J. Am. Ceram. Soc.
, 98 [10] 29482967 (2015)
Journal
Mullite: Crystal Structure and Related Properties
Hartmut Schneider,, Reinhard X. Fischer and J
Department of Geosciences, University of Bremen, Bremen 28359, Germany
Institute of Crystallography, University of Cologne, K
Institute of Geology, Mineralogy and Geophysics, Ruhr-University, Bochum 44801, Germany
Mullite is certainly one of the most important oxide materials
for both conventional and advanced ceramics. Mullite belongs
to the compositional series of orthorhombic aluminosilicates
with the general composition Al2(Al2+2xSi2-2x)O10-x. Main
members are sillimanite (x = 0), stoichiometric 3/2-mullite
(x = 0.25), 2/1-mullite (x = 0.40), and the SiO2-free phase
-alumina (x = 1, crystal structure not known). This study
gives an overview on the present state of research regarding
single crystal mullite. Following a short introduction, the sec-
ond part of the review focuses on the crystal structure of mul-
lite. In particular, the characteristic mullite-type structural
backbone of parallel chains consisting of edge-sharing MO6
octahedra and their specic cross-linkage by TO4 tetrahedra is
explained in detail, the role of cation disorder and structural
oxygen vacancies is addressed, and the possibility of cation
substitution on dierent sites is discussed. The third part of the
study deals with physical properties being relevant for technical
applications of mullite and includes mechanical properties (e.g.,
elasticity, compressibility, strength, toughness, creep), thermal
properties (e.g., thermal expansion, heat capacity, atomic diu-
sion, thermal conductivity), electrical conductivity, and optical
properties. Special emphasis is put on structureproperty rela-
tionships which allow for interpretation of corresponding exper-
imental data and oer in turn the possibility to tailor new
mullite materials with improved properties. Finally, the
reported anomalies and discontinuities in the evolution of cer-
tain physical properties with temperature are summarized and
critically discussed.
I. Introduction
T HEmineral mullite with the stoichiometric composition
3Al2O3
2SiO2 occurs very seldomly in natural rocks. The
name mullite comes from the Isle of Mull (Western Scot-
land), where the phase was described for the rst time.
D. J. Greencontributing editor
Manuscript No. 36535. Received March 7, 2015; approved July 8, 2015.
Author to whom correspondence should be addressed. e-mail: hartmut.schneider@
uni-bremen.de
DOI: 10.1111/jace.13817
2015 The American Ceramic Society
urgen Schreuer
oln 50939, Germany
Mullite has been observed at the contact of super-heated
lavas with alumina-rich sediments,13 in high-temperature
and low-pressure metamorphic rocks of the sanidinite facies
(so-called buchites4) and at the contact of bauxites with oli-
vine dolerite intrusions. Another though rare natural mullite
occurrence is the product of lightening impacts into alumina-
rich quartz sands.5 Small mullite single crystals were
described in druses of volcanic rocks of the Eifel mountain
(Germany, e.g., Ref. [6] and the literature therein), probably
grown under pneumatolytic or hydrothermal conditions.
In past years major disagreement existed on whether mul-
lite melts congruently or incongruently.1,7 The recent knowl-
edge of mullite stability bases on the phase diagrams
published by Prochazka and Klug8 and by Klug et al.,9
which shows that mullite melts incongruently (Fig. 1). The
mullite phase boundaries join at 1890C with a composition
of 77.2 wt% Al2O3, which corresponds to 2Al2O3
SiO2
(so-called 2/1-mullite). With decreasing temperature the
composition of mullite shifts toward lower Al2O3 contents.
Below about 1600C the mean Al2O3 content of mullite is
<73 wt%, corresponding to a composition of about
3Al2O3
2SiO2 (so-called 3/2-mullite or stoichiometric mullite).
Thus, the equilibrium solid solution range of mullite is about
4 wt% Al2O3 (see Fig. 1).
Homogenous and nearly inclusion-free mullite single crys-
tals with approximately 2/1-composition up to
50 mm 9 10 mm in size were rst grown by Guse and
Mateika10 and Guse,11 and later-on by the Institute for Crys-
tal Growth (Berlin, Germany), using the Czochralski tech-
nique (Fig. 2). Shindo12 produced mullite single crystals with
the slow cooling at zone method (up to 5 mm 9 70 mm in
size). Mullite single crystals have been widely used to deter-
mine the properties of mullite (see the section on Properties
of Mullite).
Obviously starting materials, environmental conditions
such as temperature, pressure and oxygen partial pressure,
and the applied synthesis and production routes signicantly
inuence the development of the mullite crystals. Mullite sin-
gle crystals grown from melts are acicular to columnar and
can be up to several centimeters in length, whereas solgel-
derived mullites usually have extremely small crystallite sizes
in the nano-scale range. The dimensions of mullites produced
by reaction sintering typically range between >1 lm and
Feature
October 2015 Mullite Structure and Properties
Fig. 1. The mullite part of the Al2O3SiO2 phase diagram
according to Klug et al.9 showing the solid solution of mullite under
equilibrium conditions. Incongruent melting occurs. Note that the
solid solution shifts with temperature toward higher Al2O3 contents.
Fig. 2. Large homogeneous, inclusion-free, and optically
transparent mullite single crystal grown by the Czochralski process
by the Institute for Crystal Growth in Berlin (Germany).
100 lm, with the crystal morphologies between acicular and
equi-axed.3
In spite of its rareness in natural rocks mullite is certainly
one of the most important ceramic phases. Mullite-based
ceramics cover a wide range of shapes and sizes from small
single crystals and whisker materials to huge, meter-scale
polycrystalline refractory blocks. The wide technical applica-
bility of mullite ceramics is derived from its outstanding
properties such as high thermal stability and excellent ther-
mal shock behavior, low density, low thermal expansion and
conductivity, together with a suitable strength and fracture
toughness. Furthermore, mullite ceramics display low gas
permeability and very good resistance against creep, high
compressive strength and good corrosion resistance in severe
atmospheres. A comparison of technically relevant properties
of mullite ceramics with those of other oxide ceramics is
given in Table I. The comparison, on the one hand, demon-
strates the high potential of mullite for ceramics, and, on the
other hand, it stresses the need of a deeper understanding of
the relationships between crystal structure and properties of
mullite.
Traditional mullite ceramics are widely used for pottery,
whiteware, and porcelain, and for refractories in the steel,
nonferrous metal, cement, glass producing and in the
2949
chemical industry. The frequent application of traditional
mullite ceramics is powered by the fact that many starting
materials of mullite ceramics are available in large quantities
at relatively low costs. For more detailed information includ-
ing references the reader is referred to the monography of
Schneider and Komarneni3 and to the papers cited therein.
Advanced or engineering mullite ceramics play a gradually
increasing role in recent years. They have often been pro-
duced from pure and homogenous solgel-derived mullite
and may be subdivided into dierent groups:
Monolithic mullite ceramics: The characteristics of mono-
lithic mullite ceramics are inuenced by amount, size, and
distribution of mullite, and by the occurrence of coexisting
phases and porosity. Typical applications are advanced
refractories, crucibles, thermocouple tubes, heat exchangers,
porous lters, catalyst supporting devices, substrates for sili-
con solar cells, hot gas lter candles, electronic packaging
materials, optical materials, dental ceramic components, and
antibacterial materials.3,1318
Mullite lms and coatings: Metals and most non-oxide
ceramics are susceptible to oxidation-induced degradation at
high temperatures. A suitable way to achieve stability in oxi-
dizing environments is the deposition of thin mullite layers
on these materials by means of physical or chemical gas
phase or by chemical deposition techniques. Mullite coatings
and membranes are also successfully applied on substrates
for hot gas and oily water cleaning1921 and if metal-doped
as antibacterial biolms.22,23 Mullite coatings are character-
ized by good corrosion resistance, excellent creep behavior
and suitable strength and toughness.24,25
Mullite bers: Mullite ber fabrics display excellent high-
temperature insulation characteristics up to about 1000C,
for example, for tube or rotary kiln seals, and for the electri-
cal insulation of electrodes in metal smelting furnaces. Mul-
lite ber fabrics have also been successfully used for diesel
emission lters.2629 Moreover, mullite whiskers, short and
continuous bers and ber bundles are suitable tools for the
reinforcement of ceramics or metals.3
Mullite-based composites: Due to their inherent oxidation
stability mullite ber and/or mullite matrix composites have
become important materials in recent years. Mullite-based
composites frequently replace formerly used non-oxide com-
posites such as C/C, C/SiC, and SiC/SiC, which, though hav-
ing superior thermomechanical properties, often are subject of
oxidation-produced degradation. High technical potential
have mullite-based composites, which in turn are protected
against water vapor attack and reducing atmosphere30,31 by
thin layers of environmental barrier coatings (EBCs, e.g.,
zirconia), thus being long-term stable under streaming water
vapor-rich gases at temperatures beyond 1100C. Applications
of mullite-based composites are burner tubes, heat exchangers,
hot gas lters, and catalytic converter supports.32 Other inter-
esting uses are thermal protection systems for combusters of
gas turbine engines. In addition to the works on mullite ber/
matrix materials, less successful investigations were performed
on platelet- or particle-reinforced mullite ceramics to improve
their lifetime (reinforcing particles and platelets, for example,
were Al2O3, ZrO2, SiC, see Ref. [3]).
A new group of mullite-based composites are metal parti-
cle/mullite matrix materials, for example, with Al and Mo as
reinforcing compounds. These composites often display very
good resistance against crack growth with controlled electri-
cal conductivity. Potential applications are metal lters, radi-
ant burners, sensors, and catalyst supports at temperatures
below 1000C.3
The relevance of mullite for crystal chemistry and espe-
cially for ceramics is documented by many research papers
and by a number of review articles and monographs (Fig. 3
and e.g., Refs. [3,3335]).
The present review gives an overview on the present
knowledge of the crystal structure and of the properties of
mullite, and it intends to contribute to a better understanding
2950 Journal of the American Ceramic SocietySchneider et al. Vol. 98, No. 10

Table I. Properties of Mullite Ceramics in Comparison to Those of Other Technical High-Temperature Oxide Ceramics
Cordierite Stabilized
Tiellite Al2TiO5 Mg2Al4Si5O18 Spinel MgAl2O4 Corundum Al2O3 zirconia ZrO2 Mullite 3Al2O3
2SiO2

Melting point, TM (C) 1860 1465 2135 2050 2600 1830

Density, q (g/cm3) 3.68 2.2 3.56 3.96 5.60 3.2
Linear thermal expansion 1 0 9 8 10 4.5
coecient, a, 20C1400C,
(106 K1)
Thermal conductivity, k
At 20C (kcal/mhK) 1.52 1015 13 26 1.5 6
At 1400C (kcal/mhK) 2.5 4 4 2 3
Strength (MPa) 30 120 180 500 200 200
Fracture toughness, KIc (MPam0.5) 1.5 4.5 2.4 2.5

Fig. 3. Cumulative numbers of publication on mullite and mullite-related topics which appeared between 1928 and 2012 (source: Web of
Science).

