Microporous and Mesoporous Materials 54 (2002) 37–49

www.elsevier.com/locate/micromeso

Nanostructured ceramic powders by

hydrothermal synthesis and their applications
a,*
C. Kaya , J.Y. He a, X. Gu b, E.G. Butler a

a
Interdisciplinary Research Centre (IRC) in Materials Processing, The University of Birmingham, Edgbaston, Birmingham,
B15 2TT, UK
b
Thermometric UK, Crown Industrial Estate, Priorswood Road, Taunton, Somerset, TA2 8QY, UK
Received 3 January 2002; received in revised form 21 February 2002; accepted 25 February 2002

Abstract

Nanoparticles of 3:2 mullite ð3Al2 O3  2SiO2 Þ þ 5 wt.% zirconia, boehmite (c-AlOOH) and pure ZrO2 suitable for
applications in the field of monolithic/fibre reinforced ceramic composites, nanoceramics and ceramic fibre coating,
respectively, have been produced by hydrothermal synthesis (HS) at moderately low temperatures. The effect of the
process parameters or starting precursor materials properties on the particle size, shape and structure have been ex-
amined by particle size measurements, TEM and scanning electron microscopy. The mullite powders synthesised tend
to be highly irregular in morphology with a wide particle size distribution from 55 nm to 7.1 lm, whereas the boehmite
(c-AlOOH) particle morphology and size are determined by the pH value of the initial hydrothermal solution. As the
pH changes from low (acid) to high (alkaline), the boehmite morphology changes from a ‘‘needle-like’’ one to a
‘‘platelet’’ one. At a pH value of 10, the boehmite particles exhibit platelet morphologies, with a maximum face di-
mension of about 40 nm and a thickness of approximately 5 nm. The synthesised boehmite particles were successfully
used to produce monolithic alumina components at lower sintering temperatures with sub-micrometer grain sizes.
Near-spherical shape monoclinic zirconia particles with dimensions in the range of 20–60 nm were also produced by
HS. The successful application of the synthesised powders in the field of mesoporous fibre-reinforced ceramic com-
posites, high-density monolithic ceramics and ceramic fibre coatings (formation of weak inter-phase between fibre and
matrix) are also presented. Ó 2002 Elsevier Science Inc. All rights reserved.
Keywords: Nanopowders; Hydrothermal synthesis; Mesoporous; Mullite; c-AlOOH; ZrO2

1. Introduction have been of great interest over the last decades

Chemical processing techniques for the fabri-
cation of high-purity/nanosize mullite powders
*
Corresponding author. Tel.: +44-121-4143537; fax: +44-
121-4143441.
E-mail address: c.kaya@bham.ac.uk (C. Kaya).
to produce monolithic or fibre-reinforced mullite
components for high-temperature applications.
This is due to their chemical and thermal stability,
resistance to thermal shock and creep, low thermal
expansion coefficient (4–5  106 °C1 ), dielectric
constant (e ¼ 6–6.7) and good high-temperature
strength [1]. Pseudo-boehmite (c-AlOOH) is the
most commonly used precursor for preparing

