibited higher degree of RIT, though
it was hipped at a relatively lower temperature. It is
also noted that slight variation in the disintegration
approach and use of certain doping additives (,0?5%)
and manipulation of sintering temperatures could lead
to the AGS between 0?4 and 5 mm without loss of
transparency. The lowest hardness (HV10) measured for
MAS body is 13 GPa when the AGS was 5?5 mm after
HIP at 1650uC. In another study also, Krell et al.10
prepared transparent MAS bodies using nanosized
powders by following the same presintering procedure
in air and then hipping in Ar atmosphere. The sintered
micrograph, RIT data and the obtained transparent
MAS tile are presented in Fig. 57.10 These results
suggests that although the hipping process is expensive,
the optically transparent MAS components with desired
properties can be fabricated by following the state-of-
the-art available at present in the literature on powder
processing.9,10 Nevertheless, further R&D is required to
develop processes by which optically transparent MAS
components can be fabricated at much affordable costs.
Applications
Optically transparent ceramic applications
Although MAS has been employed in several important
applications, the optically transparent ceramic applica-
tions are unique as far as this material is concerned,
because it has outperformed many of its counterparts in
these applications.7–16 Its fcc crystal structure that
allows light to transmit without any loss is mainly
responsible for its better performance in optical applica-
tions. The light transmission loss is a common problem
for transparent materials consisting hexagonal crystals
(e.g. for alumina). The optically transparent applications
are also very important as far as strategy sector is
concerned. For example, a great number of missiles use
transparent dome and window components including
sensor protection and multispectral windows. The
missiles are normally launched from a launch tube,

57 Transparent submicrometre spinel (grain size 0?42 mm) from powder with particle size of y100 nm: small thickness
effect in visible range because of transmission close to theoretical limit; macrohardness HV10515 GPa, four point
bending strength of y200 MPa9,10

International Materials Reviews 2013 VOL 58 NO 2 99

Ganesh A review on MAS: synthesis, processing and applications
which includes a sealing window intended to rupture
upon launch but it should be transparent to IR or UV
radiation. The typical characteristics of any sealing
window material are:
(i) stability under prolonged exposure to UV light
and conditions of high temperature, corrosive
environments, such as oxidising environments,
or acidic environments
(ii) resistance to abrasion or erosion, particularly
when subjected to dust, sand or water droplets at
a velocity of y500 m s21, and insolubility in
water
(iii) required hardness to polish to a high degree of
smoothness.
The common material that is used for these window
applications has been MgF2, which shows a degree of trans-
mittance in the IR region. As this material shows inferior
transmittance in UV wavelengths, it could not show the
required transparency at desired (i.e. several millimetres)
thickness for launch pad window applications.7 Further-
more, its high cost has also been found to be prohibitive for
single use munitions.
On the other hand, the requirements for transparent
armour differ much from those for windows and domes
but have been equally challenging, i.e. the material must
be lightweight, suffer minimal visual distortion after
sustaining multiple localised hits, and be night vision
compatible among other requirements.8–16 The funda-
mental requirements for transparent armour systems are
therefore transparency, resistance to ballistic threats and
the capability to defeat multiple ballistic impacts with
minimum distortion of surrounding areas. For all
threats greater than handguns, transparent armour
systems are based on transparent ceramic materials, of
which the oldest and the most common are silicate
glasses, but they are too weak to be used as a practical
transparent armour, as windows and domes in high
speed missiles and pods.8–16 Additionally, missile domes
and pod windows must transmit to light with 5 mm
wavelength, but silicate glasses do not transmit well
beyond 2 mm. Zinc sulphide transmits to beyond 5 mm,
but it is too weak to be used in these applications.8 In
addition to good optical properties, the ceramic
windows must also possess good abrasion resistance
and high strength, because of the extreme conditions
experienced during missile flight. Single crystal sapphire
serves as the baseline material in many of these systems;
however, its cost remains prohibitively high for many
high volume applications.8–10 Unfortunately, the cost of
sapphire windows is high due in part to the processing
temperatures involved, and because the most expensive
step by far in producing sapphire domes is the large
amount of grinding needed to turn discs cut from a
single crystal boule into domes.9 As there is no process
for fabricating near net shape single crystal sapphire
windows and domes, which would reduce their proces-
sing cost by .50%, the transition to lower cost
electromagnetic windows has taken the path of devel-
oping powders and processing techniques to convert
ceramic powders into high quality, transparent poly-
crystalline windows.8–16
Sintered polycrystalline submicrometre Al2O3 has
also been considered as desirable candidate material
for these applications, as it possesses the highest hard-
ness (HV10520–22 GPa) among all the transparent
100 International Materials Reviews 2013 VOL 58 NO
materials.9,10 However, light transmission through this
material is subject not only to absorption and to
scattering by pores (as in all other transparent
materials), but is additionally decreased by losses
caused by the hexagonal birefringent splitting of the
beam on each crossover from one crystal to the next. It
is hard to imagine that sintered alumina will ever reach
required transparency, as it is a hexagonal system
always associated with birefringence transmission
losses. The one way to minimise birefringent scattering
losses is to use a small submicrometre grain size such
that the electromagnetic wave package does not see
individual crystals.10 Typically, for a grain size of
highly dense sintered Al2O3 is y0?5 mm, the RIT is
y60% (y70% of theoretical limit) at 1 mm thickness
and with a wavelength of l5640 nm. All these losses
(e.g. 30% over 1 mm of thick dense submicrometre
Al2O3) increase with the thickness. These losses will be
higher for thicker components whereas a safe ballistic
performance requires at least 1?5–2 mm thickness. New
technologies bring the transmission closer to the limit
associating grain sizes of 0?3 mm with an RIT of 84–93%
of the theoretical maximum (0?8 mm thickness).9 Even
these extreme results give again rise to doubt that it
will ever be possible to manufacture larger and thicker
Al2O3 windows with a sufficiently high transparency.8–10
Nevertheless, the submicrometre Al2O3 has been
suggested to be a good choice for IR windows and
low threat armour applications where thinner tiles
can be employed. The successful development of
advanced near net shape forming techniques would
also reduce processing cost of these components
significantly.