of the interrelationships between crystal structure and prop-
erties of mullite.
II. Crystal Chemistry of Mullite
(1) The Family of Mullite-Type Structures
Mullite belongs to the family of mullite-type crystal struc-
tures. These structures are all characterized by the principles
classied by Fischer and Schneider36 and Fischer et al.37 The
classication says that the backbone of mullite-type crystal
structures are single chains of edge-sharing octahedra in a
tetragonal arrangement in its highest topological symmetry.
The octahedral chains are linked by tetrahedra (e.g., AlO4
and SiO4 in sillimanite and mullite),36,3841 trigonal-planar
groups (e.g., BO3 in B-doped mullite),42 trigonal bipyramids
(e.g., AlO5 in andalusite),43,44 octahedra (e.g., BiO6 in
Bi2Al4O9),45,46 or higher coordinated polyhedra (e.g., CaO8
in austenite).47 Moreover, all members of the family of mul-
lite-type structures are derived from a hypothetical tetragonal
aristotype of P4/mbm symmetry by group-subgroup relation-
ships. Finally, the classication says that the arrangement of
octahedral chains and their cross-linking should approach as
closely as possible the orthogonal metric of the aristotype
with aspect ratios of the a- and b-axes close to 1. For exam-
ple, in mullite, the octahedral chains are cross-linked by a
more or less equal distribution of di- and tri-clusters of AlO4
and SiO4 tetrahedra superimposed with oxygen vacancies in
the a and b directions. Taking, for example, 2/1-mullite the
aspect ratio a/b is about 0.99, being very close to 1 [Figs. 4(c)
and (d)]. The principle that the aspect ratio a/b is near 1 may
help to draw a dividing line between mullite-type compounds
and other phases. An interesting example is the family of oli-
vine-type structures which are characterized by similar
arrangements of octahedral chains as the mullite family.
However, olivines have strongly deviating connection
schemes of the octahedral chains, with tetrahedra in a direc-
tion and an alternating sequence of tetrahedra and octahedra
parallel to b, producing an aspect ratio a/b of 0.47, which is
far away from 1. Olivine-type phases therefore cannot be
members of the mullite structure family. Compounds might
exist having characteristics intermediate between those of oli-
vine- and mullite-type structures. In such cases, it will be
more or less an arbitrary choice to assign these compounds
to either one of the structural families.
(2) The Crystal Structure of Mullite
Mullite in the true sense of the word is part of the
orthorhombic aluminosilicate system sillimanite-alumina
with the general composition Al2(Al2+2xSi2-2x)O10-x with
mullite-type structure.a The SiO2-rich end member of the sys-
tem is sillimanite with x = 0. Sillimanite (space group: Pbnm)
was often used to explain the crystal structure of mullite, as
it is closely related to mullite (space group: Pbam), but has a
crystal structure which is more simple. The backbone of the
structures of sillimanite and mullite are edge-sharing AlO6
octahedra (designated as M sites) forming chains running
parallel to the crystallographic c-axis. The octahedral chains
in sillimanite are linked by tetrahedral T2O5 dicluster groups
(T = Al3+, Si4+) forming double chains with an ordered
distribution of Al and Si atoms as shown in Figs. 4(a) and
a
Al2(Al2+2xSi22x)O10x corresponds to M2(T12+2xT222x)O10x with M = Al in
octahedral coordination and T1 = Al and T2 = Si in tetrahedral coordination; x theo-
retically ranging from 0 to 1.
October 2015 Mullite Structure and Properties
(a)
(b)
Fig. 4. Crystal structure of (c, d) sillimanite and (c, b) mullite. Projections down to (i.e., parallel to the c-axis, a, c) and perpendicular to the
octahedral chains (i.e., parallel to the a-axis, b, d) are shown. Note that schematic views are given showing only the upper layer of polyhedra.
(b).38 In mullite [Figs. 4(c) and (d)] part of the Si4+ is
replaced by Al3+. The compensation of the substitution-in-
duced charge deciency is achieved by removal of a number
of oxygen atoms bridging the tetrahedral T2O5 groups [desig-
nated as O3 or alternatively O(C)].b This produces oxygen
vacancies (designated as O3 or O vacancies), according to
the coupled substitution 2Si4+ + O2?2Al3+ + vacancy (),
with x of the general formula giving to the number of oxy-
gen vacancies per unit cell in the composition range
0 < x < 0.67 (for mullite-type phases with x > 0.67 see
below). The formation of O vacancies is accompanied by the
displacement of the T positions next to the bridging O atoms
to the new T* positions. The T*O4 tetrahedra form trimers
or triclusters [dark blue in Figs. 4(c) and (d)] of three tetra-
hedra having a common bridging O atom. The studies men-
tioned that most of the T* sites are occupied by Al.36,37,48
The combination of octahedral chains with tetrahedral di-
and triclusters and O vacancies produces disturbed structural
channels running parallel to the crystallographic c-axis.
The distribution of the O vacancies and of the tetrahedral
Al and Si atoms in a rst approach appears random.
However, a careful screening of the X-ray, electron-, and
neutron- diraction patterns provides more detailed informa-
tion: In the (hk1/2) layer of the single crystal diraction
diagram satellite reections with q ~0.31a* + 1/2c* are obser-
ved.c In addition to the rather sharp maxima diuse intensity
b
For an overview of the site assignments of Al, Si, and O see Table 1.1.17 in
Fischer and Schneider.36
c
Some of the diraction spots do not obey the q-vector due to the k/2-component
in the monochromatic but not energetically discriminated X-ray radiation.
2951
(c)
(d)
occurs, which follows the orthorhombic symmetry of the
crystal. We interpret superstructure reections and diuse
scattering as to be due to partial ordering of oxygen vacan-
cies and/or of the tetrahedral Al and Si atoms, which alto-
gether produces the incommensurably modulated structure of
mullite.37,4851 The distribution scheme of Al, Si atoms and/
or of O vacancies in mullite is very stable: According to
Paulmann52 it persists up to the melting point near to
1900C (Fig. 1). Birkenstock et al.51 discussed a structure
model with an ordered distribution of O vacancies of 2/1-
mullite, assuming a superstructure with a vefold enlarged
unit cell containing just two vacancies. However, such an
arrangement of O vacancies inevitably leads to an unfavor-
able lining up of vacancies in chains or layers in the struc-
ture, which has the consequence that the O vacancies in
mullite cannot be ordered. On the other hand the structure
cannot be completely disordered as well, but shows a modu-
lation as indicated by satellite reections in the diraction
pattern,49 which can be described by three q-vectors in recip-
rocal space.51 Birkenstock et al.51 concluded that the real
structure of mullite due to the arrangement of tetrahedral di-
and triclusters and of O vacancies is locally ordered, but on
the long range is strongly but not completely disordered.
First principle density functional theory (DFT) simulations
of Chen et al.53 provided evidence for a preferred occurrence
of oxygen vacancies parallel to the crystallographic b-axis.
Information on the structural short-range order of mullite
may also be derived from 29Si, 27Al, and 17O magic angle
spinning nuclear magnetic resonance spectroscopy (MAS
NMR) simply by comparing the mullite spectrum with that
of sillimanite. Sillimanite shows one sharp and strong 29Si
2952 Journal of the American Ceramic SocietySchneider et al.
MAS NMR signal near 87 ppm, which was assigned to the
tetrahedral T2 site of sillimanite (referring to the general for-
mula M2 (T12+2xT222x)O10x, see above). The major 29Si
NMR peak of mullite appears at the same chemical shift.
However, contrary to the relationships in sillimanite, the 29Si
NMR peak of mullite is broad and is characterized by low
intensity sub-signals near 92 ppm and 95 ppm and shoul-
ders, indicating additional Si sites.5456 Schm ucker et al.56
referring to diractional structure data interpreted the silli-
manite NMR spectrum in terms of one tetrahedral Si site
having three AlO4 tetrahedra as next nearest neighbors with
an ordered . . .AlSiAl. . . sequence in the tetrahedral col-
umns. Obviously this structural situation is also present in
mullite. However, the 29Si NMR subsignals near 92 ppm
and 95 ppm and the shoulders in the spectrum of mullite
indicate that other structural Al/Si arrangements in the tetra-
hedra do occur additionally: Schm ucker et al.56 assigned the
subsignal near 92 ppm to two AlO4 and one SiO4 tetrahe-
dra and the 95 ppm signal to one AlO4 and two SiO4 tetra-
hedra, respectively, as next nearest neighbors of a SiO4
tetrahedron. Schm ucker et al.56 furthermore suggested that
weak Al/Si ordering occurs in the tetrahedra of mullite. 27Al
MAS NMR has frequently been used to probe for the exis-
tence of four-, ve-, and sixfold coordinated Al in mullite,
mullite precursors and in aluminosilicate glasses.54,5759 Three
dierent Al sites were described in mullite, one octahedral
(near 0 ppm, M), one tetrahedral site like in sillimanite (near
60 ppm, T), and a distorted tetrahedral site assigned to Al in
the tetrahedral triclusters (near 43 ppm, T*). Kunath-Fandrei
et al.60 even identied three dierent types of AlO4 tetrahe-
dra by means of 27Al MAS NMR satellite transition spec-
troscopy. These were assigned to the AlO4 units in the
tetrahedral double chains (T) and to two dierent AlO4 in
the tetrahedral triclusters, one being directly adjacent to oxy-
gen vacancy, T*, and the two tetrahedra, T0 , linked to the
former in the tricluster. Rehak et al.61 provided an estima-
tion of the Al occupancies at the various Al sites in 3/2-mul-
lite, with about 40% of Al being octahedrally coordinated.
About 50% of Al enters the tetrahedral double chains (T),
whereas about 5% (T0 ) and 3% (T*) occur at tricluster sites.
Kelsey et al.62 on the basis of 17O NMR spectroscopy pro-
vided further data. Although the 17O NMR bands of mullite
were broad Kelsey et al.62 were able to distinguish between
the O1 [O(A,B)], O2 [O(D)], O3 [O(C)], and O4 [O(C*)] oxy-
gen sites in the structure.b Probably further 17O, 27Al, and
29
Si NMR studies with improved line resolutions will help to
better understand the real structure and especially the T*O4
tricluster formation of mullite.
(3) Compositional Series in the Mullite-Type System
Al2(Al2+2xSi2 2x)O10 x
Burnham63 quoted that the mullite structure
(0.2 < x < 0.67, space group: Pbam) theoretically ts to any
composition in the system Al2 (Al2+2xSi22x)O10x between
sillimanite (x = 0, space group: Pbnm) and the mullite-type
alumina phase (-alumina, x = 1, space group not known).
Actually the lattice parameters of mullite show a continuous
development between sillimanite (if c of sillimanite is halved
for comparison) and high-alumina mullites as shown in
Fig. 5. The a lattice parameter increases linearly with x
(Al2O3-content), whereas b nonlinearly decreases. At x = 0.67
the a and b lattice parameters cross and become equal in
length.d The lattice parameter c rst slightly decreases and
later on slightly increases again.36,61,64 DFT-based simula-
tions in principle conrm the experimentally measured data.53
Chen et al.53 believed that clockwise and counterclockwise
d
At x = 0.67 (80 mol% Al2O3) the a- and b-constants are equal in length.78,79
Due to a = b these mullites sometimes were designated as being tetragonal. However,
