ARTICLES

Liquidus relations in Y-Ba-Cu oxides

Terry Aselage and Keith Keefer
Electronic Ceramics Division 1842 and Ceramics Development Division 1845, Sandia National
Laboratories, Albuquerque, New Mexico 87185
(Received 12 May 1988; accepted 3 August 1988)
The liquidus relations in the system YC^ 5 -BaO-CuO x in air in the compositional region near
the superconducting oxide YBa 2 Cu 3 O x were studied by differential thermal analysis, x-ray
diffraction, electron microprobe analysis, and visual observation. The temperatures of 11
invariant points and the corresponding reactions were determined. YBa2Cu3OJC was found to
melt incongruently at 1015 °C to Y2BaCuO5, which in turn melts incongruently to Y 2 O 3 at
1270 °C. These reactions mean that preparing the superconducting phase by melting and rapid
cooling will result in the presence of these two phases as well. The peritectic reaction
YY$?L2C\\3OX + CuO -> Y 2 BaCu0 5 + liquid at 940 °C accounts for the observation of partial
melting, improved synthesis purity, and grain growth at temperatures of 950 °C. The
determination of these invariant temperatures and reactions provide insight into optimal
processing conditions.

I. INTRODUCTION formation, is important to optimize the thermal process-

The report of superconductivity above 90 K in yt-
trium-barium-copper oxides by Wu et al.' and the sub-
sequent identification2 of the superconducting phase as
YBa 2 Cu 3 O ;c , where x is between 6 and 7, has generated
a tremendous amount of interest in these materials.
Typically, they are processed by solid-state reaction
between Y 2 O 3 , BaCO3 or BaO, and CuO at tempera-
tures between 900 and 1000 °C, followed by sintering at
similar temperatures. An oxygen annealing treatment,
either at 900 °C followed by a slow cool, or at 500 °C, is
used to increase the oxygen content in the materials.
An early experimental effort that was carried out by
several groups comprised the mapping of isothermal re-
gions of phase coexistence for compositions in the
Y 2 O 3 -BaO-CuO system.3"6 These studies were general-
ly carried out below the solidus temperatures in the sys-
tem, typically at 950 °C. Liquid phase formation in an
investigation of binary joins in the phase diagram at
950 °C was noted only along the CuO-YBa 2 Cu 3 O ;c join
in several reports by Frase et al.4'5 In another investiga-
tion by Wang et al.,3 formation of liquids at 950 °C was
additionally noted along the BaCuO 2 -YBa 2 Cu 3 O x bi-
nary join and for ternary CuO-BaCuO2-YBa2Cu3OJC
mixtures. Similarly, many papers describe the growth of
single crystals of YBa2Cu3O;c from liquid phases in the
system or by the partial melting of YBa 2 Cu 3 O x (Refs.
7-11). Reports of the melting temperature for pure
YBa 2 Cu 3 O x and liquid formation temperatures of other
compositions vary over a considerable range. For exam-
ple, YBa 2 Cu 3 O x is said to melt (in air) at temperatures
of925°C (Ref. 7),980°C (Ref. 12),993°C (Ref. 11),
and 1020°C (Ref. 8). An accurate knowledge of the
phase relations at high temperature, including liquid
ing of YBa 2 Cu 3 O x . Such thermal processes include the
growth of single crystals, solid-state or liquid-assisted
sintering, and processes that involve melt process-
ing,13'14 melt spinning,15'16 and plasma spraying.17"20
We are aware of only one previous discussion of the
liquidus fields in the ternary system, a preliminary study
by Roth et al.21 Melting observations were made using
mixed oxide starting materials in single-crystal MgO
containers. The compound YBa 2 Cu 3 O x was found to
melt incongruently at 1010 °C to Y2BaCuO5 plus liquid.
The lowest melting ternary eutectic was found to occur
near the BaCuO 2 -CuO tie line at about 880 "C. Mini-
mum melting along the BaCuO 2 -YBa 2 Cu 3 O x binary
join occurred at about 940 °C, while a solidus between
YBajCiVjO, and Y B a j C u ^ . was reported at 960 °C.
A eutectic temperature of 930 °C was reported in the
YBa 2 Cu 3 O x -Y 2 Cu 2 O 5 -CuO region. Using this infor-
mation, a rough primary phase field of the YBa 2 Cu 3 O x
phase was outlined.
In this paper, we extend upon the previous work by
determining the temperature and reactions that occur at
invariant points in the ternary system. We use differen-
tial thermal analysis and direct visual observation for
melting temperature determination, and x-ray diffrac-
tion and electron microprobe analysis to determine the
reactions that occur. Although these techniques do not
allow the exact location of the composition of the liquid
at the invariant points, we can present a schematic ter-
nary phase diagram for the region of the Y 2 O 3 -BaO-
CuO system in the vicinity of YBa 2 Cu 3 O x . These rela-
tions will be discussed in terms of the observations noted
above, and inconsistencies with previously reported
data will be described. The results that we will present
have been obtained in air at total pressure of 640 Torr.