The other ceramic materials that have been used to
make thicker transparent windows include MAS, AlON
(aluminium oxynitride) and aluminium niobate. The
concept of a hard transparent front layer of sapphire,
MAS or AlON, which has the function to induce
damage to the projectile core by erosion and fragmen-
tation, was introduced about four decades ago.8–10
MAS and AlON (Al23O27N5) have been found to be
better for transparent window applications when
compared with aluminium niobate. Both MAS and
AlON are significantly harder to be used as efficient
armours. Higher efficiency allows the armour system to
be thinner and lighter weight, which in many cases,
could be enabling factors for current and future ground
and air platforms. AlON is produced by Raytheon
Corporation.8–10 The incorporation of nitrogen into the
aluminium oxide lattice stabilises the spinel crystal
phase, producing an isotropic cubic crystal structure.
High temperature processing using a transient liquid
phase sintering approach produces samples with a
transmission of 85% and haze of 14%.8–10 Furthermore,
this material has a shorter transmission cut-off in the
4?5–5?5 mm spectral region, resulting in a significantly
higher coefficient of absorption in that critical band. On
the other hand, polycrystalline MAS is transparent to
UV, visible and mid-IR wavelengths and offers certain
advantages over AlON, including lower processing
temperatures and superior optical properties within
the IR region.8 As MAS crystal structure is cubic and
optically isotropic, polycrystalline shapes can be
fabricated without severe scattering problems inherent
in polycrystalline non-cubic materials like alumina.
2

a 0?8 mm thin submicrometre alumina; b 3 mm thick spinel9,10
58 Transparent sintered armour ceramics
Because of the absence of birefringent scattering in
MAS, high transmission values have been obtained with
larger grain sizes, i.e. higher temperatures can be applied
to remove the last pores (as far as exaggerated growth
does not result in intragranular porosity). Higher
transmission reduces the detrimental thickness effect,
and it is a general experience that really transparent
windows are obtained much more easily with such cubic
MAS ceramics than with Al2O3. Furthermore, MAS
does not undergo any polymorphic transformation
hence pose no problems due to thermally induced phase
changes. A ballistic testing has shown that 1/4 inches of
MAS has the same resistance as 2?5 inches of bullet
proof glass.9,10 In fact, MAS has the lowest density
among three hard transparent ceramic materials (i.e.
MAS, AlON and Al2O3), which gives it an advantage in
mass efficiency and weight, as the ballistic performance
of all these three materials has been essentially
equivalent. These properties made MAS an indispen-
sable candidate for transparent armour in light vehicles
and goggles or face shields on infantry helmets.8–10 In
addition to these, MAS domes were also qualified for at
least two IR guided missiles and for the stinger missile
launch tube window.8–10
On account of these advantages, transparent MAS
components are employed as IR domes and windows for
missiles, transparent armour for air and ground vehicles,
optical lenses, laser host materials, windows for lasers,
optical heat exchangers, arc enclosing envelopes, alkali
metal vapour discharge devices, high pressure arc lamps,
optical nanodevices, high brightness phosphor screen for
picture tube applications, optically transparent fibre
optic temperature sensors, pressure vessels, windows for
radio frequency powder injectors, plasma diagnostic
devices, watch crystals, sight glass for high pressure or
temperature vessels, passive Q-switches of lasers, non-
linear optic devices, etc.7–10 The transparent MAS
goggles are also employed for protection against the
sun, wind and dust and in some cases, lasers. Ground
vehicle equipment that is used on the battlefield, such as
tanks, trucks and resupply vehicles, are also protected
by MAS armour. These armours should withstand
multiple hits since most threats/weapons are automatic
or semiautomatic. The windows must also be full size so
that the vehicle can be operated in the manner in which
it was designed. For example, a small window on a truck
can increase ballistic survivability, but can reduce
operational safety if the driver does not have an
Ganesh A review on MAS: synthesis, processing and applications
appropriate filed of view. Helicopters and other aircraft
used in combat or in support roles are also protected by
MAS transparent armour. Helicopter applications
include windshields, blast shields, lookdown windows,
and sensor protection. The general requirements for
these helicopters are also similar to those for ground
vehicles, though the importance of the require-
ments varies. Weight is a critical factor for helicopter
applications.
In a study, Harris203 recorded the transmission
spectra of various commercially available IR materials
including MAS. MgAl2O4 spinel possesses a distinct
transmission advantage over sapphire and AlON from
4?5 to 5?5 mm, a region of particularly importance for
seeker and electro-optic imaging systems. Optical scatter
is generally very low, owing to MAS’s cubic crystal
structure; however, porosity and impurities at grain
boundaries can increase both scatter and absorption.
Figure 58 compares the different degrees of transpar-
ency of typical advanced alumina and MAS ceramics
prepared by Krell et al.9,10 MgAl2O4 spinel shows much
better transmittance than the submicrometre sized
polycrystalline alumina.
Figure 59 shows the schematic and photographs of
ballistic testing assembly.8 A typical ballistic resistance
testing unit consists of three main components:
(i) a ceramic front layer of thickness between 1?3
and 8?3 mm
(ii) a glass laminate consisting of one, two or three
layers of soda lime float glass
(iii) a polycarbonate layer of 4 mm thickness.
Figure 60 shows the residual velocity of the projectiles
as a function of the total areal density of various
transparent armour ceramics.8 The sintered Al2O3 and
the MAS were manufactured by the Fraunhofer
Institute for Ceramic Technologies and Systems
(Dresden, Germany). Armour piercing projectile was a
steel core of calibre 7?62 651 mm and a total mass of
9?5 g. The steel cores had a mass of 3?7 g and a length
of 23?5 mm. The impact velocity employed was
850¡15 m s21. The total areal density rFTOT can be
defined as the sum of the areal densities of the three
target components, whereas the areal density of the
components is defined as the product of the material
density and the thickness respectively. With the MAS
not only perforation but also projectile defeat is
reported at ceramic thickness of 1?7 and 2?2 mm. The
maximum residual velocities reported were ,120 m s21.
International Materials Reviews 2013 VOL 58 NO 2 101
Ganesh A review on MAS: synthesis, processing and applications
59 Schematic and photographs of ballistic testing assembly8
No perforation occurred at 4 mm MAS thickness. This
means, the protective strength of the tested MAS is
nearly as good as that of the sintered Al2O3, and
significantly higher than that of sapphire.
Neutron radiation resistance applications
The oxygen sublattice in MAS was found to be quite
rigid under neutron irradiation despite the lower atomic
mass of the oxygen atoms relative to the metal atoms,
and energies of .60 eV were found to be required to
displace an oxygen atom. The metal atoms (cations)
have much lower displacement energies (y20 eV for Mg
and Al), and are thus the ones that are the most easily
affected by the irradiation. There has been a debate in
the literature concerning the nature of cationic displace-
ment in MAS.220–223 A site exchange of cations Al3z
and Mg2z has been observed under neutron irradiation.