the phase is clearly orthorhombic and not tetragonal.
Vol. 98, No. 10
Fig. 5. Lattice parameters of the compositional series
Al2(Al2+2xSi22x)O10x plotted versus the Al2O3 content. Common
phases such as sillimanite (50 mol% Al2O3), 3/2-mullite (60 mol%
Al2O3), and 2/1-mullite (67 mol% Al2O3) are indicated by the red
frames, with red circles representing the lattice parameters a and b
(left ordinate), and c (right ordinate). The frame at 100 mol% Al2O3
indicates the alumina phase with mullite-type structure (-alumina).
Modied from Fischer and Schneider.36
rotations of neighboring octahedral chains contribute
essentially to a-axis expansion and b axis contraction.
The symmetry change in going from sillimanite (Pbnm) to
mullite (Pbam) with simultaneous halving of the c lattice
parameter indicates that sillimanite just represents the end
member of a compositional series but not of a structural
solid solution at the SiO2-rich side of the sillimanite-alu-
mina system. The dierent structural ordering schemes in sil-
limanite and mullite and the fact that sillimanite crystallizes
at moderate temperature and pressure, whereas mullite forms
at ambient pressure and high temperature may be one expla-
nation of it. Starting from these suggestions we believe that
the continuous series between sillimanite and 3/2-mullite
described by Hariya et al.65 by varying the synthesis pressure
(0.5 GPa2.0 GPa) and temperature (800C1300C) condi-
tions represent a compositional rather than a continuous
structural sequence. The question which individual phases or
solid solutions with compositions between sillimanite (x = 0)
and 3/2-mullite (x = 0.25) do exist has been a point of dis-
cussion. Beger et al.66 investigated natural sillimanite heat-
treated (1500C) under high pressure (up to 2.4 GPa) and
observed a change in the symmetry of sillimanite but without
change in the composition. Beger et al.66 concluded that the
tetrahedral Al and Si atoms become disordered but without
decomposition of the sillimanite toward mullite plus SiO2.
Navrotsky et al.67 performing heat of solution measurements
supported this suggestion. Holland and Carpenter68 investi-
gated the relationships at the SiO2-rich side of the system
near to sillimanite by carrying out annealing experiments on
sillimanite at high temperatures and pressures (1300C
1700C and 1.82 GPa). With increasing temperature and
pressure they observed a slight but continuous Al2O3 enrich-
ment of the newly formed aluminosilicates. The phases dis-
play a sillimanite-type ordering of Al and Si at the
tetrahedral sites with simultaneous exsolution of noncrys-
talline SiO2. Guse et al.69 and Rahman et al.70 performed
short- and long-term heat treatments on sillimanite at tem-
peratures just below the transformation to mullite plus SiO2
(1600C) employing XRD and TEM techniques. They men-
tioned that the initial states of transformation are tilts and
rotations of the octahedra and tetrahedra and disordering of
Al and Si over the tetrahedral sites.
Cameron71 interpreted the coexistence of sillimanite and
mullite in a natural rock as evidence for the presence of a
miscibility gap between the two phases. Sillimanite-mullite
intergrowth was also described in metamorphic rocks.72 In a
further paper Cameron73 described a naturally occurring
mineral phase intermediate in composition between silliman-
ite and mullite and suspected that it was stabilized by traces
October 2015
of Fe. In a subsequent work Cameron74 stated that If Ti is
absent, Fe3+ can stabilize the Si-Al ordering scheme charac-
teristic of 1:1 sillimanite to well into the previously known
mullite composition range. Just recently Fischer et al.6
described a mullite-type mineral from the Eifel area (Ger-
many) with a chemical composition intermediate between sil-
limanite and mullite with about 2% of Al3+ being replaced
by Fe3+. The mineral has features from both sillimanite and
mullite: It shows complete Si/Al ordering at tetrahedral sites
like in sillimanite, but with neighboring double chains of
SiO4 and AlO4 tetrahedra being oset by a unit cell rela-
tive to each other in c direction. This causes a change in the
space group setting from Pbnm (sillimanite) to Pnam (new
phase). Dierence Fourier calculations and renements with
anisotropic displacement parameters revealed the formation
of O vacancies and triclusters as known in the crystal struc-
ture of mullite. The phase is considered to represent a new
mineral intermediate between sillimanite and mullite, and
therefore was tentatively designated as sillimullite (not yet
approved by the IMA commission on new minerals). The
symmetry of sillimullite (Pnam) is a subgroup with respect
to the mullite space group (Pbam).36 In light of these results
we believe that the phases described by Beger et al.,66
Navrotsky et al.,67 and Guse et al.69 (see above) rather corre-
spond to sillimullite or to a beginning transformation to
mullite than to Al/Si-disordered sillimanite.
Numerous studies have shown that most synthetic mullites
produced from various starting materials (e.g., kaolinite,
andalusite, and kyanite, alumina plus silica mixtures, refrac-
tory-grade bauxite)75 at temperatures below about 1600C
have compositions near 60 mol% (72 wt%,) Al2O3
(x = 0.25). These mullites have been designated as 3/2-mul-
lites (3Al2O3
2SiO2) or sinter-mullites, as they normally form
by solid-state reactions. Mullites formed from 3/2-mullite
above about 1600C or those crystallized from alumino silica
melts (e.g., from Bayer alumina plus silica as starting materi-
als) at temperatures above 1900C are termed 2/1-mullite
(2Al2O31SiO2) or fused-mullites and have compositions close
to 66.7 mol% (77 wt%) Al2O3 (x = 0.4).35,36 Chemically very
pure, ne-grained, and reactive mullites of dierent composi-
tions were synthesized from inorganic and organic sources
(e.g., tetraethyloxysilane, TEOS; tetramethyoxysilane,
TMOS; aluminum nitrate nanohydrate, ANN, aluminum-sec-
butylate; aluminum-isopropylate) by means of the solgel
process, with subsequent temperature-controlled sintering.
They were designated as chemical mullites.75 Al2O3-rich mul-
lites with compositions beyond that of 2/1-mullite (Al2O3
>66.7 mol% and x > 0.4, see Figs. 1 and 5), although not
being thermodynamically stable (see Fig. 1), form by solgel-
based reactions at relatively low temperatures (<1000C),36
whereas the synthesis of mullites very rich in Al2O3 (>
80 mol% and x > 0.67) requires specic solgel synthesis
routes.76,77
Very Al2O3-rich mullites with x > 0.67 are structurally
interesting, as at x = 0.67 the maximum possible number of
oxygen vacancies in the mullite structure has formedd and all
tetrahedral diclusters are replaced by tetrahedral triclusters.
Consequently, at higher x-values (higher Al2O3 contents)
other charge compensation mechanisms must become
eective to compensate for the Al3+ to Si4+ substitution.
Schneider et al.76 and Fischer et al.80 investigating a very
Al2O3-rich mullite with 89 mol% Al2O3 (x = 0.83) postulated
that in compositions with x > 0.67 the tetrahedral triclusters
of mullite sensu stricto (0.2 < x < 0.67) are gradually
replaced by tetrahedral tetraclusters, where 4 tetrahedra are
connected by a bridging oxygen atom instead of 3 in the case
of the triclusters.e A chemical vapor-deposited Al-rich mullite
e
For an overview of the site assignments dependent on the x-value of the mullite-
type phases of the system Al2(Al2+2xSi22x)O10x, see Table 1.1.20 in Fischer and Sch-
neider.36
Mullite Structure and Properties 2953
layer (x  0.82) was studied by Wang et al.81 by high-resolu-
tion transmission electron microscopy. They described an
ordered and twinned (601) and (601) multidomain structure,
separated by (001) twin planes with well-ordered oxygen
vacancies in individual domains and antiphase boundaries,
separated by the shift vector of [001].
The Al2O3 end-member of the Al2 (Al2+2xSi22x)O10x
compositional series with mullite-type structure has been des-
ignated as -alumina. -alumina was described in the literature
as either orthorhombic82,83 or tetragonal,84 whereas one
author85 suggested that -alumina has sillimanite structure.
Korenko et al.86 obtained -alumina as a byproduct in a
mixture of cryolite with alumina after rapid solidication.
Ebadzadeh and Shari87 published data on the synthesis of
-alumina from a mixture of aluminum nitrate and carboxyl
cellulose heat-treated in a high-energy microwave furnace,
but provided no data on the crystal structure and the exact
composition of the phase. According to the structural model
of Fischer et al.,80 -alumina is composed of mullite-type
chains of edge-connected AlO6 octahedra, which are linked
solely by AlO4 tetrahedral tetraclusters. Aryal et al.88,89 sim-
ulated the crystal structure of -alumina by the DFT method
in a 2 9 2 9 4 supercell, starting from the parameters of the
Al2O3-rich mullite described by Fischer et al.80 with
x = 0.83. Aryal et al.88,89 proposed a highly disordered struc-
ture of -alumina with AlO5 and AlO6 polyhedra in the back-
bone chains parallel to c, with di-, tri- and tetraclusters
cross-linking the chains. The occurrence of AlO5 and AlO6
polyhedra in the backbone chains strictly spoken would
mean that -alumina does not belong to the family of mul-
lite-type structures. Due to the occurrence of the energetically
highly unfavorable tetrahedral tetraclusters the phases with
x > 0.67 gradually should become unstable with the Al2O3-
content. This agrees with the observation of Ebadzadeh and
Shari87 that -alumina rapidly transforms to a-alumina on
annealing at 1000C. It has to be noted, however, that the
models discussed above just represent hypothetical structures.
More detailed studies with a structural renement of -alu-
mina are required for a better understanding.
Summarizing the knowledge on the compositional series of
mullite-type Al2(Al2+2xSi22x)O10x phases dierent struc-
ture types can be distinguished:
1. Sillimanite (x = 0) with diclusters of ordered AlO4
and SiO4 tetrahedra cross-linking the AlO6 octahedral
chains and no O vacancies.
2. Sillimullite (0 < x <  0.2) with diclusters of
ordered AlO4 and SiO4 tetrahedra cross-linking the
AlO6 octahedral chains and some O vacancies. The
solid solution range of these phases remains unclear.
3. Mullites in the true sense of the word
(0.2 < x < 0.67) with di- and triclusters of disor-
dered AlO4 and SiO4 tetrahedra cross-linking the AlO6
octahedral chains and the number of O vacancies
increasing with x.
4. Very Al2O3-rich mullites (0.67 < x < 1) probably
with tri- and tetraclusters of disordered AlO4 and SiO4
tetrahedra cross-linking the AlO6 octahedral chains
and the number of O vacancies being constant. The
solid solution range of these phases is unclear.
5. -alumina (x = 1) probably with tetraclusters of AlO4
cross-linking the AlO6 octahedral chains. Details of
the possible crystal structure of -alumina are unclear.
(4) Foreign Cation Incorporation in Mullite
Mullite is able to incorporate a large number of foreign
cations into its crystal structure.34,90,91 Controlling factors of
the incorporation of foreign cations are their oxidation states
and ion radii on the one hand, and temperature, pressure,
and chemical environment during incorporation, on the other
hand. No direct anion incorporation in mullite was described
2954 Journal of the American Ceramic SocietySchneider et al. Vol. 98, No. 10