J. Mater. Res. 3 (6), Nov/Dec 1988 0884-2914/88/061279-13$01.75 © 1988 Materials Research Society 1279

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 T. Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides
II. EXPERIMENTAL PROCEDURES
Powders of YBa 2 Cu 3 O x were prepared by typical
ceramic processing techniques. Stoichiometric amounts
of Y 2 O 3 (Cerac, 99.9%, or Alfa Products, 99.99%),
CuO, and Ba(NO 3 ) 2 (both Fisher Chemicals, A.C.S.
reagent grade) were mixed by ball milling with metha-
nol in polyethylene jars with high-purity A12O3 media,
and dried. Samples were calcined in high-purity A12O3
crucibles by heating in air at 2°C/min to 550 °C,
0.5 °C/min from 550 to 750 °C (to allow for nitrate de-
composition), and 2 °C/min to 925 °C. Samples were
held at 925 °C for 4 h, followed by furnace cooling to
room temperature. Phase purity of these powders was
increased by regrinding in a porcelain mortar and pestle
and subsequent heat treatments at 925 °C.
In order to accurately determine pure phase and
mixture transition temperatures, we found it necessary
to synthesize the other pure phases of interest, BaCuO2,
Y 2 BaCuO 5 , and Y 2 Cu 2 O 5 . BaCuO2 was prepared by
ball milling stoichiometric mixtures of BaCO3 and CuO.
Pellets were pressed and heated to 950 °C in air for 8 to
24 h. BaCO3 impurity was observed in x-ray diffraction
powder patterns until several repetitions of the process-
ing were completed. We were not successful in synthe-
sizing pure Y2BaCuO5 from the mixed oxides, as Y 2 O 3
impurities were observed even after several repetitions
of ball milling, cold pressing, and heating at 950--
1050 °C. Consequently, we used Y(NO 3 ) 3 -6H 2 O,
Cu(NO 3 ) 2 -3H 2 O (both Alfa Products, A.C.S. reagent
grade), and Ba(NO 3 ) 2 (Mallinckrodt, A.C.S. reagent
grade) as starting materials. These were ground in an
agate mortar and pestle in a dry room (water vapor less
than 300 ppm) and spread evenly in a shallow A12O3
boat. The samples were processed in flowing Ar/O 2
mixtures (50%-100% O 2 ) in order to prevent the for-
mation of BaCO3 upon nitrate decomposition. Samples
were heated to 950 °C, held for 6 h, and furnace cooled.
X-ray diffraction revealed little Y2 O 3 ; a subsequent re-
grinding and heating step resulted in pure Y2 BaCuO 5 .
This pure material was light lime green in color. Similar
difficulties were encountered in attempts to prepare
pure Y2 Cu2 O5 from Y2 O3 and CuO, as Y2 O 3 and CuO
impurities were observed. Synthesis from Y ( N O 3 ) 3
• 6H2 O and CuO at 950 °C for 24 h with an intermediate
grinding step resulted in Y 2 Cu 2 O 5 with major Y 2 O 3
and minor CuO impurities by x-ray diffraction. After
addition of 2 mole % excess CuO, regrinding, and heat-
ing to 1000 °C for 60 h, the powder diffraction pattern
showed only Y2 Cu2 O 5 reflections.
The thermal stability of the phases and mixtures
was analyzed using differential thermal analysis
(DTA), powder x-ray diffraction, direct visual observa-
tion, and electron microprobe analysis (EMPA). DTA
experiments were performed in high-purity Al 2 O 3 sam-
ple cups with either a DuPont 1090 or 9900 thermal
1280 J. Mater. Res., Vol. 3, No. 6, Nov/Dec 1988
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analysis system. Heating rates were 10 °C per minute,
and A12O3 powder was the reference material. Tem-
peratures of thermal events are reported as the onset
temperatures. All cycles were performed in air flowing
at 50 seem. Samples that contained a relatively large
amount of barium (e.g., BaCuO 2 ) were found to wet
the A12O3 cup after melting. Other compositions did
not interact with the Al2 O 3 , forming an easily removed
ball in the center of the cup. Powder diffraction data
were collected using a Siemens D500 6 /26 automated
diffractometer. Direct melting observations were made
in a horizontal tube furnace with an optical pyrometer
telescope, or with a hot stage optical microscope. Sam-
ples were prepared for EMPA by cutting with a low-
speed diamond saw using methanol as the cutting fluid,
potting in epoxy, and polishing with diamond paste us-
ing freon as the polishing fluid. EMPA was carried out
at an accelerating voltage of 15 kV and beam current of
20 nA.
III. EXPERIMENTAL RESULTS
A. Single-phase thermal behavior
In this section, we shall present the results of inves-
tigations of the melting behavior of pure phases of inter-
est. These melting points will provide the basis for the
remaining investigation of the ternary phase relations.
The temperatures of melting events and the nature of
the melting (congruent versus incongruent) were deter-
mined for YBa2Cu3Ox, Y 2 BaCuO 5 , BaCuO 2 , and
Y2 Cu2 O 5 . Also, the thermal behavior of pure CuO in
air was investigated. The samples of pure phases that
were studied are listed in Table I, runs 1-16. Provided
are the sample composition, maximum sample tempera-
ture, thermal events observed, and phases observed in
the resulting material by x-ray diffraction or other tech-
niques.
Our initial study was of YBa2Cu3O;c powder pre-
pared by single calcination of the mixed oxides at 925 °C
as described above. DTA revealed two endothermic
events when this powder was heated to 1062 °C, one be-
ginning at 939 °C and one at 1014 °C. Figure 1 shows the
DTA trace for this sample, and is representative of other
DTA runs. Our initial attempt at observing these events
using high-temperature (real-time) x-ray diffraction
failed due to reactions between YBa2Cu3OJC and the Pt
heating ribbon of the hot stage. Therefore, samples were
heated to 950, 974, 994, and 1026 °C in the DTA system
and held for 2 h. In each case, similar endotherms were
observed. The materials were cooled to room tempera-
ture by shutting off the DTA furnace, and were subse-
quently ground and examined by x-ray powder diffrac-
tion.
Figure 2(a) shows a powder pattern for typical
once-calcined YBa 2 Cu 3 O x . This superconducting
 T. Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides

TABLE I. Compositions studied, thermal events recorded, and reaction products observed.

Maximum (°C) Thermal" Phases

Run# Initial phases temperature events (°C) observed13

1 Once calcined 123; 1062 939, 1014 123(T),211,BaCuO 2

211, BaCuO2, CuO
impurities

2 Once calcined 123; 950 123

211,BaCuO2, CuO
impurities

3 Once calcined 123; 974 941 123

211, BaCuO2, CuO
impurities

4 Once calcined 123; 994 941 123

211,BaCuO2, CuO
impurities

5 Once calcined 123; 1026 945, 1013 123 (T),211,BaCuO 2

211, BaCuO2, CuO
impurities

6 Once calcined 123; -1040 Visual melting at 211, 123, BaCuO2, CuO
211,BaCuO2, CuO -1020 (microprobe)
impurities

7 211 (x-ray pure) 1400c 1233, 1270 211,Y 2 O 3 , 123

8 211 (x-ray pure) 1290 1274 211, Y 2 O 3 , 123

9 BaCuO2; BaCO3, 1070 817,929, 1015 BaCuO2

CuO impurities

10 BaCuO2; BaCO3, 1250 820, 927, 1024 BaCuO2

CuO impurities

11 BaCuO2 (x-ray pure) 1150 1014 BaCuO2

12 BaCuO2 (x-ray pure) -1030 1005-1010

(Optical Microscope
Hot Stage)

13 Y 2 Cu 2 O 5 , Y2O3, 1180 1035, 1111 Y2O3, Y 2 Cu 2 O 5 , CuO

CuO impurities

14 Y 2 Cu 2 O 5 (x-ray pure) 1270 1020, 1122 Y 2 O 3 , Y 2 Cu 2 O 5 , Cu 2 O, CuO

15 CuO 1090 1026

d
16 CuO 1215 1028, 1140

d
17 50 mole % BaCuO2 1000 920
+ 50 mole % CuO

18 40 mole % BaCuO2 970 912 CuO, BaCuO2, BaCu 2 O 2

+ 60 mole % CuO

d
19 50 mole % BaCuO2 1100 1003
+ 50 mole % 123

20 50 mole %BaCuO 2 1100 1000 211,BaCuO 2

+ 50mole%211

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 T. Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides

TABLE I. (Continued.)