1387-1811/02/$ - see front matter Ó 2002 Elsevier Science Inc. All rights reserved.
PII: S 1 3 8 7 - 1 8 1 1 ( 0 2 ) 0 0 3 3 4 - 7
38 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49
high-purity and high-strength monolithic a-alu-
mina ceramics by sol–gel technology. Microstruc-
turally controlled boehmite-derived high-purity
a-alumina ceramics with enhanced mechanical and
thermomechanical stability, chemical inertness,
optical and electrical properties, are used in a va-
riety of applications, such as substrates for elec-
tronic circuits, abrasive grains, high-temperature
refractory materials, fibres and thin films. Boeh-
mite is also a crucial precursor for preparing c-
Al2 O3 which is used as a high-temperature catalyst
support and as a membrane due to its high surface
area and mesoporous properties [2,3]. Zirconia is
one of the prime candidate materials for both
structural and functional ceramics as zirconia ce-
ramics produced from very fine zirconia particles
have the highest strength and toughness at room
temperature of all advanced monolithic ceramics.
These are used for structural applications as pump
parts, engine parts and pressing dies due to their
very good surface smoothness, high tenacy and
strength, refractories in glass melting and steel
fabrication industry due to their heat insulating
and chemical stability and also electronics industry
as oxygen sensor in measuring oxygen content in
molten steel due to their ionic conductivity.
Nanosize zirconia particles are also essential ma-
terials for ceramic fibre coating in oxide ceramic
matrix composites as zirconia is thermally stable
and chemically compatible with most of the oxide
systems (for example mullite and alumina) and
also show good resistance against oxidation.
The high surface area to volume ratio of a ce-
ramic sol makes the material highly sinter-active,
thus sintering temperatures can be lowered by
several hundred °C as a result of enhanced sin-
tering rates. The challenge in synthesising nano-
structured powders using wet chemical routes is to
control and engineer the physical properties (size,
shape and composition etc.) of the starting pow-
ders as they affect the properties of the final
products. Many advanced processing techniques,
such as sol–gel synthesis, spray pyrolysis, ultra-
sonic nebulized spray pyrolysis and precipitation
have been described extensively in order to pro-
duce fine powders [2–12]. However, from the in-
dustrial point of view, cost-effective and less
complicated synthesis techniques are required for
large scale applications. Hydrothermal synthesis
(HS) refers to the synthesis of a compound in a
hydrothermal solution under the effect of temper-
ature (>100 °C) and pressures above 1 atm. In this
method, ceramic sols are produced by chemical
reactions in an aqueous or organo-aqueous solu-
tion under the simultaneous application of heat
and pressure in the presence of an alkali or acid
that has a pseudo-catalytic effect upon the reaction
[13–17]. Synthesis under hydrothermal conditions
offers some significant advantages over other
chemical synthesis techniques. First, it is easy to
control particle size and morphology by varying
the synthesis conditions. Secondly, many materials
can be synthesised directly in the desired crystal-
line phase at low temperature. Finally, a substance
with an elemental oxidation state can be produced
and since the particles are produced in a sol form,
the resultant sol can be used directly in the pro-
duction of green bodies using pressure filtration or
extrusion [18]. The chemically synthesised nano-
structured powders using the hydrothermal route
possess better chemical homogeneity and a finer
particle size together with better control of particle
morphology due to nucleation and particle growth
that occur under these conditions. These charac-
teristics enhance the sinterability of ultrafine ce-
ramic powders at lower temperatures and also
produce a uniform fine grained sintered micro-
structure possessing better mechanical or electrical
properties. Thus, the main objective of the present
work is to prepare and characterise some of the
widely used ceramic materials, i.e. nanostructured
mullite þ 5 wt.% zirconia, boehmite and pure zir-
conia powders suitable for the fabrication of fibre-
reinforced composites, high-density monolithic
ceramics and colloidal dispersions suitable for ce-
ramic fibre coating using cost-effective and rela-
tively simple low-temperature HS.
2. Experimental work
2.1. Hydrothermal synthesis
2.1.1. Mullite þ 5 wt.% ZrO2
The precursor chemicals used in the present
work for the HS of mullite with 5 wt.% zirconia
 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49 39

were: aluminium tri-sec-butoxide [C2 H5 CH(CH3 )- processed hydrothermally by heating in a PTFE-

O]3 Al, tetraethylorthosilicate (TEOS, [Si(OC2 H5 )4 ])
and zirconium (IV) butoxide (Zr[O(CH2 )3 CH3 ]4 ).
The TEOS was first mixed with excess ethanol and
then hydrolysed using an aqueous solution of HCl.
The aluminium tri-sec-butoxide was then added to
this solution and stirred for 30 min. The zirconium
(IV) butoxide was then added to this mixture in a
quantity that would yield 5 wt.% of zirconia in the
final product. All three precursors could be com-
bined into the one mixture because the formation
of mullite from the aluminium tri-sec-butoxide and
TEOS would be the thermodynamically more fa-
vourable reaction, leaving the zirconium (IV)
butoxide to form zirconia. The batch was then
lined Berghof autoclave (250 ml capacity) to a
temperature of 170 °C for a period of 2 h under
autogenous pressure with stirring (see Fig. 1). After
hydrothermal treatment, dilute ammonia solution
was added to the sol, which caused it to form a
gelatinous precipitate. This precipitate was dried in
an oven at 60 °C for 8 h and then calcined in an air
muffle furnace at 600 °C for 4 h.
2.1.2. Boehmite (c-AlOOH) synthesis
Boehmite sols were produced by dispersing al-
uminium acetate powder (Aldrich Chemical Co.
Ltd.) in deionized water, and adjusting the pH by
the addition of 35 vol% ammonia or 1.75 M acetic