However, this disorder created by irradiation made the
MAS either mixed or completely inverse, but did not
lead to any change in the crystallographic symmetry or
the lattice parameter. As is known, the thermodynami-
cally stable ground state of MAS is the normal spinel,
and hence energy is required to disorder it in the inverse
form. No radiation induced swelling, no microcrack
formation and no degradation in its mechanical pro-
perties were observed in MAS ceramics over a wide
60 Residual velocity versus areal density for ceramic/glass/polycarbonate ballistic testing targets8
102 International Materials Reviews 2013 VOL 58 NO
temperature range. The radiation resistance of MAS was
attributed to high recombination rates of point defects
generated by displacement collisions in the presence of a
large population of unoccupied interstices. The ability of
MAS to tolerate radiation damage is also thought to be
a result of two factors. The first is a high interstitial–
vacancy (i–v) recombination rate. The second is the
ability of the lattice to tolerate significant intrinsic
antisite disorder on the cation sublattice as described by
equation (44)220–223
| 0
.
Mg|
Mg zAlAl ?MgAl zAlMg (44)
This is supported by neutron diffraction data from
stoichiometric MAS, which demonstrated significant
cation disorder in a sample exposed to a high radiation
dose (249 dpa at 385uC). Recent atomistic simulations
of displacement cascades in MAS also resulted in high
concentrations of cation antisite defects, often grouped
as clusters.220–223
Based on a study, Gupta222 concluded that the
radiation induced cation disorder in the MAS depends
on the nature of irradiation, too. For low energies, the
exchange between the Mg atoms at the tetrahedral sites
and the Al atoms on the octahedral sites is more fa-
vourable, since it requires less energy, and this disorder
2

61 Impedance data at 40uC as function of RH for MAS pellet sintered at 1300uC for 8 h presented in a complex impe-
dance plane plot and b Z0 and M0 spectroscopic plots20
leads to simple inversion of MAS. The original MAS
structure is preserved in this disorder. At this stage there
is no crystallographic transformation or a division of the
lattice parameter by a factor of 2. At higher energies, the
cations at the tetrahedral sites in inverse MAS are
displaced to previously unoccupied 16c octahedral sites.
The resulting structure is a pseudocubic structure, and
can be indexed with the original space group Fd3m.
However, with further irradiation this pseudocubic
structure also transforms to an ideal defective cubic
NaCl type structure as with inversion. The total energy
required for transformation to the defective NaCl type
structure is the same, 2?16 eV, in both processes.
In another study, Yano et al.221 irradiated MAS
ceramics having different stoichiometry with neutrons
up to 3?861023 and 5?761023 n m22 below 200uC, and
then isochronally annealed up to 1000uC. No change in
property within the two irradiation conditions was
noted. The amount of macroscopic length change due
to these irradiations increased almost linearly with
increasing Al2O3 content. During the annealing process,
macroscopic length of the specimens started to decrease
at y200uC and reduced monotonically up to 550uC.
After that, the length increased slightly up to 650uC and
then decreased again until 800uC. These final values
corresponded to the length of the specimens before the
irradiation. It is supposed that neutron irradiation
induced both anion Frenkel defects (vacancies and
interstitials) and cation disorder into MAS at tempera-
ture below or around 200uC. In the case of 1 h
annealing, cation disorder was preserved up to 600uC
and recovered above that temperature, whereas Frenkel
defects of anions gradually annihilated from irradiation
temperature up to 800uC.223
Humidity sensor applications
Monitoring and controlling environmental humidity is
receiving ever wider attention, mainly for comfort and
for industrial processes.17–23 There are widespread uses
and applications of humidity sensors in many different
fields. Each field of application requires different
operating conditions, and therefore, different kinds of
humidity sensors are required in order to meet the
different requirements. The materials used in humidity
sensors exploiting variations of electrical parameters
were roughly classified into three groups: electrolytes,
organic polymers and ceramics. Among these three
types, ceramics have shown advantages in terms of their
Ganesh A review on MAS: synthesis, processing and applications
mechanical strength, their resistance to chemical attack
and their thermal and physical stability. The only
problem for ceramic humidity sensors is related to their
need for periodic regeneration by heat cleaning to
recover their humidity sensitive properties, as pro-
longed exposure to humid environments leads to the
gradual formation of stable chemisorbed OH2 on the
surface, causing a progressive drift in the resistance of
the ceramic humidity sensor. The hydroxyl ions are
removed by heating to temperatures higher than
400uC.17–23 Moreover, humidity sensors are usually
exposed to atmospheres that contain a number of
impurities, such as dust, dirt, oil, smoke, alcohol,
solvents, etc. The adhesion or adsorption of these
compounds on the ceramic surface causes irreversible
changes in the sensor’s response. Contaminants act in
the same way as chemisorbed water, and may be
removed by heating, too. Commercial sensors based on
ceramic sensing elements are equipped with a heater for
regeneration.17–23 Among the various ceramic based
humidity sensors tested so far, MAS exhibited some
promising results in terms of sensitivity, stability and
response time on account of its basic nature. Since the
conduction mechanism for sintered MAS pellets is that
the ionic, the conductivity increases with increasing
chemisorption, physisorption and/or capillary conden-
sation of water within the pore structure. The conduc-
tion mechanism of MAS both in bulk and thin film
form at different environmental humidities has been
found to be ionic.17–23
In a study, Laobuthee et al.20 studied the humidity
sensing properties of MAS pellets. Figure 61 shows the
impedance data for the MAS pellet sintered at 1300uC
for 8 h, measured at 60, 70 and 80% relative humidity
(RH).20 Figure 61a shows the complex impedance plane
plots and Fig. 61b the spectroscopic plots of the
imaginary part of the complex impedance Z0, and of
the imaginary component of the complex electronic
modulus M0.20 For both pellets, the complex impedance
plane plots recorded at low RH values (,20% RH)
showed a single semicircle which was slightly inclined to
the real axis and did not start from the origin. At larger
RH values, the spectrum loci decomposed in a semicircle
at higher frequencies and in a linear spur at low
frequencies, which was a Warburg-like line. The larger
the RH, the smaller the impedance of the pellets. The
frequency at which the relaxation of the RC element
occurred, increased with increasing RH. The value of the
International Materials Reviews 2013 VOL 58 NO 2 103
Ganesh A review on MAS: synthesis, processing and applications
intercept at high frequencies with the real axis did not
change with RH.20
Refractory applications
Although the use of MAS in refractory bricks has been
known since the 1920s, it has only been in the last
35 years or so that MAS is seen as a potential refractory
raw material.1,24,66,70–72,224–226 A major barrier to MAS
development for these applications has been its relatively
high cost, which still remains an influencing factor in
certain applications. The main driving force responsible
for the recent surge of interest in MAS in these
applications has been its use as a substitute refractory
brick material for magnesia chrome bricks in cement
kilns (started in the mid-1970s), and its use in monolithic
steel ladle linings (pioneered in Japan during late 1980s).