Maximum (°C) Thermal* Phases

Run # Initial phases temperature events (°C) observed15

21 90 mole % BaCuO2, 1086 1000

10mole%211

22 50 mole % 123 + 1000 895, 940

50 mole % CuO

23 50 mole % 123 + 985 887, 932 123, CuO, 211, BaCuO2

50 mole % CuO

24 80 mole % CuO + 983 886, 934 123, CuO, 211,BaCu2O2

20 mole % 123

25 50 mole % 123 + -965 123, CuO, 211, BaCu,O,

50 mole % CuO
(pellet)

26 80 mole % CuO + -965 CuO, BaCu2O2, 211, minor 123;

20 mole % 123 211, CuO, Cu2O, BaCuO2,
(pellet) BaCu2O2, 123 (microprobe)

27 70 mole % CuO, 1125 948, 980, 1037 CuO, Cu,O, 211, Y2Cu,O5> 123
30 mole % 211

28 70 mole % CuO, 1040 948, 977 211, CuO, Y2Cu2O5, 123

30 mole % 211

29 50 mole % Y2Cu2O5, 1057 1033 Y2Cu2O5, CuO, Y 2 O, (reduced)

50 mole % CuO
+ Y 2 O, impurity

30 75 mole % Y2Cu2O,, 1180 1035, 1108, 1122 Y2O3, Y2Cu2O5, Cu2O, CuO
25 mole % CuO

31 62.5 mole % CuO + 1033 905, 937, 970

32.8 mole % BaCuO,
+ 4.7 mole % 123

32 15 mole % 211 + 1028 1004 211, 123, BaCuO,

15 mole % 123 +
70 mole % BaCuO2

33 8.1 mole % 211 + 1032 937, 962 123 (greater intensity),

9.8 mole % 123 + 211, CuO, BaCuO,, Y2Cu2O5
82.1 mole % CuO

"DTA, except where noted.

bX-ray diffraction, except where noted. 123—orthorhombic YBa,Cu 3 O x , 123 (T)—tetragonal YBa 2 Cu 3 O x , 211— Y,BaCuO 5 .
•"Stagnant air.
dSample not x rayed.
"Sample not x rayed, however, EDS and XRD on many single-crystal growth runs using this composition reveal phase assemblage to be
123 + CuO + BaCuO2.

phase was orthorhombic as observed by the relative
intensities of the (013)—(103,110) doublet reflections at
about 32° 26, and impurity peaks due to Y2 BaCuO5 and
BaCuO2 were observed (CuO was, therefore, also pres-
ent due to overall stoichiometry). After holding for 2 h
at 950 °C, however, the diffraction peaks due to the im-
purity phases were no longer evident, as shown in
Fig. 2 (b). The pattern of the orthorhombic YBa 2 Cu 3 O x
was unchanged. Although 950 °C is well above the or-
thorhombic-tetragonal transition of YBa 2 Cu 3 O x in
air,22'23 the sample garnered enough oxygen during
cooling to revert to orthorhombic symmetry.

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 T. Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides

Upon cooling, the Y2 BaCuO5 and liquid undergo the

reverse reaction to form YBa 2 Cu 3 O x again. Under equi-
librium conditions, this reaction would proceed to com-
pletion, resulting in pure YBajC^O^. However, under
conditions of fractional crystallization, Y2 BaCuO5 is
effectively removed from the system so that the remain-
ing liquid crystallizes at more yttria-poor compositions.
Thus, fractional crystallization leads to the presence
of Y 2 BaCu0 5 , BaCuO 2 , and CuO in samples of
YBa 2 Cu 3 O x heated above 1015 °C.
In an additional experiment designed to confirm
this reaction, a sample of YBa 2 Cu 3 O x powder was
pressed into a pellet, suspended between two high-puri-
700 800 900 1100 1200
TEMPERATURE (°C) ty A12O3 beads (to minimize contact with container
material), and heated in a tube furnace in air. The pellet
FIG. 1. Differential thermal analysis heating as calcined, impure was observed with an optical pyrometer telescope as a
YBajG^O,. The onset temperatures for the thermal events are
function of temperature. At about 1020 °C, the pellet
shown. The event at 939 °C is the peritectic reaction of YBa,Cu 3 O x
with CuO impurities and the event at 1014 °C is the incongruent melt- began to slump between the beads. The sample did not
ing of YBajCiijO*. flow due to the solid phase (Y 2 BaCuO 5 ) that was nu-
cleated in the incongruent melting step. The sample was
examined by EMPA as described above. Figure 3 pre-
Similar results were obtained for samples heated to sents the results of this experiment as a backscattered
974 and 994 "C, suggesting that the 939 °C event in the electron image (BSE) [Fig. 3 (a)] and a compositional
thermal analysis was caused by impurity phases. Final- yttrium x-ray mapping [Fig. 3(b) ].
ly, the sample heated to 1026 °C showed an endotherm The BSE image reveals the presence of three phases:
onset at 1013 °C and the powder pattern revealed the (i) a very light phase (BaCuO 2 ) and (ii) a dark phase
presence of tetragonal YBa 2 Cu 3 O x , Y 2 BaCuO 5 , (CuO) that are found at grain boundaries, triple points,
BaCuO 2 , and CuO [ Fig. 2 (c) ]. and the sample surface; and (iii) large gray grains.
These observations are consistent with incongruent Based on the BSE image it is difficult to distinguish the
melting of Y B a j C u ^ at 1015 °C to Y 2 BaCuO 5 plus a presence of two phases within these latter grains, how-
liquid, ever two phases are readily discerned in the yttrium x-
ray compositional mapping. Quantitative microprobe
YBa 2 Cu 3 O x -Y 2 BaCuO 5 + L.
analysis shows that the regions with high yttrium counts
correspond to Y 2 BaCuO 5 , whereas the less yttrium-
rich phase is YBa 2 Cu 3 O x . The crystallization sequence
apparent in Fig. 3 is consistent with that discussed
above. At temperatures above 1015 °C, Y 2 BaCuO 5 co-
exists with a liquid phase. As the sample is cooled to
1015 °C, the peritectic reaction takes place with the for-
mation of YBa 2 Cu 3 O x by reaction of the Y2 BaCuO5
with the liquid. As Y2 BaCuO5 grains are coated with
YBa 2 Cu 3 O x , they are effectively removed from the
system (i.e., the liquid is unable to penetrate the
YBa 2 Cu 3 O x grains to react with the Y2 BaCuO 5 ).
Hence, the remaining liquid, which is rich in BaO and
CuO compared to YBa 2 Cu 3 O x , solidifies at some lower
temperature. We will discuss this in more detail in a
later section. It is worth noting here, however, that there
24 28 32 36 40 44 48 52 56 60
is no evidence of yttrium present in the CuO or BaCuO 2 ,
TWO - THETA (DEGREES)
and little YBa 2 Cu 3 O x is found in the solidified liquid.
FIG. 2. X-ray diffraction patterns of as calcined, impure YBa2Cu3OJ. This would indicate that the ultimate freezing point in
(a), the same material after heating to 950 °C, above the peritectic the system is at a composition with very little Y 2 O 3
reaction point pi (b), and heating to 1026 °C, above the incongruent
melting point of YBa 2 Cu 3 O, (c). The filled circles indicate peaks due
present.
to Y 2 BaCuO 5 , the open squares BaCuO 2 , and the open diamonds We also noted the presence of BaCuO2 on the sur-
CuO. face of the sample. This coating was apparent on all