Fig. 1. The schematic representation of the autoclave used for synthesising mullite þ 5 wt.% zirconia, boehmite and zirconia powders
under low-temperature hydrothermal conditions.
40 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49
acid, as appropriate. The solution was then pro-
cessed hydrothermally in an autoclave at different
temperatures (200–300 °C) for different times (1–
10 h). The resultant sols were vacuum-filtered in a
Buchner funnel and washed with deionized water.
This process was repeated four times to remove
soluble impurities from the sol. Finally after fil-
tering, the sols were dried naturally at room tem-
perature.
2.1.3. ZrO2 synthesis and sol preparation
Commercial zirconium acetate solution ZrO-
(CH3 COO)2 (MELâ Chemicals, UK) was used as
the precursor material. The precursor solution was
placed in the autoclave and heated to 220 °C under
autogenous pressure for 2 h. The hydrolysis prod-
uct was a zirconia sol, i.e. colloidal zirconia par-
ticles, suspended in an acid solution. This sol was
then dried in an oven for 8 h at 80 °C and the
resultant powder cake ground to a fine powder
using a mortar and pestle. The powder was then
calcined in an air muffle to 600 °C for 4 h to re-
move any residual zirconium acetate. The powder
was redispersed in an aqueous solution to the re-
quired concentration by ball milling. The calcined
and redispersed sol solution had a pH in the range
of 2–3, indicating that the zirconia sol particles
had retained an adsorbed layer of Hþ ions
throughout the calcining procedure. The pH value
of the ZrO2 sol was adjusted to around 2 using
hydrochloric acid. This stage was also required to
maximise the positive surface charge on the ZrO2
particles to make electrostatic attraction between
the ZrO2 sol and fibre mats.
2.2. Laser diffraction particle size analysis
The particle size distribution of the powders
synthesised was measured using a Coulter LS 230
laser particle size analyser. The main advantage of
this particle size measurement technique for sizing
is that the dispersions or sols can be analysed in a
state very similar to that in which they were pres-
sure filtrated, thus it provides very reliable results
about the degree of agglomeration prior the green
body formation. Hydrothermally synthesised
mullite powders were first dried at 110 °C for 4 h
and then dispersed in deionized water. Ultrasonic
agitation (VCX 600 Ultrasonic) was used in order
to obtain well dispersed and agglomerate-free sus-
pensions. The particle size distribution (number or
volume percent) of the suspension synthesised was
produced by the computer-controlled Coulter LS
230 instrument via a software program.
2.3. Particle characterisation by transmission elec-
tron microscopy
Hydrothermally synthesised powders were pre-
pared for TEM observations. A small amount of
dried powder was dispersed in deionized water in a
ratio of about 10 parts of water to 1 part of powder.
A carbon film of the required thickness was pro-
duced using a ‘‘Speedivac Model 12 E 6/964’’
coating unit. To prepare the carbon film, a glass
slide was cleaned and coated with a thin layer of
liquid soap. The glass substrate was then coated
with a carbon film in the coating unit. The carbon
film on the substrate was subsequently scratched
into squares. When immersed in water, the carbon
film squares on the substrate floated onto the water
surface. The films were removed from the water
and placed on copper grids. Then, a drop of sol
containing the particles was placed onto the carbon
film coated copper grid and dried. The individual
particles were identified by EDX analysis during
TEM. The shape, size and degree of agglomera-
tion, of the particles were observed on: (i) a Philips
CM 20 TEM operating at 200 keV and (ii) a JEOL
4000 FX TEM operating at 400 keV, each equip-
ped with an energy dispersive X-ray analysis
(EDX) unit. Selected area diffraction (SAD) was
used to detect the presence of any crystalline pha-
ses. The chemical composition of the powders
synthesised was quantitatively determined by EDX
analysis using a spot size of 40 nm in diameter.
2.4. Other characterisation techniques
The phase identification of as-produced pow-
ders and sintered compacts was carried out using a
computer controlled X-ray diffractometer (Cu Ka
radiation and nickel filter to remove the Cu Kb
peak, Philips X’Pert, Germany) operated at 40
keV and 30 mA. The diffractometer scanned from
5° to 85° with a scan step of 0.02° 2h and a count
 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49 41

time of 2 s per step. The obtained peaks were

compared with the d-spacing for standard phase
compositions listed in the JCPDS-ICDD archive.
Microstructural examinations on as-produced
powders and sintered samples were also carried
out using a field emission gun SEM (FEG SEM
FX-4000, Jeol Ltd. Japan).Green bodies were
formed using pressure filtration. Comprehensive
information about this technique can be found
elsewhere [19,20].