MgAl2O4 spinel found as a suitable alternative in these
applications as it has also proven to give superior
performances over the original materials. Since MAS is
an environmentally benign material, it has replaced
magnesium chromite based refractories market, as the
latter material is toxic being chrome bearing compound.
MgAl2O4 spinel finds its major applications, in burning
and transition zones of cement rotary kilns and bottom
and sidewalls of steel teeming ladles, and is used as a
major component in magnesia rich or alumina rich
matrix. Again another important application is the
checker work of the glass tank furnace regenerators
where pure MAS products are important. Hence, all the
stoichiometric, magnesia rich and alumina rich MAS
compositions are important from the refractory applica-
tion point of view. In addition to these there are also
fused MAS grains used in refractory applications.24
In a study, Ganesh et al.224 prepared 20 wt-% MAS
incorporated high alumina (70%Al2O3, Chinese bauxite
based) and magnesia–carbon (Chinese fused magnesia
based) refractory bricks and compared their perfor-
mance against pure high alumina and magnesia carbon
bricks for slag erosion, slag penetration and permanent
linear change tests. The MAS containing bricks have
exhibited improved resistance to slag erosion and
penetration quite significantly. In the case of high
alumina, the slag erosion resistance along the side wall
(along the radius of the hole) and bottom (along the
depth of the hole) were improved by 58?26 and 26%
respectively, and its slag penetration resistance also
increased by 14?45%, after MAS addition. In the case of
magnesia carbon bricks, slag erosion resistance along
the side wall and bottom were improved by 47?72 and
45?31% respectively. Since magnesia carbon bricks are
black in colour, the degree of slag penetration could not
be measured. The MAS incorporated high alumina
exhibited steadier and balanced positive permanent
linear change (PLC) values when compared to pure
high alumina testpiece.224 The relatively lower thermal
expansion of MAS at elevated temperatures has been
attributed for these beneficial PLC values.
Catalyst and catalyst support applications
Owing to its good chemical stability, surface basic cites,
mechanical strength and high melting temperature
(2135uC), the MAS has been identified as an excellent
catalyst and catalyst support for a great variety of
organic reactions, such as petroleum processing, fine
chemicals production, Oleflex and Star processes for
propane and butane dehydrogenation respectively,
104 International Materials Reviews 2013 VOL 58 NO
de-SOx reaction/catalytic SOx abatement, SCR of NOx,
etc.27–41,225–250 For industrial applications, it is of
utmost important for support materials to have enough
high temperature (at least 700uC) withstanding cap-
ability. Further, support materials have to maintain the
metal dispersion of the catalyst during operation. This
implies that support material is also a very important
part of the catalytic system. MgAl2O4 spinel has been
identified as a better support material than Al2O3
thermodynamically for several catalytic reactions. The
molecular structure of MAS is similar to c-Al2O3, with
32 oxygen ions packed into a close packed cubic
structure. The difference lies in that there are totally
24 cations inserted into oxygen ion gaps in MAS, while
only 21 and 1/3 aluminium cations are distributed
among the close packed cubic matrix in c-Al2O3. This
saturated structure makes MAS more thermally stable
than c-Al2O3, with its melting point at 2135uC. The
various reactions catalysed by MAS as catalyst and
catalyst supports are summarised in Table 6.27–41,225–250
Lercher et al.251 reported that the strength of the acid
sites decreases and that of the basic sites increases with
increasing magnesia content in MAS. Three different
kinds of Lewis acid sites (OH groups, Mg2z and
Al3zcations) were reported for MAS. Owing to its high
basic nature, MAS has been found to be the most sought
catalyst and catalyst support for some of the reactions
where basic nature of the support is desired. Some
important reactions catalysed by MAS or by those
supported on MAS are presented in the following
sections.
Catalytic SOx abatement
The emission of gaseous acid oxides into the atmo-
sphere, ultimately leading to acid rain, is increasingly
unacceptable. Sulphur dioxide is a particularly serious
pollutant as it is a product of the combustion of non-
desulphurised fuels and coke. Emissions of SOx (about
90%SO2 and 10%SO3) from fluid catalytic cracking (fcc)
units are receiving increased scrutiny from regulatory
agencies in connection with smog and acid rain
problems.227–229,251,252 Flue gas scrubbing and feedstock
hydrodesulphurisation are effective means of SOx
control, but are laborious and expensive. The least
costly alternative is the addition of a SOx reduction
catalyst to the fcc unit catalyst inventory. The ideal
transfer catalyst should be able to easily facilitate the
oxidation of SO2 to SO3, have a high sorption capacity
for the sulphur(VI) species produced, and be easily
regenerated. The regeneration is carried out by reducing
the sulphates to hydrogen sulphide which are then
treated via the modified Claus process (SO2z2H2S
R3/n Snz2H2O) to give elemental sulphur. The trap-
ping of S in fcc reactor is shown in a step wise manner in
the following equations. The sulphur in the coke is
mainly oxidised to SO2 (equation (45)).228 SO2 should
be further oxidised to SO3, (equation (46)) so that it can
react with metal oxides to form sulphates (equa-
tion (47)).
S(in coke)zO2 (air)?SO2 zSO3 (45)
2SO2 zO2 ~2SO3 (46)
SO3 zMO~MSO4 (47)
2
 Ganesh A review on MAS: synthesis, processing and applications

The free energy of formation of SO3 (equation (45)) is
29?5 kJ mol21 at 675uC and 24?4 kJ mol21 at 730uC.
Therefore, the regenerator temperature of an fcc unit is
between 650 and 775uC. Catalysing reaction (equa-
tion (46)) is one of the major functions of a SOx catalyst.