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 T. Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides
- \
r similar to that shown in Fig. 4(b).
•m
i Y2 O 3 is effectively removed from the system so that the
FIG. 3. Electron microprobe images of a pressed pellet of YBaXu,O<
after heating it above its incongruent melting point. The surface of the
sample is in the upper right corner. Fig. 3(a) is a backscattered elec-
tron image. The very light regions are BaCuO 2 , the very dark regions
are CuO, and the medium gray regions are YBa,Cu,O^ and
Y 2 BaCuO 5 , which are virtually indistinguishable from each other.
Fig. 3 (b) is an yttrium x-ray image of the same region, revealing small,
evenly distributed grains of Y 2 BaCuO 5 surrounded by YBa,Cu 3 O x .
Scale bar = 100 /im.
sides of this and other samples of "melted" YBa 2 Cu 3 O x .
We suggest that this coating is responsible for the fact
that the YBajCujO^ was tetragonal after melting; the
crystallized BaCuO2 on the surface served as an oxygen
diffusion barrier so that the high-temperature tetra-
gonal state was preserved. Such a tetragonal sample,
after grinding and heating in flowing oxygen at 460 °C
for 510 min, gained 1.4% in weight and was orthorhom-
bic.
Since Y2 BaCuO5 is formed during the melting of
YBa 2 Cu 3 O x , the melting behavior of Y2 BaCuO5 is also
of interest. Again, the synthesis of pure starting material
was crucial to this experiment in order to avoid low
melting eutectics and reactions between the components
and the DTA cup material. A sample heated to 1400 °C
showed a very small event at about 1233 °C and a larger
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endotherm with onset at 1270 °C. After removal from
the DTA cup, the sample was much darker green than
the starting Y2 BaCuO5 powder. X-ray powder patterns
of the pure starting material and the sample after heat-
ing to 1400 °C are shown in Figs. 4(a) and 4(b). In a
subsequent experiment, pure Y 2 BaCuO 5 was again
heated in the DTA to temperatures between 1239 and
1290 °C in 10-20 deg increments. The sample was exam-
ined after each cycle to look for change in color. No
color change or any thermal events were noted as the
sample was heated to temperatures up to 1267 °C. How-
ever, the sample heated to 1290 °C showed an onset
at about 1274 °C and had clearly changed color, indicat-
ing that the 1270 °C event is the melting point of
Y2 BaCuO 5 . The diffraction pattern of this sample was
Y 2 O 3 is apparent in the sample of Y2 BaCuO5 heat-
ed above melting, proving that this phase also melts in-
congruently:
Y 2 BaCuO 5 ^Y,O 3 + L.
The YBa 2 Cu 3 O x (and BaCuO2 and CuO) observed in
Fig. 4(b) are a result of the fractional crystallization of
the sample during cooling. At 1270 °C, Y 2 O 3 reacts
with the liquid to produce Y2 BaCuO 5 . Once again, the
liquid, which is enriched in BaO and CuO, will crystal-
lize at a lower temperature to phases with less yttria
than Y2 BaCuO 5 .
Similarly, pure BaCuO2 was examined by DTA
and direct observation on an optical microscope with
hot stage. DTA of BaCuO2 with BaCO3 and CuO im-
purities resulted in three endotherms: at 817, 929, and
1015 °C. The 817 °C event is clearly the y-/3 transition of
TWO - THETA (DEGREES)
FIG. 4. X-ray diffraction patterns of Y2 BaCuO5 as prepared by calci-
nation (a) and after heating to 1400 °C, 130 °C above its incongruent
melting point (b). The open circles indicate peaks due to Y 2 O 3 , the
open triangles YBa,Cu,O x , and the open squares BaCuO 2 .
 T, Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides
the BaCO3 impurity. Reproduction of the runs with
pure BaCuO2 resulted in a melting endotherm at
1014 °C. The 928 °C event is the BaCuO 2 -CuO eutectic
discussed below. By direct visual observation, the
BaCuO2 sample was seen to undergo melting at a tem-
perature of 1005-1010 °C. The observed temperature
was calibrated using the melting point of a piece of silver
in proximity to the BaCuO 2 . A number of samples were
x rayed following the melting experiment. In each case
the samples were found to consist of only BaCuO 2 . This
illustrates that BaCuO2 undergoes congruent melting,
i.e., the liquid is of the same composition as the solid that
melts/crystallizes.
In an initial experiment to determine the melting
behavior of Y2 Cu2 O 5 , a sample that contained CuO
and Y 2 O 3 impurity was used. Here, endotherms were
observed at about 1035 and 1111 °C. Subsequently, the
x-ray pure Y2 Cu2 O5 was prepared and used in the DTA
experiment. Here, a small baseline shift was observed at
about 1020 °C, followed by a large endotherm with on-
set at 1122 °C. The presence of Y2 O 3 in large amounts in
the x-ray diffraction pattern after melting proves that
Y2 Cu2 O5 also melts incongruently, to Y2 O3 plus a liq-
uid. Evidence provided by binary mixtures of CuO and
Y 2 Cu 2 O 5 (discussed below) suggests that the endoth-
erm at 1111 °C corresponds to the Cu 2 O-Y 2 Cu 2 O 5 eu-
tectic, and the 1122 °C endotherm to the incongruent
melting of Y2 Cu2 O 5 . These results are similar to those
reported by Roth et al?x
Since the reported decomposition temperature of
CuO (to Cu 2 O) is 1026 °C (Ref. 24), the endotherms
observed in this range are likely due to the presence of
CuO as an impurity. We examined the thermal behavior
of CuO in several experiments, runs 15 and 16 in Table I.
Large endotherms were observed in the vicinity of
1026 °C in both experiments, confirming the CuO-
Cu 2 O decomposition. In the sample heated to 1250 °C,
another endotherm was observed at about 1140 °C. Ac-
cording to the Cu-O phase diagram,25 CuO decomposes
in air before melting to form Cu2 O. With further heat-
ing, the Cu2 O melts with oxygen pick up (to an oxygen
content between Cu 2 O and CuO) at about 1130°C.
Thus, our results are consistent with decomposition at
about 1026 °C and melting at 1130-1140 °C.
B. Binary mixtures of phases
Having identified the melting temperatures of the
pure phases in the system, we next investigated binary
mixtures of phases. The purpose of this study is twofold:
(i) to determine the temperatures at which melting or
reactions occur between phases, and (ii) to determine
whether binary joins in the phase diagram have mini-
mum melting eutectics or if more complicated melting
relations hold. The binary joins that we have studied are
J. Mater. Res., Vol. 3, No. 6, Nov/Dec 1988
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BaCuO 2 -CuO, BaCuO 2 -YBa 2 Cu 3 O x , BaCuO 2 -
Y2BaCuO5, CuO-YBa 2 Cu 3 O x , CuO-Y 2 BaCuO 5 , and
CuO-Y 2 Cu 2 O 5 .
In the studies that follow, we have used pure start-
ing phases rather than mixtures of oxides. The purity is
ascertained by x-ray diffraction; impurities at a level of
several percent are not detected. These impurities may
give rise to small thermal events in the DTA, as de-
scribed in the results. Impurities observed in the powder
patterns of the samples resulting from the melting ex-
periments, however, are due to the fractional crystalli-
zation path that is followed during cooling. In this case,
the impurities provide information about the melting
event that occurred. Given the rapid cooling rates, if no
phases other than the starting phases are observed, the
melting was assumed to be of a eutectic nature.
First, the binary BaCuO 2 -CuO join was investigat-
ed. Two samples, runs 17 and 18 in Table I, were heated
to about 1000 °C in the DTA. Endotherms occurred at
920 and 912 °C in these two samples. As noted above,
BaCuO2 samples with CuO impurities showed an endo-
thermic event at 927 °C. This event is the BaCuO 2 -CuO
binary eutectic. X-ray patterns of the binary mixtures
after heating to 1000 °C revealed CuO, BaCuO 2 , and a
phase which was not immediately identified from the
JCPDS powder diffraction data file.26 This phase was
subsequently identified as BaCu 2 O 2 , as described be-
low.
Next, mixtures of BaCuO2 with YBa 2 Cu 3 O x and
Y 2 BaCuO 5 were studied, runs 19-21. In each experi-
ment, the onset of melting occurred at temperatures of
1000-1003 °C, which are very close to the melting tem-
perature of BaCuO 2 . In addition, these temperatures
are within 10 deg of the incongruent melting point of
YBa 2 Cu 3 O x . The sample from run 20 was x rayed fol-
lowing the DTA, and only Y 2 BaCuO 5 and a minor
amount of BaCuO2 were observed. The reduced x-ray
intensity of BaCuO2 relative to the starting materials
may be attributed to the wetting of the sample cup by the
liquid. The observance of only the starting phases in the
sample after melting indicates that a eutectic exists on
the Y2 BaCuO5 -BaCuO 2 tie line, and the closeness of
the eutectic temperature to the melting point of pure
BaCuO2 indicates that the eutectic composition is close
to BaCuO 2 . The beginning of melting of BaCuO 2 -
YBa 7 Cu 3 O x mixtures also occurs close to the BaCuO2
composition, however, the proximity to the
YBa 2 Cu 3 O x incongruent melting temperature prevents
an analysis based on x-ray diffraction data.
The observation of partial melting at 950 °C in mix-
tures on the CuO-YBa 2 Cu3 O x binary join by previous
investigators has already been noted. Our next studies
were of this melting event, in runs 22-26. In DTA ex-
periments, a small shoulder at about 890 °C was noted in
samples that contain a minor amount of impurity phase
1285
 T. Aselage and K. Keefer: Liquidus relations in Y~Ba-Cu oxides