3. Results and discussion

3.1. Mullite formation

A bright-field transmission electron micrograph

of hydrothermally synthesised mullite þ 5 wt.%
zirconia powders is shown in Fig. 2a. The TEM
micrograph shown in Fig. 2a reveals a more an-
gular particle morphology and as-produced pow-
ders have a porous nature and non-spherical
irregular shapes. The porous nature of the near-
hexagonal shape mullite particles synthesised is
clearly visible from the bright-field TEM micro-
graph shown in Fig. 2a. Additional information on
the type of particle morphology and size is pro-
vided by scanning electron micrographs. The SEM
microstructures of the produced mullite þ 5 wt.%
zirconia powders using a hydrothermal tempera- Fig. 2. (a) Bright-field TEM image of hydrothermally syn-
ture of 170 °C for 2 h are shown in Fig. 2b. As can thesised mullite þ 5 wt.% zirconia powders showing the porous
nature of near-hexagonal shape mullite particles and (b) field
be seen from Fig. 2b, the majority of the particles emission gun SEM micrograph of mullite powders synthesised
are in a highly agglomerated state, and there is a confirming the presence of very fine zirconia particles embedded
wide range of particle size distribution resulting in within mullite particles as pointed with arrows.
the presence of some very fine, 50 nm particles as
well as larger 5 lm particles. It also shows the gated morphology is caused by the presence of a
presence of very fine zirconia particles embedded certain amount of sodium ions in the crystal
within the mullite particles as indicated by the structure, although the reasons for that are not
arrows. This complex mullite morphology has not very clear at the moment [18].
been reported in the literature. However, it is be- The particle size distribution (volume percent)
lieved that the hydrothermal conditions used in of hydrothermally synthesised mullite þ 5 wt.%
this work lead to the formation of a three-dimen- zirconia powders is shown in Fig. 3 and Table 1.
sional tabular morphology resulting from the The cumulative statistics shown in Table 1 for as-
growth of mullite crystallites in different directions produced powders are given as D10 , D25 , D50 , D75
with different particle growth rates. On the other and D90 which indicate the particle sizes which are
hand, it has been shown that the presence of below 10%, 25%, 50%, 75% and 90% of the total
sodium ions may affect the particle morphology, volume of particles analysed, respectively. Particle
and the tendency for particles to adopt an elon- size distribution is a very critical issue in green
42 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49

Fig. 3. Particle size distribution (volume percent) of hydro-

thermally synthesised mullite þ 5 wt.% zirconia powders.

body formation using pressure filtration [19]. A

mixture of coarse, medium and very fine particles,
where sufficient fine particles are present to fill in
the interstices results in a green body compact of
high green density. As shown in Table 1, there are
some very fine particles, as fine as 55 nm, within
the synthesised powders as well as very coarse ones
(7.1 lm).
The SEM microstructure of a pressure filtrated
sample after sintering at 1300 °C for 2 h is shown
in Fig. 4a. A polished and thermally etched (at
1100 °C for 20 min) surface clearly indicates the
presence of the zirconia particles located mostly
inter-granularly within the sintered mullite, as
shown in Fig. 4a. Woven mullite fibre-reinforced Fig. 4. (a) SEM images of sintered, polished and thermally
etched mullite matrix produced from the powders synthesised in
mullite ceramic matrix composites produced using this work showing the size, location and shape of the zirconia
pressure filtration and pressureless sintered at 1200 particles within the sintered mullite matrix (the sample was
°C for 3 h is shown in Fig. 4b. Very tight inter- and produced by pressure filtration and pressureless sintered at 1300
intra-fibre tow regions were successfully infiltrated °C for 2 h) and (b) the sintered microstructure of mullite fibre-
with the synthesised mullite þ 5 wt.% zirconia reinforced mullite ceramic matrix composites obtained from the
hydrothermally synthesised mullite þ 5 wt.% zirconia powders
powders leading to the formation of a crack-free (M: 3:2 orthorhombic mullite, Z: monoclinic zirconia).
composite structure, as shown in Fig. 4b.

