Vol, 12 No. 3 J. CENT. SOUTH UNIV. T E C H N O L . Jun.

2005

Article ID: 1005 - 9784(2005)03 - 0243 - 03

Preparation and structure characteristics of nano-BizO3 powders

with mixed crystal structure ®
LI W e i ( ~ TJ)
(State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China)

Abstract. The nano-Bi20a powders were prepared by a chemical precipitation method with B i ( N O a ) 3 , HNOa and
NaOH as reactants. The structural characteristics and morphology of nano-Biz Oa powders were investigated by X-
ray diffraction and transmission electron microscopy, respectively. The results show that under the optimum condi-
tion that 300 g / L Bi(NO3 )a reacts at 90 °C for 2 h, the Bi2Oa powders with 60 nm on the average and 9 9 . 5 ~ in puri-
ty are obtained. The prepared nano-Bi2 O3 powders contain a mixed crystal structure of monoclinic and triclinic in-
stead of traditional structure of monoclinic a-Bi2 O3. And the mixed crystal structure is stable in air. The reason for
the appearance of the mixed crystal structure may be that the ionic radius ratio of Bi3+ to O z- changes easily during
the formation of nano-Biz O3 particles by a chemical precipitation method.
Key words, nano-BizOa powders; chemical precipitation method; mixed crystal structure
CLC number: TB34; TB39 Document code: A

1 INTRODUCTION were prepared by the chemical precipitation meth-

The five kinds of characteristic phases of
BizOa are a-, /3-, y-, 8-, and o)-phases. Among
them, the monoclinic a-phase and cubic a-phase are
a low-temperature stable phase and a high-temper-
ature stable phase, respectively. The others are
metastable phases at high temperature E>a?. Each
phase obtains a distinct crystal structure and some
physical properties (electrical, optical, photoelec-
trical, etc. ). For example, at 300 K, the band gap
of monoclinic a-Biz Oa is 2.85 eV, while that of tet-
ragonal/?-phase is 2.58 eV E47. Owing to the pecul-
iar characteristics, BizOa powders are used in vari-
ous fields, such as microelectronics, electrolyte
materials, sensor technology, optical coatings,
transparent ceramic glass manufacturing, super-
conductive material and catalyst, etc ES?.
Compared with several conventional synthesis
techniques, such as solid-state synthesis, sol-gel
and hydrothermal methods, the chemical precipita-
tion method for preparing nano powders has many
advantages, such as well-controlled morphology
and particle size. Nano-Bi~Oa powders prepared by
chemical precipitation method under a wet-process
circumstance have many excellent properties, such
as a high activity, a high purity and a narrow parti-
cle size distribution. And they can be fabricated to
high quality functional ceramics and catalyst.
In this paper, the nano-Bi203 powders with a
mixed crystal structure of monoclinic and triclinic
od, and the nucleation and growth mechanisms of
nano-BieOa powders were analyzed.
2 EXPERIMENTAL
The solutions of Bi (NO3)3 and HNO3 were
mixed uniformly with a stirrer in a certain propor-
tion. A solution of NaOH was quickly added into
the mixed solution with a filling capacity of 800//00.
By the chemical precipitation method, the synthe-
sis of Bi203 was conducted at different concentra-
tions of Bi (NO3)3 and reaction temperatures for
different reaction time. The concentrations of
Bi(NO3)3 are 100, 200, 300 and 400 g / L , respec-
tively. The reaction temperatures are 70, 80, 90
and 100 °C, respectively. And the reaction times
are 1, 2, 3 and 4 h. And then the products were
filtered, washed with de-ionized water to NO 3
tested to be qualified, and dried at 60 °C in a vacu-
um drier.
The crystal phase of the product was deter-
mined by X-ray diffraction (XRD, Rigaku Model
D/max2550VB + 18 kW) with CuKa radiation at
40 kV and 300 mA. The morphology and grain size
of the synthesized Biz O3 powders were observed by
transmission electron microscopy ( T E M , Hitachi-
800). The size distribution was analyzed with laser
size analysis equipment (Mastersizer2000). The
purity of Bi20a was determined by a chemical titra-
tion method.

