Physica C 200 (1992) 31-42
North-Holland
PHYSICA
Characteristics of Bi-Pb-Sr-Ca-Cu-O powders produced by aerosol
decomposition and their rapid conversion to the high-Tc phase
Timothy L. Ward, Shirley W. Lyons and Toivo T. Kodas
Centerfor Micro-Engineered Ceramics, Department of Chemical and Nuclear Engineering, Universityof New Mexico,
Albuquerque, NM87131, USA
Jorulf Brynestad, Donald M. Kroeger and Huey Hsu
Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN 37831, USA
Received 30 January 1992
Bi---Pb-Sr-Ca-Cu-O powders were produced by aerosol decomposition of nitrate solutions. The effects of reactor temperature
and residence time on particle morphology and evaporative Pb loss from particles were demonstrated, and conditions necessary
to control Pb loss established. Pb loss was roughly proportional to residence time, and minimal loss occurred with short residence
times (3s) and T< 800 °C. Particles produced at 700 °C typically contained significant porosity, while those produced at T> 800 °C
were solid. Mixtures of the Bi2Sr2CuOy (2201 ) and Bi2Sr2CaCu2Oy (2212 ) phases were produced at 700-900 °C in nitrogen and
air. However, after heating in air for 16 h at 850°C, pellets of powder produced at 700°C with nominal composition
Pb0.44BiLsSr2Ca2.2Cu3Oy converted to approximately 79 vol.% of the Bi2Sr2Ca2Cu3Oy (2223) phase and displayed a T~ (onset)
of 110 K. Rapid conversion to 2223 was promoted by powder synthesis conditions, leading to controlled Pb loss and a homoge-
neous fine-grained dispersion of mixed-oxide precursor phases within particles.
1. Introduction
The Bi-Sr-Ca-Cu-O (BSCCO) family of super-
conducting compounds has received a great deal of
attention since the first reports of a transition tem-
perature (To) exceeding 100 K with a BSCCO com-
position [ 1,2 ]. The great interest in these materials
stems from the higher Tc, better atmospheric stabil-
ity [ 1 ], and potential processing advantages, such as
ability to melt-process, relative to YBa2CuaOT_x
[3,4 ]. Three superconducting phases with compo-
sition Bi2Sr2Ca,_ iCu,Oy have been identified; 2201
(n= 1 ), 2212 (n=2) and 2223 (n=3) with T¢= 10,
85 and 110 K, respectively [ 5 ]. Synthesis of mate-
rial with a large volume fraction of the high-T¢ phase
(2223) has proven to be difficult, requiring long sin-
tering times [ 6 ] within a narrow temperature range
which is sensitive to 02 partial pressure [ 7 ]. Partial
substitution of Pb for Bi was first reported by Tak-
Author to whom correspondence should be addressed.
ano et al. [ 6 ] to promote the formation and/or sta-
bility of the high-Tc phase, and led to studies of Pb
doping as a means of obtaining 2223 in higher purity
with less effort.
Solid-state reaction techniques have several dis-
advantages for the synthesis of complex multicom-
ponent oxides such as BSCCO, one being that it is
difficult to obtain chemically homogeneous material
because of transport limitations in the solid state.
These inhomogeneities can result in extremely slow
kinetics for 2223 formation, making it difficult to
form the high-To phase in high phase purity. Endo et
al. [7] reported that co-decomposition of nitrate
precursors produced a uniform mixture of cations
which shortened the reaction time necessary to pro-
duce the high-To phase. A considerable enhancement
in the formation rate of the high-To phase during
powder calcination using spray-dried nitrate precur-
sor powder has also been reported [ 8 ].
We have been investigating the use of aerosol de-
composition to produce chemically homogeneous
0921-4534/92/$05.00 © 1992 Elsevier Science Publishers B.V. All fights reserved.