so far. X-SiAlON, where part of the O2 ions are replaced

by N2 contain octahedral chains similar to those of the
mullite family. However, the dierent connection schemes
perpendicular to the octahedral chains indicates that it does
not belong to the family of mullite-type structures [see Sec-
tion II(1)].92
(A) Transition-Metal Incorporation: The incorpora-
tion of transition-metal cations into mullite was often
described in the literature.90,91 Natural mullites contain
Fe3+, Ti4+, and less frequently Cr3+ though the cation
oxide content in most cases is below 1 wt%.1,71,93 Frequent
transition-metal cations described in synthetic mullite are
Ti4+, V3+, Cr3+, and Fe3+. The cations mainly occupy the
octahedral site in mullite replacing Al3+, although minor
amounts can also enter the oxygen tetrahedra, substituting
Al3+(Refs. [90,91] and the literature cited therein). The struc-
tural incorporation of Cr3+ was discussed in a controversial
manner. Electron paramagnetic resonance, extended X-ray
absorption ne structure, and uorescence studies revealed
that most of Cr3+ occurs in the chain octahedra, whereas a
smaller quantity enters strongly distorted sixfold coordinated Fig. 6. Amount of transition-metal incorporation in mullite plotted
interstitial positions.9496 This interpretation is in conict versus the cation radii of the substituting element. Given are the
with the X-ray diraction-based structural renement of a maximum equivalent cation oxide contents. The Ga3+- incorporation
Cr2O3-rich mullite (6.5 mol% Cr2O3) carried out by Fischer is included for comparison.34
and Schneider.97 The latter investigations yielded Cr3+ in the
octahedral chain site only. Fischer and Schneider97 presented
a model which tries to explain both spectroscopic and
diraction data: It starts from the presence of -Cr-Cr-Cr-
clusters in the octahedra chains. Depending on the assump-
tion that Cr has Al or, alternatively, Cr as next nearest octa-
hedral neighbor, the polyhedra are dierently distorted,
which may produce the slightly dierent spectroscopic behav-
ior.
The highest foreign cation incorporation in synthetic mul-
lite was achieved for V3+, Cr3+, and Fe3+ (6.5 mol% of
the oxides), which is in the same order of magnitude as the
maximum incorporation of the nontransition-metal cation
Ga3+ (Figs. 6 and 7). 91 The high degree of the V3+, Cr3+,
and Fe3+ incorporation can be explained by the fact that the
radii and oxidation states of these cations t best with those
of Al3+.f Ti4+ and V4+ with tting ion radii but deviating
oxidation states achieve lower amounts of incorporation
(23 mol% of the oxides).
Other transition-metal cations such as Mn2+, Fe2+, Co2+,
Ni2+, Cu2+, Y3+, Zr4+, and Mo3+ also enter the mullite
structure though in very low quantities.91,98100
(B) Rare-Earth Element Incorporation: In spite of
their low incorporation rates (in most cases below 1 mol%
of the oxide) rare-earth element (REE)-doped mullites are
interesting, as they can inuence the optical properties signi-
cantly (see Section III). Lee and Kim101 produced Eu2+-
doped mullite ceramics by reaction sintering of the oxides
with the composition 3Al2O32SiO20.005Eu2O3 between
1500C and 1600C under reducing H2 atmosphere, and con-
rmed earlier studies.102104 The large REE ions most proba-
bly enter the oxygen vacancies in mullite.
Zhang et al.105 described mullite nano particulates doped
with 8% Tb3+ and 0.1% Ce3+. Sanad et al.100 investigated
Gd3+- and La3+-doped mullite nanoparticles produced by
coprecipitation techniques and found that the doped samples
exhibit slightly distorted crystal structures with respect to the
undoped material. In a more detailed investigation Sanad
et al.106 found that up to 1% of Gd3+ was incorporated into
mullite. Gd3+-incorporation causes a contraction of the Fig. 7. Microstructure of transition-metal-doped mullite ceramics,
structure parallel to the a- (0.17%) and c-axes (0.27%), but consisting of mullite (M) and glass phase (G). (a) V3+-doped,
containing 8.7 wt% V2O3. (b) Cr3+-doped, containing 11.5 wt%
an expansion parallel b (0.56%, all data refer to the dier- Cr2O3. (c) Fe3+-doped, containing 10.3 wt% Fe2O3. Note the
ence between undoped and 1% Gd3+-doped mullite). The dierent mullite grain evolutions, which are certainly controlled by
the viscosity of the coexisting melt during crystal growth.34
f
A special case is Mn3+. Mn3+ shows a relatively low degree of incorporation in authors suggested a replacement of octahedral Al3+ by
mullite although cation radius and oxidation state are similar to those of Al3+. This
certainly is caused by the diculty to produce Mn3+-doped mullite at high temperature
Gd3+, in spite of the rather large cation size of Gd3+
and ambient oxygen partial pressure.  instead of 0.535 A
(0.938 A  for Al3+)107. Sanad et al.106
October 2015 Mullite Structure and Properties
mentioned that mullite nanoparticles incorporate more Gd3+
than do the larger crystals. Obviously, the nanoparticles with
their large grain surfaces are able to compensate the incorpo-
ration-induced strain more easily.
(C) Miscellaneous Element Incorporation: B3+ enters
the mullite structure in high amounts91,108,109 L uhrs
et al.110,111 on the basis of X-ray diraction, prompt gamma
activation energy, and 11B MAS NMR spectroscopy postu-
lated that B3+ substitutes up to 15% of the tetrahedral
Si4+ at 1200C and ambient pressure. In mullites synthesized
at moderate temperature and elevated pressure (0.71.0 GPa,
875C) even up to 40% of the tetrahedral Si4+ can be
replaced by B3+.112 According to 11B MAS NMR results
most of the B3+ is in a near-trigonal planar environment
(BO3) in mullite, although some B3+ occurs in fourfold tetra-
hedral coordination (BO4) as well.112 B3+-doped mullites are
stable up to about 1000C, whereas higher temperatures
cause B-release.
Up to 0.4 wt% Na2O was described in mullites from elec-
trical arc fused-mullite refractory bricks.113 Schneider,114
Worden et al.115 and Rodriguez-Navarra et al.116 found up
to 1.5 wt% MgO in mullites from dierent natural and tech-
nical sources. It was suggested that the large Na+ and Mg2+
ions enter the structural holes or oxygen vacancies of mullite.
Interesting are alkali aluminates (Al6Alk0.67O9.33) and gal-
lates (Ga6Alk0.67O9.33, Alk = Na+, K+, Rb+)117119 with
mullite structure. These phases structurally directly corre-
spond to aluminosilicate mullite with x = 0.67 (80 mol%
Al2O3). With respect to the aluminosilicate mullites all Si4+
is replaced by Al3+ in the mullite-type alkali aluminates and
gallates and the necessary charge compensation is eected by
the entry of alkali ions into the O vacancies. Interestingly,
Na+ in contrast to K+ enters the vacancies at two slightly
dierently distorted sites,118,120 probably due to its relatively
small ion size. The mullite-type aluminates and gallates can
be considered as stued mullite structures. The relatively
weak bonding probably should allow a rather high mobility
of the alkali ions in the mullite-type structure.
Ge-mullites with all Si being replaced by Ge are isostruc-
tural with Si-mullites. Crystallo-chemical data on Al,Ge-mul-
lites with 3/2-composition (3Al2O3
2GeO2) were published by
Gelsdorf et al.,121 Perez Y Jorba,122,123 Schneider and Wer-
ner,124,125 and Schneider.126 A Ge-mullite isostructural with
2/1-mullite (2Al2O3
GeO2) was described by Durovic and
Fejdi.127 Complete Ga3+ and partial Fe3+ for Al3+ replace-
ment was described in Ge-mullites.124,125 Saalfeld and Ger-
lach128 synthesized Al,Ge-mullites with x ranging between
0.13 and 0.39 using the ux synthesis technique, and men-
tioned that the solid solution may extend the given limits. A
Pb- and Nd-doped Ge-mullite with a composition
Al2[Al3.03Ge0.97]Pb0.15Nd0.06O9.71, (x = 0.29) was prepared by
Saalfeld and Klaska129 using the PbO/PbF2 ux technique.
They found that Pb2+ and Nd3+ ions enter the large oxygen
vacancies of the Ge-mullite structure, producing a partially
lled mullite structure. The symmetry of the Pb-Nd-doped
Ge-mullite is lower than that of Si-mullite (space group
P212121 instead of Pbam).
Sn which belongs to the same group of the periodical sys-
tem of elements as Si and Ge enters the mullite structure in
low amounts only (Ref. [130] and own unpublished results).
Obviously the size of the Sn4+ ion is too big to replace for
the terahedrally coordinated Si4+ or Ge4+ and thus Sn4+
may be incorporated octahedrally or at interstitial sites
 Ge4+: 0.40 A,
(cation radii: Si4+: 0.26 A,  Sn4+: 0.69 A. The
ion radii of Si and Ge refer to fourfold coordination,
whereas that of Sn refers to sixfold coordination as no data
on fourfold coordination are available).107
III. Properties of Mullite
Relations between crystal structure and properties are crucial
to understand and predict the behavior of mullite under
2955
various environmental conditions. The following sections
essentially deal with properties being relevant for the techni-
cal application of mullite. Mainly single crystal data will be
reported with the focus on:
1. Mechanical properties including elasticity, compress-
ibility, strength, toughness, creep, and microhardness.
2. Thermal properties including thermal expansion, heat
capacity, atomic diusion, and thermal conductivity.
3. Miscellaneous properties including electrical conductiv-
ity and optical behavior.
Some information on polycrystalline mullite ceramics will
be given additionally. However, it should be taken in mind
that in the case of polycrystalline and ceramic materials the
properties are additionally aected by their microstructure
(size, shape, and orientation of the grains and grain bound-
aries, see section IV).
The physical properties of orthorhombic mullite are
referred to the Cartesian reference system with axes ei which
are related to the crystallographic basis vectors ai according
to the standard convention by e1 || a1 = a, e2 || a2 = b, and e3
|| a3 = c.
(1) Mechanical Behavior
(A) Elastic Properties and Compressibility: A number
of papers dealt with the elastic properties of single crystal
mullite. Kriven et al.131 and Palko et al.132 determined the
nine independent elastic stiness coecients cij by applying
Brillouin spectroscopy to directionally solidied 2.5/1-mullite
bers. Hildmann et al.133 published data for 2/1-mullite
obtained from a small sample of about 1 mm3 in volume
using resonant ultrasound spectroscopy. In a comprehensive
study employing the same technique to 6 large high-quality
single crystals Schreuer et al.135 reported the cij of 2/1-mullite
and their temperature derivatives between ambient tempera-
ture and 1400C. The variation of cij values at room
temperature given by the dierent authors (Table II) is about
5% at maximum and can be attributed to the dierent
chemical composition and the quality of the samples used.
Pabst et al.134 gave a review on the elastic properties of
mullite.
Schreuer et al.135 mentioned that the mean elastic stiness
coecient C = (c11 + c22 + c33 + c44 + c55 + c66 + c12 +
c13 + c23)/9 of mullite is lower than that of sillimanite (cf.
Table II).136,137 This probably is due to the occurrence of
structural oxygen vacancies in mullite but not in sillimanite.
The vacancies reduce the number of bonding interactions per
unit volume which weakens the structure in comparison to
that of the vacancy-free sillimanite. The decrease in the elas-
ticity of mullite with the number of oxygen vacancies
(x-value) is supported by simulation calculations.89
The longitudinal elastic stinesses of mullite display a dis-
tinct anisotropy being characterized by c33 c11 > c22
(Fig. 8), which means that the stiest direction in the struc-
ture coincides with the direction of the octahedral bond
chains along the c-axis. A single linear chain of edge-con-
nected octahedra is quite soft as it allows for tilting of the
octahedra. This mechanism, however, is suppressed in silli-
manite and mullite where the free tips of adjacent octahedra
are linked by tetrahedra leading to a rigid backbone built up
of interconnected chains of octahedra and double chains of
tetrahedra running along to the c-axis (Fig. 9). Within the
(001) plane the longitudinal stinesses generally are lower.
The relation c11 > c22 was explained with the elastic behavior
of the octahedron in mullite. The longest and thus most elas-
tic octahedral AlO bonds lie to about 60 to the a-axis and
about 30 to the b-axis and thus has a stronger inuence
along b than along a.
A deeper insight into the network of bonding interactions
is provided by the deviations from Cauchy relations, gij, a
second rank tensorial invariant of the elasticity tensor.138,139
2956 Journal of the American Ceramic SocietySchneider et al. Vol. 98, No. 10

Table II. Elastic Stiness Coecients cij, Mean Elastic Stiness C = (c11 + c22 + c33 + c44 + c55 + c66 + c12 + c13 + c23)/9,
Mean Deviation from Cauchy Relations g, and Density q of Sillimanite and Mullite Single Crystals at Room Temperature
References [136] [133] [135] Unpublished results [131] [132]
Composition Sillimanite 2/1 2/1 2/1 2.5/1 2.5/1
x 0 0.38 0.38 0.38 0.5 0.5
Method BS RUS RUS RUS BS BS
c11 (GPa) 287.3 291.3 279.5 278.1 280 281.9
c22 231.9 232.9 234.9 233.1 245 244.2
c33 388.4 352.1 360.6 360.2 362 363.6
c44 122.4 110.3 109.49 109.14 111 111.7
c55 80.7 77.39 74.94 74.57 78.1 78.2
c66 89.3 79.90 79.89 79.45 79.0 79.2
c12 94.7 112.9 103.1 102.2 105 105.1
c13 83.4 96.2 96.1 95.0 99.2 100.3
c23 158.6 121.9 135.6 134.7 135 142.3
C (GPa) 170.7 163.9 163.8 162.9 166.0 167.4
g = Spur (gij)/3 (GPa) 14.8 21.1 23.5 22.9 23.7 26.2
q (g/cm3) 3.241 3.096 3.126 3.128 3.10 3.11
The compositional parameter x refers to the general formula Al2(Al2+xSi2x)O10x.
Experimental methods: BS, Brillouin spectroscopy; RUS, resonant ultrasound spectroscopy.

T.F. Krenzel, J. Schreuer, D. Laubner, H. Schneider, Unpublished results.

