15512916, 1994, 12, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1994.tb04558.x by MUHAMMAD PANACHIKKOOL , Wiley Online Library on [21/03/2023].
See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Phase Equilibria of the Bismuth Oxide-Copper Oxide System in
Oxygen at 1 atm
Department of Chemistry and Texas Center for Superconductivity, University of Houston, Houston, Texas 77204
Phase equilibria of the Bi,O,-CuO system have been deter-
mined from 700" to 1040°C in oxygen at 1 atm pressure.
Bi,O, is stable in the Bi-rich portions of the system and
undergoes a phase transition from cu-Bi,O, to 6-Bi,O, at
730°C. Bi,CuO, is the only binary compound found to be
stable; it melts incongruently to CuO + liquid at 849°C.
CuO is the stable copper oxide at temperatures below
1040°C. The liquidus is composed of three segments. The
Bi,O, +liquid segment intersects the Bi,CuO, + liquid
segment at a eutectic at 784°C with 92% Bi,O,. The
Bi,CuO, +
liquid segment and the CuO +
liquid segment
meet at a peritectic at 849°C a t 66% Bi,O,. Superliquidus
liquids with Bi:Cu = 2 were formed at 950°C at values of
oxygen fugacity between 0.05 and 1.Glasses quenched from
these liquids were analyzed for Cu+ and total Cu. All
contained both Cu' and Cuz+. The value of Cuz'/Cu+
increases as the oxygen fugacity increases hut, even in pure
oxygen, more than half the copper in the glasses is monova-
lent. The variation in Cu+:Cuz+in liquids with Bi:Cu = 4
at an oxygen fugacity of 1 is analyzed as a function of tem-
perature. At the lowest temperatures (<900"C), the copper
is almost all divalent; at >=llOO"C, most of the copper is
univalent. There is more univalent copper relative to diva-
lent in liquids at lower oxygen fugacity and higher tempera-
ture. The value of Bi:Cu in the glass also affects the ratio of
Cu' to C d + . At T < =900"C (andfO2 = l),copper in liq-
uids with Bi:Cu = 4 is dominantly divalent, whereas copper
in liquids with Bi:Cu = 2 is composed of subequal amounts
of Cuz+and Cu'. The system Bi,O,-CuO is a pseudobinary
as at least some liquids in the system are actually in the
Bi,O,-Cu,O-CuO system.
I. Introduction
T HE discovery of high-temperature superconductivity in
cuprates of bismuth and alkaline earths'.' has led to a revi-
talized effort to better understand the synthesis of compounds
in systems involving Bi,O,, CuO, SrO, and CaO. We are
attempting to systematically evaluate phase equilibria in the
Bi,O,-SrO-CaO-CuO system. Part of that effort, presented
here, is determination of the phase equilibria of the Bi,O,-CuO
pseudobinary join in a pure oxygen atmosphere.
Three earlier studies of the phase equilibria of this pseudobi-
nary system, determined in air, have been reported. Cassedanne
and Campelo4 indicate the presence of an intermediate phase
that melts incongruently at 820°C. This phase has a nominal
composition of Bi,CuO, but is a solid solution that incorporates
up to 87% Bi,O,. (All percentages are expressed in terms of
P. Gallagher~oiitributingeditor
Manuscript No. 194137. Received October 14, 1993; approved April 22, 1994.
Presented in pan at the 204th National Meeting of the American Chemical Society,
Washington, DC, August 25, 1992 (Abstract No. 274, Abstracts of the Division of
Inorganic Chemistry).
Supported by grants from the State of Texas to the Texas Center for
Superconductivity.
3119
Chi-Fo Tsang, James K. Meen, and Don Elthon
moles of Bi,O, and CuO.) The coexisting solid phase at 820°C
is nominally CuO but contains -4% Bi,O,. These authors sug-
gest that Cu,O replaces CuO in the Bi-free system at = 1040°C
and that there is a small region of coexistence of a BizO,-
-
bearing CuO solid solution and a Bi,O,-bearing Cu,O solid
solution to a maximum temperature of I 130°C. They further
suggest that Cu,O melts at 1320 i 20°C although their phase
diagram shows that the melting temperature is near 1220°C.
Cassedanne and Campelo also report a binary eutectic where a
liquid with -90% Bi,O, coexists with Bi,O, and Bi,CuO, solid
solution at 600°C.
Boivin et ~ 1 also
. ~indicate the presence of an intermediate
compound, but its composition is Bi,CuO,. Bi,CuO, does not
have a significant solid solution range and melts congruently at
840°C. Boivin et al. report the presence of two eutectics. At one
eutectic, a liquid with 85 mol% Bi,O, is in equilibrium with
Bi,O, and Bi,CuO, at 770°C; at the other, at 835"C, a liquid
with 46% Bi,O, coexists with Bi,CuO, and CuO. These authors
do not indicate the presence of any Bi,O, in CuO and their study
was not conducted at temperatures sufficiently high for the sta-
bilization of Cu,O.
Kakhan et ~ 1describe
. ~ subsolidus results in the Bi,O,-CuO
system and their results generally agree with those of Boivin
et al. They report an intermediate phase, Bi,CuO,, which melts
congruently at 850 t 5°C. They determined that the eutectic
where a liquid with 88% Bi,O, is in equilibrium with Bi,O, and
Bi,CuO, is at 770 t 5°C.
Insofar as these studies do not agree on the phases that are
stable nor on their chemographic relations, they contain some
important inherent contradictions. Our experimental study is
not directly comparable to these earlier studies as this study
investigates phase equilibria in a pure oxygen atmosphere, not
in air. Future investigations of the Bi,O,-CuO system will be
conducted at lower values offo,.
11. Experimental Procedure
Starting materials were prepared by conventional solid-state
synthesis techniques in which dry, high-purity Bi,O, and CuO
were mixed and ground under acetone. The dried powder was
sintered in an alumina crucible at 750°C in air for 24 h. The
powder was then ground under acetone, pressed into a pellet
with a diameter of 13 mm, and fired at 750°C for 24 h. The pro-
cess of grinding, pressing into a pellet, and sintering was
repeated three times. At the end of this homogenization proce-
dure, the sample was again ground and 20-30 mg of powdered
sample was loaded onto a loop of Pt or Au wire of diameter 130
pm. A hydraulic press was used to press the powder and the
metal loop together at -5 MPa. No binder was used. The s m -
ple and loop remained attached during heating and quenching.
The metal loop used was 0.5-1 .0 mm in diameter in order to
maximize the exposure of the sample to oxygen in the furnace
and to minimize the amount of Pt or Au that entered the reac-
tion. For a given composition, experiments were performed at
the higher temperatures first. The liquidus temperature was
determined by heating the samples until totally liquid, holding
them at that temperature for 10-30 min, and then reducing the
 15512916, 1994, 12, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1994.tb04558.x by MUHAMMAD PANACHIKKOOL , Wiley Online Library on [21/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
3120 Journal of the American Ceramic Society-Tsang et al. Vol. 77, No. 12

