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journal
J Am Cerom SOC 74
[ l o ] 2343-58
(1991)
Wiederhorn-contributing
editor
L343
2344
AI,O,
20
40
component (wt%)
60
80
2200
2000
liquid
2z
1800-
Alumina
1600-
mullite (ss)
I
2
20
Mullite
I
40
AI,O, component (mol%)
80
(A) Stable and metastable phase diagram of the Si02-A1203 system, as determined
by diffusion-couple experiments and through characterization of melt-quenched samples 02
Insert in ( 6 ) superimposes the solid-solution range of mullite (shaded region) as determined by
Klug e t a / 2221 on the diagram of (A)
Fig. 2.
60
AI,O,
62
component (mot%)
64
66
68
70
1900
-oe
e) 1800
3
!i
F
1700
1600
i2
74
?S
i8
AI,O, component (wt%)
Fig. 3. SiO2-Al2O3 phase diagram, as determined through microstructural characterization of quenched samples 2 2 2 3 Note that
when this diagram i s superimposed on
Fig 2(A) the solid-solution range falls completely within the solid-solution range of ordered mullite (Fig 2(B))
2346
Interference-contrast micrographs of the reaction zone between a diffusion couple of alumina single crystal (bottom) and fused silica
(top) annealed at 1903C for 900 s and quenched at different rates (A) the fastest and (C) the slowest Precipltates in the top portion of the
diffusion zone are (A) mullite (light gray) (B)alumina (light-gray needles) and mullite (fine precipitates between the alumina needles) and (C)
alumina (light-gray needles) All three have identical concentration profiles ''
Fig. 4.
October 1991
2347
Fig. 6. Projection along [OOI] direction of the ideal unit cell of mullite showing T to T* tranSition of the cations (indicated by an arrow) following the formation of oxygen vacancy (large dotted circle) and readjustment of oxygen in the O(3) positions.
2348
Conventional
1000
I
1zoo
I
1400
Temperature (C)
1600
October 1991
Mrr lli tc jbr St r iict I L ra I , Elec f rott ic, a ntl ClpricaI Applicrit ions
( 2 ) Microstructure Evolution
During (c1300C) Heat Treatment
In the conventional approach, when
mullite is produced through reaction
sintering of alumina and silica at tem(I) tow-Temperature ( ~ 7 2 5 0 C )
peratures above 1650"C, the nucleation
Reaction Pathways to Mullite
and
growth of mullite occurs as an
The reaction sequences of mointerfacial reaction product between
lecularly and/or colloidally prepared
alumina and silica.20~"In this case, the
mullite-forming precursors show strong
growth rate is controlled by the diffuresemblances to those observed in
sion of aluminum and silicon through
clay-based systems.65O 9 When the
the mullite layer. Since this is a
scale of chemical homogeneity is at
parabolic rate process, mullitization
the atomic level (i e., monophasic preslows down with time, and, consecursors), mullite formation is typically
quently,
the elimination of the siliceous
observed at -980C through an
liquid phase becomes difficult with
exothermic reaction.6669 For instance,
grain growth.
amorphous powders produced by
In the case of low-temperature
chemical vapor deposition (CVD) or
(<1300"C)
processing of mullite with
spray pyrolysis directly transform to
diphasic precursors, however, a comm ~ l l i t e . ~Similarly,
~ , ~ ~ ~ slow
'
hydrolysis
pletely different mechanism than what
of mixed alkoxide or salt-solution conis observed at high temperatures apstituents can retain a finer scale of
pears to control the nucleation and
mixing between the two components
growth of mullite.55'566074
In diphasic
and thus promote mullite formation
systems,
although
alumina
is present
direct ly.49
52 6672
prior to the formation of mullite, the nuIn contrast, when the scale of homocleation of mullite is not at the aluminageneity is in the nanometer range (-1
matrix interface but instead is within
to 100 nm) (i.e., diphasic precursors),
the siliceous amorphous r n a t ~ i x . ~The
'.~~
mullite formation is generally preceded
apparent mechanism is the nucleation
by the formation of transient alumina
of mullite within the matrix as the matrix
phases and can be delayed to temreaches the saturation concentration
peratures as high as 1300"C, as
necessary to support mullite nucleaevidenced by a second exothermic
t i ~ nThis
. ~ ~
nucleation is then the cause
reaction at ~ 1 2 0 0 C5769
. ~For
~ ~in-~ ~ ~
of the second exothermic reaction disstance, powders or gels that are precussed above. Subsequent growth of
pared through rapid hydrolysis of salt
mullite is controlled by the dissolution
or alkoxide solutions yield diphasicof alumina in the matrix but not by intertype precursor^.^^^'^"^^ Coincidentally,
in these systems, the cubic alumina
(spinel) phase that is usually observed
as the transient alumina also crystallizes through an exothermic reaction at
-980C The occurrence of mullite and/
or the spinel phase almost at the same
temperature then becomes the source
of confusion in deciding which one of
the phases is responsible for the 980C
react ion.
