J Am Ceram Soc, 73 [7] 1965-72 (1990)
Phase Composition and Compatibilities in the
Bi-Sr-Ca-Cu Quaternary Oxide System at 800°C in Air
Byungsun Hong, Joon Hahn, and Thomas 0. Mason*
Department of Materials Science and Engineering and Materials Research Center,
McCormick School of Engineering and Applied Science, Northwestern University,
Subsolidus phase relations in the system (Bi-Sr-Ca-Cu)-0 at
800°C were investigated via powder X-ray diffraction and
electron probe microanalysis of solid-state reaction prod-
ucts. Two recently reported (Bi-Sr-Ca)-0 phases were de-
tected in quaternary assemblages and had the approximate
cation stoichiometries of 9115 and 825. The only truly qua-
ternary compound detected is the superconducting phase
with the cation stoichiometry 2212. Tie lines, tie triangles,
and compatibility tetrahedra involving this phase and the
2201 superconducting phase were determined. Both super-
conducting compounds exhibit small but detectable Sr-to-Ca
solubility and are Sr-deficient with respect to the "ideal'' for-
mulas. [Key words: superconductors, phases, composition,
phase diagrams, solid solutions.]
I. Introduction
F OLLOWING the discovery of =6 to 9 K superconductivity in
the (Bi-Sr-Cu)-0 system,lP2additional superconductors
with =80 to 85 K and =lo5 to 110 K transition temperatures
were obtained in the (Bi-Sr-Ca-Cu)-0 ~ y s t e m .The ~ 110 K
phase now known to have a 2223 Bi:Sr:Ca:Cu stoichiometry,
requires additional stabilizing elements, e.g., Pb, andlor high-
temperature (melt) processing for its f ~ r m a t i o n .Recently,
~ In the (Sr-Cu)-0 system, Teske and Miiller-Buschbaum re-
the 80 K phase, now known to have a 2212 stoichiometry,
was found to have a 98 K transition temperature when
heavily doped with Li.' These two phases therefore have the
highest known transition temperatures to date except for the
thallium-based superconductors.
In spite of numerous works concerning synthesis of the
2212 and 2223 (Bi-Sr-Ca-Cu)-0 superconductors and a few
studies of superconductor phase compositions, the authors are
unaware of any systematic studies of overall phase composi-
tions and compatibilities in this important quaternary oxide
system. Several versions of the (Bi-Sr-Cu)-0 ternary diagram
have been published6-8 and these provided a basis for the
present study.
The goals of the present study were to determine the stable
solid phases in the (Bi-Sr-Ca-Cu)-0 system with special at-
tention to the reported superconducting phases, 2201 (9 K),
2212 (80 K), and 2223 (110 K), to establish the approximate
compositions of each phase in the system and to determine
the equilibrium compatibilities between phases in the quater-
nary diagram. An issue of particular importance to the defect
chemistry of the superconducting phases is solid solubility.
The present study also sought to establish whether or not the
H. OBryan, Jr. -contributing editoi
Manuscript No. 197940. Received November 27,1989; approved March 21,
1990.
Supported by and carried out largely in facilities of the Northwestern Uni-
versity Materials Research Center under National Science Foundation