The mean value g = (g11 + g22 + g33)/3 is closely related to
the predominant type of bonding in the crystal. In ionic crys-
tals with nondirectional interactions the transverse interac-
tion coecients usually dominate over the corresponding
shear resistances resulting in positive deviations from Cauchy
relations. Strong covalent bonds with preferred bonding
directions lead to opposite eects. As a consequence of the
high covalency of the SiO bond, silicates like pyroxenes,
olivines, and the SiO2-modications possess very small or
even negative values of g. In contrast, mullite exhibits rela-
tively large positive deviations from Cauchy relations, which
can also be interpreted as a result of the specic linkage of
octahedral and tetrahedral chains. According to Fig. 9, any
longitudinal deformation along the octahedral chain leads to
changes of certain OSiO bond angles in the connected tetra-
hedral chains, which is energetically unfavorable due to the rel-
atively strong covalent character of the SiO interaction.
Therefore, the resistances against transverse interactions are
high compared to the corresponding shear stinesses. This
mechanism of transverse interaction, characteristic for the
structural backbone of the mullite structure-type, also aects
the anisotropy of thermal expansion as outlined below.
Up to about 1000C the evolutions of the elastic stinesses
with temperature are almost linear (Fig. 10). However, while
above 1000C this behavior persists for the longitudinal sti-
nesses and the transverse interaction coecients, the shear
resistances c44, c55, and c66 display accelerated softening
along with increased ultrasound dissipation.135 The observed
anomalies were explained by a glass-like transition of mullite
in this temperature range [see Section III(5) for details].
Regarding the elastic behavior of mullite ceramics there
are remarkably few complete experimental datasets available
so far (Table III). Ledbetter et al.140 provided the elastic
moduli of a hot-pressed 3/2-mullite ceramic. The most com-
prehensive study so far, which includes the elastic properties
of four dierent mullite ceramics between ambient tempera-
ture and 1400C, has recently been carried out by T.F. Kren-
zel, J. Schreuer, D. Laubner, H. Schneider, Unpublished
results. It is found, that the elastic coecients of isostatically
hot-pressed ceramics are in excellent agreement with the
aggregate elastic stinesses derived from the single crystal cij
using the VoigtReussHill averaging scheme. The situation
gets worse for sintered but not hot-pressed ceramics. The
softer elastic behavior of such ceramics is caused by higher
porosity and/or less tight contacts between the constituting
grains. The properties of mullite ceramics will be addressed
in more detail in a forthcoming paper.
Kalita et al.141 used synchrotron X-ray diraction with a
diamond anvil cell to determine the compressibility of silli-
manite, and of 3/2- and 2/1-mullite at room temperature.
The pressure impact leads to an amorphization above about
20 GPa for 2/1-mullite and above about 22 GPa for 3/2-mul-
lite. Sillimanite displays a higher stability against compres-
sion and only partial amorphization is observed above
40 GPa. The compressibility is lowest parallel to the crys-
tallographic c-axis in all cases, which again was explained
with the strong binding forces in the edge-connected octahe-
dral chains and in the tetrahedral double chains. Similarly
the lower stability of mullite in comparison to sillimanite was
interpreted as to be due to the occurrence of oxygen vacan-
cies in mullite. According to Rietveld renements carried out
on the high pressure X-ray diraction data of 7/4-mullite
powder the compression up to 20 GPa is dominated by a
reduction of octahedral AlO distances, whereas the more
rigid tetrahedral ones show less eects. Above 20 GPa the
distortion especially of the tetrahedra becomes very strong.
Kalita et al.142 believed that the (Al,Si)O4 tetrahedra may
gradually transform toward vefold coordinated (Al,Si)O5
polyhedra at these high pressures.143
(B) Strength, Toughness, and Creep: Systematic stud-
ies of fracture, tensile, and torsional strength of mullite single
crystals are not available so far, and the properties reported
here refer to polycrystalline mullite ceramics. Okada and
Schneider144 and Duval et al.145 published data on strength
and fracture toughness of mullite ceramics of 3/2-composi-
tion, the latter essentially basing on results of Torrecillas
et al.146,147 and Huang et al.148 The fracture strength, r, of
polycrystalline mullite ceramics at room temperature ranges
between about 200 MPa and 400 MPa, depending on the
chemical composition and microstructure of the material.
Especially the porosity has a distinct negative inuence on
the fracture strength. Hot-pressed mullite ceramics with little
impurities, a low amount of glass phase, and an equiaxed
mullite microstructure show a signicant strength decrease
above 1200C to 1300C, probably due to grain boundary
glidings.149152 Obviously these ceramics contain little
additional viscous phase at high temperature, which essen-
tially occurs in triple point junctions but not at the grain
boundaries. The high-temperature strength of these materials
thus is superior to those of other oxide ceramics such as a-
alumina and zirconia.144 The fracture toughness KIC of
mullite ceramics, which is a measure for the ability to with-
stand plastic deformation, is relatively low (2.5 to
3.5 MPa
m1/2) and does not change signicantly up to
October 2015 Mullite Structure and Properties 2957

Fig. 8. Representation surfaces of longitudinal eect of elastic stiness (in GPa), linear thermal expansion (in 106 K1), thermal conductivity
[in W
(m
K)1], and electrical conductivity (in 105 1 cm1, high-temperature data only) of 2/1-mullite single crystal.

1400C. It demonstrates the brittle character of mullite.
Selected data are given in Table IV.
In their pioneer work, Dokko et al.153 stated that mullite
single crystal submitted to compressive stresses up to
480 MPa at 1400C display no detectable plastic deformation.
A recent study of M. L. Mecartney (personal communication)
conrmed this observation but identied plastic deformation
in polycrystalline mullite ceramics. Some, though indirect,
information on the plastic deformation and correlated creep
of mullite can be derived from the behavior of the structurally
closely related sillimanite. Menard and Doukhan154 found
low-energy dislocations and gliding occurring parallel to the
crystallographic c-axis in sillimanite. This means that the
strong bonding within the edge-connected octahedral chains
and within the rigid tetrahedral double chains running paral-
lel [001] hinders that deformation systems cross these struc-
tural elements. The complexity of stress distribution,
however, does not allow a simple interpretation of the little
creep of mullite. According to Okamoto et al.,155 creep in
very ne-grained mullite ceramics proceeds via diusion,
whereas larger grain-sized mullite are subject of slow crack
growth, initiated by higher stresses.145 In single crystals with
their very large grain sizes the stress necessary for creep
obviously is beyond the applied ones. The dierent deforma-
tion behavior which yields structure-controlled deformation
in sillimanite but not in mullite under comparable conditions
indicates that deformation velocity in mullite is much slower
than in sillimanite.
(C) Microhardness: The development of microhard-
ness versus temperature of mullite single crystals was
described by Kollenberg and Schneider156 and Pitchford
et al.157 up to 1000C, and by Kriven et al.158 up to 1400C.
Kriven et al.158 mentioned three sequential temperature-
dependent stages of microhardness:
1. Stage I between room temperature and 300C with a
relatively strong decrease in the microhardness from
16 to 13 GPa (0.01 GPa/C).
2. Stage II between 300C and 1000C with only little
reduction of the microhardness from 13 to 10 GPa
(0.004 GPa/C).
2958 Journal of the American Ceramic SocietySchneider et al. Vol. 98, No. 10

(a) (b)

Fig. 9. Crystal structure of mullite. (a) View parallel [001], the shaded area is shown in (b) from a dierent angle. (b) View parallel to the [110]
direction, showing the backbone of the mullite structure which consists of linear chains of edge-connected AlO6 octahedra reinforced by TO4
tetrahedra. Red and blue arrows indicate movement of atoms upon tensional and compressional stress, respectively.

(a) Temperature [C] (b) Temperature [C]

0 400 800 1200 0 400 800 1200
10
Longitudinal stiffness [GPa]

400 c44 33
Shear stiffness [GPa]

8
100 Strain ij [10 ] 22
360
-3

c33 6 11
320 80 4
c66
280
c11 c55 2
60
240 0
c22
200 40 -2
200 600 1000 1400 1800
200 600 1000 1400 1800
Temperature [K]
Temperature [K]

(c) Temperature [C] (d) Temperature [C]

0 400 800 1200 14001200 1000 800 600
9 -4
8 11
log(ii [ cm ] )

-5
22
-1
ii [W m K ]

7
-1

33
6 -6
-1

-1

5 -7
22 11
4
-8
3 33
2 -9
200 600 1000 1400 1800 6 7 8 9 10 11 12
-1
Temperature [K] 10000/T [K ]
Fig. 10. Temperature dependence of (a) longitudinal (red symbols) and shear (blue symbols) stinesses,135 (b) strains,135 (c) coecients of
thermal conductivity,182 and (d) electrical conductivity of 2/1-mullite (high-temperature data).185

3. Stage III between 1000C and up to 1400C with a axis, can more easily be activated as gliding parallel {h0l} in
relatively strong microhardness decrease to a mean the case of (010) indentation.
value of 6 GPa at 1400C (0.01 GPa/C). Transmission electron microscopic studies on indented
mullite single crystal (001) faces showed that microindenta-
The structural interpretation of the microhardness is di-
tion produces a complex array of deformation eects.
cult, due to the complexity of the indentation process. The
Directly under the indenter, in the region of maximum stres-
relatively strong decrease in microhardness between room
ses mullite can become completely amorphous. Further out
temperature and about 300C (Stage I) is not understood
to the undeformed parts of the crystal areas of high plastic
yet, whereas the lower decrease between 300C and
deformation with dislocation networks, radial microcracks
1000C (Stage II) was explained by the temperature-in-
and bend contours occur.159 Degradation of the mullite crys-
duced decrease in the elastic moduli. The discontinuous
tal structure versus a complete loss of the long-range order
change in microhardness above 1000C (Stage III),158 may
by microindentation may be compared with similar eects
be caused by thermally activated lattice gliding and amor-
produced by static141 and dynamic pressure loading160 and
phization, and/or by a phase transformation which is sug-
by intense ball milling.161
gested to take place at high temperatures [see Section III(5)].
Up to about 1000C no signicant anisotropy of the micro-
hardness of mullite is observed. However, above this temper-
ature limit the microhardness on (001) decreases more (2) Thermal Behavior
rapidly than that on (010), (e.g., H(010) 8 GPa and H(001) (A) Thermal Expansion: A major property which
4 GPa at 1400C). Lattice gliding parallel {h0l} in the case makes mullite an outstanding technical ceramic material is
of (010) indentation, and parallel {hk0} for (001) indentation the low thermal expansion, and the associated excellent
may be the reason of it. Obviously gliding parallel to {hk0}, thermal shock resistance. Several datasets on the thermal
which do not cross the structural backbone parallel to the c- expansion of mullite-type aluminosilicates up to 900C
October 2015 Mullite Structure and Properties 2959

Table III. Elastic Properties of Dense Mullite Ceramics (MC) and Aggregate Elastic Properties of Sillimanite (SX) and Mullite
Single Crystals (MX) at Room Temperature
SX (sillimanite) MC (3/2-mullite) MC MC MX ( 2/1-mullite) MX (2.5/1-mullite)

References [136] [140] Unpublished Unpublished [135] [132]

results results
x 0 0.25 0.27 0.34 0.38 0.50
(%) 0 0.4 1.6 0.6 0 0
c11 (GPa) 295.2 290.9 284.9 284.8 284.8 290.9
c12 109.5 113.1 111.8 111.0 110.2 114.9
c44 = (c11c12)/2 = G 92.9 88.9 86.55 86.91 86.8 88.0
B (GPa) 171.4 172.4 169.5 168.9 170.0 173.6
E (GPa) 235.9 227.6 221.9 222.5 223.3 225.8
@c11/@T (MPa/K) n.a. 24.4 27.2 26.5 26.2 29.2
@c12/@T n.a. 17.8 12.5 10.8 10.9 11.6
@c44/@T n.a. 3.3 7.3 7.9 7.6 8.8
The compositional parameter x refers to the general formula Al2(Al2+xSi2x)O10x. denotes the porosity of the ceramic, B and G are bulk and shear modulus,
respectively, E = 1/s11 = (c11  c12)
(c11 + 2c12)/(c11 + c12) denotes Youngs modulus, and @cij/@T are the rst-order temperature coecients of the elastic stiness
coecients cij.
n.a., not available.

T.F. Krenzel, J. Schreuer, D. Laubner, H. Schneider, Unpublished results.