[as in Fig. 2(a) ], followed by an endotherm with onset investigated by DTA, runs 27 and 28. In addition to a
temperatures in the range of 932-940 °C similar to those shoulder with an onset at 948 °C (which we attribute to
observed in the impure YBa2 Cu3 Ox. X-ray diffraction the CuO-YBa2Cu3OJC reaction with Y B a j C u ^ as a
of an equimolar sample following DTA indicated that, minor impurity in the Y 2 BaCuO 5 ), a melting event at
in addition to the starting YBa2Cu3O^ and CuO, 978 °C was observed. In the sample heated to 1125 °C,
Y2 BaCuO5 and BaCuO2 were produced. A DTA sam- we also observed an event at 1037 °C. The x-ray patterns
ple with a much larger molar ratio of CuO to of both samples, after DTA, revealed the presence of
YBa2Cu3O^ (80:20) also has Y2 BaCuO 5 present in ad- Y 2 Cu 2 O 5 and YBa2Cu3O;c in addition to Y 2 BaCuO 5
dition to the YBa 2 Cu 3 O x and CuO. Also, reflections and CuO. The sample heated to 1125 °C also had Cu 2 O
due to BaCu 2 O 2 were observed. The fact that present. The 1037 °C event corresponds to the CuO-
Y 2 BaCuO 5 was observed in both samples (where none Cu 2 O transition. The formation of Y 2 Cu 2 O 5 and
was initially present) indicates that the 940 °C event be- YBa2 Cu3 O^ are taken as evidence that the melting be-
tween CuO and YBa2Cu3O^. is not a simple eutectic, but tween CuO and Y2 BaCuO5 is not a simple eutectic.
rather a more complicated melting event. Finally, mixtures of CuO and Y 2 Cu 2 O 5 were ex-
Pressed pellets of these two compositions were amined. In addition to the CuO-Cu 2 O transition, a
heated in a tube furnace in flowing air to about 965 °C in melting endotherm with a shoulder at 1108 °C and ma-
an attempt to observe melting events visually. Although jor peak at about 1122°C were observed. These two
no flow was noted during the furnace treatment, the peaks correspond to the Cu 2 O-Y 2 Cu 2 O 5 eutectic and
CuO-rich sample had clearly rounded edges after remo- the incongruent melting of Y2 Cu2 O 5 , respectively. Al-
val from the furnace. X-ray diffraction patterns of both though the observed temperatures are close to each oth-
samples were obtained, and the 80 mole % CuO sample er, the observation of both in a single sample supports
was prepared for EMPA. Both samples showed clear the assignment.
evidence of Y 2 BaCuO 5 as well as CuO. YBa 2 Cu 3 O x
was present in both samples as well, although in minor
quantity in the 80 mole % CuO sample. In addition, x- C. Ternary mixtures of phases
ray reflections due to BaCu2 O2 were observed in both In this section we consider several experiments that
samples. EMPA suggested the presence of six stoichio- were performed with ternary mixtures of phases. The
metries in the 80 mole % CuO sample; in addition to the intent of these experiments is to provide additional in-
Y 2 BaCuO 5 , CuO, BaCu 2 O 2 , and YBa2Cu3OJC ob- formation about the noneutectic melting events ob-
served in the x-ray patterns, Cu2 O, and BaCuO2 were served in the binary mixtures, and to look for the possi-
found. The microprobe observations provided the stoi- bility of ternary eutectic formation. Similar phase purity
chiometry of the phase BaCu2 O 2 . The structure of this arguments pertain to this section as were given above.
latter phase has been reported from single-crystal We have performed three experiments, one each in the
work27; our observed reflections are listed in Table II YBa 2 Cu 3 O x -CuO-BaCuO 2 triangle, the YBa 2 Cu 3 0 x -
and agree very well with a pattern calculated28 from the Y 2 BaCuO 5 -CuO triangle, and the YBSL2CU3OX-
published crystal structure using the POWD10 comput- Y 2 BaCuO 5 -BaCuO 2 triangle.
er program. 29
The sample containing YBa 2 Cu 3 O x , CuO, and
Two binary mixtures of CuO and Y2 BaCuO5 were BaCuO2 showed three distinct thermal events, at 905,
937, and 970 °C. The 905 °C endotherm observed in this
sample and the shoulders noted above at 886-895 °C are
TABLE II. Calculated powder diffraction lines for BaCu2O2 (Ref.
the lowest melting temperatures in the system and cor-
27), and observed intensities. respond to the ternary eutectic. Although the sample
from the DTA run was not x rayed, x-ray patterns and
2THETA D(A) H K L Intensity energy dispersive x-ray analysis on crystal growth runs
on this and similar compositions indicate that the phase
28.28 3.153 1 1 2 S assemblage after solidification is YBa 2 Cu 3 O x plus CuO
30.87 2.894 1 0 3 S
31.24 2.861 2 0 0 W
plus BaCuO 2 . The 937 °C and 970 °C endotherms are
36.08 2.487 2 0 due to the reactions between CuO and YBa2Cu3O;c and
36.19 2.480 2 1
2i CuO and Y 2 BaCuO 5 . The sample in the Y 2 BaCuO 5
l\ vs
47.87 1.8988 1 0 + YBa 2 Cu 3 O x + BaCuO2 region did not melt until
48.12 1.8893 2 0
H
4? w 1004 °C, again indicating the proximity of the solidus
53.79 1.7027 3 1 2 w boundary to the BaCuO2 composition. The x-ray dif-
55.37 1.6581 3 0 3 w
58.50 1.5766 2 2 4 fraction pattern of the material after DTA did not differ
s
58.86 1.5676 3 2 1 s from the starting material. Finally, the sample in the
Y2 BaCuO5 + YBa 2 Cu 3 O x + CuO region exhibited en-