Equation (47) represents the capture of SO3 in the
regenerator by the catalyst. The catalyst then moves to
the fcc reactor where the sulphate is reduced by
hydrogen and other reducing gases to metal oxide and
H2S or metal sulphide
MSO4 z4H2 ~MOzH2 Sz3H2 O (48)
MSO4 z4H2 ~MSz4H2 O (49)
Metal sulphide can be hydrolysed in the stripper to form
the original metal oxide
MSzH2 O~MOzH2 S (50)
This is the generally accepted mechanism and a
schematic diagram of an fcc unit is shown in
Fig. 62.228 For the de-SOx catalyst to successfully work
in a commercial fcc operation, the SOx picked up in the
regenerator must be stripped by the reducing atmosphere
in the cracking reactor section. If the sulphur cannot be
removed, the sulphur build-up would saturate the de-SOx
catalyst and render it useless.228,229
As is known, SO2 is an acidic gas; its adsorption on
the catalyst is strongly affected by the basic property of
the solids. Because of its basic nature together with high
temperature stability and high abrasion and attrition
resistant properties, MAS has become the most lucrative
catalytic material for this purpose. A solid solution of
MAS and MgO, i.e. Mg2A12O5 (i.e. MgAl2O4zMgO)
has been employed as catalyst support, which has shown
hardness close to a typical fcc catalyst. The SOx removal
activity increased as the MgO content increased in the
solid solution of CeO2/MgA12O4–yMgO catalyst and
became a maximum at y51.228,229 This material at y51
is the most widely used SOx reduction catalyst today.
These solid solution materials are very stable even after
severe steam treatments, and the steamed catalysts are
equally or sometimes surprisingly more active than their
virgin catalyst counterparts. A relationship between the
reduction efficiency of sulphated catalysts and the
composition of the solid solution catalyst was clearly
established.228 Further, it was established that the solid
solution of MAS and CeO2 provides an optimum

Table 6 Summary of various reactions catalysed by MAS catalyst and catalyst support27–41,225–250

Reaction Catalyst Preparation method

Oxidation of SO2 to SO3 MgAl2O4 Solid state reaction27

Oxidation of SO2 to SO3 MgAl2O4 Coprecipitation28
SOx abatement CeO2/MgAl2O4 Coprecipitation/impregnation227
De-SOx reaction CeO2/MgA12O4.MgO Coprecipitation/impregnation29
De-SO2 reaction CeO2/MgAl2O4 Coprecipitation/impregnation228
De-SO2 reaction MgFe2O4zMgAl2O4 Coprecipitation30
De-SO2 Reaction MgAl2O4 and CeO2/MgAl2O4 Coprecipitation/impregnation229
SCR of NO CuO/MgAl2O4 Co-precipitation31
NOx storage and reduction K/Pt/MgAl2O4 Sol–gel/impregnation230
NOx storage/reduction MgAl2O4 Coprecipitation231
Ammonia synthesis Ru or Ba–Ru/MgAl2O4 Solid state reaction/impregnation32,33
Ammonia decomposition Ba–Ru and Cs–Ru/MgAl2O4 Precipitation deposition/impregnation232
n-Butane dehydrogenation PtSn/MgAl2O4 Solid phase reaction/impregnation34
n-Butane dehydrogenation InPtSn/MgAl2O4 Solid phase reaction/successive impregnation35
n-Butane dehydrogenation Pt/MgAl2O4 Mechanochemical synthesis, solid state
reaction, or coprecipitation/impregnation233
Propane dehydrogenation Pt/MgAl2O4 Coprecipitation/impregnation41
Propane dehydrogenation Pt–Sn/MgAl2O4 Coprecipitation/impregnation234
Propane hydrogenolysis Ni/MgAl2O4 Coprecipitation/impregnation235
Oxidative dehydrogenation of propane V2O5/MgAl2O4 Sol–gel/Grafting from solution236
Dry reforming of methane Ni/MgAl2O4 Coprecipitation/impregnation237
Dry reforming of methane Ni/MgAl2O4/Al2O3 Impregnation36
Dry reforming of methane NiCeO2ZrO2/MgAl2O4 Coprecipitation/impregnation37
Methane reforming Ni–Pt/MgAl2O4 Coprecipitation/impregnation238
Steam reforming of methane Ni/MgAl2O4 Coprecipitation/impregnation239
Steam reforming of n-heptane Rh/MgA12O4 Solid state reaction/impregnation240
Ethanol steam reforming Rh/MgxNi12xAl2O3/Al2O3 Solid state reaction/impregnation241
Ethanol condensation MgAl2O4 Coprecipitation242
Gas phase and catalytic Pt/MgAl2O4 Coprecipitation/incipient
oxidative cracking of hexane wetness impregnation243
Chemical looping combustion Fe2O3/MgAl2O4 Coprecipitation/impregnation38
Catalytic oxidative cracking Pt/MgAl2O4 Coprecipitation/impregnation244
of higher hydrocarbons
Pyrolysis of diesel fuel Co–MgAl2O4 Self-propagating high temperature synthesis84
Chemical looping combustion NiO/MgAl2O4 Coprecipitation/freeze granulation245
Chemical looping combustion and Fe or Mn/MgAl2O4 Coprecipitation/dry impregnation246
chemical looping reforming
Synthesis of carbon nanotubes (CNT) Fe/Co–MgAl2O4 Combustion synthesis247
Hydrogen production from bio ethanol Rh/MgAl2O4 Solid state reaction/impregnation248
Methanolysis of soybean oil MgO–MgAl2O4 Hydrothermal synthesis249
Gas phase amination of 2,6-diisopropyl phenol Pd–La/MgAl2O4 Coprecipitation250
Water gas shift reaction RuzFe2O3zLa2O3/MgAl2O4 Coprecipitation/impregnation39

International Materials Reviews 2013 VOL 58 NO 2 105

Ganesh A review on MAS: synthesis, processing and applications
62 Schematic diagram of typical fcc unit and SOx reduction chemistry228
structure, so that the SO3 molecule can be picked up as
sulphate on the –O–Mg–O–Al–O– moiety in the MAS
surface. The SOx activity of the CeO2/MgO catalyst was
found to be higher than that of the solid solution
catalyst, CeO2/MgAl2O4.MgO (1 : 1 molar ratio of MgO
in MAS). Contrary to this solid solution system, the
pure MgO catalyst was drastically deactivated by the
steam treatment. Finally, the CeO2 containing MgO
excess MAS catalysts (CeO2/MgA12O4–yMgO) are
determined to be the best SOx removal catalysts.228
The absorption and reduction half cycles of de SOx
process was shown by Bhattacharyya et al.227 Certain
commercial tests have indicated that the sulphur can
easily be removed from the MAS based catalysts. At
temperatures of 732uC, the reduction is extremely fast,
reaching y90% sulphur removal in the laboratory in
,2 min.241,242 This is important since the regenerated
catalyst at temperatures in excess of 700uC will see the
reducing atmosphere of the reactor section for a short
time before the temperature is reduced to reactor
temperatures (y540uC) due to the endothermic cracking
reaction and heat transfer. The sulphated MAS resulting
from the laboratory SOx activity test are then reduced
with H2 or propane to regenerate the catalyst. The SOx
pick-up test is the oxidation and absorption half cycle,
and the H2/propane reduction reaction is the regenera-
tion half cycle. Reduction of sulphate becomes easier
and requires lower temperature as the alumina content
in these MAS materials increases. These results indicate
that CeO2/MgAl2O4.MgO is the best SOx abatement
catalyst among various catalysts employed for this
reaction so far.241,242
Chemical looping combustion and chemical looping
reforming (CLR)
Combustion of fossil fuels during power generation
emits a significant amount of greenhouse gas CO2 into
the atmosphere. It is generally accepted that reduction in
greenhouse gas emission is necessary to avoid major
106 International Materials Reviews 2013 VOL 58 NO
climatic changes. Chemical looping combustion has
emerged as a new combustion technology in which
gaseous fuel is burned and resulting CO2 is inherently
separated from the rest of the flue gases.253–256 The CLC
system is normally composed of two fluidised bed
reactors, an air reactor and a fuel reactor.253 In CLC,
fuel and air never mix; instead, a metal oxide is used as
an oxygen carrier, which transfers oxygen from air to the
fuel reactor. Fuel is oxidised by the metal oxide in the
fuel reactor as shown
(2nzm)My Ox zCn H2m ?