Grant No. DMR-88.
*Member, American Ceramic Society.
1965
Evanston, Illinois 60208
superconducting phases exhibited compositional variations,
i.e., solid solubility.
11. Background
We will represent the quaternary system (Bi-Sr-Ca-Cu)-0
as a tetrahedron with 95 BiZO3, SrO, CaO, and CuO at the
corners. Before approaching quaternary phase relationships,
it is necessary to review what is known about binary equi-
libria (the six edges of the tetrahedron) and ternary equilibria
(the four faces of the tetrahedron). The experimental tem-
perature of 800°C was selected for two reasons. First, the
phase relations in the (Bi-Sr-Cu)-0 are best known for this tem-
perature.6 Second, at much higher temperature considerable
melting OCCUTS.~(Even at 800°C melting occurs for Bi-rich
compositions.)6
(Bi-Cu)-0 is the simplest of the six binary diagrams. Only
one compound exists, BizCu04, which is highly stoichiomet-
ric.' (We have used synthetic Bi2Cu04 as an electron micro-
probe standard in the present study.) The 770°C eutectic
between Biz03and Bi2Cu04is the origin of melting in the Bi
end of the (Bi-Sr-Cu)-0 system.6 Therefore, high bismuth
compositions were avoided altogether in the present study.
ported on the synthesis and structure of S r z C ~ 0 3 1and
0 Sr-
CuOz." A third phase, initially reported to be Sr2Cu30,'20r
S~-,CU~O,,'~ was later shown to have the unusual stoichiom-
etry Sr14C~z4041.'4,15 All three phases are stable at 800°C ac-
cording to the phase diagram of Roth and co-workers.16
The first phase diagram for the (Ca-Cu)-0 system showed
only one compound, CazCu03," whose structure was subse-
quently reported by Teske and Miiller-Buschbaum." A second
compound, CaCuz03, was also synthesized," but was later
shown to be stable only above 950"C.I9A modified CaO-CuO
phase diagram has been published by Roth et d Z showing 0
Ca2Cu03 as the only stable compound at 800°C.
The (Bi-Ca)-0 and (Bi-Sr)-0 systems have considerably
more complex phase diagrams. At 800°C in the (Bi-Ca)-0 sys-
tem21there are two Bi-rich solid-solution phases (aand p) plus
relatively stoichiometric compounds, CaBizO4, Ca7BiloOzz,
and Ca7Bi6016. None of these phases were detected in the
present study. At 800°C in the (Bi-Sr)-0 system" there are
also two Bi-rich solid-solution phases (a and p), another
solid-solution phase ( y ) with the stoichiometry Sro.9Bil,102.5~3
at 800°C, and the stoichiometric compound Sr2BizOs. Just
above 800°C an additional compound, Sr3Bi206,was re-
ported, whereas just below 800°C the compound SrBizOd was
reported. More recently a new compound with the stoi-
chiometry Sr3BiOxhas been reported? In the present study
only the Sr3Bi206and Sr3Bi0, phases were observed.
No binary compounds have been reported in the CaO-SrO
system, and apparently no phase diagram has been published.
The only phase from this system to be detected in quaternary
assemblages was essentially pure CaO. (See below for a dis-
cussion of sluggish reaction kinetics in the SrO corner of the
tetrahedron.)
1966 Journal of the American Ceramic Society - Hong et al. Vol. 73, No. 7

