J. Am. Ceram. Soc.
, 87 [8] 1559 –1566 (2004)
journal
Thermodynamic Modeling of the YO1.5–ZrO2 System
Department of Materials Science and Engineering, The Pennsylvania State University,
The YO1.5–ZrO2 system consists of five solid solutions, one
liquid solution, and one intermediate compound. A thermody-
namic description of this system is developed, which allows
calculation of the phase diagram and thermodynamic proper-
ties. Two different solution models are used—a neutral species
model with YO1.5 and ZrO2 as the components and a charged
species model with Y3ⴙ, Zr4ⴙ, O2ⴚ, and vacancies as compo-
nents. For each model, regular and subregular solution param-
eters are derived from selected phase equilibrium and ther-
modynamic data. The neutral species and charged species
modeling results are compared.
I. Introduction
O NE of the most important ceramic oxides is the YO1.5–ZrO2
system. Compositions within this system find such wide-
spread applications as thermal barrier coatings in gas turbines,
electrolytes in fuel cells, and high-temperature crucibles. To gain
a better insight into their behavior and further improve their
performance, it is essential to understand the thermodynamic
properties of these materials. Today thermodynamics involves
both experimental measurements and development of databases
which contain the Gibbs energies of the individual phases.1 These
databases are constructed as follows. A thorough examination of
available experimental data is conducted. The parameters in
appropriate solution models are derived from these data. The goal
is to obtain a set of relatively simple equations which provide a
complete thermodynamic description of a system—all phase
boundaries and thermodynamic properties can be calculated
through minimization of the Gibbs energy under given conditions.
Further, binary system descriptions are building blocks for higher
order systems.
There are numerous studies of the YO1.5–ZrO2 system in the
literature. Metastable phases are readily formed in this system, and
it is important to recognize which data correspond to equilibrium
J. R. Hellman Jr.—contributing editor
Manuscript No. 10409. Received July 21, 2003; approved March 10, 2004.
This work was supported financially from the Ultra-Efficient Engine Technology
Program, NASA Aerospace Technology Enterprise (to N.S.J.) and the NSF Career
Award (to Z.-K.L.) under Grant DMR-9983532.
**Fellow, American Ceramic Society.
1559
Nathan S. Jacobson**
NASA Glenn Research Center, Cleveland, Ohio 44135
Zi-Kui Liu
State College, Pennsylvania 16803
Larry Kaufman
Consultant, Brookline, Massachusetts 02146
Fan Zhang
Computherm LLC, Madison, Wisconsin 53719
phases and which data correspond to metastable phases. There are
several calculations of the YO1.5–ZrO2 system in the literature.
Kaufman2 approaches this type of psuedobinary by treating each
neutral species (i.e., YO1.5 and ZrO2) as a component. This readily
allows development of quite useful databases with a minimum
number of parameters. The experimental phase diagram for
YO1.5–ZrO2 is dominated by a large cubic phase field for ZrO2 as
well as a smaller phase field for YO1.5. Degtyarev and Voronin3,4
point out that the YO1.5 structure can be derived from the ZrO2
structure by removing two oxygen anions. Thus they treat the two
phases as one cubic phase with a miscibility gap. Du et al.5,6 model
the YO1.5–ZrO2 system using the miscibility gap simplification
and treating YO1.5 and ZrO2 as components. They conduct a
thorough literature survey and derive their model parameters using
experimental data.7 They use only limited experimental data below
⬃1300 K, due to difficulties in attaining equilibria. Yokokawa8
calculates the YO1.5–ZrO2 diagram and phase diagrams for a
number of other rare earth oxide–zirconia systems. He also treats
the neutral species as components and derives solution parameters
from both phase-boundary data and correlations between ionic
radii of the rare earth oxides. Fabrichnaya and Aldinger9 have
calculated the YO1.5–ZrO2 pseudobinary as part of an assessment
of the YO1.5–Al2O3–ZrO2 using a charged species model. Chen et
al.10 have recently modeled the Y–Zr–O system using a charged
species model, including the nonstoichiometry of ZrO2.
In this paper we examine available experimental equilibrium
data for the YO1.5–ZrO2. We construct two databases— one based
on neutral species (YO1.5 and ZrO2) and one based on charged
species (Y3⫹, Zr4⫹, O2⫺, and vacancies). We examine the avail-
able experimental data and derive parameters from these data.
II. Review of Experimental Data
(1) End Members
Gibbs energies with the standard element reference state (SER)
are used to describe the end members. We will focus on a cut
through the Y–Zr–O ternary and thus select YO1.5 and ZrO2 as the
end members. We designate yttrium oxide as YO1.5 instead of
Y2O3 to maintain a 1:1 cation ratio in this system. For a given
composition in the Y2O3–ZrO2 system, the equivalent composition
in the YO1.5–ZrO2 system is given by
2x共Y2O3 in Y2O3⫺ZrO2兲
x 共YO1.5 in YO1.5⫺ZrO2兲 ⫽ (1)
1 ⫹ x共Y2O3 in Y2O3⫺ZrO2兲
1560 Journal of the American Ceramic Society—Jacobson et al. Vol. 87, No. 8
†
Table I. Heats of Transition
Phase transition Temperature (K) (reference) ⌬transH (kJ/mol) (reference)