Table IV. Data of Bending Strength, r, and Fracture

Toughness, KIC, of 3/2-Mullite Ceramics at Dierent
Temperatures T
T (C) r (MPa) KIC (MPa
m1/2)
RT 2.5
1200 260 3.6
1300 200 3.5
1400 120 3.3
1000C were published (H. Schneider, H. L uhrs, R.X.
Fischer, Th. Gesing, Unpublished results).135,162165 The ther-
mal expansion of mullite exhibits a distinct anisotropy
(Fig. 8), and the coecients depend on both temperature
[Fig. 10(b)] and composition (Fig. 11). For the comparison
of the results of the dierent authors linear thermal expan-
sion coecients aii obtained by tting rst-order polynomials
to the experimental data are presented for selected tempera-
ture ranges in Table V. Table V shows that the expansion
parallel to the a-axis (a11) is lower than parallel to b (a22),
and that the expansion parallel c (a33) always is relatively
high. In stable crystals far from structural phase transitions
the direction of the lowest thermal expansion often correlates
with the elastically stiest direction. In the case of mullite
and associates this would mean that the thermal expansion
a33 should be lowest, as [001] is the direction of the strongest
bonds. This, however, has not been observed. The violation
of this empirical rule can be understood by the transverse
interaction between the octahedral and tetrahedral chains
running along to the c-axis as outlined in Section III(1)A.
The expansion of the octahedral chains due to increasing
thermal motions of the Al atoms in the octahedra pulls the
connected tetrahedra toward the octahedral chains giving rise
to a negative contribution to the thermal expansion within
the (001) plane (cf. Fig. 9). Strictly speaking, it is not a33
that violates the empirical rule but a11 and a22 are unusually
small. In summary, the favorable (small) thermal expansion
of mullite is a direct consequence of the special spatial link-
age of octahedra and tetrahedra in its crystal structure.
Brunauer et al.163 and J. Schneider and H. Schneider (un-
published results) provided thermal expansion data from
room temperature up to 1600C. Below 1000C the expan-
sion coecients are similar to those of the other authors
(Table V). At about 1000C an expansion anisotropy occurs
with the expansion generally increasing in the high-tempera-
ture regime (a22 > a33  a11, Table V). The discontinuous
change in the lattice expansion at about 1000C was associ-
ated with a phase transformation [see Section III(5)].
The development of the thermal expansion coecients aii
below about 1000C depending on the Al2O3-content (x-value)
of the mullite-type aluminosilicates of the composition
References Al2(Al2+2xSi22x)O10x are given in Fig. 11 between x = 0
(sillimanite) and x = 0.67 [pseudo-tetragonal point, see Sec-
[148] tion II(3)].d Let us rst have a look on the thermal expansion
[147] of the mullite-type phases within the (001) plane. Sillimanite
[147] (x = 0) displays higher expansions parallel the b-axis
[147] (a11  3.0 9 106C1) than parallel a (a22  8.0
9 106C1).164 With increasing Al2O3-contents and simulta-
neously increasing numbers of associated vacancies (x-value)
a11 linearly increases, whereas a22 linearly decreases, with the
eect being stronger parallel b than parallel a. Na0.67Al6O9.33
(x = 0.67118,119,166).g shows very similar expansion coecients
parallel to the a- and b-axes, that is, a11  a22 
4.8 9 106C1 (Fig. 11). Within the (001) plane parallel a
and b a sequence of sti (Al,Si)O4 tetrahedra and more compli-
ant AlO6 octahedra occurs [Fig. 4(b)]. It is believed that the
thermal expansion in the (001) plane is essentially controlled
by the compliant octahedra. The longest and most elastic octa-
hedral AlO2 bonds lie to about 30 to b, and to about 60 to
a. This has the consequence that the thermal expansion paral-
lel b is higher than parallel a (a22 > a11). With increasing num-
ber of oxygen vacancies and associated higher Al2O3-contents
of the mullite phases the octahedral AlO2 and AlO1 bond
lengths approach each other. Simultaneously clockwise and
counterclockwise rotations of the octahedral chains around
the c axis may occur.53 This has the result that mullites with
x  0.67 (80 mol% Al2O3) have equal thermal expansions
coecients a22 and a11. The development of the a22 and a11
expansions coecients of mullites with x > 0.67 (> 80 mol%
Al2O3) is dicult to predict, as the structural situation is not
fully understood yet [see Section II(3)]. Following the course
of lattice constants with the Al2O3 content, a11 should become
larger than a22. However, further investigations are required
to understand the behavior.
The situation is dierent parallel to the crystallographic
c-axis. Here, the thermal expansion is controlled by the speci-
c linkage of octahedral and tetrahedral chains building up
the backbone of the mullite structure. In sillimanite the tetra-
hedral OSiO bond angle of the highly covalent and thus
directional SiO bonds connecting the tips of the two adja-
cent AlO6 octahdra is at ambient temperature already larger
g
As no thermal expansion data of Al2(Al2+2xSi2-2x)O10x aluminosilicate mullites
with Al2O3 contents higher than 70 mol% are available so far the data of
Alk0.67Al6O9.33 (i.e., Alk2O
9Al2O3, Alk = Na+ and K+) with mullite structure are
included instead. The mullite-type Alk2O9Al2O3 correspond structurally to the alumi-
nosilicate mullites with 80 mol% Al2O3 (x = 0.67, Fig. 11)117119
2960 Journal of the American Ceramic SocietySchneider et al. Vol. 98, No. 10

0.78 J g1 K1 at room temperature and 1.25 J g1 K1 at

Thermal expansion coefficient [10-6K-1]
10
8 manite, which was investigated for comparison, exhibits a
6
4 (C) Atomic Diusion: Because of the oxygen vacancy-
2 11
22
33
0
sil 3/2-mu 2/1-mu 4/1-mu
-2
50 60 70 80 90
Al2O3-content [mol-%]
Fig. 11. The linear thermal expansion coecients a of mullite (mu)
plotted versus the Al2O3 content (x-value, 3/2-mu = 3Al2O32SiO2, 2/
1-mu = 2Al2O3SiO2, 4/1-mu = 4Al2O3SiO2,). The data of sillimanite
(sil = Al2O3SiO2) are plotted for comparison (H. Schneider, H.
Luhrs, R.X. Fischer, Th. Gesing, Unpublished results). 162165
than the ideal tetrahedral angle. This produces compressive
stresses along the direction of the octahedral chains. With
increasing Al2O3 content (x-value) of mullite the substitution
of tetrahedral Si4+O by the less covalent Al3+O bonds
and the associated introduction of oxygen vacancies reduce
the intrinsic compressive stress and allows for a larger ther-
mal expansion coecient a33 (Fig. 9). Other mullite-type
phases such as Bi2M4O9 (M=Al3+, Fe3+, Ga3+)167,168 also
display this remarkable and unusual anisotropy of the longi-
tudinal thermal expansion.35, 167
Doping of mullite with foreign cations has a signicant inu-
ence on thermal expansion. Schneider and Eberhard,162 Bru-
nauer et al.,163 and L uhrs et al.110 found that Cr3+-, Fe3+-,
and especially B3+-substituted mullites exhibit a lower thermal
expansion than pure Al,Si-mullite. A reduction of even 15% of
the mean thermal expansion coecient was reported for a
6.4 mol% B2O3-doped mullite.110 B3+-substituted mullite
ceramics thus are technologically interesting, for example, for
the use for substrates at temperatures up to 1000C.
(B) Heat Capacity: Based on older studies of Pank-
ratz et al.,169 Barin and Knacke170 and Barin et al.,171
Hildmann and Schneider172 determined the heat capacity Cp
of mullite (single crystal and polycrystalline) in the
temperature range between 125C and 1400C. The
temperature-dependent Cp curve shows a parabolic shape
with values of about 0.415 J g1 K1 at 125C,
1000C. At temperatures above 1100C, a weak though
reversible step-like Cp anomaly is observed in mullite. Silli-
similar temperature-dependent behavior but does not show
? this anomaly. A possible explanation of the Cp anomaly of
mullite is given in Section III(5).
induced defect structure of mullite one would expect high
ionic diusivity in mullite at high temperature, as was sug-
gested for O2 by Rommerskirchen et al.173 However, more
recent diusivity studies do not support this suggestion, in
yielding relatively slow diusion rates.174178 Al and O atoms
-alumina display very similar diusivities with activation energies of
550 kJ/mol. The Si diusion velocity is two orders of mag-
100 nitude slower than that of Al and O with the activation
enthalpies being slightly higher (600 kJ/mol1), (Fig. 12). It
conrms the statement of Sacks et al.181 that the diusion
coecients of Al in mullite are higher than those of Si at
temperatures above the mullite-silica eutectic.145 One expla-
nation of the relatively slow diusivity of Si is the strong
covalent SiO bonding, which hinders Si site exchange pro-
cesses. No structural anisotropy of O, Al, and Si diusion is
observed in mullite, especially no preferred diusivity parallel
to the crystallographic c-axis does occur. This is astonishing,
as structural channels, although distorted by T*O4 tetrahe-
dra, run parallel c, and the O vacancies occur more fre-
quently in this lattice direction. Both factors should trigger
diusion parallel c, which, however, is not the case. Obvi-
ously the structural channels and vacancies do not serve as
preferred diusion paths.
In this context it might also be of interest that Schreuer
et al.135 observed an ultrasound dissipation peak in single
crystal 2/1-mullite with maximum attenuation at about 70C
in the frequency range 2001000 kHz. The phenomenon
resembles the well-known Snoek eect and is probably
caused by anelastic relaxation of point defects. The rst idea
that these defects are related to the O vacancies in mullite
seems no longer plausible because Krenzel et al.167 detected
similar relaxation eects in mullite-type Bi compounds with-
out structural vacancies in the anion lattice. Additional inves-
tigations are required to clarify the nature of these defects
and of the relaxation process, and their impact on atomic
diusion in mullite.
(D) Thermal Conductivity: Low thermal conductivity
is a characteristic property of mullite and is crucial for the use
of mullite ceramics and coatings as heat protection systems.
The thermal conductivity of a mullite single crystal (2/1-com-
position) parallel to the crystallographic a-, b- and c-axes was
measured by Hildmann and Schneider182 up to 1200C. The

Table V. Linear Thermal Expansion Coecients of Sillimanite, Mullites, and Cr-Doped Mullites (10 wt% Cr2O3)
a11 a22 a33 aV
Composition Method T range of linear t
Compound x (C) (106 K1) References

Low temperatures (T < 1000C)