temperature. Samples were drop-quenched in liquid N, and
checked optically and by electron microprobe analysis (see
below).
Starting materials for subliquidus experiments were heated to
10-15°C above the previously determined liquidus and held
there for 15-30 min; the temperature was then brought to the
desired run temperature, at which it stayed for 0.3 to 46 h. These
samples were also drop-quenched in liquid N,. Tables I and I1
list experimental compositions, temperatures, run durations,
and compositions of phases.
Samples were mounted in epoxy after quenching and the
upper surfaces polished flat for electron microprobe analysis.
All phases identified in this paper were analyzed on a JEOL
JXA-8600 electron microprobe using wavelength dispersive
spectrometers. Electron microprobe standards used here were
Bi,,GeO,,] for Bi, cuprite (Cu,O) for Cu and 0, and pure metals
for Pt and Au. Counting times were 100 s on the peaks and 50 s
on backgrounds. Intensity data were processed by on-line
Noran +pZ software to obtain elemental concentrations. The
phases stable below the solidus were also identified by X-ray
powder diffraction.
Electron microprobe analyses of glasses in experimental run
products suggest that copper occurs in both the Cu' and Cu2+
states within the liquid in these experiments. A series of experi-
ments was, therefore, conducted on the composition Bi,CuO,
above its liquidus temperature (950°C) at oxygen fugacities of
0.05 to 1.O in order to determine the oxidation state of copper in
the liquid. The values of the fugacity of oxygen were controlled
by mixing extrapure 0, and Ar. The liquids were quenched to
glasses in liquid N, and then dissolved in 0.7M HCI in an inert
atmosphere of N,.
Determination of the relative amounts of Cu' and Cu2+ in
these samples was by an iodimetric method modified from
Quadir and Khundkar.' Excess sodium citrate added to the solu-
tion reacted with the Cu2+ ions to form a stable Cu2+ citrate
complex that was effectively inert in the subsequent reactions.
A known amount of 0.03M I, solution was then added. The Cu'
ions reacted with the iodine to produce Cu2+and I-. As Cu2+
ions were generated, they reacted with the citrate to form more
Cu2+-citratecomplex. The excess I, over that required to oxi-
dize the Cu+ was then back-titrated with 0.01M sodium thio-
sulfate solution, permitting calculation of the amount of Cu +