® Foundation item.. Project (2003AA305820) supported by the National High Technology Research Plan of China
Received tiate: 2005 - 01 - 27 ~ Accepted date.. 2005 - 03 - 28
Correspondence= LI Wei, PhD; Tel.. + 86-731-8836043 ~ E-mail: 973@mail. csu. edu. cn
 • 244 • Journal CSUT
3 RESULTS AND DISCUSSION
The influences of reaction temperature, reac-
tion time and concentration of Bi (NOa)3 on the
particles size and the yield of Bie03 were investiga-
ted under different conditions. From the orthogo-
nal experimental results, it can be seen that the
concentration of B i ( N O a ) 3 , the reaction tempera-
ture and the time are the most important factors
that influence the grain size and the yield and puri-
ty of products, respectively. Under the optimum
condition that 300 g / L Bi(NOa)3 reacts at 90 °C for
2 h, the Bi203 powders with about 60 nm on an av-
erage and 99.5 G in purity can be obtained. Fig. 1
is the XRD patterns of Biz03 powders.
(a)
- Monoclinic
-
o-- Triclinic
t, ~ • •
20 30 40
20( ° )
(b)
- -
Z*
20 30 40
20( ° )
Fig. 1 XRD patterns of BizO3 powders
prepared by different methods
(a) By optimum chemical precipitation method;
(b) By common method
T h e XRD patterns (Fig. 1 ( a ) ) reveals that
some of the diffraction peaks can be readily as-
signed to a-BizOa. It is indicated that the Bi2Oa
powders consist of monoclinic structure. T h e lat-
tice parameters for the monoclinic BizOa are deter-
mined to be a = 0 . 584 8 nm, b = 0 . 816 6 nm, c =
Vol. 12 No. 3 2005
0. 751 0 nm a n d / 3 = 113 °. Others peaks can be in-
dexed as the new triclinic crystal structure Bi2Oa,
which is stable in the ambient condition and does
not belong to any of a-, fl-, y - , & , and co-BizOa.
T h e lattice parameters for the new triclinic Bi2Oa
are as follows: a = 0 . 726 9 nm, b = 0 . 8 6 3 9 nm, c =
0 . 1 1 9 7 n m and a = 8 7 . 714 ° , / 3 = 9 3 . 227 °, y =
86. 653 °. The proportions of monoclinic and tri-
clinic BiEOa are 4 6 . 3 2 % and 5 3 . 6 8 ~ , respective-
ly. T h e XRD pattern indicates that the product is
highly pure BizO3 with a mixed crystal structure of
monocline and triclinic under the current synthetic
conditions.
In the crystal a-Bi2Oa, there are two kinds of
nonequivalent Bi a+ both with a distorted octahedral
coordination. T h e character of highly polarizable
6s z lone pair of Bi 3+ that is dominant in a-Bi2Oa at
the atmosphere conditions may reduce the local site
s y m m e t r y of structure and govern the property of
the compounds E6'77. During the formation of nano-
Bi2Oa powders by a chemical precipitation method,
nano-BizO3 powders stand great pressure Es?. T h e
nano powders are so small that the atoms diffuse
quickly and the relative displacement and sliding
resistance become smaller along the boundary of
grain. T h e r e f o r e , the great force can change the
ionic radius ratio of Bi 3+ to O z-. It is an important
factor leading to the transition of BizOa from mon-
oclinic to triclinic.
50 60 On the other hand, nano powders have some
characters, such as big specific surface area, insuf-
ficient coordinating atoms and high surface energy.
So their surface tension is enhanced with the de-
Monoclinic
crease of grain size. Moreover, the numbers of
atoms on the nearest surface are less than that in
the body, which leads to the declining of repulsive
force of the non-band electron pair. All of these
will lead to the distortion of lattice, especially on
the surface layer Eg?. When the triclinic BizO3 is
about 50 ~ , the interior of lattice tends to balance,
Bi203 with the monoclinic and triclinic crystal
structure become more stable.
The microstructures of Bi203 prepared under
the optimum condition are shown in Fig. 2(a). It is
50 60 found that the as-prepared powders are non-
agglomerated sphere Bi203 with about 60 nm in
grain size. Fig. 2 ( b ) shows the microstructures of
Biz03 powders after being stored in the air for six
months. It is found that the microstructure and the
grain size of Bi203 powders are similar to those in
Fig. 2 ( a ) , which indicates that the products have
excellent storage stability.
Additionally, it can be found that the synthe-
sis of the nano-Biz Oa is affected also by concentra-
tion O H - . The reactions are as follows.
Bi (NOa)3 --* BiONOz --* Bi ( OH)3, -" . . . . .
Bi(OH)3--*Bi(OH) 2+--*Bi(OH) 2+__,Bi2 03.