3.2. Boehmite formation
3.2.1. Effect of initial solution pH on boehmite
particle morphology
Boehmite sols were synthesised hydrothermally
from the solutions with initial pH values of 2, 4, 6,
8 and 10. TEM BFI micrographs of the boehmite
sol particles are shown in Fig. 5. The majority of
particles are oriented with their faces parallel to
the TEM grid, with only a minority being tilted,
enabling the particle thickness to be determined.
The boehmite particles synthesised under highly

Table 1
Particle size analysis for hydrothermally synthesised mullite þ 5 wt.% zirconia powders by laser diffraction particle size analysis
%< D10 D25 D50 D75 D90 Mean Median
Volume statistics Size (lm) 0.055 0.95 1.74 2.4 7.1 2.65 2.45
 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49 43

Fig. 5. TEM micrographs of hydrothermally synthesised boehmite sols using different initial pH values showing the effect of the pH on
the particle size and morphology: (a) pH 2, (b) pH 6, (c) pH 8 and (d) pH 10.

acidic conditions (pH 2) are elongated, having
cross-section dimensions of about 50 nm and a
cross-section to length aspect ratio of between 1:5
and 1:35, as shown in Fig. 5a. Under these con-
ditions, the particles are easily agglomerated into
large clusters along their longer axes. As the initial
solution pH is increased from 2 to 6, the degree of
agglomeration decreases as a result of decreased
particle size, as shown in Fig. 5b. It should also be
noted from Fig. 5b that the boehmite particle
morphology changes from a lath shape to a hex-
agonal shape. The particle aspect ratio further
reduced gradually, changing the morphology of
the particles from elongated fibrils to hexagonal
platelets, as shown in Fig. 5c and d. At pH values of
8 and 10, the particles exhibited platelet morpho-
logies, with a maximum face dimension of about 40
nm and a thickness of approximately 5 nm with no
particle agglomeration, as shown in Fig. 5d. It can
be concluded from the TEM images shown in Fig.
5 that the effect of the pH of initial solutions on the
boehmite particle morphology is significant. An
elongated particle morphology usually has a dele-
terious effect on the microstructure and hence
the mechanical properties of ceramics because the
random orientations of elongated particles will
not allow dense, uniform particle packing in the
green body state, and therefore in the final sintered
44 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49
product. However, by adjusting the initial solution
pH, the morphology of the hydrothermally derived
boehmite particles can be modified as desired, as
shown in Fig. 5c and d.
The mechanism of crystal growth for boehmite
and the effect of pH on the particle morphology
are not well understood. It has been proposed [21–
25] that the different morphologies observed cor-
respond to different growth mechanisms; direct
crystal growth from solution produces particles
with a well-defined growth morphology, while a
particle coagulation mechanism produces particles
of variable morphology. TEM observations by
Buining et al. [26] indicated that elongated boeh-
mite particles were built up of small sub-units.
They suggested that the process involved particle
coagulation, i.e. very small crystallite units nucle-
ated from the solution first, and then coagulated
into the final fibril structure observed. According
to this view, the balance of attractive and repulsive
interaction forces between the sol particles would
play a very important role in the process of bo-
ehmite particle growth. So, given the generally
significant effect of pH on the zeta potential and
hence dispersion stability of ceramic sols, the rea-
son why the pH affects the boehmite particle
morphology becomes apparent.
The XRD results for the boehmite sols obtained
under different pH values are presented in Fig. 6
indicating that all the samples show boehmite as
the only crystalline phase detected by X-ray dif-
fraction. However, the powders produced using
different initial solution pH values gave XRD
traces in which the order of the relative peak in-
tensities differed from the standard pattern [27].
Fig. 6. XRD patterns of boehmites obtained under different pH
values.
The elongated boehmite particles synthesised using
a starting pH of 2 gave an XRD trace whose peak
intensity order and d-spacing most closely mat-
ched the standard pattern. With higher starting pH
values, the order of the relative peak intensities
differed from the standard pattern, as shown in
Fig. 6 (initial pH values of 6 and 8 produced XRD
peaks as pH values of 4 and 10, therefore their
peaks were not included in Fig. 6). This is most
likely related to the change in boehmite particle
morphology producing varying degrees of pre-
ferred orientation. Furthermore, the intensity of
XRD reflections depends on the degree of crys-
talline perfection; thus, an apparent increase in the
amount of any given phase could just be due to an
increase in the crystalline order. The presence of
any amorphous material may also hinder quanti-
fication of the amount of crystalline phase.
3.2.2. Effect of hydrothermal processing parameters
on particle size
The effects of the hydrothermal processing time
and temperature on the cumulative particle size
distribution of the boehmite synthesised are shown
in Fig. 7a and b, respectively, when using a con-
stant initial solution pH value of 10 and a fixed
precursor concentration of 6 wt.% for both cases.
Assuming that during hydrothermal processing,
the boehmite particles form via a nucleation and
growth mechanism, particle growth rather than
nucleation will be favoured by an increase in
temperature. As shown in Fig. 7a, as the synthesis
time increased from 1 to 10 h (for a fixed pro-
cessing temperature of 200 °C), the median particle
size D50 increased slightly from 71.8 to 75.6 nm.
Thus, as would be expected, a longer synthesis
time results in further particle growth.
It can be seen from Fig. 7b that, as the synthesis
temperature was increased from 200 °C to 300 °C
(for a fixed processing time of 1 h), the median
particle size D50 increased from 71.8 to 78.5 nm.
3.3. Dense a-alumina compacts from seeded boeh-
mite
During thermal treatment, boehmite undergoes
the following transformations to form a-Al2 O3
[28]:
 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49 45