originally present. The titration employed by Quadir and

Khundkar to determine the amount of Cu'+ could not be used in
Table I. Experimental Probe Results this system because of an interference with the end point from
Composition Temp Time Wire BiI, produced during the first titration. Instead, the Cu2+-citrate
(%Bi203) ("C) (h) loop Phases present complex was decomposed using 6M HC1 and the total Cu in
100.0 821 Liquidus determined visually solution determined by atomic absorption spectrometry. The
95.0 803 1.0 Pt +
Liq Bi,Oi amount of Cu2+ was calculated from the difference between
797 1.3 Pt +
Liq Bi,O, the total number of copper ions and the number of Cu' ions.
795 3 Pt +
Liq Bi,O, Table 111 shows these results.
790 1 Pt +
Liq BiZO,
90.0 805 1.0 Pt +
Liq Bi,CuO,
799 0.5 Pt +
Liq Bi,CuO, 111. Results
782 1.0 Pt Bi,O, + Bi,CuO,
763 1.0 Pt Bi,O, + Bi,CuO, (1) Phase Diagram
750 50.0 A1,0,* Bi,O, + Bi,CuO;
700 50.0 AI,O,* Bi,O, +
Bi,CuO,' The results of our experiments are listed in Table I, with the
80.0 781 10.0 Pt Bi,O, +
Bi,CuO, resulting Bi20,-CuO phase diagram shown in Fig. 1. The com-
70.0 750 50.0 A1,0,* Bi,O, +
Bi,CuO,' positions of phases, as determined by electron probe microanal-
700 50.0 A1,0,* Bi,O, + Bi,CuO,i ysis, are listed in Table 11.
66.7 850 0.5 Pt Bi,CuO, +
Liq Bi,O, is stable in the Bi-rich portions of the system and con-
843 0.7 Pt Bi,CuO, + Llq tains only a small amount of Cu (0.07-0.26%) in solution.
827 0.6 Pt Bi,CuO, +
Liq Bi,O, also contains a very small amount (<0.04%) of Pt, which
777 17.0 A1,0," Bi,O, + Bi,CuO;
765 3.5 Pt Bi,O, + Bi,CuO,
is a contaminant derived from the Pt wire loop used to suspend
758 36.0 Pt Bi,O, + BiZCuO, the sample. Gattow and Schrodernshowed that Bi,O, undergoes
748 11.0 AI,O,* Bi,O, + Bi,CuO,' a phase transition from the low-temperature monoclinic
50.0 750 50.0 A120,* Bi,CuO: a-Bi,O, to the face-centered cubic S-Bi20, at 750 k 5°C.
I00 50.0 A1,0,* Bi,CuO,' 6-Bi20, is not a quenchable phase and is, therefore, not present
58.0 850 19.0 Pt Liq + Bi,CuO, in any of our run products. Bi,O, melts congruently at 821°C.
835 3.0 Pt +
Liq Bi,CuO, Bi,CuO, is the only binary compound found to be stable in
827 5.0 Pt +
Liq Bi,CuO, the Bi,O,-CuO system at temperatures above 700°C. Bi,CuO,
826 3.0 Au +
Liq BiZCuO,
melts incongruently to CuO + liquid at 849°C. These results
817 5.5 Pt Liq + Bi,CuO,
807 4.0 Pt Liq + Bi,CuO, contrast with those of Boivin et d.,' who concluded that
156 2.3 Au Bi,O, + Bi,CuO, Bi,CuO, melts congruently at 840"C, and with those of
45.0 943 0.5 Pt +
Liq CuO Cassedanne and Campelo; who concluded that Bi,CuO, rather
40.0 800 50.0 A1,0,* CuO + Bi,CuO; than Bi,CuO, is the intermediate compound.
30.0 973 1.0 Pt Liq + CuO Figure 2 is a backscattered electron image of a typical super-
903 1.0 Pt +
Liq CuO solidus run product. Lighter shades in this image indicate a
874 1.5 Pt +
Liq CuO
higher average atomic number than darker ones. The experi-
872 1.0 Au +
Liq CuO
700 95.0 A1,0,* CuO + Bi,CuO,' ment was conducted at 807°C with a bulk composition of 58%
20.0 996 1.0 Pt Liq + CuO Bi,O,, 42% CuO. The darker phase is Bi,CuO,; the lighter one
962 24.0 Pt +
Liq CuO is a glass quenched from a liquid. (The black areas are holes in
903 260 Pt Liq + CuO the run products now occupied by epoxy.) The glass has higher
800 50 Al,Olx CuO + Bi,CuOl Bi:Cu than the solid phase, resulting in the lighter color. The
10.0 1020 10.0 Pl Liq + CuO Bi,CuO, crystals are generally anhedral with escalloped faces
982 11.0 Pt +
Liq CuO
and re-entrants. Inspection of Fig. 2 shows that the intensity of
862 12.0 Pt Liq + CuO
850 13.0 PL Liq + CuO electrons backscattered from the glass was essentially constant
849 18.0 Pt +
Liq CuO throughout the field of view. This uniformity indicates that the
5.0 1018 1.5 Pt Liq + CuO liquid was homogeneous under the run conditions and that no
1010 1.5 Pt +
Liq CuO crystals formed during quenching of the run. These observa-
1000 1.5 Pt Liq + CUO tions were confirmed by microprobe analysis of several differ-
*AI,O, crucihle. 'From XRD, no probe data. ent areas of glass.
 15512916, 1994, 12, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1994.tb04558.x by MUHAMMAD PANACHIKKOOL , Wiley Online Library on [21/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
December 1994 Phase Equilibria of the Bismuth Oxide-Copper Oxide System in Oxygen at I atm 3 121

