August 1996

EISEVIER Materials Letters 27 (1996) 287-292

A colloidal approach to nanometre-sized mixed oxide ceramic

powders
Horst Herrig, Rolf Hempelmann *
Uniuersitiit des Saarlandes, Institutftir
Physikalische Chemie, Posrfach 151150. 66041 Saarbriickrn. Germany

Received 10 November 1995; accepted 15 November 1995

Abstract

Binary metal oxides (TiO,, ZrO,) and ternary metal oxides (BaTiO,, BaZrO,, SrTiO,, SrZrO,) have been prepared as
nanometre-sized particles using a microemulsion mediated method. A detailed description of the synthesis is given. Electron
micrographs and X-ray diffraction were used to determine average particle size, morphology and crystallite size distribution.

Keywords: Metal oxides; Binary; Ternary; Synthesis; Microemulsion; Nanoporticles

-

1. Introduction technique is the ability to restrict reactions in a wet

chemical system to the so called “nanoreactors” of
Nanoscale particles are of interest for fundamental reversed micelles. Precipitated material in such com-
as well as applied research because many material partments can conserve the two most important prop-
properties change drastically if the crystallite sizes erties of the nanodroplets - subp-size and monodis-
reach the submicron range [1,2]. Impressive exam- persity - and thus the tailoring of fine particles is
ples are the significant lowering of sintering temper- possible. Numerous authors have reported about syn-
atures of ceramic powders or the increased mechani- thesis in microemulsions. Kumar et al. used the
cal strength of ceramic components due to improved mixing, of two microemulsions loaded with metal
homogeneity and controlled particle size distribution salt solution and oxalate solution for the coprecipita-
in green bodies [ 1,3-61. Particularly for materials of tion of Bi-Pb-Sr-Ca-Cu-0 oxide [9]. Pathak and
the perovskite ABO, class some properties such as Chen performed their precipitation reactions with
ferroelectricity, permittivity or even structure are microemulsions containing ammoniumcarbonate or
strongly related to the crystallite size [7,8]. citrate solutions [ IO,1 I]. Burgard et al. produced
In our study, the promising microemulsion method ZrO,/Y,O, mixed oxide particles by bubbling am-
was used to prepare nanoscale perovskite particles. monia through a microemulsion carrying ZrO(NO,),
Microemulsions for the preparation of oxide and and Y(NO,), [3]. Sager et al. used in a related
mixed oxide particles are well known since the end method the in situ generation of ammonia out of
of the last decade. The essential feature of this urotropine for preparing Fe(OH), particles [12].
Comprehensive reviews concerning wet chemical
small size particle synthesis are given by Phule and
* Corresponding author. Risbud (sol-gel-, citrate-, alkoxide-route) [ 131 and

00167-577X/96/$12.00 Copyright 0 1996 Elsevier Science B.V. All rights reserved

PII SO1 67-577X(96)0001 1-O
288 H. Herrig, R. Hempelmann/Materials Letters 27 (19961 287-292