(2nzm)My Ox{1 znCO2 zmH2 O (51)
where MyOx is a fully oxidised oxygen carrier and
MyOx21 is the oxygen carrier in reduced form. The exit
stream from the fuel reactor contains only CO2 and
H2O. Thus, pure CO2 can be obtained by condensing
H2O. The reduced metal oxide, MyOx21, is sent to the
air reactor, where it is oxidised as shown
1
My Ox{1 z O2 ?My Ox (52)
2
The flue gas stream from the air reactor contains N2 and
some unreacted O2. The reaction between fuel and metal
oxide in the fuel reactor may be endothermic, as well as
exothermic, depending on the oxygen carrier used, while
the reaction in the air reactor is always exothermic. Since
air and fuel never mix in CLC and combustion takes
place without flame at a temperature below 1400uC,
NOx formation is totally avoided.254,255 This technology
has been successfully demonstrated in 10 and 50 kW
prototypes of interconnected fluidised beds.253–256
Oxygen carriers based on transition state metals, Mn,
Fe, Co, Ni and Cu supported on different inert
materials, e.g. SiO2, TiO2, Al2O3, MgO, YSZ and
MgAl2O4 (MAS) have been investigated for CLC. In
general, NiO exhibits very high reactivity and has been
successfully used as an oxygen carrier in prototypes
2

based on interconnected fluidised beds of 10 and 50 kW
respectively.253–256 A number of research groups have
tested different types of oxygen carriers with different
types of inert (support) materials. A detailed review on
this work was published by Mattisson et al.256 Of the
investigated oxygen carriers, the system of NiO and
MAS was found to be very promising.
Zafar et al.246 investigated the oxides of Ni, Mn, Fe
and Cu supported on MAS formed via impregnation
route following TGA using 10%CH4 for reduction and
5%O2 for oxidation and found that NiO/MAS was a
promising candidate both for CLC and CLR due to its
high reactivity during reduction and excellent regener-
ability. In another study, Villa et al.255 investigated
NiO/NiAl2O4 and NiO/MAS carriers using CH4 as
fuel. They also found the prevention of crystal size
growth of NiO oxygen carrier in the presence of
NiAl2O4 spinel. Further, the added Mg prevented the
sintering of the cubic oxide phase and improved
regenerability upon repeated redox cycles.255 In their
study, Mattisson et al.256 also investigated NiO sup-
ported on NiAl2O4, MAS, TiO2 and ZrO2 in a labora-
tory fluidised bed reactor. They noted high reactivity for
all oxygen carriers together with no particle breakage or
agglomeration.
NOx storage and reduction (NSR)
To meet the stringent emission regulations, a new after
treatment system for lean burn gasoline engines is
suggested, because the conventional three way catalysts
are not able to detoxify NOx under excess oxygen
conditions, although the lean burn engine contributes to
the prevention of global warming.257–260 A NSR catalyst
system has been proposed and is currently being
employed as one of the most feasible and attractive
solutions to this technical challenge. A typical NSR
catalyst consists of barium or potassium compounds as
a NOx storage material on Pt doped c-Al2O3.259 In an
oxidative atmosphere, NO is first oxidised to NO2 over
Pt, then combined with the NOx storage material, and
finally stored as a nitrate ion. During the following
reduction stage, the stored nitrate ion is released as NO
or NO2 from the NOx storing material, and then reduced
to nitrogen.257–260 The conventional NSR catalysts
for the lean burn engine are mainly operated at a
temperature around 400uC, because these catalysts have
a maximum NOx removal efficiency between 300 and
400uC. The study of Ryden et al.261 revealed that the
NOx storage amount in the lean atmosphere is same as
the NOx reduction amount from the subsequent rich
spike over 400uC; thus, the NSR capability above 400uC
is restricted by the NOx storage amount. For a motor
vehicle with a lean burn gasoline, engine travels at
100 km h21 or more generates temperature of 600uC or
higher. It is well known that the electronic states of
metals are affected and changed by interactions with the
support oxides or additives in the supported metal
catalysts.257–260 These facts suggested that the basicity of
the potassium NOx storage material could be enhanced,
if it is supported on support material having higher
basicity than c-Al2O3.