Table 11. Compositions of Phases (%)

Comp Temp Liquid Biz03 Bi,CuO, cu0
(%Bi,O,) (“C) BI Cu 0 PI B I.D ,- BI Cu 0 Pt Bi Cu 0 Pt Bi Cu 0 Pt
95.0 803 40.7 0.93 58.3 0.1 I (95.1 t 0.7) BLO, from EDS
791 40.6 1.1 58.2 0.21 (94.1 t 1.6) Bi;O;fromEDS
795 40.3 1.0 58.6 0.26 (93.9 t 0.7) Bi,O, from EDS
790 40.8 1.34 57.6 0.35 (92.3 t 1.5) Bi,O, fromEDS
90.0 805 39.2 1.9 58.7 0.20 (91.1 t 0.3) 29.4 9.8 56.2 4.4
799 39.9 1.4 58.3 0.42 (93.5 ? 0.7) 29.4 10.7 56.1 3.8
782 41.7 0.08 58.2 0.01 30.0 10.7 55.3 4.10
763 42.1 0.07 57.8 0.01 30.2 10.5 54.8 4.50
80.0 781 41.9 0.07 58.0 0.02 29.6 13.6 56.8 0.01
66.7 850 37.0 5.4 57.6 0.0 (77.5 i 0.9) 31.1 10.0 57.1 1.7
843 34.7 7.2 58.1 0.06 (81.6 2 1.2) 28.9 12.8 56.9 1.4
827 38.2 2.9 58.7 0.1 (86.5 t 1.5) 29.3 11.2 56.5 3.1
765 40.0 0.18 59.8 0.0 29.4 13.9 56.2 0.52
758 42.0 0.26 57.7 0.04 29.8 14.4 55.7 0.11
58.0 850 36.7 7.4 55.9 0.10 (71.3 i 0.5) 30.0 13.0 55.2 1.76
835 36.1 8.7 55.2 0.01 (67.5 i 1.3) 29.4 13.6 56.2 0.82
827 37.4 5.3 57.4 0.00 (78.0 t 0.4) 29.6 14.0 56.0 0.49
826 38.5 4.0 57.4 0.21* (82.9 t 6.0) 29.8 14.3 55.8 0.13*
817 38.7 4.1 57.2 0.02 (82.4 t 3.5) 29.4 13.8 56.2 0.60
807 38.4 5.0 56.5 0.01 (79.3 t 0.8) 29.9 14.2 55.5 0.35
756 41.5 0.34 58.1 0.03* 29.7 14.5 55.7 0.04*
45.0 943 29.1 15.9 55.0 0.11 (47.8 2 0.5) CuO from EDS
30.0 973 27.2 19.8 52.9 0.04 (40.7 t 1.2) 0.0 50.5 49.4 0.1
903 33.1 12.0 54.8 0.06 (57.8 ? 1.3) 0.0 50.4 49.5 0.0
874 35.2 9.55 55.2 0.10 (64.6 t 1.3) 0.0 50.5 49.5 0.0
872 31.2 12.5 56.3 0.02* (55.6 t 1.3) 0.0 50.0 50.0 0.0*
20.0 996 23.0 27.5 49.5 0.02 (29.5 ? 0.5) 0.0 50.9 49.0 0.0
962 28.4 19.3 52.2 0.07 (42.3 ? 0.5) 0.0 51.4 48.6 0.0
903 31.3 15.1 53.5 0.14 (50.9 t 0.4) 0.0 50.8 49.2 0.0
10.0 I020 13.6 32.4 54.0 0.02 (17.4 i 0.2) 0.0 51.0 49.0 0.0
982 27.8 19.7 52.5 0.06 (41.4 t 1.0) 0.0 51.2 48.7 0.1
862 34.6 9.9 55.4 0.1 1 (63.6 i 3.5) 0.0 51.0 49.0 0.0
850 36.3 8.9 54.6 0.12 (67.0 t 1.1) 0.0 51.5 48.5 0.0
849 34.6 8.6 56.6 0.09 (66.9 ? 3.0) 0.0 50.3 49.6 0.0
5.0 1018 21.4 28.4 50.2 0.03 (27.4 t 2.0) CuO from EDS
1010 24.3 25.1 50.6 0.00 (32.7 i 0.5) 0.0 51.2 48.8 0.0
1000 24.6 23.1 52.3 0.03 (34.8 i 2.0) CuO from EDS
*Experiments were done on Au wire loops rather than Pt. The value listed IS for the Au content of the phasc.