ZrO2 (monoclinic 3 tetragonal) 1445 (Gurvich et al.11) 5.94 (Coughlin and King12)
ZrO2 (monoclinic 3 tetragonal), from modeling 1448 (Arroyave et al.17) 5.94 (Arroyave et al.17)
ZrO2 (monoclinic 3 tetragonal), from modeling 1476 (Liang et al.16) 6.53 (Liang et al.16)
ZrO2 (tetragonal 3 cubic) 2620 (Gurvich et al.11) 0–5.5 (see discussion in Lee et al.13)
ZrO2 (monoclinic 3 tetragonal), from modeling 2641 (Arroyave et al.17) 6.04 (Arroyave et al.17)
ZrO2 (monoclinic 3 tetragonal), from modeling 2625 (Liang et al.18) 21.7 (Liang et al.18)
ZrO2 (cubic 3 liquid) 2983 (Gurvich et al.11) 90 (Gurvich et al.11)
ZrO2 (cubic 3 liquid), from modeling 3048 (Arroyave et al.17) 111 (Arroyave et al.17)
ZrO2 (cubic 3 liquid), from modeling 2961 (Liang et al.18) 86.5 (Liang et al.18)
YO1.5 (C-type 3 cubic) 2493‡ (Katagiri et al.14) 24.3 (Lee et al.13)
YO1.5 (C-type 3 hexagonal) 2600 (Shpil’rain et al.15) 12.5 (Shpil’rain et al.15)
YO1.5 (C-type 3 hexagonal), from modeling 2600 (Swamy et al.18) 12.5 (Swamy et al.18)
YO1.5 (hexagonal 3 liquid) 2703 (Shpil’rain et al.15) 42 (Shpil’rain et al.15)
YO1.5 (hexagonal 3 liquid), values used in modeling 2712 (Swamy et al.18) 42 (Swamy et al.18)
†
Data are from tabulations and experiments unless indicated as being from previous modeling studies. ‡Approximate.