1286 J. Mater. Res., Vol. 3, No. 6, Nov/Dec 1988

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 T. Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides
dotherms at about 937 and 962 °C. The x-ray pattern of
this sample after DTA showed the presence of the start-
ing materials (the intensities of the YBa 2 Cu 3 O x reflec-
tions being enhanced), and, in addition, Y 2 Cu 2 O 5 and
BaCuO 2 . The presence of phases that were not in the
starting assemblage indicates that the melting event is
not a simple ternary eutectic.
IV. DISCUSSION
In order to piece together a picture of the liquidus
relations in the system, one must put the results and
observations described above into a consistent order.
We have relied heavily on the interpretation of disequi-
librium (fractional) crystallization paths in our inter-
pretation of the results. We have also relied on the
theorem of van Rijn van Alkemade (see, e.g., Ref. 30).
This theorem states that the point of intersection of the
boundary curve separating the primary crystallization
fields of two solid phases of fixed composition and the tie
line connecting the compositions of the two solid phases
or its extension is a maximum in temperature on the
boundary curve and a minimum in temperature on the
tie line. Although we have not performed the number of
experiments required tofixthe composition of the liquid
phases at the invariant points that we have determined,
geometric considerations such as van Rijn van Alke-
made's theorem and mass balance constraints provide
information about the possible locations of such points.
As an example, consider again the incongruent
melting of YBazOisCX, at 1015 °C to Y 2 BaCuO 5 and a
liquid. The texture of the resulting sample after cooling
indicates that the crystallization path was fractional,
i.e., the Y 2 BaCuO 5 was not able to completely react
with the liquid. The presence of Y2 BaCuO5 proves that
the melting was incongruent. The theorem of van Alke-
made provides additional information regarding this re-
action. Figure 5 shows the CuO-rich corner of the
YO 1 5 -CuO-BaO ternary composition triangle. The
constraint of mass balance dictates that the liquid
formed by the incongruent melting of YBa 2 Cu 3 O x to
Y2 BaCuO5 must lie on the extension of the line con-
necting these two phases. This point, labeled ml in Fig.
5, is on the boundary curve separating the primary crys-
tallization fields of Y 2 BaCuO 5 and YBa 2 Cu 3 O x (i.e.,
the curve in the composition diagram on which a three
phase equilibrium between a liquid with composition
along the curve and Y 2 BaCuO 5 and YBa 2 Cu 3 O x ex-
ists). Application of van Alkemade's theorem at point
ml tells us that ml is the maximum temperature along
the boundary curve (i.e., the highest temperature at
which Y 2 BaCuO 5 , YBa 2 Cu 3 O x , and liquid can coex-
ist), and a minimum temperature on the liquidus sur-
face along the line segment connecting m 1, Y2 BaCuO 5 ,
and YBa 2 Cu 3 O x .
J. Mater. Res., Vol. 3, No. 6, Nov/Dec 1988
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YO-i.5
Y2BaCu05 Y2Cu205
BaO -•
BaCuC>2 CuOv
FIG. 5. Ternary phase diagram of the liquidus surface in the system
YO, 5 -BaO-CuO ( in equilibrium with air. The positions of all bound-
ary curves and invariant points are approximate. The temperatures of
the observed invariant points are given in Table III. Eutectics are
denoted as "e," peritectics as "p," and melting points as "m." The
primary crystallization fields are labeled as follows: 200—Y 2 O 3 ,
202—YjCu 2 O 5 , 001—CuO^, 011—BaCuO2, 211—Y 2 BaCuO s ,
123—YBa2Cu3Oje.
In Table III, we have grouped similar observed
thermal events from Table I and assigned a reaction to
each. These reactions are listed along with the reaction
temperature (rounded to the nearest 5 deg unless evi-
dence indicates otherwise), the invariant point as la-
beled in Fig. 5, the reaction occurring at the invariant
point, and the observed thermal events and run numbers
from Table I. This table provides the major results of
this study.
The lowest melting point in the system is the ter-
nary eutectic between YBa 2 Cu 3 O x , CuO, and BaCuO 2 ,
invariant point el in Fig. 5. The temperature we ob-
serve, 890 °C, is consistent with previous reports.21 The
composition for run number 31 is that described by
Holtzberg et al.H as the point at which the largest
amount of melting occurred for compositions that they
investigated. Ba/Y ratios larger than 9 were not exam-
ined in Ref. 8. The thermal events that we observe in run
number 31 at 937 and 970 °C are due to the reactions of
YBa2Cu3OJC and Y 2 BaCuO 5 with CuO, showing that
these two phases are present after the ternary eutectic
melting and therefore that the sample at this composi-
tion is still more yttrium-rich than the eutectic composi-
tion. Therefore, the eutectic composition must lie very
close to the BaO-CuO boundary. This conclusion is also
supported by the similarity in temperature of el to the
binary eutectic temperature e2, about 920 °C.
We have not included the phase BaCu2 O2 on the
diagram shown in Fig. 5. This phase is observed in sever-
1287
 T. Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides

TABLE III. Temperature of observed invariant points, reactions at those points and experiments in which reaction was observed.

Temperature, °C Invariant point" Reaction11 Observed temperatures (run number) 0 , °C

818 r BaCO 3 -/?BaCO 3 817(9), 820(10)

890 el YBa2Cu,O^ + BaCuO2 + C u O - L ( e l ) 886(24), 887(23), 895(22), 905(31)
920 e2 BaCuO2 + CuO^L(e2) 912(18), 920(17), 927(10), 929(9)
940 Pi Y B a ^ u . O , + CuO^Y 2 BaCuO 5 + L ( p l ) 932(23), 934(24), 937(31), 937(33),
939 (1), 940(22), 941(3), 941(4),
945(5), 948(27), 948(28)
975 p2 Y2BaCuO5 + CuO-Y 2 Cu,O 5 + L(p2) 962(33), 970(31), 977(28), 980(27)
1000 e3 Y2BaCuO5 + BaCuO 2 -L(e3) 1000(20), 1000(21)
1000 p3 YBa,Cu 3 O, + BaCuO 2 ^Y 2 BaCuO 5 + L(p3) 1000(20), 1000(21), 1003(19), 1004(32)
1015 ml YBajCujO^ -. Y 2 BaCuO 5 + L(ml) 1013(5), 1014(1), 1020(6)
1015 m2 BaCuO 2 ^L(BaCuO 2 ) 1005-1010(12), 1014(11), 1015(9), 1024(10)
1026 CuO^Cu 2 O 1020(14), 1026(15), 1028(16), 1033(29),
1035(13), 1037(27)
1110 e4 Y 2 Cu 2 O 5 + Cu 2 O-»L(e4) 1108(30), 1111(13)
1122 m3 Y 2 Cu,O 5 ^Y 2 O, + L(m3) 1122(14), 1122(30)
1270 m4 Y 2 BaCuO,^Y 2 O 3 + L(m4) 1270(7), 1274(8)

aLabelof point in ternary phase diagram Fig. 5. The letter "e" is used for eutectics, "p" for peritectics, and "m" for melting points.
b The
approximate composition of each liquid is noted in parentheses.
Table I.