The reaction series of kaolinite
(2Si02 A1203.2H20) or metakaolinite
(2Si02 Al7O3) is similar to that of
diphasic precursor^.^^^^^ Initially, a y
alumina-type spinel forms at 980C.68
Then, mullite crystallization follows at
higher temperatures, often with a distinct second exotherm at -1200C. This
similarity between the reaction series
of kaolinite and diphasic precursors is
important since it establishes a clear
standard for the type of mixing that is
Corning's luminescent window made of Cr3'-doped mullite glassceramic. Low dielectric constant and optical transparency of finerequired to convert a precursor directly
grained polycrystalline mullite has led to interest in potential
to mullite. Although kaolinite is an
applications as a host material as a sohd-state laser activator In
atomically layered structure of (Si205)'highly crystalline glass-ceramic, quantum efficiencies of 30% to
and (A12(OH)4)2+
molecular sheets, this
40% have been reported, in glass, quantum efficiencies are less
level of mixing is still not sufficient to
than 1%; in single crystal, efficiencies are close to 100%.
prevent the segregation of alumina and
silica. In fact, there is evidence that fur-
2340
2350
October 1991
2351
100-
-s
80-
60-
0
._
c
40-
6
20-
01300
1400
ioo
RT
Sinteringtemperature ("C)
Fig. 10. Evolution of phases in a colloidally consolidated compact
of composite powders during viscous phase sintering 62 Densification is completed in the temperature range of 1300" to 1400C In
this range cristobalite crystallization is dominant Mullite nucleation
and growth starts at -1350C and coincides with the dissolution of
alumina
1300
1200
Temperature ("C)
1400
Temperature ("C)
1394 1340
1290
I
Units:kJimol
Q=866+47
6.0
6.2
10V (K-')
6.4
6.6
2352
Wavelength (Fm)
2.5
"
I
4000
3.0
4.0
I
3000
5.0
7.0
6.0
2000
1500
Wavenurnber (crn ')
8.0
10
I
1000
Fig. 14. In-line transmission spectra for monolithic ceramic materials in the mid-infrared
(4000sVs400 cm-') ("Alon is an abbreviation for aluminum oxynitride) Mullite has a higher
cutoff at h=5 pm. but the presence of a strong absorbance band at 4 3 gm further reduces Its
effectiveness as an infrared window This absorbance has been shown to be related to the
process method used and may be caused by the presence of nanometer-sized inhomogenei
ties in the rnullite matrix (Fig 16) Molecular-scale processing eliminates the 4 3-gm absorption
band and improves the utility of mullite as a window material
low-thermal-expansion coefficient
(4xlO-'//"C in the 20" to 200C range)
which is almost that of silicon Consequently mullite and mullite-based
glass-ceramics have now emerged as
candidates in high-performance packaging applications 9 3 9 4 As illustrated
in Fig 13 Hitachi's multilayer ceramic
system is now totally based on a mullite substrate
Recent research has shown that
further reductions in the dielectric constant to values as low as 4 5 can be
achieved with a mullite-glass compositeg' As illustrated in Section IV
with sol-gel or composite powder
methods pure mullite can now be sintered at temperatures as low as
1250C Thus it is quite likely that further reductions in sintering temperatures c a n be achieved with a
mullite-glass composite, thus making
mullite an ideal candidate for cosintering with copper
October 1991
2353
Wavelength (pm)
3.0
4.0
5.0
6.0
Mullite
--. CVDpowder
i+, -~,
Cfrom
Mullite
from
I
3000
I
2000
Wavenumber (cm -')
I
1500
Fig. 15. Optically transparent mulhtes made using three processes sol-gel CVD and polymeric precursors Two techniques
which use atomic-scale mixing of the alumina- and silica-containing
moieties (CVD and polymer) succeed in eliminating the absorption
band centered at 4 3 prn observed in the sol-gel-derived material
However it is possible to reduce or eliminate this band in mullite
from carefully prepared sol-gels indicating that the 4 3-pm band
may be used as a quality-control indicator in mullite processing
Fig. 16. HREM image of a mullite grain recorded in the [OlO] projection of the mullite lattice revealing a pocket of amorphous phase
engulfed within the grain as indicated by an arrow Composition of
the pocket is 88 mol% silica and 12 mol% alumina
2354
VIII. Conclusions
The current intense interest in mullite
as an important candidate material for
demanding structural, electronic, and
optical applications is well justified. Its
attractive properties include excellent
high-temperature strength and resistance to creep and thermal shock, low
dielectric and thermal-expansion constants, and good transmission at high
temperatures in the mid-infrared band.