Sillimanite 0 XRD 300900 2.3 7.6 4.8 14.7 [164]
Mullite (Cr-doped) 0.21 ND 3001000 3.6 5.9 5.2 14.7 [163]
Mullite (Cr-doped) 0.21 XRD 3001000 3.1 6.2 5.6 14.9 [162]
Mullite 0.24 XRD 300900 3.9 7.0 5.8 16.7 [162]
Mullite 0.25 XRD, ND 3001000 4.1 6.0 5.7 15.8 [163]
Mullite 0.38 XRD 300900 4.1 5.6 6.1 15.8 [162]
Mullite 0.38 DIL 3001000 4.5 6.1 7.0 17.6 [135]
High temperatures (T > 1000C)
Mullite (Cr-doped) 0.21 ND 10001600 5.8 11.0 6.1 22.9 [163]
Mullite 0.25 ND 10001600 6.8 9.3 6.3 22.4 [163]
Mullite 0.38 DIL 10001400 6.2 7.3 6.9 20.4 [135]
The coecients aii were obtained by tting rst-order polynomials to experimental data. aV  a11 + a22 + a33 is the linear coecient of volume expansion. XRD,
high-temperature X-ray diraction, ND, high-temperature neutron diraction, DIL, high-temperature dilatometry. The x-value refers to the general composition of
mullite Al2(Al2+xSi2x)O10x.
October 2015 Mullite Structure and Properties
Fig. 12. 18O-, 26Al-, and 30Si- tracer diusivities in single crystal 2/
1-mullite plotted parallel to the b- ([010]) and c-axis ([001]).180 The
18
O diusivity of single crystal 3/2-mullite is given for comparison.179
Also shown are data of the parabolic growth constant, k, of mullite
formation.180
thermal conductivity is highest parallel c and with lower but
similar values parallel a and b (k11 = 4.563 W
(m
K)1,
k22 = 4.400 W
(m
K)1 and k33 = 6.862 W
(m
K)1, all values
at 100C). With increasing temperature the thermal conductiv-
ities decrease exponentially, and above about 800C the con-
ductivities become nearly constant [Figs. 8 and 10(c)]. The
temperature-induced development of the thermal conductivity
of mullite was essentially explained with phononphonon
interactions, which at high temperature become a main factor
in addition to the vibrational energy. At high temperature the
mean free path of phonons decreases to a value near to that of
the lattice spacing, which makes the conductivity more or less
independent from temperature [see Fig. 10(c)].183 The thermal
conductivity in mullite is highest parallel to the c-axis, proba-
bly due to phononphonon interactions along to the strongly
bonded octahedral and tetrahedral chains.182 It has been
quoted that crystal structures with complex and/or distorted
crystal structures have a tendency toward thermal scattering,
which in turn reduces the thermal conductivity.183 This may
explain why mullite with its O vacancy defects displays a lower
mean thermal conductivity as, for example, undoped MgO
and Al2O3. On the other hand, stabilized ZrO2 shows an even
lower conductivity than mullite, probably due to scattering at
the numerous occurring O vacancies. In this context it would
be very interesting to compare the thermal conductivity of
mullite with that of sillimanite. As the latter has a crystal struc-
ture very similar to that of mullite but contains no O vacancies
its thermal conductivity should be higher than that of mullite.
However, no data on sillimanite are available so far.
(3) Electrical and Optical Behavior
(A) Electrical Properties: Mullite is an electrical isola-
tor at ambient and moderate temperatures, and therefore is
suitable, for example, as a substrate material for electronic
devices. However, in spite of its importance for high-temper-
ature ceramics only few and contradicting experimental
results exited on the electrical conductivity of mullite at high
temperature. Rommerskirchen et al.173 on the basis of elec-
tromagnetic eld measurements quoted that between 1400C
and 1600C mullite ceramics displays high electrical
conductivities, being even superior to that of CaO-doped
zirconia in the same temperature region. Chaudhuri et al.184
carrying out direct current measurements on mullite ceramics
up to 1400C, however, yielded a much lower electrical
2961
conductivity. Their ndings were supported by electrical
conductivity studies on 2/1-mullite single crystals of Malki
et al.185 parallel to the crystallographic axes. According to
Malki et al., the temperature evolution of the electrical
conductivity in mullite is characterized by two regions: A
low-temperature region below about 850C950C with
low, essentially electronic conductivity (e.g.,
rav  5.4 9 109 O1 cm1 at 550C, rav = mean values of
the electrical conductivity) with r22 > r11 > r33. It correlates
with the isolating character of mullite described in the techni-
cal literature (see Section I). The high-temperature region
exhibits higher predominantly ionic electrical conductivities
(e.g., rav  1.1 9 105 O1 cm1 at 1400C) with
r33 > r11  r22 [Figs. 8 and 10(d)]. Malki et al.185 explained
the discontinuous change in the electrical conductivity curves
near 900C with a static to dynamic transition due to
hopping of O atoms bridging the tetrahedral double chains
toward O vacancies in the high-temperature region [see Sec-
tion III(5)]. These O site changes may contribute to an over-
all increased electrical conductivity at high temperature. It
can be made responsible for the fact that the electrical con-
ductivity of mullite is higher than that of a-alumina (no O
vacancies), but still is much lower than that of doped zirco-
nia (frequent O vacancies).
According to calculations of Aryal et al.89 pure mullite is
a wide band gap isolator at low temperature. The band gap
of mullite linearly decreases up to the composition x = 0.67.
At higher x-values it becomes irregular, possibly due to
uncertainties of the structure models used for the simulation.
Positron annihilation experiments on Fe3+-, Cr3+-, Ti4+-,
and Mn2+-doped mullite186 provided evidence for a transi-
tion from an insulator (undoped) to a semimetal behavior in
transition-metal-doped mullite.
The alternating current (ac) conductivity of mullites doped
with Co2+, Ni2+, and Cu2+ were investigated by Roy
et al.187 The authors observed a decrease in the resistivity
with increasing doping content. Mullite doped with Ni 2+
exhibits the lowest dielectric constant.99 These materials have
a good potential, for example, for the use as electronic sub-
strates. However, dielectric measurements at radiowave fre-
quencies, carried out by Sanad et al.100 exhibited a very
strong dielectric loss of about 80% for Yb3+-doped
nanoparticle mullite (0.5% Yb3+), whereas Gd3+-doped
mullite (0.5% Gd3+) yielded a dielectric loss of even 96% in
the microwave region.
(B) Optical Properties: Only few refractive indices on
synthetic, pure, and aw-free phases of the mullite-type alu-
minosilicates are available so far.8, 188190 Aryal et al.89 pro-
vided calculated refractive indices n in the sequence
sillimanite (x = 0) and -alumina (x = 1). They showed that n
linearly decreases as the x-value increases. The decrease of n
with the Al2O3 content of mullite (x-value) at least up to
x = 0.67 is reasonable, as the density, due to the increasing
number of O vacancies, also strongly and linearly decreases.
Things are less clear at x > 0.67, as neither experimental data
nor structural details are available yet.
The refractive indices of natural mullites are wide spread
with na = 1.6301.670, nb = 1.6361.675, and nc = 1.640
1.691, and the birefringence and the optical axes angle 2V
range between 0.010 and 0.029 and between 45 and 61,
respectively. The spread of optical data is explained with the
varying chemical composition of natural mullites, especially
the incorporation of Ti4+, Cr3+, and Fe3+. While pure and
Ti4+-doped mullites are colorless, Cr3+- and Fe3+-doped
mullites are green and reddish-brown, respectively. Holand
and Beal191 mentioned that Cr-doped mullite can been used
in laser applications and solar concentrators.
Schneider et al.,192 on the basis of homogeneous, dense
(porosity <1%), high isostatically pressed mullite ceramics,
mentioned a very high optical transmittance (>90%) for
wavelengths up to 5 lm, whereas above 5 lm there exists a
transmittance cut-o. The transmittance was highest in the
2962 Journal of the American Ceramic SocietySchneider et al.
infrared, but lower in the visible and especially in the ultravi-
olet. The optical transparency or translucency of mullite sin-
gle crystals and of dense mullite ceramics, respectively,
makes the materials suitable particularly for optical windows
of high-temperature furnaces.193 No data on the structure
control of the optical transmittance of mullite are available
so far.
In recent years the incorporation of REEs into mullite has
become an important research topic. Lee and Kim101 investi-
gated Eu2+-doped mullite ceramics [see Section II(4)B]. The
material exhibits strong greenish-blue emissions between
about 475 nm and 485 nm, conrming earlier studies of
Kutty and Nayak103 and of Park et al.104 Eu2+-doped mul-
lite ceramics have potential for the use as phosphors for uo-
rescent lamps and for white-emitting diodes. Zhang et al.105
showed that mullite nanoparticles (35 nm50 nm in size)
doped with 8% Tb3+ and 0.1% Ce3+ are characterized by
strong green luminescence. These materials again are interest-
ing for uorescent lamps and display devices. Photolumines-
cence spectroscopic analyses of Y3+-, Gd3+-, and La3+-
doped mullites (0.5% of the dopant in each case) exited at
256 nm yielded similar results.100 It was shown that the pho-
toluminescence increases with the Gd3+-content.106
(4) StructureProperty Relations
As discussed in detail in Section II(2) the crystal structure of
mullite possesses two characteristic features that are crucial
for the stability and the properties of the material: (i) parallel
octahedral bond chains reinforced by tetrahedral double
chains, and (ii) structural disorder of Al and Si on tetrahe-
dral sites and of O vacancies required for charge compensa-
tion.
In comparison with sillimanite (ordered), mullite (dis-
ordered) displays at room temperature a slightly softer elas-
tic behavior suggesting a less favorable lattice energy of
mullite. The situation gradually changes with increasing tem-
perature because the higher congurational entropy of mul-
lite related to its intrinsic structural disorder stabilizes the
mullite structure at high temperatures. Eventually, the dier-
ent entropic contributions to the free energy trigger the
decomposition of sillimanite into 3/2-mullite and SiO2.
The special linkage of the linear octahedral and tetrahe-
dral bond chains running along to the c-axis aects in partic-
ular the mechanical and thermal properties of mullite as
outlined in Sections III(1)A and III(2)A. The generally low
thermal expansion and the deviations from Cauchy relations
mainly result from the pronounced transverse interaction of
mechanical forces parallel with those in the plane perpendic-
ular to the octahedral chains. The strong binding interactions
between the constituents of the chains do not only lead to a
corresponding anisotropy of the longitudinal elastic stiness
but also control the mobility of dislocations. Glide processes
can be activated more easily in {hk0} planes because they do
not cross the octahedral and tetrahedral chains. The intense
binding forces are also made responsible for strong phonon
phonon interactions parallel c, where electron orbitals are
intensively overlapping. Consequently, the maximum of the
thermal conductivity is observed in c-direction. A similar
argument was employed for the interpretation of the aniso-
tropy of the refractive indices (nc > na, nb). However, simple
structureproperty relationships cannot be used to explain
qualitatively the anisotropy of all properties of mullite. For
example, a preferred atomic mobility could be expected par-
allel to the partially open structural channels and thus paral-
lel to the c-axis, which is not the case. Obviously these
structural elements do not serve as preferred diusion ways.
Also some semi-empirical rules relating chemical composi-
tion to scalar invariants of certain properties have been suc-
cessfully applied to mullite. These rules can be exploited to
estimate the impact of variations in chemical composition on
the corresponding property. In this context the elastic S-factor,
Vol. 98, No. 10
S = C
Vm, dened as the product of mean elastic stiness
C = (c11 + c22 + c33 + c44 + c55 + c66 + c12 + c13 + c23)/9 and
the molecular volume Vm = Mw/(NA
q) plays an important
role (Mw = molar weight, NA = Avogadros number, q = den-
sity). Under the assumption that the interactions between
cations and surrounding anions are similar in a compound X
and in its stable constituents Xi the S-factor of X can be
decomposed into additive contributions S(Xi) according to S
(X) = S(Xi). This quasi-additivity rule holds for many ionic
crystals and even silicates within about 10%.139, 194 In the
case of mullite the rule reads S[Al2(Al2+2xSi22x)O10x] = S
(Al2VIO3) + (1 + x) S(Al2IVO3) + (22x) S(SiO2). Using the
S-factors of coesite, corundum, and hypothetical Al2O3 with
Al in tetrahedral coordination139 one obtains S(2/1-mullite,
x = 0.39) = 2310 9 1020 Nm. The underestimation of the
experimental value of 2756 9 1020 Nm135 by about 14% is
probably caused by the strong contribution of the special type
of linkage of octahedral and tetrahedral chains to the elastic
stinesses of mullite. According to L uhrs et al.,112 about 15%
of Si4+ in reaction-sintered mullite and up to 40% in high tem-
peraturehigh pressure produced mullite can be substituted by
B3+. With S(B2O3) for B3+ in trigonal-planar coordination195
and taking into account the lattice constants of B3+-doped
mullite112 and 2/1 mullite135 one can estimate for the 15% sam-
ple C(Al4.5Si0.9B0.6O9.4)/C(2/1-mullite) 1.05. According to
the well-known Gr uneisen relation this should lead to a corre-
sponding decrease of about 5% in the mean thermal expansion
coecient. In fact a decrease of up to 15% has been experi-
mentally observed in B3+-doped mullite.112
(5) Evidence for Structural Phase Transformations
An unusual temperature dependence of thermal expansion of
mullite was reported by Schneider et al.196 Employing high-
resolution X-ray diraction techniques the authors have
shown that mullite displays a weak, although characteristic
reversible expansion discontinuity between about 400C and