Table 111. Ratio of [Cu’] to [Cu”] in Superliquidus Liquids at 950°C with Bi:Cu = 2

fb,*

0.05
logj;,>
- 1.301
*.
4
Mass ofglass
dissolved
(mg)
30.649.3
[CU‘]’

0.140 ? 0.011
IZCUl‘
0.167 -C 0.011
[CU ’ ]/[CU” Jq

5.19 2 1.57
0.10 - 1.000 5 28.7-32.8 0.106 t 0.003 0.144 t 0,005 2.79 ? 0.32
0.15 - 0.824 5 32.841.4 0.106 t 0.001 0.142 ? 0.004 2.94 t 0.62
0.20 - 0.699 4 30.9-31.6 0.109 t 0.002 0.143 2 0.004 3.21 t 0.23
0.25 - 0.602 4 29.8-30.1 0.096 t 0.010 0.129 ? 0.011 2.91 i 1.14
0.30 - 0.523 4 28.8-30.2 0.100 2 0.008 0.143 ? 0.001 2.33 t 0.75
0.40 - 0.398 3 28.8-30.2 0.093 t 0.014 0.146 2 0.006 1.76 t 1.08
0.50 - 0.301 4 27.9-31.5 0.082 t 0.006 0.146 t 0.008 1.28 i 0.38
0.60 - 0.222 4 30.8 0.1 15 ? 0.005 0.1767 i 0.0003 1.86 t 0.33
1.OO 0.000 5 29.0-31.6 0.080 t 0.001 0.137 t 0.006 1.40 ? 0.39
determined atsuming ideal mixing of 0, and Ar. Extrapure gases were mixed before they entered the furnaces. Flow rates
were controlled to -0.3 mLls. +Numberof separate experiments performed at each T-f condition. ‘Mole fraction of Cu+ deter-
mined for each glass by iodimetry. Error is lo of values of experiments. 4Molefraction%f total Cu in glass determined hy AAS.
Error is lo of values of experiments. ’Ratio of [Cu’] tv [Cu” 1. Error is In of values of experiments.