al samples that have two characteristics: a large concen-
tration of CuO and temperatures greater than some
melting event involving CuO. The Cu-O phase dia-
gram24-25 shows that CuO dissociates to Cu2 O plus O2
in an ambient of air at 1026 °C. Our experiments with
pure CuO agree quite well with this temperature. Upon
further heating, the Cu2 O melts to a liquid that contains
more oxygen than Cu2 O but less than CuO. According
to Ref. 25, this melting temperature is approximately
1130 °C. In an ambient of pure oxygen, CuO melts di-
rectly to a liquid that is between Cu2 O and CuO in com-
position. Thus, the tendency of CuO to form a liquid
with reduced oxygen content explains the observation of
the phase BaCu2 O2 under the described conditions. If a
Cu x O-rich liquid phase is formed under such condi-
tions, then oxygen uptake is required to form the equi-
librium Cu(II) crystalline phases. The formation of
such phases at the surface has already been shown to
limit the oxygen transport to the interior of such sam-
ples. This argument is supported by the reported prep-
aration conditions for pure BaCu 2 O 2 (Ref. 27): mixed
oxides were heated in pure argon (no moisture or air) at
900 °C, and samples were oxidized by exposure to labo-
ratory air. Thus we regard the presence of BaCu 2 O 2 as
arising from oxygen transport limitations rather than
from thermodynamics.
The formation of a liquid phase in compositions
along the CuO-YBa 2 Cu 3 O x join below 950 °C has been
reported by several authors, although the nature of the
reaction has not previously been investigated. We ob-
serve the onset of melting in these compositions at about
940 °C. If this melting were a simple eutectic, only
YBa 2 Cu 3 O x and CuO could be present in the melted
and cooled sample. However, several experiments along
this join indicate that at least Y2 BaCuO 5 and BaCuO2
are present in addition to YBa 2 Cu 3 O x and CuO. As dis-
cussed above, Y 2 BaCuO 5 can result from the partial
fractional crystallization of a sample heated above a per-
itectic point. We thus regard the 940 °C event between
CuO and YBa2Cu3OA as a ternary peritectic point at
which the primary phase field of YBa 2 Cu 3 O x is termin-
ated. This point is labeled pi in Fig. 5. The reaction that
occurs is
YBa 2 Cu 3 O x + CuO^Y 2 BaCuO 5 + L ( p l ) .
As the liquid cools, the reverse reaction occurs, with
YBa 2 Cu 3 O x formed by reaction of the liquid with
Y2 BaCuO 5 . However, as Y2 BaCuO5 is removed from
the system by the formation of a reaction shell of
YBa 2 Cu 3 O x around it, the liquid composition follows
the liquidus from pi to the ternary eutectic el at which
point BaCuO2 is crystallized. Again, although the evi-
dence confirms the presence of the ternary peritectic pi,
the information is not sufficient to precisely locate the
composition of pi.
Similar arguments can be applied to the melting re-
lations between Y2 BaCuO5 and CuO. Although nomi-
nally pure starting materials were used, the x-ray dif-
fraction results clearly show the presence of Y 2 Cu 2 O 5
and YBa 2 Cu 3 O x in the melted sample. In addition, the
diffraction patterns of the ternary composition studied
in the YBa 2 Cu 3 O x -Y 2 BaCuO 5 -CuO triangle also
showed Y2 Cu2 O 5 and BaCuO2 to be present after melt-
ing, with an increase in the relative intensities of the

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 T. Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides

YBa 2 Cu 3 O x reflections. This is evidence of a ternary that have been heated to 1300 °C; in other words, the
peritectic reaction between CuO and Y 2 BaCuO 5 that first phase to crystallize from a liquid of composition
forms Y2 Cu2 O 5 , viz., YBa 2 Cu 3 O x is Y 2 O 3 . Additionally, van Alkemade's
Y2BaCuO5 + CuO-^ Y 2 Cu 2 O 5 + L(p2). theorem requires that the intersection of the Y 2 O 3 -
Y2BaCuO5 boundary curve and the Y 2 O 3 -Y 2 Cu 2 O 5
The temperature of this point, labeled p2 in Fig. 5, is boundary curve be a ternary peritectic point. We have
about 975 °C. shown this junction on the ternary diagram (p4), al-
At the other end of the YBa 2 Cu 3 O x primary crys- though we have not investigated this reaction in any
tallization field, YBa 2 Cu 3 O x , Y 2 BaCuO 5 , BaCuO 2 , way.
and a liquid must be in equilibrium. However, thermal
Figure 5 represents our picture of the ternary
events in Y2 BaCuO 5 -BaCuO 2 or YBa 2 Cu 3 O x -
liquidus relations in this region of the YO[ 5 -CuO-BaO
BaCuO2 binary mixtures, or in the ternary mixture, are
ternary diagram. As we have pointed out, the reactions
not observed until the temperature is near the melting
and temperatures at which they occur are established,
temperatures of BaCuO2 and YBa 2 Cu 3 O x . This fact has
but our data are insufficient to locate the liquid compo-
made it difficult to determine if this coexistence point is
sitions accurately. The arrows on the boundary curves
a ternary peritectic or a ternary eutectic. In either case,
signify a decrease in temperature. Single arrows desig-
the location of this invariant point must be close in com-
nate congruent crystallization paths (i.e., L ^ A + B),
position to BaCuO 2 . When pure phases are used as
while double arrows designate incongruent crystalliza-
starting materials, little difference is observed between
tion paths (i.e., L + A ^ B ) . To help in visualizing the
the x-ray diffraction patterns of the starting materials
liquidus surface in such a diagram, one may draw a
and the materials after melting. This is true for both the
pseudobinary temperature-composition diagram for a
binary eutectic between Y2 BaCuO5 and BaCuO 2 , la-
cut through the ternary. Figure 6 is such a diagram, in
beled e3, and for the ternary composition. The ternary
which we have plotted the liquidus and solidus surfaces
invariant point is drawn as a peritectic point in Fig. 5
for a cut along the line connecting Y 2 BaCuO 5 and
based on the observation of several attempts to grow
YBa 2 Cu 3 O x . Here, the only temperature that is firmly
single crystals of YBa 2 Cu 3 O x using compositions near
established is that of ml, the incongruent melting point
the tie line between YBa 2 Cu 3 O x and BaCuO 2 .
ofYBa 2 Cu 3 O x ,at 1015 °C.
EMPA of these samples reveals the presence of small
In comparing our results to those reported pre-
Y2 BaCuO5 grains poikilitically enclosed within larger
viously, we have several observations that agree very
grains of YBaaCujO^, quite similar to the texture
well with previous reports and several that do not. The
shown in Fig. 3(b). Once again, this indicates the reac-
binary eutectic between BaCuO2 and CuO and the pres-
tion of Y 2 BaCuO 5 to form YBa 2 Cu 3 O x on cooling, in
ence of a low melting ternary eutectic have been well
this case
established. The incongruent melting of YBa 2 Cu 3 O x is
YBa2Cu3O;c + BaCuO 2 -*Y 2 BaCuO 5 + L(p3).
In any event, the primary crystallization field of
YBa 2 Cu 3 O x terminates near the composition of
BaCuO 2 .
As discussed previously, Y2 BaCuO5 melts incon-
gruently at 1270 °C to Y 2 O 3 plus a liquid with approxi- 5C
mate composition m4 in Fig. 5. Little evidence of
BaCuO2 is observed in the x-ray patterns after this melt- Ill 011 + L—
ing. The presence of BaCuO2 would be expected if, on s
HI 211
cooling, the liquid composition followed the liquidus 123+011
200
+001
surface to e3. However, the samples were heated to 210
1300 °C or higher in A12O3 sample cups and, as noted
above, molten BaCuO2 wets the A1 2 O 3 . In addition, 3BaCuO2 YBa 2 Cu 3 0 x Y 2 BaCu0 5
BaAl2 O 4 has been observed in samples that have been +2CuO
heated to high temperature in Al2 O 3 . Therefore, we re-
gard the presence of trace BaCuO2 and YBa 2 Cu 3 O x as
resulting from interactions between the BaO-rich liquid FIG. 6. Section through the ternary phase diagram along the join
YBajCujO-j-YjjBaCuO,. Positions of all lines are approximate ex-
phase and the sample containers.
cept for the incongruent melting point of YBa,Cu 3 O J[ . Omitted for
The boundary curve between Y 2 BaCuO 5 and simplicity is a small region where BaCuO2 and YBajC^CK, coexist
Y 2 O 3 is drawn in Fig. 5 such that Y 2 O 3 is on the with the ternary eutectic liquid el. The phases in coexistence regions
liquidus surface at the point YBa 2 Cu 3 O x . This is based are labeled as follows: 200—Y2 O,, 001—CuO, 011—BaCuO 2 ,211—
on the observation of Y2 O3 in samples of YBa 2 Cu 3 O x Y 2 BaCuO 5 , 123—YBa2Cu3Ox, 210—Y2BaO4 (Refs. 3-5).