However, despite the advances in fundamental research on mullite in recent
years, much more laboratory research
and development is required before the
full potential of mullite, as an advanced
ceramic material, can be realized.
After decades of controversy, uncertainties about the phase equilibria of
the silica-alumina system still continue. Conflicting views mainly arise
when only one method of analysis is
used to determine the phase diagram.
More properly, in addition to microstructural characterization, the overall
composition must also be profiled to
determine the stable and metastable
equilibrium conditions. On this basis,
the phase diagram shown in Fig. 2(A)
is the most unifying one since it combines the results of various methods to
provide an overall view for all stable
and metastable states.
Large variations in the composition
of mullite, ranging from 3AI2O3 2Si02
to 3AI2O3 Si02, appear to relate to the
defect structure as manifested by the
ordering/disordering of oxygen vacancies. Additional studies are needed to
determine the limits of sub-phase fields
for mullites of different compositions
Controversy still attends the nature of
the ordered and disordered structures
which appear in mullites prepared under different conditions. Although it is
probable that several different forms of
mullite exist in a given sample, much
more work is needed to clarify these
structures and their effect upon phase
stabilities and physical properties.
Almost single-phase rnullite can now
be produced at temperatures between
1250" and 1500C using molecular and/
or colloidal mullite precursors. Precursors with atomic-scale homogeneity
convert directly to mullite at temperatures near 980C, but these precursors
are not ideal for the low-temperature
sintering of mullite. In contrast, with
diphasic precursors (with a scale of homogeneity from 1 to 100 nm) and silicacoated particles, mullite formation is
delayed to the 1300" to 1550C range,
and, thus, these systems provide the
Acknowledgments:
References
'
October 1991
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2357
2358
llhan A. Aksay is a Professor in the Department of Materials Science and Engineering and the Director of the
Advanced Materials Technology Center
of the Washington Technology Center
at the University of Washington. He
earned his B.Sc. degree (with honors)
in ceramic engineering at the University of Washington in 1961 He received
his M.Sc. degree in 1969 and Ph.D. degree in 1973, both in materials science
and engineering at the University of
California, Berkeley. Upon completing a
one-year postdoctoral appointment at
the University of California, Berkeley,
he worked at Xerox, Webster Research
Center (1973-1975) and the Middle
East Technical University in Ankara,
Turkey (1975-1981). In 1981, Dr. Aksay
joined the Materials Science and Engineering Department at the University
of California at Los Angeles as a Visiting Associate Professor. Since 1983,
he has been at the University of Washington. His most recent research activities have been on the utilization of
colloidal and bioinspired processing
techniques in the development of ceramics. In recognition of his contributions in this area, he received the
Richard M. Fulrath Award of the American Ceramic: Society in 1987 In 1982
he was also named as the first recipient of the Pacific Northwest Laboratory
Professorship by the U.S. Department
of Energy. He received the 1988 Academic Engineer of the Year Award of
the Puget Sound Engineering Council
for his "contributions to advances in
ceramic processing technology and
the transfer of this technology to industry and students." Dr. Aksay is a Fellow of the American Ceramic Society.