Experiments performed in the CuO-rich part of the system at
temperatures below 1040°C contained CuO as the only stable
copper oxide. The CuO formed in our runs typically contained
less than 0.1% of each of Bi and Pt. At temperatures above
1O4O0C, experimental results were not reproducible, and this
portion of the phase diagram is shown in Fig. I with dashed
boundaries. In many of these runs, both CuO and Cu,O existed,
but attempts to reverse the experiments were generally unsuc-
cessful. We believe that these irreproducible results were due,
at least in part, to reaction between copper oxide and Pt. Micro-
probe analysis indicated that Pt wire in these experiments con-
tained up to 22 wt% Cu. Extensive experimentation with
different wires and crucibles revealed no substance that was
inert with respect to both copper oxide and to oxygen in this
highly oxidizing environment. In addition, rapid nucleation of
both copper oxides from liquids with Cu:O between I and 2
(see below) plausibly resulted in replacement of copper oxide
liquids by mixtures of quench CuO and Cu,O crystals.
Several studies have investigated the system Cu-0 and are
summarized by Santander and Kubaschewski’ and Neumann
et al.“’ At values offo, < 0.60, CuO reacts to form Cu,O at tem-
peratures below its sohdus. In air, CuO is replaced by Cu,O at
1031°C and Cu,O melts at 1134°C. This is a much lower tem-
perature than shown by Cassedanne and Campelo4 in their
phase diagram. At higherLl2, Cu,O is not stable and CuO melts
directly to a liquid. Atf,, = 1, CuO melts at 1 12 1 “C to a liquid
 15512916, 1994, 12, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1994.tb04558.x by MUHAMMAD PANACHIKKOOL , Wiley Online Library on [21/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
3122 Journal ($the American Ceramic Society-Tsang et al. Vol. 77, No. 12

1200 1

1100
n

W
1000
21
Y
2aJ 900

$ 800

t I
-
v I " I
-
v I v

PI
!
i,
Y
i I CUO + L1q

f4
ti
c 800
CuO + Bi ,CuO
--------
i,CuO, + a-Bi203 ~ I T
700 I I I

0 20 40 60 80 100

%Bi,O,
Fig. 1. Phase diagram for the system BizOi-"CuO" with,f;,, = 1, showing the bulk compositions and temperatures of runs: (A) Shaded quadrants
of each circle indicate the presence of that phase in the run products. Most runs contained two phases. Their compositions lie at the intersections of
horizontal lines drawn through the circle and the vertical composition lines or the liquidus. The liquidus is, therefore, defined by a large number of
analyzed liquid compositions. Run products in several subsolidus runs were analyzed by X-ray diffraction, not by electron microprobe, and chemical
analyses of phases in those runs are not available. Experiments at T > 1040°C did not yield reproducible results (see text) and that region of the
liquidus is denoted by a dashed line. (B) Summary of fields in Bi,O,-"CuO' giving temperatures of invariant reactions and phases present in each
divariant field

-
with Cu:O 1.5. We have indicated the liquidus at T > 1040°C
in Fig. 1 with a dashed line that is consistent both with our
results at T < 1040°C and with melting of CuO at 1121°C.
(2) Oxidation State of Copper
Table 111gives results of our analysis of Cu and total copper
+
in glasses with Bi:Cu = 2 formed at 950°C. The amount of
Cu(1) relative to the amount of Cu(I1) varies regularly with,f,,.
Figure 3 shows this variation by plotting the ratio of the amount
of copper in the univalent state to the amount of divalent copper
against the value off,2 at which the liquid formed. The data are
well fitted by a straight line ( y , = 0.91) with the amount of Cu'
0' - in the liquid increases as A,, increases, thus elevating
-
the coefficient of log (fo,) above -0.25. The best-fit line
to the data has a coefficient of log (fo,) of - 0.43. This value
is much lower than expected, indicating that the assumption of
the simple ionic reaction given above is invalid and suggesting
a more complex equilibrium between Cu', Cuz+,and 0,.
We calculated the atomic fraction of copper in the univalent
state in the liquids from the relative proportions of Bi, Cu, and
0 in the glass, assuming that all Bi is trivalent and that all 0 is
divalent (Table IV). Glasses coexisting with either Bi,CuO, or
CuO contain some Cu . Those produced at higher temperatures
+