As of the writing of this manuscript, the only ternary dia-
grams to have been published are for the (Bi-Sr-Cu)-0 and
(Ca-Sr-Cu)-0 systems. At least three versions of the (Bi-
Sr-Cu)-0 diagram exist?-* There is a general consensus that
the 6 to 9 K superconducting phase does not have the
221 Bi:Sr:Cu stoichiometry but is slightly Sr-deficient. It ex-
hibits a range of solid solubility (see Table I) and is compat-
ible with CuO, Sr14Cu24041, and a nonsuperconducting
compound very near the 221 stoichiometry (or perhaps
Bi17Sr16C~70,).7 All four of these phases were major phases in
the present study of quaternary relations. Additional ternary
compounds with Bi:Sr:Cu stoichiometries of 272 and 491
were reported in one study6 and of 232 and 485 in a n ~ t h e r . ~
None of these phases were detected in the present study.
The recently published (Sr-Ca-Cu)-0 950°C phase dia-
gram2' shows three extended solid solutions. A complete solid
solution exists between Sr2Cu03and CazCu03,an extensive
solid solution extends from SrCuOz out to (Sro.2sCao.7s)Cu02,
and a narrower solid solution extends from Sr14Cu24041out to
Sr7Ca7Cu24041.In addition, a second limited solid-solution
phase exists in the vicinity of the composition (Sro.16Cao.84).
CuOz. This phase and the Ca-rich end of each of the other
solid solutions exhibit compatibility with CuO. In the present
study at 800°C in quaternary compositions, only the Ca-rich
extreme of the (Sr, Ca)2Cu03 solid solution was observed.
Only the Sr-rich end of the (Sr,Ca)Cu02 solid solution was
obtained. A more extended (Sr, Ca)14Cu24041 solid solution
was observed. The new phase at (Sro.16Cao.84)Cu02 was not
detected in any of the quaternary compositions studied.
In the (Bi-Sr-Ca-Cu)-0 system, only the 2212 and
2223 superconducting compounds have been reported to date.
There has been considerable controversy concerning the sta-
bility of the 2223 compound, since high temperatures (melt-
ing?) and/or Pb additions are required for synthesis. In the
present study, 2223 could be obtained only at higher tempera-
tures (860" to 875°C) and only in the presence of Pb. At 800°C
Table I. Reported Solid-Solution Range for the 220l(SC) Phase
Ref. Solid-solution range
6 Bill-xSr9+xC~SOy (0 5 x I 0.4)
7 Bi2+xSr2-xC~l+yOr (0.1 < x < 0.6, 0 < y < x/2)
8 B i ~ S r 2 - ~ C u 0(0.1
~ I x 5 0.5)
no 2223 compound could be obtained in spite of lengthy
reactions at this temperature in the absence of Pb. Our con-
clusion is that the 2223 compound is not stable at 800°C.
A list of compounds reported for the various binary and
ternary systems is given in Table I1 along with the code we
will employ to refer to them. In each case the cation stoi-
chiometry will be given in the order Bi:Sr:Ca:Cu, e.g., 2201
and 2212 for the two superconducting phases. To differentiate
between the 6 to 9 K superconductor and the nonsupercon-
ducting compound nearby, 2201(SC) and 2201(NSC) will be
employed. Numbers greater than 9 will appear underlined,
e.g., 91150 for Bi9SrllCa50x(see below). Where solid solution
is involved, and "X" is used to account for variable Ca con-
tent relative to Sr, e.g., 014x24 for (Sr, Ca)14Cu24041 and
01x1 for (Sr, Ca)CuOz.
The strategy for the present study was to begin with the
relatively well-established (Bi-Sr-Cu)-0 face of the quater-
nary tetrahedron and to study constant Ca planes. The 10%
Ca plane was selected as it is intermediate to the 2201(SC)
compound (0% Ca) and the 2212 compound (14.3% Ca). The
15% Ca plane was then selected to place it between the 2212
compound (14.3% Ca) and where the 2223 compound should
occur (22.2% Ca). Additional work was done in the vicinity
of the 2223 composition, i.e., at 22.2% Ca.
111. Experimental Procedure
Ultrapure Biz03, SrC03, CaCO,, and CuO were mixed
under acetone with mortar and pestle, dried under a heat lamp,
and prereacted as a loose powder or in pellet form at 750" to
800°C for 24 h in air. Compositions were then reground, pel-
letized, and reacted at 800°C for 40 to 120 h with numerous
intermittent grindings. The earliest work was performed on
the 10% Ca plane, and 0.5 wt% Li2C03was added as miner-
alizer to these compositions. No mineralizer was added to
compositions on the 15% Ca plane and, as a result, signifi-
Superconducting range
x = 0.4
x < 0.13
0.1 5 x I 0.25