J. Mater. Res., Vol. 3, No. 6, Nov/Dec 1988 1289

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 T. Aselage and K. Keefer: Liquidus relations in Y-Ba-Cu oxides
also well known although, as indicated in the introduc-
tion, the reported temperature of melting varies consid-
erably. We believe that the discrepancy is due to the
presence of ternary peritectic points at temperatures be-
low 1015 °C, so that the presence of impurity phases (or
the direct reaction of mixed oxides) may lead to the
lowering of the observed "melting temperature."
Our agreement with the previous preliminary
liquidus study 2 ' is limited to the points listed above. As
outlined previously, our evidence indicates that the re-
gion near the YBa 2 Cu 3 O x -CuO tie line is characterized
by two ternary peritectic points, one at the intersection
of the phase fields of YBa 2 Cu 3 O x , CuO, and Y2 Ba-
CuO 5 , and the other at the intersection of those of CuO,
Y2 BaCuOj, and Y2 Cu2 O 5 . The previous report lists a
ternary eutectic between Y2 BaCuO 5 , YBa 2 Cu 3 O x , and
CuO at about 930 °C. The explanation for this discrep-
ancy may be the use of mixed oxides as starting materi-
als rather than the pure compounds used in this study.
This may also explain the difference on the BaO-rich
side of the YBa 2 Cu 3 O x field, where the previous investi-
gation found that Y2 BaCuO5 and BaCuO2 coexist only
in the subsolidus region below 960 °C. We have heated
binary mixtures of these phases up to temperatures near
1100°C, with no indication that they are not on the
liquidus. Likewise, we see no thermal events occurring
until 1000 °C, unlike previous reports of melting on the
YBa 2 Cu 3 O x -BaCuO 2 tie line at less than 950 °C (Refs.
3 and 21).
There are several important implications for pro-
cessing of YBa 2 Cu 3 O x that result from this investiga-
tion. As noted above, heating impure YBa 2 Cu 3 O x to
temperatures between 950 and 1000 °C helps remove the
impurity phases from the sample (Fig. 2). The liquid
phase generated by the peritectic reaction between CuO
impurities and YBa 2 Cu 3 0 x facilitates complete reac-
tion. Holding at temperature for several hours (as in
runs 1-5, and as opposed to the rapid cooling imposed in
later runs) allows the reaction to go to completion.
Thus, heating to temperatures above 940 °C is beneficial
for synthesis. However, the formation of the liquid
phase may also enhance grain growth in YBazCujO^.
ceramics. Small volume contractions due to the inver-
sion from tetragonal to orthorhombic symmetry is be-
lieved to induce cracking in ceramic samples. Thus, a
small grain size is preferred for the ceramic microstruc-
ture, and heating above 940 "C would be detrimental.
The implications of the results for single-crystal
growth are consistent with the many reports of crystal
growth in the literature.8™12 The best results are ob-
tained for sample compositions within the primary
crystallization field of the YBa 2 Cu 3 0 x phase. Melting
YBa 2 Cu 3 O x produces Y2 BaCuO 5 ; in order to recrys-
tallize it as a pure phase the cooling cycle must proceed
slowly enough for the peritectic reaction to go to com-
1290 J. Mater. Res., Vol. 3, No. 6, Nov/Dec 1988
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pletion. Indeed, because of fractional crystallization, it
is unlikely that pure YBajC^O,, is attainable by such
processing. Melt processing that involves rapid cooling
such as melt spinning and plasma spraying inherently
result in the formation of Y2 BaCuO5 and/or Y2 O 3 , de-
pending on the temperature of the liquid. These inclu-
sions may be beneficial, however, as it is possible that
inclusions of Y2 BaCuO5 or Y2 O3 may act as magnetic
flux pinning sites.
V. CONCLUSIONS
The liquidus relationships in the CuO-rich corner
of the YO, 5-BaO-CuO ternary diagram have been in-
vestigated using the pure phases of interest. Invariant
temperatures and reactions have been determined, al-
though the compositions of the liquid phases at these
invariant points have not been determined. A total of
eleven invariant points have been identified, including
the incongruent melting points of YBa 2 Cu 3 O x and
Y 2 BaCuO 5 . The former occurs at 1015 °C resulting in
Y 2 BaCuO 5 plus liquid, the latter at 1270 °C producing
Y2 O 3 plus liquid. In addition, ternary peritectic points
between CuO, YBa 2 Cu 3 O x , and Y 2 BaCuO 5 (940 °C);
CuO, Y 2 BaCuO 5 , and Y 2 Cu 2 O 5 (975°C); and be-
tween BaCuO 2 , YBajCujO^, and Y 2 BaCuO 5
(1000 °C) have been identified. The incongruent melt-
ing of YBa 2 Cu 3 O x and the fact that Y2 O3 is the phase
on the liquidus surface at this composition prevent the
processing of pure YBa 2 Cu 3 O x directly from the melt.
The ternary peritectic reaction between YBa 2 Cu 3 O x
and CuO at 940 °C is responsible for liquid phase forma-
tion, enhanced phase purity, and grain growth observed
at this and higher temperatures.
ACKNOWLEDGMENTS
X-ray diffraction spectra were obtained by M. O.
Eatough, R. G. Tissot, and R. Lujan; electron micro-
probe data by P. F. Hlava, and DTA data by E. Bina-
siewicz and S. Van Deusen. Technical assistance was
proved by Z. Lawson. W. F. Hammetter and W. H.
Casey contributed several useful discussions.
This work performed at Sandia National Laborato-
ries supported by the U.S. Department of Energy under
contract number DE-AC04-76DP00789.
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