500C, which is strongest parallel to the crystallographic a-
axis. It was attributed to rotations of the octahedral chains
and to slight deformations of the tetrahedra. It has to be sta-
ted, however, that this discontinuity was not conrmed by
dilatometric experiments on large single crystal mullite
[Fig. 10(b)].135
At higher temperatures various weak but well reproducible
anomalies in the temperature evolution of physical properties
of mullite were described:
1. The heat capacity CP of mullite [Fig. 13(a)] displays a
relatively strong step-like discontinuity at 1100C.172
2. The linear thermal expansion coecients aii
[Fig. 13(b)] show signicant discontinuities at about
1100C.135
3. An accelerated softening of the shear resistances
accompanied by an exponentially increasing sound dis-
sipation occurs above about 1000C.135,163
4. The slope of the temperature dependence of the electri-
cal conductivity [Fig. 10(d)] changes between about
800C and 900C.185
Other properties like thermal conductivity [Fig. 10(c)] or
atomic diusion coecients do not show any discontinuity
within experimental error up to about 1400C. Obviously the
above-mentioned anomalies are not characteristic for any
particular type of phase transition. Hildmann and Schnei-
der,172 Lacks et al.,197 Schreuer et al.,135 Schneider et al.35
and Malki et al.185 explained the eects with a static to
dynamic transformation in mullite similar to those in
glasses at the glass transition point. Here, static means that
at low temperature no atomic site changes take place, though
temperature-induced atomic vibrations occur. For the high-
temperature dynamic state site changes essentially between
O atoms linking the tetrahedral double chains (O3) and
nearby O vacancies have been suggested. The O atom
October 2015 Mullite Structure and Properties
(a) Temperature [C]
0 400 800 1200
1.4
1.3
CP [J g K ]
-1
1.2
-1
1.1
1
0.9
0.8
200 600 1000
Temperature [K]
Fig. 13. Anomalies in (a) heat capacity and (b) thermal expansion of 2/1-mullite at high temperatures. CP data were taken from Hildmann and
Schneider,172 thermal expansion coecients were calculated as rst derivatives of the temperature-induced strains observed by Schreuer et al.135
hopping between O3-atoms and nearby O vacancies is a
complicated process, as it requires a simultaneous formation
of tetrahedral T*O4 triclusters adjacent to the newly formed
vacancies and the formation of new TO4 tetrahedra at the
site of the lled former vacancy. According to ndings of
Paulmann52 on the basis of high-temperature X-ray dirac-
tion studies the static to dynamic transition does not involve
any change in the ordering scheme of mullite. Schneider
et al.35 believed that site exchange processes oscillate around
their initial sites. The static-dynamic model agrees with the
observation that sillimanite, which contains no oxygen
vacancies, shows no heat capacity discontinuity.
IV. Summary and Conclusions
Mullite is part of the orthorhombic mullite-type aluminosili-
cates with the general composition Al2(Al2+xSi2x)O10x.
Main compounds, being the topics of the following discus-
sion and which are relevant for technical ceramics, are 3/2-
mullite (3Al2O3
2SiO2, x = 0.25) and 2/1-mullite
(2Al2O3
SiO2, x = 0.40), the latter being stable in air up to
about 1900C. The backbone of the crystal structures of the
phases are chains of edge-connected AlO6-octahedra cross-
linked by tetrahedral di- and triclusters. Al and Si are ran-
domly distributed over the tetrahedral diclusters, with most
of the triclusters being occupied by Al. The crystal structure
of mullite contains oxygen vacancies, with the number x cor-
responding to the general aluminosilicate formula. The tetra-
hedral di- and triclusters and the O vacancies of mullite are
locally ordered but on the long-range they are strongly but
not completely disordered in a modulated way. The struc-
tural arrangement of di- and triclusters and of O vacancies is
thermally very stable and persists up to the melting point
(ca. 1900C). Mullite is able to incorporate a large variety of
foreign cations, especially Ga3+ and B3+, transition metals
(e.g., V3+, Cr3+, and Fe3+), and the REEs Eu2+/3+, Gd3+,
and La3+, although in strongly dierent amounts.
The crystal structure of mullite controls its properties. For
example, the anisotropy of mechanical properties and the
favorable low thermal expansion are directly inuenced by
the special structure and cross-linkage of the principal bond
chains. Furthermore, the material undergoes only little plas-
tic deformation leading to an excellent creep resistance up to
high temperatures. We believe that the rmly bound edge-
connected octahedral chains and the (distorted) tetrahedral
double chains running parallel to the crystallographic c-axis
hinders the deformation systems to cross these structural ele-
ments. The high mechanical stiness and low compressibility,
the high thermal and electrical conductivity and the high
refractive index parallel c-axis in comparison to the relation-
ships perpendicular to c have also been explained with the
strong bonding due to intensive overlapping of orbitals in
this lattice direction. The O vacancies, on the other hand,
should weaken the structure: Actually the mean elastic sti-
ness of mullite is lower than that of sillimanite, the latter
containing no O vacancies. We believe that the congura-
2963
(b) Temperature [C]
0 400 800 1200
Thermal expansion ij [10 K ]
-6 -1
10
8 33
6 22
4 11
2
0
1400 1800 200 600 1000 1400 1800
Temperature [K]
tional entropy due to the intrinsic structural disorder of mul-
lite stabilizes the structure at high temperatures.
The occurrence of O vacancies may be responsible for the
high-temperature anomalies of heat capacity, thermal expan-
sion, and shear resistance of mullite, whereas sillimanite does
not show such eects. Atomic site changes between the O
atoms, bridging the tetrahedral diclusters, and adjacent O
vacancies are believed to occur in mullite above about
1000C (dynamic state), whereas below 1000C no signi-
cant O site changes (static state) take place on the labora-
tory time scale. The energy involved in these processes is
very small, and thus has no impact on the technical relevant
properties of mullite.
In spite of the many property data reported here, there is
still important work to be done in the future. One open crys-
tallo-chemical question, for example, is crystal structure and
composition of mullite-type phases in the range between silli-
manite (x = 0) and 3/2-mullite (x = 0.25, so-called sillimul-
lite), of the Al2O3-rich mullite-type phases with x > 0.67
and of the mullite-type -alumina (x = 1). Another point of
interest is the optical, electrical, and magnetic properties of
transition-metal- and REE-doped mullites, together with the
evaluation of their technical signicance. It will also be inter-
esting to carry out investigations on the structureproperty
relations of other technical relevant phases belonging to the
family of mullite-type structures, such as Bi2M4O9/10,
PbMBO4, and LiAl7B4O17, as these phases have interesting
optical, electrical, and magnetic properties.
In summary due to the high-temperature stability in air,
the favorable thermomechanical properties, and the ability of
foreign cation-produced variation of optical, electrical, and
magnetic properties, mullite has become a most important
ceramic material. Moreover, raw materials for mullite are
widely available, and often there exist easy and low-cost mul-
lite production routes. Mullite and mullite ceramics have
widely been used as monolithic ceramics (e.g., pottery and
whiteware, refractories, crucibles, substrates, lters, optical
materials, dental components), coatings and membranes (e.g.,
biolms, thermal barrier coatings (TBCs) and EBCs), sub-
strates, bers and ber fabrics (lters, thermal, and electrical
insulation tools, reinforcements of ceramic matrix compos-
ites), and as composites (e.g., high-temperature and oxida-
tion- resistant thermal protection systems, lters, burner
tubes). It should be kept in mind, however, that technical
mullite ceramics normally are polycrystalline, and thus struc-
tureproperty relationships of single crystal mullite cannot
fully describe the properties of ceramic materials. Microstruc-
tural features, including grain morphology, grain size and
distribution, and the occurrence and distribution of sec-
ondary crystalline or glassy compounds and phases also have
a property-controlling inuence. The evolution of the
microstructure in turn is strongly dependent from composi-
tion and processing of mullite materials. A planned system-
atic overview of the many literature data and further
investigations thus can increase the understanding and help
to broaden the application range of mullite ceramics.
2964 Journal of the American Ceramic SocietySchneider et al.
Acknowledgment
The authors thank Dieter Buhl (Bochum, Germany) for his great commitment
in taking high-quality photos of mullite crystals.
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96
R. Bauchspiess, H. Schneider, and A. Kulikov, EXAFS Studies of Cr-
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97
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98
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2965
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talline-to-Amorphous Transition in Shockloaded Mullite Al2IV(Al2+2xSi22x)VI
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Amorphization of Mullite and Thermal Recrystallization, J. Non-Cryst.
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Thermal Expansion of Mullite: An In Situ Neutron Diraction Study up to
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Ambient Pressure: X-Ray Powder Diraction Study up to 1000C, Miner.
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Vol. 98, No. 10
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H. Schneider, Thermal Expansion and Elastic Properties of Mullite-Type
Bi2Ga4O9 and Bi2Fe4O9 Single Crystals, Int. J. Mater. Res., 103, 43848 (2012).
168
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Chemistry and Properties of Mullite-Type Bi2M4O9: An Overview, Int. J.
Mater. Res., 103, 4229 (2012).
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stances, Vols. 1,2. Springer, Berlin, 1973.
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ical Data of Pure Substances, Vols. 1,2. VCH, Weinheim, 1993.
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Ceram. Soc., 87, 22734 (2004).
173
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viour of Mullite (3Al2O32SiO2) at 1400 to 1600C, Solid State Ionics, 74,
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176
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177
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etry, Solid State Ionics, 177, 4936 (2006).
178
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Controlled Mullite Formation Reaction Model Based on Tracer Diusivity
Data for Aluminium, Silicon and Oxygen, Phil. Mag., 87, 11127 (2007).
179
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October 2015 Mullite Structure and Properties
Hartmut Schneider got his doctoral
degree at the University of Tubingen
(Germany) in 1971 and hold research
positions there and at the University
of Karlruhe (Germany) until 1976.
From 1976 to 1989 he was a member
of the German Industrial Refractory
Institute in Bonn (Germany). He
got his Habilitation degree at the
University of M unster (Germany) in
1986. From 1989 until 2006 he was
the head of the Ceramic Materials
Department at the German Aero-
space Center in K oln (Germany). In 1996 he became a
Professor at the University of Hannover, and has been a
Guest Professor at the Universities of Wien (Austria) and
Taipei (Taiwan). From 2006 to 2014 he hold a guest position
at the University of Koln (Germany), and since 2012 he is a
member of the University of Bremen (Germany). Main
research topics of Hartmut Schneider are mullite and mullite-
type materials and related ceramics and composites. He pub-
lished more than 270 scientic papers, 2 books and several
book contributions. He is winner of a Japanese Governmen-
tal Research Award, the Lilienthal Award, and he is a
Fellow of the American Ceramic Society and of the University
of Bremen.
Reinhard X. Fischer studied mineral-
ogy at the University of Mainz
(19751983) where he received his
doctoral degree in 1983. Between
1983 and 1985 he was a Research
Associate at the University of Illi-
nois at Chicago and from 1985 to
1986 he had a postdoctoral position
at the DuPont Company in Wilm-
ington, Delaware. He nished his
Habilitation as a lecturer at the
University of Wurzburg in 1991 and
then received a Heisenberg fellow-
ship of the Deutsche Forschungsgemeinschaft (DFG)
between 1991 and 1995 and the Victor-Moritz-Goldschmidt
2967
Prize of the German Mineralogical Society. Since 1995 he is
a professor for crystallography at the University of Bremen.
He is a member of several supervisory and executive boards,
member of the Review Board (geochemistry, mineralogy, and
crystallography) of the DFG, and member of College 5A of
the Institut Laue Langevin in Grenoble. His research inter-
ests are in the eld of crystal chemistry, especially zeolites
and mullite-type compounds, crystal growth, and crystal
optics.
urgen Schreuer received his diploma
J
degree in mineralogy and his doc-
toral degree from the University of
Koln (Germany) in 1989 and 1994,
respectively. From 1995 until 2002
he hold a research position at the
Laboratory of Crystallography of
the Swiss Federal Institute of Tech-
nology in Z urich (Switzerland). In
2003 he returned to Germany where
he worked as research scientist at
the University of Frankfurt before
he became Professor for Crystallog-
raphy at the Ruhr-University Bochum in 2006. His research
is mainly devoted to the exploration of structure-property
relationships with the focus on elastic and electromechanical
properties of crystals and ceramics as functions of chemical
composition, microstructure, temperature and frequency.