Table 11. Compounds Reported at 800°C

Code in
System Compound Ref. this study
Biz03-Cu0 Bi2Cu04 9
SrO-CuO SrzCu03 10 0201
SrCu02 11 0x1
Sr14Cu~404~ 14, 15 OLX22
CaO-CuO Ca2Cu03 11, 17 0021
BizO3-CaO CaBi204 21
Ca7Bi10022 21
Ca 7Bi6OI6 21
Bi203-SrO Sr0.9Bi1.102.~~
(Y) 23
SrzBi20s 22
Sr3Bi206 22 2300
SrBi204 22
Sr BiO, 7 1300
Bi203-Sr0-Cu0 Bi2Sr2Cu06
or
Bi 17Sr16Cu70y
Bi2Sr2-xC~Oy*
Bi2Sr7Cu20x
76 ' 8
6-8
6
2201(NSC)
2201(SC)
1
Bi 4Sr9Cu 0, 6
BiZSr3Cu2Ox 7
Bi4Sr8Cus0, 7
Sr0-Ca0-Cu0 Sr2Cu03-Ca2Cu03 20 0201,0021
20
SrCu0z-(Sro.25Cao.75)Cu02 0x1
S ~ ~ ~ C U ~ ~ O ~ , -20S ~ ~ C ~~CU~~O~~
014x22
Bi203-Sr0-Ca0-Cu0 Bi2Srz-,CaCuz0, 3,4 2212
*See Table I.
July 1990 Phase Composition and Compatibilities in the Bi-Sr-Ca-Cu Quaternary Oxide System at 800°C in Air
cantly longer times were required for these reactions to reach
completion. Nevertheless, results on both planes are similar
(see Figs. 1 and 2), suggesting that Li2C03 does not adversely
affect phase relationships. A mineralized assemblage consist-
ing of mostly 2201(SC) and 2212 phases showed an onset tem-
perature of 80 K. Although samples did not exhibit moisture
sensitivity like other high-T, phases, care was taken to store
samples in a desiccator and to perform phase and composi-
tion determinations as soon as possible after reactions. Nearly
100 individual compositions were prepared in this way, whose
compositions are summarized in Figs. 1. and 2.
Phase identification was carried out via powder X-ray dif-
fraction (XRD)* using CuKa radiation and a Ni filter. Silicon
powder was used as an internal standard. Composition analy-
sis was carried out via electron probe microanalysis (EPMA)+
at a 1-pm beam size. Standards employed included synthetic
Bi2Cu04for Bi and Cu, Sr-anorthite for Sr, and Ca-Kakanui
pyrope (garnet) for Ca. A lengthy grain growth anneal was
employed to achieve grain sizes large enough to accommo-
date the 1-pm probe. Samples were polished with y-alumina
grinding media down to 0.05 pm. With these procedures, ex-
cellent agreement with known cation contents was obtained,
e.g., Table 111 and copper contents in Fig. 3, and grain-to-
grain variations within a single specimen were minimal.
Where previously unreported compounds were concerned,
essentially phase-pure materials were made at the EPMA-
derived compositions, and magnetic susceptibility measure-
ments were made.* Unfortunately, the new phases discovered
were not superconducting under any conditions employed
to date.
IV. Results: Phases and Compositions
The phases detected in the present study and the composi-
tions where each occurred are given in Fig. 1 for the 10% Ca
'Rigaku Co., Tokyo, Japan.
i733 Superprobe, JEOL, Tokyo, Japan.
VTS susceptorneter, series 800, S.H.E. Corporation, San Diego, CA.
cu
Bi Sr Bi
cu
Fig. 1. Compositions in the 10% Ca plane showing major phases as indicated (via X-ray diffraction). See Table I1 for a code of phases.
1967
plane and in Fig. 2 for the 15% Ca plane. EPMA was per-
formed only for the 15% Ca compositions; average phase
compositions are listed in Table 111. It should be pointed out
that not every phase could be detected in a given assemblage
via XRD. This is due to the great disparity in X-ray scattering
power between Bi and the other elements; Bi-free phases sim-
ply do not show up in the XRD patterns if Bi-rich phases are
present. In such cases EPMA was extremely useful for con-
firming the presence of low-Bi phases. As mentioned above,
the grain-to-grain agreement in EPMA results within a given
specimen was usually excellent. Similarly, the sample-to-
sample agreement in EPMA results for a given phase was also
surprisingly good. This implies that the compositional varia-
tions for the various solid-solution phases are not great in
moving from tetrahedron to tetrahedron within the quater-
nary diagram, a very helpful fact in constructing quaternary
phase relationships (see below). The only exceptional cases
were the new compound at 91150 and the OLMg phase (see
below) which did exhibit some grain-to-grain variability, e.g.,
Table 111 and Fig. 3. We take this as evidence for extended
solid solubility, as is known to be the case for 01_4xg.
Two new (Bi-Sr-Ca)-0 phases were detected in quaternary
compositions with EPMA compositions of 9115 and 825. The
principal XRD peaks of these phases occur at 28 values (rela-
tive intensities) of 29.9 (loo), 29.4 (93, 38.2 ( 7 9 , and 43.2 (30)
for 9115 and 29.3 (loo), 30.1 (43,42.3 (57), and 19.4 (33) for
825. During the preparation of this manuscript, the authors
were made aware of the recent work of Roth et aLZ4reporting
new (Bi-Sr-Ca)-0 solid-solution phases with approximately
constant bismuth contents in the vicinity of 211 and 231.
There is good agreement between the bismuth contents of the
phases detected in the present work (36% for 9115 and 53.3%
for 825) and in Roth et al.24(33.3% for 231 and 50% for 211).
Three (Ca-Sr-Cu)-0 phases were detected in the present
study, namely the (Sr1-xCar)14Cu24041 solid solution (OgX24),
the (Srl-,CaX)Cu02 solid solution (OlXl), and essentially pure
Ca2Cu03(0021). Average compositions are given in Table I11
and individual EPMA data are plotted in Fig. 3 on the pro-
cu cu
Sr Bi Sr
cu
Bi Sr
1968 Journal of the American Ceramic Society - Hong et al. Vol. 73, No. 7