Fig. 8a shows the SEM microstructure of a

boehmite-derived a-alumina sample obtained from
the hydrothermally synthesised boehmite particles
shown in Fig. 5d. A dense alumina microstruc-
ture (relative density is about 99.7%) with sub-
micrometer alumina grains is achieved from the
a-alumina-seeded boehmite after sintering at 1400
°C for 2 h, as shown in Fig. 8a. The dense mi-
crostructure and inter-granular fracture mode of
boehmite-derived alumina is also evident from the
fracture surface shown in Fig. 8b.

Fig. 7. (a) Effect of synthesis time on the particle size distri-

bution of boehmite synthesised at 200 °C using an initial pH
value of 10 and (b) effect of synthesis temperature on the par-
ticle size distribution of boehmite synthesised for 1 h using an
initial pH value of 10.

400 °C 800 °C
c-AlOOH ƒƒƒ! c-Al2 O3 ƒƒƒ! d-Al2 O3
1000 °C 1200 °C
ƒƒƒƒ! h-Al2 O3 ƒƒƒƒ! a-Al2 O3
As a result of the difference in the specific vol-
ume of boehmite (0.332 cm3 /g) and a-Al2 O3 (0.251
cm3 /g), 24 vol% porosity develops in the body after
transformation. The porosity is distributed as pore
channels between the growing a-Al2 O3 dendrites
to form a vermicular microstructure. Tempera-
tures >1600 °C are required for sintering Al2 O3
with high density. Therefore, when using boehmite
as a raw material for the preparation of monolithic
alumina, alumina/particulate or alumina/whisker
composites, the boehmite is seeded with, for ex- Fig. 8. SEM micrographs of (a) unseeded boehmite-derived
ample, particles of TiO2 or a-Al2 O3 ), in order to alumina showing the porous microstructure of the sintered
matrix after sintering at 1400 °C for 3 h and (b) fracture surface
lower the crystallisation temperature, and enhance of seeded boehmite-derived alumina microstructure indicating
densification of a-Al2 O3 with a refined micro- the presence of inter-granular fracture behaviour and also its
structure. dense nature after sintering at 1400 °C for 2 h.
46 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49