in the liquid increasing as fo2 decreases. Even at fd, = 1, the
glass, and thus the liquid, contain significant Cu' at 950°C.
Thus, despite the fact that solid phases produced at this temper-
ature contain only divalent Cu, the liquid contains both univa-
lent and divalent copper.
If the equilibrium between Cu' and Cu2+is described by the
simple ionic reaction 2Cu2',,, + 0*-,,,= 2Cu+,,, + 0.50,,,,,
then log (Cu[I]/Cu[lI]) = 0.5 log { X ( 0 2 - ) ] - 0.25 log (,fol)
if all species act ideally in the liquid and if the amount of
0 -is not a function of tif;,,. More plausibly, the amount of
have more Cu ' than those at lower temperatures. Table IV doc-
uments this for glasses with Bi:Cu = 4 formed at temperatures
of 883" to 1126°C. (At higher temperatures, Cu reacted with
the Pt loop and Bi was lost from the run, apparently by
volatilization.)
Figure 4 shows the variation of log {Cu[I]/Cu[Il]} for a
liquid (Bi:Cu = 4) with temperature. The rather large errors on
the abscissa result from the use of analyses of several elements
in the calculations. At the lowest temperatures studied, only
-5% of the Cu is univalent. The amount of Cu increases until,
+
 15512916, 1994, 12, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1994.tb04558.x by MUHAMMAD PANACHIKKOOL , Wiley Online Library on [21/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
December 1994 Phase Equilibria of the Bismuth Oxide-Copper Oxide System in Oxyge~at 1 atm 3123

100

: R.0.96
log(Cu(I)/Cu(II)i~-7.140+6.820e-31
Bi:Cu=l

.01 I
800 900 1000 1100 1200

TPC)

Fig. 4. Variation of ratio of Cu' to Cu'+ with temperature in liquids

Fig. 2. Backscnttered image of a typical run product. The starting
material was 58% Bi,O, and 42% CuO and the experiment was at
807°C. Two phases formed in this experiment. The dark gray colored
phase (lowcr average atomic number) is Bi,CuO,; the lighter colored
phase is a glass that was quenched from a liquid present at 807°C. The
constant coloration of the latter indicates that it is homogeneous and
was not modified by formation of crystals during the quench. Note the
scale in the lower right corner, indicating a length of 100 p n i n the
field of view.
-2.0 -1.5 -1.0 -0.5
logf(02)
Fig. 3. Ratio of amount of Cu' to amount of Cu2+in a liquid plotted
against,fo2o f experiments. Both scales are logarithmic. Oxygen fugac-
ity controlled by mixing ultrapure 0, and Ar. Bulk composition of
starting material had Bi:Cu = 2 and experiments were all at 95WC-
above the liquidus of that composition. Analytical techniques for total
copper and for Cu' are described in the text. Error bars are la and
determined by propagation of analytical errors through an algorithm
used to calculate the ordinate.
with Bi:Cu = 4 run with&, = 1. Amounts of Cu' and Cu2' were cal-
culated from electron microprobe analysis of glasses for Bi, Cu, and 0,
assuming that all bismuth is trivalent and all oxygen is divalent. Error
bars are I u and reflect propagation of all analytical errors through an
algorithm used to calculate the ordinate. Line determined by regression
for the eight lower temperature points (883" to 1044°C); the steeper
part of the curve at higher temperature was drawn by eye.
at -1050°C, Cu' and Cu2' each constitute -50% of the cop-
-
per. The change in log (Cu[I]/Cu[II]) with temperature is
approximately linear (r,, 0.96) for this temperature range. In
the two experiments conducted at > 1050°C, at most only a few
percent of the Cu is divalent. In fact, the copper may all be uni-
valent in these liquids. There must, therefore, be a rapid change
in valence state of copper in the liquid between 1044" and
1094°C.
Liquids that coexist with Bi,O; contain relatively small
amounts of Cu compared to their oxygen contents. Calculated
X(Cu[I]) for glasses to the Bi,O,-rich side of the eutectic are
within error of zero. The liquids all formed at relatively low
temperatures (<850"C) so this observation is consistent with
the pattern in Fig. 4 that shows that the copper is dominantly
divalent at <-90O"C.
The copper in a liquid with B X u = 2 at,fo, = 1 and 950°C
is -60% Cu', =40% Cu'+ (Fig. 3). At the same conditions,
copper in a glass with Bi:Cu = 4 is -15% C u ' , 4 5 % Cu'+
0.0 (Fig. 4). In a similar way, one can compare liquids at 1 100°C at
fo, = 1. A liquid with Bi:Cu = 4 has essentially all of its cop-
per univalent, whereas a liquid formed from CuO under approx-
imately the same conditions has approximately equal amounts
of Cu' and Cu'+.'.'" The relative amounts of Cu' and Cu' ' in a
liquid are, therefore, not simple functions of temperature and
fo, but also depend on bulk composition of the liquid. This is not
a simple variation insofar as liquids with Bi:Cu = 2 have
higher Cu '/Cu* ' than do more Bi-rich liquids at lower temper-
atures (<90OoC) and higher Cu'/Cu" than do more Cu-rich
liquids at 1100°C.