cu cu cu

Bi Sr Bi Sr Eli Sr

cu cu cu

/
/
/
*.
\

4
/ 8 . **./
.
BI Sr BI Sr

cu cu cu

Bi Sr Bi Sr

Fig. 2. Com ositions in the 15% Ca plane showing major phases as indicated (via X-ray diffraction and/or electron probe microanalysis).
See Table I1 gr
a code of the phases.
posed 950°C phase diagram. In contrast to 0021 and 01x1,
which exhibited narrow ranges of Sr-to-Ca solubility via
EPMA, 014x3 showed a wide range of Sr-to-Ca solubility.
The average Cu content of O g X 3 was 62.3% ? 1.1% so ei-
ther the Sr14C~2404114915(63.2% Cu) or Sr3C~50,13 (62.5% Cu)
proposed stoichiometries would be allowed. The apparent
discrepancy between the EPh4A compositions of the present
study and the reported phase compositions in Fig. 3 suggests
that the (Bi-Sr-Ca)-0 phase diagram is substantially different
at the two temperatures, i.e., 800°C versus 950°C.
The only (Bi-Sr-Cu)-0 phases detected in quaternary as-
semblages were the 6 to 9 K superconductor, 2201(SC), and
the nonsuperconducting 2201(NSC) phase. The latter phase
was not detectable with EPMA, most likely because of its
needlelike m~rphology;~ however, it could be easily detected
in XRD patterns. Normalized to the measured Cu content,
the composition of the 6 to 9 K superconductor is approxi-
mately Biz.os(Sro.~2Caa.~s),.ssCu0,. The alkaline-earth defi-
ciency has been reported previously and may be responsible
for electron hole generation in this superconductor. (See Ref. 6
for a discussion of this.) The most novel aspect of the present
work on this compound is the 3% Ca solubility (See Table 111).
An investigation of solid solubility on the high-temperature
and superconducting properties of this phase is in progress.
The only (Bi-Sr-Ca-Cu)-0 quaternary compound detected
in any of our reaction products was the 2212 phase. As
pointed out above, the 2223 compound can be synthesized
only with the presence of Pb and only at higher temperatures.
Normalized to 2Cu, the EPMA results for the 2212 phase
in Table I11 correspond t o an average composition of
Bil,wSrl.56Cal.WC~20x. Again, a pronounced Sr deficiency is
observed. On the 15% Ca plane there was very little sample-
to-sample variation in EPMA-derived composition. However,
work at the nominal 2223 composition, also summarized in
Table 111, shows a slightly different composition, Biz.asSr1.54-
Ca1.26C~20x.The 3% difference in Ca content of the
2212 phase on the 15% Ca versus 22.2% Ca planes is similar
in magnitude to that between pure and Ca-doped 2201(SC) as
discussed above. Currently, attention is being given to pin-
ning down the exact solubility limits for both superconduct-
ing phases.
July 1990 Phase Composition and Compatibilities in the Bi-Sr-Ca-Cu Quaternary Oxide System at 800°C in Air 1969

Table 111. Electron Probe Microanalysis Results

Average phase composition (mol%) Initial composition (mol%)
Phase Bi Sr Ca cu Bi Sr Ca cu
91150 34.6 k 2.3 43.7 ? 3.8 18.2 ? 3.1 3.5 ? 1.4 13 34 15 38
4 43 15 38
17 43 15 25
25 47 15 13
8250 53.0 f 0.4 12.1 2 1.0 31.4 2 0.9 3.5 2 0.5 25 9 15 51
2212 29.4 ? 0.9 24.1 ? 0.7 15.5 ? 1.1 31.0 ? 0.8 9 25 15 51
23 23 15 39
13 28 15 44
2201(SC) 42.2 ? 1.8 34.5 ? 0.7 3.0 ? 0.7 20.3 r 2.1 30 30 15 25
014x24 0.6 f 0.4 25.6 f 4.7 11.5 ? 4.7 62.3 2 1.2 9 26 15 50
13 34 15 38
4 43 15 38
30 30 15 25
0021 0.6 2 0.7 3.0 t 1.4 64.1 2 1.3 32.3 2 0.6 26 9 15 50
23 23 15 39
13 28 15 44
Olxl 0.9 ? 0.8 43.5 2 1.5 6.2 +. 1.5 49.4 k 1.5 4 43 15 38
17 43 15 25
25 47 15 13
2212 30.0 r 0.62 22.5 r 0.27 18.4 ? 0.42 29.1 ? 0.74 22.2 22.2 22.2 33.4
OEX22 2.1 f 0.34 24.7 f 1.91 12.9 ? 2.24 60.3 f 0.01 22.2 22.2 22.2 33.4