Osseo-Assare and Arriagada (microemulsion medi- Z&prop), and Ti(nprop), from Aldrich (commer-
ated synthesis) [ 141. cial grade), and Brij 30 ‘” (polyoxyethylene-(4)
In this article we present a microemulsion medi- laurylether, commercial grade) from Aldrich. Analyt-
ated sol-gel process for processing nanometre-sized ical grade acetone, cyclohexane and isopropanol were
ceramic particles. Ceramics may be binary metal purchased from Merck. All solvents were dried with
oxides (TiO,, ZrG,) or ternary metal oxides molecular sieves before use. Water was ion-ex-
(BaTiO,, BaZrO,, SrTiO,, SrZrO,). The synthesis changed and active-coal filtered.
produces ultrafine particles stabilized as colloid in an
organic solvent and, after calcination, nanoscale 2.2. Synthesis
powders. The microemulsions used for this work
consisted of cyclohexane, water and polyoxyethy- (See also Table 1, 2 and 3 and the flow chart in
lene-(4)-laurylether (Brij 30’“) ICI). Reactions were Fig. 1.)
performed by adding the microemulsion to a metal
2.2. I. Microemulsions
alkoxide solution as proposed by Osseo-Assare et al.
The microemulsions were prepared by mixing
[14] or to a mixture of metal alkoxides as recently
Brij 30’” with cyclohexane and adding water with a
demonstrated by Schlag et al. [15]. The water con-
microsyringe. The water-clear appearence of the
tents in our microemulsions were adjusted to values
mixture upon vigorous stirring indicated the forma-
below 0.1 ~01% in view of the discussions of Guizard
tion of the microemulsion.
et al. [16] for such hydrolysis reactions.
2.2.2. Metal alkoxide solutions
2. Experimental procedure The reactions were performed under an inert gas
atmosphere of N, 5.0 which had been further dried
2.1. Chemicals by bubbling through concentrated H, SO,. In a 3-
necked reaction vessel equipped with gas inlet, re-
Barium and strontium were purchased from Her-
flux condenser and dropping funnel the metal was
aeus (commercial grade, under mineral oil),
placed under isopropanol and refluxed at 125°C until
solving. After vehement reaction under H, develop-
ment, the mixture appeared as a transparent reddish-
metallic solution, sometimes with white or grey sedi-
ments due to impurities of metal hydroxide.

2.2.3. Precipitation
The mixture was cooled to room temperature, and
equimolar amounts of Ti(nprop), (10% excess) or
Zr(nprop), (5% excess), respectively, were added
through the dropping funnel under stirring. Immedi-
ately thereafter the microemulsion was poured into
the vessel. A slow adding, e.g. dropwise, would lead
to a polycondensation reaction between the metal
alkoxides followed by gelation. After the addition of
the microemulsion the transparent clear solution was
stirred for 15 min. In that time the precipitation of
raw perovskites occurred invisibly for the naked eye
within the mixture.

2.2.4. Isolating the crude material

The solution was filtered to remove sediments, if
Fig. 1.Flow chart of all steps involved in the synthesis. necessary. Alcohols, cyclohexane and water were
 H. Herrig, R. Hempelmann/ Materials Letters 27 (1996) 287-292 289

evaporated at 60°C under vacuum to give an oily Table 2

Preparation of ternary metal oxides without calcination
transparent residue which was taken up with 120 ml
of acetone and heated to 60°C resulting in the precip- Products BaTiO? SrTiO?

itation of a yellow, quickly sedimenting fluffy stuff. Alcoholic n-propylotthotitanate n-propylorthotitanate

The precipitate was repeatedly washed by the use of alkoxide isopropanol cabs.1 isopropanol (abs.)
solution vol. ratio 1 : 1 vol. ratio 1 : 1
a table centrifuge and acetone. A better way of
purification proved to be one day’s soxhlet extrac- Metals 10 g barium 10 g strontium
tion of the sedimented material with cyclohexane. isopropanol (abs.) isopropanol cabs.)
mol. ratio 1:lO mol. ratio 1: 15

2.2.5. Sintering Microemulsion 50 ~1 water 50 ~1 water

6 g Brij 30” 6gBrij30’”
Sintering served to bum out the residues of the
36 ml cyclohexane 36 ml cyclohexane
organic solvents and detergents still attached to the
raw material after purification. Furthermore, the state Sintering no calcination 1h/7OO”C for
of crystallization and the resulting phases could be conditions purification

influenced by the choice of the sintering conditions. Resulting average 9 nm 18 nm

The burnout was performed in a laboratory tube crystallite size
furnace equipped with temperature programming.