Table IV. Variation of Ratio of Cu+ to CuZ+in Liquid at Bi:Cu = 4 =1

Temp ("C) Mole ratio of Cut Mole ratio of Cu' ' cu /CU' +

1126 0.970 2 0.080" 0.030 i- 0.002" 32.3 ? 10.7

1094 0.980 2 0.070" 0.020 ir 0.001" 49.0 ? 13.9
1044 0.440 t 0.030" 0.560 i- 0.038" 0.786 ? 0.215
1000 0.350 2 0.030" 0.650 2 0.056" 0.538 ? 0.186
982 0.320 2 0.020" 0.680 i- 0.043" 0.471 t 0.119
960 0.180 2 0.004" 0.820 2 0.018" 0.220 t 0.019
940 0. I50 2 0.010" 0.850 i_ 0.057" 0.176 t 0.047
92 1 0.120 2 0.008" 0.880 ir 0.059" 0.136 t 0.037
900 0.130 -+ 0.004" 0.870 ir 0.027" 0. I49 t 0.0 18
883 0.050 i 0.003" 0.950 i_ 0.057" 0.053 ? 0.013
*Error< calculatcd by propagation of Im analytical errors on Bi, Cu, and 0 thmiigh calculatioii for valence slate

3124 Journal of the American Ceramic Society-Tsang
(3) Mixing Properties of CuO and Bi,0,3in Liquids with
High Bi:Cu
Activity coefficients of CuO in liquids along the liquidus
from the eutectic to the Bi,O, end member were calculated from
the freezing point depression effect of CuO on Bi,O,. Thermo-
chemical data for liquid and crystalline bismuth oxide have
been compiled by Pankratz.” Data summarized in Fig. I pro-
vide information on how the Bi,O, liquidus changes as CuO is
added and this can be used to calculate the activity of Bi,O, in
liquids along the liquidus at temperature T according to the
equation
a”q(Bi,O,) = a‘””d(Bi,O,)exp( ( 1/R)[AHo,,
- AC,T,)( UT,,, - 1 /n+ AC, In (T/T,J]1
assuming that AC, is a constant over the temperature range
studied. AH‘’, is the enthalpy of fusion at the melting point, T,.
a(Bi,O,) is unity in solid bismuth oxide, so the expression can
be solved as a function of T and X”q(Bi,O,). Values of the activ-
ity coefficient of Bi,O, in the liquid calculated in this way are
all slightly above but very near unity, suggesting that BizO,
dissolves in Bi-rich liquids ideally.
The remainder of the phase diagram is not amenable to this
kind of analysis because of the lack of thermochemical data for
Bi,CuO, and the experimental problems for the CuO-end of the
binary at T > 1040°C.
IV. Conclusions
We have determined that the liquidus in the system Bi,O,-
CuO in pure oxygen is composed of three segments. The
Bi,O, +
liquid segment and the Bi,CuO, + liquid segment
intersect at a eutectic at 784°C with 92% Bi,O,. The Bi,CuO, + Temperature Fonn of Bismuth(II1) Oxide (&Bi,O,),” 2. Anorg. Alleg. Chem.,
liquid segment meets the CuO + liquid segment at a peritectic
at 849°C at 66% Bi,O,. Phase relations at T > 1040°C were not
determined because of experimental difficulties.
Many, and perhaps most, liquids in this system contain
copper in both univalent and divalent states, even at fb, = I .
At higher temperatures, copper in liquids has higher Cu’/
15512916, 1994, 12, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1994.tb04558.x by MUHAMMAD PANACHIKKOOL , Wiley Online Library on [21/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
et al. Vol. 77, No. 12
Cu2+than has copper in low-temperature liquids. The value of
Cu+/Cu2+also depends on the Bi-to-Cu ratio of the liquid and
not in a simple way. Low-temperature, Bi-rich liquids have
almost, if not all, their Cu in the 2 + state and that part of the
phase diagram is a true binary Bi,O,-CuO. Much of the super-
solidus portion of the Bi,O,-CuO system, however, is part of
the Bi,O,-CuO-Cu,O system and is a pseudobinary.
Acknowledgments: We thank two anonymous reviewers for their com-
ments that greatly improved the manuscript.
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