V. Results: Compatibility Tetrahedra
Using a three-dimensional wire model, the quaternary (Bi-
Sr-Ca-Cu)-0 phase relationships were explored based upon
the phase composition and compatibility information con-
tained in Table I11 and Figs. 1 to 3. In certain cases assem-
blages of four equilibrium phases were obtained, and these
six tetrahedra were assigned a high degree of certainty, e.g.,
“confirmed in Fig. 4. (The 2212-825O-CuO-220l(SC) tetra-
hedron was confirmed by a supplementary firing at the nomi-
nal composition 4223 which showed these four phases.) A
number of additional compatibility triangles were confirmed
and a group of nine “probable” tetrahedra were constructed
based upon these (see Fig. 5). Overall, the 15 tetrahedra, con-
firmed or probable, pack and fill space within the quaternary
tetrahedron in such a way that there are no violations of the
phase rule; i.e., no tie lines intersect other compatibility tri-
angles. We have opted to present individual tetrahedra as in
Figs. 4 and 5 for the sake of clarity; the overall quaternary
diagram is extremely complex and difficult to visualize in
only two dimensions.
The most stable phases in the quaternary diagram are evi-
dent from Figs. l and 2 in their frequency of occurrence and
from Figs. 4 and 5 from the number of tetrahedra in which
CUO
:a2Cu0,
L--- . - ___ -~
S rO
Fig. 3. Electron probe microanalysis points (small dots)
superim osed on the Sr0-Ca0-Cu0 phase diagram
from Rei! 20.
they are involved. At low Cu contents, the most frequently
obtained phase was the 91150. A large number of tie lines
radiate away from this ternary compound into the quaternary
system. To a lesser degree, the same can be said of the
8250 phase. However, lever rule considerations are respon-
sible for this phase showing up in smaller amounts relative to
other phases, given its larger Ca content (33%) relative to the
experimental 10% Ca and 15% Ca planes. Similarly, a large
number of tie lines connect to CaO and Ca2Cu03 (0021),
which showed up in EPMA results but were noticeably absent
in XRD patterns because of the absence of Bi in this phase.
By lever rule, very small fractions of CaO (100% Ca) and
Ca2Cu03 (66% Ca) would be expected in 15% Ca assem-
blages. At large Cu contents, CuO is ubiquitous in our experi-
mental results (see Figs. 1 and 2). This is primarily due to
tie lines connecting CuO to both superconducting phases,
2201(SC) and 2212. To date the authors are aware of no
high-T, cuprate superconductors for which this is not true. All
are compatible with CuO.
Phase relations on the 10% Ca plane strongly resemble the
(Bi-Sr-Cu)-0 phase diagram:-* , particularly at high-Cu con-
tents. This is due to the compatibility of each superconductor
with the 014x24 phase, their compatibility with one another,
and the compatibility of the 2201(SC) superconductor with
the 01x1, (Srl-,Ca,)CuOz phase. The major differences occur
as a result of tie lines involving the 911.50 phase at low Cu
contents. This effect is even more pronounced at the 15%
Ca plane.
The frequency of occurrence of the 2212 phase (Figs. 1 and
2) and the large number of tie lines and compatibility tetra-
hedra involving this phase (see Figs. 4 and 5 ) support our
contention that it is the only quaternary compound in the
(Bi-Sr-Ca-Cu)-0 system. (We have not investigated the Bi
end of the diagram because of melting considerations, and
reactions in the Sr end of the diagram were too sluggish to be
certain of equilibrium phases; additional phases could exist
in these regions without our knowledge. Furthermore, high
Ca compositions need to be investigated to confirm our tie
line assignments in this part of the diagram.) The phases
with which the 2212 superconductor is compatible include
2201(SC), 8250, 91150, CuO, 014x24, Ca2Cu03 (0021), and
CaO. The tie line with the 2201 superconductor is not unex-
\ pected. Multiple superconducting transitions are often seen in
CaO multiphase assemblages of high-T, superconductors.
It should be emphasized that our knowledge of quaternary
phase relationships is only partial. As mentioned before, Bi-