2.3. Characterization 2.3.2. Electron microscopy

The SEM pictures were taken using a JEOL
2.3.1. X-ray diffraction JXA-840A scanning electron microscope of the as-
The average size determination of crystailites was prepared calcined powders. The TEM record was
performed using Scherrer’s equation [17] for the line made on a JEOL JEM 200CX transmission electron
broadening of XRD profiles by small crystallites. All microscope by drawing a copper net through the
samples were measured at room temperature on a calcined powder containing dispersion and drying
Siemens D500 diffratometer as powder without pre- the net at ambient temperature. Polyacrylic acid as
vious grinding in a flat hollowed plastic sample steric stabilizer and ultrasonication were used to
holder. Radiation was Cu Ka, the sampling condi- disperse the particles in water at pH 11.
tions were a scan in steps of 0.02 deg with a step
time of 2 s.
Table 3
Preparation of ternary metal oxides with calcination
Products BaZrO, SrZrO,
Table 1 Alcoholic n-propylortho- n-propylottho-
Preparation of binary metal oxides alkoxide zirconate zirconate
Products TiO solution isopropanol cabs.) isopropanol cabs.)
2 ZQ
vol. ratio 1 : 1 vol. ratio 1 : 1
Alcoholic n-propylorthotitanate n-propylorthozirconate
alkoxide isopropanol cabs.) isopropanol (abs.) Metals logbarium 10 g strontium
solution vol. ratio 1 : 1 vol. ratio 1 : 1 isopropanol cabs.) isopropanol cabs.)
mol. ratio 1:lO mol. ratio 1:lS
Microemulsion 50 p,l water 50 ~1 water
6 g Brij 30’” 6gBrij30’” Microemulsion 50 p,l water 50 p,l Water
36 ml cyclohexane 36 ml cyclohexane 6gBrij30” 6gBrij30”
36 ml cyclohexane 36 ml cyclohexane
Sintering 6 h/6OO”C 6 h/4OO”C
conditions for target phase for target phase Sintering 1 h/8OO”C for 1 h/9OQ”C for
formation formation conditions formation formation

Resulting average 10 nm 8 nm Resulting average 11 nm 19 nm

crystallite size crystallite size
 mw mater
A

cakined 1 h 600’

n A

calcined 1h 700’1

A A ^ A, n A

20 40 60 40 60 80

2% [“I

cakined 1h 6OO’C

calclned 1h 700°C

calcined 1h 700-C
h

caltined 1h 800-C
A

20 40 60 80 I 40 60 80

20 [“I 20 ["I
Fig. 2. XRD patterns of perovskite phase formation. (a) Barium titanium oxide formation; the pure perovskite phase forms without calcination, the profile matches the
JCPDS-File 31 174. (b) Strontium titanium oxide formation (I) and (2) show SrTiO, with impurities of &CO, and ZrO,, the profile of (3)matches the JCPDS-File 35 734. (c)
Barium zirconium oxide formation (1) and (2) show mixtures of BaZrO,, BaCO, and ZrO,, (3) depicts BaZrO, with impurities of BaCO, and ZrO,, the profile of (4) matches
the JCPD S-File 6 399. (d) Strontium zirconium oxide formation: (I) and (2) show mixtures of SrZrO,, &CO, and ZrO,, (3) and (4) depict SrZrO, with impurities of SrCO,
and ZrO,, the profile of (5)matches the JCPDS-File IO 268.
 H. Herrig, R. Hempelmann / Materials Letters 27 (1996) 287-292 291