In a study, Takahashi et al.258 prepared stoichio-
metric MAS from magnesium acetate tetrahydrate
((CH3COO)2Mg.4H2O) and aluminium isopropoxide
(Al[OCH(CH3)2]3 following sol–gel route by calcining
at 850uC for 5 h. This MAS powder was wash coated on
Ganesh A review on MAS: synthesis, processing and applications
a hexagonal cell monolithic substrate (62 cells/cm2)
having a diameter of 30 mm and length of 50 mm. The
coated sample was then immersed in a nitric acid
solution of dinitrodiamino platinum (Pt(NH3)2(NO2)2),
for 1 h, then the remaining solution was removed by air
flushing, dried at 120uC overnight, and finally calcined
at 250uC for 1 h in air. The coated substrate was
thereafter immersed in an aqueous solution of potassium
acetate (CH3COOK) for 10 min, purged with air to
remove the remaining solution, dried at 120uC over-
night, and finally calcined at 500uC for 3 h. The
resultant material is K/Pt/MAS catalyst. The NOx
storage amount on the K/Pt/MAS catalyst at any K2O
loading was found to be higher than that on the K/Pt/
Al2O3 catalyst, which is the same as the fresh catalysts.
However, distinct from the fresh catalysts, the difference
in the NOx storage between these two thermally aged
catalysts increased upon increasing the loading amount
of K2O. Takahashi et al.258 also found that the NOx
storage residual ratio (i.e. the percentage of the NOx
storage amount on the thermally aged catalyst to that on
the fresh one) with the K/Pt/MAS catalyst was found to
be consistently higher than those of the K/Pt/Al2O3
catalyst. In addition, the NOx storage residual ratio on
the K/Pt/MAS catalyst increased versus the K2O
amount, while that for the K/Pt/Al2O3 remained nearly
unchanged. The value for the 3?3%K2O containing K/
Pt/MAS catalyst was almost 100%, indicating that this
catalyst did not deteriorate due to the thermal aging
treatment. These results suggest that usage of basic
MAS as a support for potassium NOx storage is a
promising breakthrough solution to improve the per-
formance of NSR catalysts at high temperature.
Dry reforming of methane
During the last decades, great attention has been paid
to dry reforming of CH4 with CO2 (CH4zCO2
2COz2H2, DH2985247 kJ mol21) from the perspective of
global warming and alternative energy sources. The dry
reforming process offers several opportunities. Depending
on the kind of energy source used to overcome the reaction
endothermicity, dry reforming can be environmentally
beneficial, since it converts two abundant greenhouse gases
(CH4 and CO2) into synthesis gas. The produced synthesis
gas has a H2/CO molar ratio typically lower than that of
steam reforming, making dry reforming more compatible
with Fischer–Tropsch processes for liquid fuels synthesis.
Reactions of interest using dry reforming are the conver-
sion of CH4 enriched in CO2 into syngas. Biogas, a mixture
of CH4 and CO2 produced from the fermentation of
biomass and agricultural and industrial food wastes, is a
promising renewable energy source. Owing to the high
CO2 content, dry reforming could be one of the most
suitable processes to convert biogas into synthesis gas. In
addition, the transformation of natural gas into synthesis
gas recently has attracted great attention, since overall
reserves of natural gas exceed those of oil. A variety of
catalysts have been developed for this reaction.262–265 The
Ni based catalysts showed high activity and selectivity and
are cheap, but involve heavy carbon deposition (i.e. coke).
Coke deposition on these catalysts has a significant
influence on their cracking activity and selectivity and is
the main reason for catalyst deactivation. The origin of
inactive carbon C(s) during dry reforming of CH4 may
occur either via CH4 decomposition
International Materials Reviews 2013 VOL 58 NO 2 107
Ganesh A review on MAS: synthesis, processing and applications
CH4 ?2H2 zC(s)(DH o ~z17:9 kcal mol{1 )
or CO disproportionation (i.e. the Boudouard reaction)
2CO?CO2 zC(s)(DH o ~z41:2 kcal mol{1 )
These deposited cokes may have different structure orders,
morphologies and reactivity, depending on the specific
reaction conditions and structures of the catalyst. Re-
cently, Guo et al.36 found that the MAS could effec-
tively inhibit the coke formation when used as a
support for Ni catalysts. Furthermore, regardless of
the amount of coke deposited on Ni/MAS, no loss of
activity was observed during 55 h on stream indicating
that part of this carbon was not poisonous. In contrast,
Ni/MgO–Al2O3 and Ni/c-Al2O3 underwent severe
deactivation during 10 h on stream.36 These results
suggest that MAS is an excellent support material for
several catalysts suitable to perform different types of
commercially important reactions.
Concluding remarks and future
perspectives
As natural occurrence is little, MAS is artificially
synthesised, which exists in an fcc crystal structure.
MgAl2O4 spinel possesses a high melting point (2135uC),
high hardness (16 GPa), relatively low density (3?58
g cm23), high mechanical strength both at room (135–
216 MPa) and elevated temperatures (120–205 MPa
at 1300uC), high resistance against chemical attack,
wide energy band gap (.7 eV), high electrical resisti-
vity, relatively low thermal expansion coefficient (96
1026uC21 between 30 and 1400uC), high thermal shock
resistance, and does not react with SiO2 until 1735uC,
with MgO or CaO until 2000uC, with Al2O3 until
1925uC and, excepting alkaline earth metals, it can be in
contact with all other metals. These properties made
MAS an indispensable material for certain important
applications, such as transparent windows, domes and
armours in the wavelength range of 2–5?5 mm, and for
refractory in burning and transition zones of cement
rotary kilns and for steel ladles, etc. MgAl2O4 spinel has
also proved its efficacy in several other applications
including fusion reactor power core insulation, electro-
nic humidity sensors, refractories, TBCs, catalysts,
catalyst supports, etc. However, a major drawback
associated with MAS is a considerable amount of
volume expansion (y8%) associated with its phase
formation from alumina and magnesia. On account of
this volume expansion problem dense MAS bodies
cannot be prepared by following a single stage reaction
sintering process. In order to avoid this volume
expansion problem, normally, a double stage firing
process is employed. In this latter process, initially,
MAS powder is synthesised with .80% spinel phase by
calcining the compact mixture of alumina and magnesia
at .1400uC, and thus obtained MAS powder is then
subjected to grinding operation to create fresh reactive
surfaces, then to recompaction to achieve a GD of at
least 60% of the theory. This green body is then sintered
at temperatures .1700uC for sufficient time intervals to
achieve the desired density. Owing to the involvement of
two consecutive high temperature firing cycles, the
manufacturing cost has been increased. This cost has
108 International Materials Reviews 2013 VOL 58 NO
been a real concern for certain refractory applications,
(53) which consume a larger portion of MAS products.