rich compositions were avoided because of problems associ-
1970 Journal of the American Ceramic Society - Hong et al.
cu
Bi
cu
Bi Bi
Fig. 4. Compatibility tetrahedra “confirmed” by coexistence of the four phases via X-ray diffraction and/or electron probe microanalysis.
(See Table I1 for a code of the phases.)
ated with melting. The most Bi-rich tetrahedra investigated
were the “confirmed” 8250-2212-CuO-220l(SC) and the
“probable” 8250-2212-2201(SC)-9lJ50. At the Sr corner of
the diagram, phase relations are uncertain because of the
sluggishness of reaction kinetics. This is not unreasonable
given the refractoriness of SrO and the high decomposition
temperature of SrC03. The most Sr-rich compatibility we
have confirmed is the 2212-2201(SC)-ON2+9lJ50 tetra-
hedron. The confirmation of two additional Sr-rich tie trian-
gles, namely O~%-OlX1-91150 and CaO-9lJ5O-OuX24,
support the additional Sr-end tetrahedra assignments in
Fig. 5. However, this corner deserves additional study and
experiments are in progress. Additional reactions are also
planned at higher Ca contents as part of an ongoing solid
solubility study; these should help to confirm the phase rela-
tions at the Ca end of the diagram.
As mentioned in the previous section, many of the phases
involved in the (Bi-Sr-Ca-Cu)-0 quaternary are solid-solution
phases. Fortunately, we have not detected extreme variations
in composition for most of these phases in going from
compatibility tetrahedron to compatibility tetrahedron. The
only exception to this is the OuXH phase, whose average
composition varied in the 0.6 5 x 5 0.8 range of (Srl-,Ca,)14-
c1.1~ in ~
the0present
~ ~ study and whose overall solid solubility
is known to be much more extensive. Strictly speaking, the
representation of such phases as “points,” two-phase equilibria
involving these phases as tie-lines and three-phase equilibria
involving these phases as tie triangles, is incorrect. There are
actually two-phase and three-phase volumes separating the
compatibility tetrahedra. A more precise assignment of phase
Vol. 73, No. 7
C” cu
Bi
C” cu
Sr
Bi
relationship will require much more thorough study of solid
solubilities. Nevertheless, the schematic representation of
phase relationships in Figs. 4 and 5 is presented as a first-
order approximation of the 800°C subsolidus phase diagram.
VI. Concluding Remarks
Of particular interest to the defect chemistry of the super-
conducting phases is their extent of solid solution. At least a
3% Ca-to-Sr solubility was detected in the present work via
EPMA for both the 2201(SC) and 2212 phases. Current plans
are to perform careful EPMA studies in each of the tetra-
hedra involving the superconducting phases in order to
identify the extent of solid solution. Single-phase terminal
solid-solution compositions can then be prepared to correlate
superconducting behavior with composition.
A most significant result of the present study is the appar-
ent instability of the 2223 phase at 800°C. We believe this to
be thermodynamically determined as opposed to merely a
kinetic problem associated with the formation of 2223. Both
Li2C03 and PbO were added in small amounts as mineraliz-
ers. Lithium carbonate is particularly effective in aiding the
reaction of 2201(SC) with other phases to form 2212.6 In no
instance was any 2223 detected at 800°C via XRD, EPMA, or
magnetic susceptibility measurements. Much larger Pb addi-
tions combined with higher temperatures (860” to 875°C) were
required to isolate the 2223 phase. We conclude that 2223 is
not a stable compound in the (Bi-Sr-Ca-Cu)-0 system at
800°C.
July 1990 Phase Composition and Compatibilities in the Bi-Sr-Ca-Cu Quaternary Oxide System at 800°C in Air 1971
cu cu cu

Sr

Bi Bi
8250B’2212-2201 SC)
(8250-CUO-0021 ) [91150-2212-221 !!(SC\) (9 1150-0 13X)(24-2201(SC))

cu cu cu

Bi Bi Bi
(8250-221 2-0021) (91150-221 2-0021) (91150-221 2-2201 (X))

C” C” cu

81 Bi Bi

(91150-COO-0 lAX24) (91150-COO-01 X1) (Ol~X~-OlX1-9~50)

Fig. 5. Probable compatibility tetrahedra based upon confirmed tie triangles as indicated. (See Table I1 for a code of the phases.)

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