3.4. Zirconia formation Fig. 9a are baddeleyite (JCPDS 37-1484) with a

The TEM sol microstructure of hydrothermally
synthesised zirconia particles is shown in Fig. 9a
indicating that most zirconia particles are rounded
with dimensions in the range of 20–60 nm, al-
though some of them are slightly elongated rather
than spherical in morphology. Fig. 9a also shows
that there is no agglomeration within the produced
sol which is a good indication of a stable suspen-
sion microstructure. Fig. 9b shows a TEM EDS
trace from one of the small clusters of particles
shown in Fig. 9a. This trace shows strong peaks
for Zr and O. The peaks for Cu and C arise from
stray scattering of X-rays from the copper grid and
the carbon film, respectively. XRD analysis showed
that the synthesised zirconia particles shown in
monoclinic crystal structure [29].
Fibre coating experiments using dip coating
(detailed information about this technique and its
application can be found elsewhere [29,30]) were
carried out on plain-woven alumina (Almax,
Mitsui Mining Co., Japan) fibre mats. Briefly,
during zirconia coating, the fibre mats were im-
mersed in the ZrO2 sol synthesised under sonica-
tion in an ultrasonic bath or under vacuum
causing the positively charged ZrO2 particles to
adhere to the negatively charged fibre surface. The
immersed fibre mats were extracted to air through
an octanol layer, which is a less dense immiscible
liquid floating above the zirconia sol, to prevent
intra-tow filament adherence. Afterward, the fibre
mats were dried in air and then fired to 600 °C for

Fig. 9. (a) TEM image of hydrothermally synthesised zirconia powders and (b) TEM EDS analysis of the zirconia clusters.
 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49 47

Fig. 10. SEM images of (a) uncoated, (b), (c) zirconia coated almax alumina fibre cloths indicating the suitability of the hydrother-
mally synthesised zirconia powders for ceramic fibre coating using dip coating.