As discussed, the processing cost of refractory grade
MAS could be considerably reduced by following either
(54) a single stage firing process in which the attrition milling
is used to reduce the particles size of starting (alumina
and magnesia) raw materials to below one micron size,
or by following a double stage firing process that involve
precise control of optimised processing parameters and
highly reactive starting raw materials and aluminium or
magnesium based sintering aids, such as AlCl3, AlF,
MgF2, etc. Mechanical milling and MA techniques can
also be employed to reduce the processing cost of
refractory grade MAS significantly, if the entering of
impurities into the final product from graining media
can be controlled.
Recently, the SAMH also found to be an economic
and simple technique for densifying MAS powders at far
lower temperatures than the conventional ones. At
1400uC, MAS do not need any susceptor for undergoing
densification, as it possesses desired dielectric loss at this
temperature. Thus, MAS utilises the in situ generated
MW activity during SAMH and undergoes desired
densification at 1400uC itself. Even, MAS phase forma-
tion can also be achieved in this process at relatively far
lower temperatures than the conventional ones. Hence,
there is a scope to upgradation of SAMH furnaces for
synthesising powders, as well as dense MAS grains,
suitable for refractory applications at much lower
manufacturing costs.
Although, the HP technique utilising LiF as a
sintering aid has been found to be successful to fabricate
acceptable quality optically transparent MAS compo-
nents, the processing cost is still a concern. Considering
the great number of important applications of optically
transparent MAS ceramics particularly in the strategic
and personnel protection sectors and the better perfor-
mance of these MAS components than their counter
parts, such as alumina, sapphire, AlON, lanthanum
niobate, MgF2, ZnS, etc., the reduction in processing
cost can really improve the applicability of MAS in
several other sectors of the industry too. The inferior
reactivity of involved starting powders and impurities
present in them have been found to be responsible for
employing stringent sintering conditions during hipping,
which have increased the manufacturing cost consider-
ably. As discussed in this review article, there are several
soft solution chemistry based powder synthesis techni-
ques, such as sol–gel, hydrothermal, freeze drying,
normal micelle synthesis, etc., which can produce the
high purity and highly reactive MAS powders suitable
for fabricating transparent MAS ceramics with excellent
optical properties under relatively milder HIP or HP
conditions.
The materials, LiF and Y2O3 have been identified as
excellent sintering additives to improve the densification
ability of MAS powder under relatively milder hipping
conditions. LiF has also been found to be more effective
in cleaning C and S impurities from MAS ceramics
during hipping operation, otherwise, they cause swelling
of MAS components by converting into gases. Normally
C enters as an impurity into MAS transparent bodies
during SPS, due to sputtering of graphite dies under
high currents employed and renders opacity to the
sinterd bodies. Since LiF was found to be effective in
2

cleaning C from MAS ceramics, by uniformly coating
LiF by following wet chemical impregnation technique
on high purity nanosize MAS powder, highly transpar-
ent MAS components with much improved optical
properties can be fabricated in SPS furnace. However,
the size of the graphite dies normally used in SPS
furnaces is a limitation for fabricating large size
components. If the size of the SPS furnace graphite dies
increased, by using LiF as a sintering aid, the production
yields of transparent MAS ceramics for several impor-
tant applications can be improved significantly. On the
other hand, a nanostructured MAS densified with Y2O3
under relatively milder hipping conditions exhibited a
room temperature strength of 470 MPa, a reliability
(Weibull modulus) of 6?2, improved erosion resistance
(sand and rain) and thermal shock resistance, a near
theoretical in-line IR transmission at RT and an optical
scatter of ,0?2 cm21 at 3?39 mm wavelength, which are
far better properties than those normally exhibited by
transparent MAS ceramics sintered without involving any
sintering additive. Nevertheless, certain complex shaped and
large size MAS components cannot be fabricated by
following HIP or HP techniques as near net shaped
components cannot be fabricated in these routes.
Recently, a surface passivation technique against
hydrolysis was developed for MAS powder, so that
certain novel net shape forming aqueous colloidal
processing techniques, such as GCHAS, gelcasting, slip
casting, etc., can be employed to fabricate MAS
radomes and domes at significantly lower manufacturing
costs as expensive and extensive post sintering machin-
ing operations using diamond tools can be totally
minimised or eliminated.
By following MOCVD technique, reliable and high
quality MAS thick/thin films can be prepared using
single bimetallic organic precursors for several other
applications including TBCs. Flame fusion method is
suitable for making MAS fibres and single crystals as
latter crystals are widely used for bulk acoustic wave and
MW devices and fast IC epitaxial substrates.
The non-stoichiometry and Frenkel or Schottky type
defects also greatly influence the densification behaviour
of MAS powder. Excess magnesia causes the formation
of oxygen vacancies, which have been identified as rate
determining steps in the densification process. On the
other hand, excess alumina impedes the densification
ability to some extent but improves the grain size signi-
ficantly so that they can perform better as refractory in
certain corrosive environments, including burning and
transition zones of cement rotary kilns and steel teeming
ladles. The theoretically constructed Brouwer diagram
predicts the formation of defects and their nature in
MAS ceramics upon insertion of excess magnesia or
alumina into stoichiometric MAS, which determine the
densification ability of MAS powder.
Since certain hitherto unknown properties, such as
Weibull modulus, thermal shock resistance, thermal
conductivity, erosion behaviour against high speed sand
and dust, etc., of MAS dense bodies, and the photo-
luminescence, photoemissivity, the degree of cation
inversion, refractive index, density of states, band gap
energy, etc., of MAS powders have been estimated by
following certain advanced characterisation techniques,
now it is relatively easy to choose the new applications
for which MAS can be a candidate material of choice.
Ganesh A review on MAS: synthesis, processing and applications
The strong basic character together with high
temperature withstanding capability and excellent abra-
sion and erosion resistance made MAS a better catalyst
and catalyst support for several commercially important
reactions, such as abatement of SOx, CLC and CLR,
NSR, dry reforming of methane, etc. Nanosize powders
formed in certain advanced soft solution chemistry
powder synthesis routes, such as hydrothermal, normal
micelle synthesis, sol–gel, etc., would have certain
additional active sites in addition to the existing basic
sites and high temperature withstanding capability.
Hence, the nanosize MAS powders are expected to
show much more promising for various reactions of
practical significance and are expected to gain great
interest in the coming years.
Acknowledgements
I wish to specially acknowledge all the researchers whose
work is described in this review for their valuable
contributions. I also thank Dr G. Sundararajan,
Director, ARCI for his kind encouragement and
permission to publish this review article. I would also
like to express all my colleagues who have given the
valuable suggestions while performing the study on
MAS ceramics.
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