3. Results and discussion

Table 1, Tables 2 and 3 give a summary of the

starting materials used for synthesis. The sintering
conditions and the resulting average crystallite sizes
are also presented.
We found that the velocity of hydrolysis could be
strongly affected by the water contents of the mi-
croemulsion. If the water content exceeded 0.7 ~01%
we could observe immediate hydrolysis resulting in
pasting up the reaction mixture to a solidifying gel.
The same course of reaction could be obtained by
simply adding 20 ml of water to the mixture of metal
alkoxides. Nevertheless, powders prepared in this
manner exhibited nanometre-sized crystallites after
calcination. The latter case of fast hydrolysis has
been described by Schlag et al. [151.
Fig. 2a-2d show the XRD-patterns of raw and
calcined perovskite powders, corresponding to vari-
ous firing times and temperatures. Significant differ-
ences in the conditions leading to the target com-
pounds were visible. BaTiO, and SrTiO, could be
obtained directly from the microemulsion reaction;
the latter needed a thermal treatment to transform the
impurities of &CO, and ZrO, into the perovskite. In
case of BaZrO, and SrZrO,, the raw powders were
intimate mixtures of barium (or strontium) carbonate
and zirconium oxide, which had to be calcined to
form the pure perovskite phase in a solid state
reaction. Fig. 3a shows in an SEM record the parti-
cles of BaTiO, after calcination for 6 h at 600°C.
The material looks strongly agglomerated with pri-
mary particle sizes around 20 nm.
For Fig. 3b the material of Fig. 3a was treated
with polyacrylic acid as a steric stabilizer and dis-
persed in water at pH I I using ultrasonication. Thus,
the state of aggregation could be drastically reduced,
as can be seen from this TEM record.
Fig. 4 shows the crystallite size distribution of a
BaTiO, powder determined using XRD and the
method of Warren/Averbach [18]. The sample was
calcined for 1 h at 600°C. A good fit could be
obtained with the lognormal function

1’
Fig. 3. SEM and TEM micrographs of BaTiO, powders. (a) SEM
records at different magnifications of a BaTiO, sample which was
1 calcined for 6 hours at 600°C. (b) TEM record of the same
P(L)= LGLlno exp BaTiO, powder dispersed in water at pH I I using polyacrylic
acid as steric stabilizer.
292 H. Herrig, R. Hempelmann/Materials
In
Model: lo&mm
.
P 9.2,.Y16
* Reilcxer:
100/200,L:grainsize
d lb 26 36 46
L(nm)
Fig. 4. Crystallite size distribution of a BaTiO, sample according
to Warren/Averbach; the powder was calcined 1 h at 600°C.
where the parameters lo and o describe the median
and the width of the distribution. The values of 9.2
nm for the median and only 1.6 nm for the width
indicate the narrow size distribution of the sample.
4. Conclusions
Nanoscale binary and ternary metal oxides could
be prepared using the hydrolysis of metal alkoxide
mixtures by microemulsions containing water; the
synthesis of TiO,, ZrO,, BaTiO,, BaZrO,, SrTiO,
and SrZrO, showed significant differences in the
conditions that led to the target compounds.
The formation of BaTiO, and SrTiO, took place
in a wet chemical precipitation reaction without cal-
cination; to the best of our knowledge, this is the
first low temperature generation of well crystallized
barium titanate and strontium titanate by the mi-
croemulsion route.
XRD techniques were employed to estimate the
average crystallite size of all materials in the size
range of 8 to 19 nm. SEM and TEM micrographs of
BaTiO, particles showed that sintering of the crude
material led to strongly agglomerated structures
which could be deagglomerated by using polyacrylic
acid as a steric stabilizer in water dispersions. The
very narrow crystallite size distribution of a BaTiO,
powder which was calcined for 1 h at 600°C could
be described with a lognormal function.
Letters 27 (1996) 287-292
Acknowledgements
We thank H. Natter for evaluating the size distri-
bution, Dr. Th. Krajewski, Intitut fur Neue Mater-
alien (INM), Saarbriicken, for his skilled support in
electron microscopic work and Dr. R. Nass (LNM)
for fruitful discussions. This work has been sup-
ported by the Deutsche Forschungsgemeinschaft
within the Sonderforschungsbereich SFB 277
5b
“Grenzfllchenbestimmte Materialien” at the univer-
sity of the Saarland and this financial support is
gratefully acknowledged. In addition, RH thanks the
Fonds der Chemischen Industrie for generous sup-
port.
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