1 h to strengthen the ZrO2 coating layer on the the wetting of the fibres by the ZrO2 sol and
fibre surface. A key factor in the coating process is electrostatic attraction between the fibre surface
48 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49
and ZrO2 sol particles. In this work, the ‘‘in-
house’’ zirconia sol produced by HS was success-
fully used for fibre mats coating. Fig. 10a and b
show SEM images of uncoated and coated (with
zirconia) woven fibre cloths. SEM analysis results
showed that ZrO2 particle infiltrated the tows of
the fibre mat, and surrounded individual fibres, as
shown in Fig. 10b. The light regions around the
fibres correspond to the presence of ZrO2 indi-
cating a coating thickness of approximately 1–2
lm with minimal inter-fibre bridging, as shown in
Fig. 10c. It is concluded from Fig. 10 that hydro-
thermally synthesised nanosize zirconia particles
are effective in coating tightly woven ceramic fibre
cloths using dip coating.
4. Conclusions
(1) Stoichiometric 3:2 mullite þ 5 wt.% zirco-
nia, boehmite and zirconia powders were produced
using low-temperature HS. The hydrothermal
conditions used in this work led to the formation
of near-hexagonal shape mullite powders with a
porous morphology on a nanometer scale. This
particle morphology is considered to be due to the
mullite crystallites that grow in different directions
with different growth rates. Both monolithic and
fibre-reinforced composites were produced using
the synthesised mullite þ 5 wt.% zirconia powders.
(2) For boehmite particles, as the pH of the
initial solution changes from low (acid) to high
(alkaline), the morphology of hydrothermally
synthesised boehmite changes from ‘‘needle-like’’
to ‘‘platelet’’. Under the conditions investigated
here, the synthesis temperature and time in com-
parison with the initial pH value have little ap-
parent effect on the boehmite particle size. The
boehmite particles synthesised under highly acidic
conditions (pH 2) are elongated, having cross-sec-
tion dimensions of about 50 nm and a cross-section
to length aspect ratio of between 1:5 and 1:35,
whereas the particle aspect ratio further reduced
gradually, changing the morphology of the parti-
cles from elongated fibrils to hexagonal platelets
when the pH is increased to 8 or 10. At pH values
of 8 and 10, the particles exhibited platelet mor-
phologies, with a maximum face dimension of
about 40 nm and a thickness of approximately 5
nm and there is no particle agglomeration. The
synthesised nanosize boehmite particles are used to
produce high-density (>99% of theoretical density)
monolithic ceramics with a sub-micrometer grain
size.
(3) Near-spherical shape monoclinic zirconia
particles with dimensions in the range of 20–60 nm
were also hydrothermally produced. The resultant
zirconia particles dispersed in distilled water were
used to coat tightly woven fibre cloths using dip
coating. It was found that the ZrO2 particles infil-
trate the intra-tow regions of the fibre mat, and
surround the individual fibres with a coating
thickness of approximately 1–2 lm and with min-
imal inter-fibre bridging.
Overall, the successful application of the
synthesised powders in the field of mesoporous
fibre-reinforced ceramic composites, high-density
monolithic ceramics and ceramic fibre coatings
(formation of weak inter-phase between fibre and
matrix) was demonstrated.
Acknowledgements
Helpful discussion with Dr. K.C. Chan from
3M is gratefully acknowledged.
References
[1] I.A. Aksay, D.M. Dabbs, M. Sarikaya, J. Am. Ceram. Soc.
74 (1991) 2343.
[2] O. Chusid, Y. Ein Ely, D. Aurbach, J. Power Sources 43
(1993) 47.
[3] K. Okada, N. Otsuka, J. Am. Ceram. Soc. 69 (1986) 652.
[4] P.K. Sharma, M.H. Jilavi, D. Burgard, R. Nass, H.
Schmidt, J. Am. Ceram. Soc. 81 (1998) 2732.
[5] P. Murugavel, M. Kalaiselvam, M.K. Renganathan, A.R.
Raju, Mater. Chem. Phys. 53 (1998) 247.
[6] W.C. Wei, J.W. Halloran, J. Am. Ceram. Soc. 71 (1988)
581.
[7] J.C. Hulling, G.L. Messing, J. Am. Ceram. Soc. 74 (1991)
2374.
[8] J. Pascual, J. Zapatero, M.C.J. de Haro, A.J.R. del Valle,
J.L. Perez-Rodriguez, P.J. Sanchez-Soto, J. Am. Ceram.
Soc. 83 (2000) 2677.
[9] G. Pfaf, J. Eur. Ceram. Soc. 12 (1993) 159.
[10] K. Yanagisawa, C.P. Udawatte, S. Nasu, J. Mater. Res. 15
(2000) 1404.
 C. Kaya et al. / Microporous and Mesoporous Materials 54 (2002) 37–49
[11] J.R. Dahn, R. Fong, M.J. Spoon, Phys. Rev. B 42 (1990)
6424.
[12] A. Douy, J. Eur. Ceram. Soc. 7 (1991) 117.
[13] A. Ataie, I.R. Harris, C.B. Ponton, J. Mater. Sci. 30 (1995)
1429.
[14] A. Ataie, M.R. Piramon, I.R. Harris, C.B. Ponton, J.
Mater. Sci. 30 (1995) 5600.
[15] M.G.M.U. Ismail, H. Tsunatori, Z. Nafai, J. Am. Ceram.
Soc. 73 (1990) 537.
[16] S. Hirano, S. Somiya, J. Am. Ceram. Soc. 59 (1976) 534.
[17] D.E. Collins, E.B. Slamovic, J. Mater. Res. 15 (2000) 1834.
[18] I. Maclaren, C.B. Ponton, J. Mater. Sci. 33 (1998) 17.
[19] C. Kaya, Processing and properties of alumina fibre-
reinforced mullite ceramic matrix composites, Ph.D. The-
sis, June 1999, The University of Birmingham, UK.
[20] C. Kaya, X. Gu, I. Al-Davery, E.G. Butler, Sci. Technol.
Adv. Mater. 3 (2002) 35.
49
[21] J.C. Hulling, G.L. Messing, J. Non-Cryst. Solids 147
(1992) 213.
[22] Y. Wang, W.J. Thomson, J. Mater. Res. 10 (1995) 912.
[23] D.X. Li, W.J. Thomson, J. Am. Ceram. Soc. 73 (1990) 964.
[24] C. Kaya, F. Kaya, P.A. Trusty, J. Mater. Sci., submitted
for publication.
[25] T. Sugitomo, E. Matijevic, J. Colloid Interf. 74 (1980) 81.
[26] P. Buining, C. Pathmamanoharan, J. Jansen, H. Lekker-
kerker, J. Am. Ceram. Soc. 74 (1991) 1303.
[27] JCPDS-ICDD Standard (1997) 21-1307.
[28] R. Bagwell, G. Messing, J. Am. Ceram. Soc. 82 (1999) 825.
[29] X. Gu, P.A. Trusty, E.G. Butler, C.B. Ponton, J. Eur.
Ceram. Soc. 20 (2000) 675.
[30] C. Kaya, E.G. Butler, A.R. Boccaccini, M.H. Lewis, in: W.
Krenkel, R. Naslain, H. Schneider (Eds.), High Temper-
ature Ceramic Matrix Composites, Wiley-VCH, Weinheim,
2001, p. 639.