Table I lists the phases of YO1.5 and ZrO2 and enthalpies of following brief review of experimental phase-boundary data, we
transformation.11–18 Both experimentally measured enthalpies of emphasize data over 1400 K. We discuss the experimental studies
transformation are listed and those derived from recent modeling and select data to be used in the present study to determine model
studies of the Zr–O system16,17 and the Y–O system.18 Note that parameters.
YO1.5 may have three different structures. The phase stable over a There have been three measurements of the liquidus line.23–25
wide range of temperature is the C-type phase or bixbyite phase.18 This is in the 3000 K range, and accurate temperature measure-
Most investigators report a high-temperature hexagonal phase.18 ment is extremely difficult. Skaggs25 used a laser heating method
However a cubic phase has also been reported at high tempera- to create a “pendant drop”. Temperature measurements were taken
tures.14 It is unclear whether there are two high-temperature phases with a small amount of solid in the drop and then again with
or one cubic high-temperature phase or one hexagonal high- approximately half the drop solid. The average of these gave the
temperature phase.18 Our calculated phase diagram will include liquidus temperature. However, these data show a large amount of
C-type YO1.5 and a high-temperature hexagonal phase; however, scatter and are not used in the present study. Noguchi et al.23 used
we consider a cubic form of YO1.5 in developing the database. a solar furnace in conjunction with a pyrometer. Cooling curves
Table II lists the Gibbs energies for the four phases of zirconia clearly revealed the solidification point. Rouanet24 has used a
and three phases of yttria.11–19 There is as yet no universally similar technique, and his data are in basic agreement with those of
accepted choice of standard reference energies for compounds. Noguchi et al.23 The data of Noguchi et al.23 are thus used in the
However, it is essential to specify the reference energies chosen. present modeling study.
The Gibbs energy for the room-temperature phases are taken from The ZrO2-rich side of the diagram is the area of the greatest
the SGTE19 database. The Gibbs energies for the higher temper- technological interest. As noted, the equilibrium phases of ZrO2
ature phases are derived from the experimental tabulated phase- are monoclinic, tetragonal, and cubic as temperature increases.
change data given in Table I.11–18 These phase-change data are Yashima et al.22 point out that there are two metastable tetragonal
consistent with those chosen by other investigators in modeling phases, which are designated as t⬘ and t⬙. There is also a metastable
studies of the Zr–O16,17 and Y–O18 systems. monoclinic phase, which is designated as m⬘. Yashima et al.22
have proposed both a stable phase diagram and a metastable phase
(2) Phase-Boundary Data for the Solution Phases diagram, the latter including only the t⬘, t⬙, and m⬘ phases.
A recent compendium20 lists 12 different experimental phase Consider first the monoclinic phase, which is stable below 1445
diagrams for the YO1.5–ZrO2 system. There are many discrepan- K. A number of investigators have measured a monoclinic to
cies among the experimental phase-boundary measurements, par- tetragonal phase transformation as a function of mole fraction of
ticularly at low temperatures. The YO1.5–ZrO2 system can be YO1.5. This transformation is accompanied by a 3%–5% volume
viewed as a rigid cation lattice with mobile anions. Due to the low increase and is readily observed with dilatometry.26 –28 All inves-
diffusivity of the cations, phase changes are very slow at low tigators show that the transformation temperature decreases with
temperatures. Yoshimura21 and Yashima et al.22 show that only increasing YO1.5 content. However, on the basis of the slow
data above ⬃1400 K can be regarded as equilibrium data. This diffusion arguments of Yashima et al.,22 it seems unlikely that
explains many of the discrepancies in the literature. In the these are true equilibrium measurements. Nonetheless, it is rea-
sonable to expect a small amount of solubility of YO1.5 in ZrO2.
We follow the proposed stable phase diagram of Yashima et al.22
and allow about 0.005 mole fraction solubility of YO1.5 in ZrO2.
Table II. Gibbs Energies for End Members
The cubic/tetragonal equilibria at the ZrO2-rich side has been
Phase Abbreviation Gibbs energy (J/mol) studied by a number of investigators.27,29 –39 Duwez et al.29 used
X-ray diffraction (XRD) to determine the cubic/(cubic ⫹ tetrago-
Monoclinic ZrO2 mz Gmz(T) (see Ref. 19) nal) boundaries at 1648 and 2273 K. Ruh et al.,27 Scott,30 Stubican
Tetragonal ZrO2 tz Gmz(T) ⫹ 5940 ⫺ 4.11T et al.,31–34 and Pascual and Duran36 have taken similar measure-
Cubic ZrO2 cz Gmz(T) ⫹ 9700 ⫺ 5.55T
Liquid ZrO2 lz in liq Gmz(T) ⫹ 99700 ⫺ 35.71T ments with XRD. Lanteri et al.,35 Rühle et al.37 and Chaim et al.38
C-type ZrO2 Cz Gmz(T) ⫹ 20000 used analytical electron microscopy (AEM) to determine the
Hexagonal ZrO2 hz Gmz(T) ⫹ 20000 tetragonal/(tetragonal ⫹ cubic)/cubic phase boundaries. Yo-
C-type YO1.5 Cy Gcy(T) ⫽ 0.5GY2O3(T) shikawa et al.39 used electron microprobe analysis to determine
(see Ref. 19) these phase boundaries. For the tetragonal/(cubic ⫹ tetragonal)
Hexagonal YO1.5 hy Gcy(T) ⫹ 12550 ⫺ 4.83T phase boundaries the data of Ruh et al.,27 Chaim et al.,38 and
Liquid YO1.5 ly in liq Gcy(T) ⫹ 54390 ⫺ 20.31T Yoshikawa et al.,39 all show reasonably good agreement and are
Monoclinic YO1.5 my Gcy(T) ⫹ 20000 used in this study. For the cubic/(cubic ⫹ tetragonal) phase
Tetragonal YO1.5 ty Gcy(T) ⫹ 20000
Cubic YO1.5 cy Gcy(T) ⫹ 20000 boundary, the Chaim et al.38 and Yoshikawa et al.39 data show
good agreement and are used.
August 2004 Thermodynamic Modeling of YO1.5–ZrO2 1561

Table III. Experimental Invariant Points and Decomposition Temperature of Delta Phase
Temperature
Invariant (K) xYO1.5 Reference Comments

Eutectic liq ⫽ hy ⫹ cy 2688 0.899 31

2603 0.864 23
2646 0.904 24
Peritectic cy ⫽ liq ⫹ hy 2720 0.875 31 Introduced, not measured
Euctectoid cz ⫽ delta y ⫹ cy 1650 0.606 33
Euctectoid tz ⫽ mz ⫹ cz 1273 0.05 22 Difficult to attain equilibria at this low temperature
Euctectoid cz ⫽ mz ⫹ delta 500 0.4 31 Difficult to attain equilibria at this low temperature,
estimated
Decomposition temperature of 1523 0.571 31
delta phase
1655 0.571 33

As noted, there is a large cubic ZrO2-rich region40 and a smaller
C-type YO1.5-rich region, as well as a large region of the two
phase equilibria between them. Stubican et al.31–34 have deter-
mined the phase boundaries of both sides of this two-phase field by
XRD. Pascual and Duran36 have also used XRD to determine the
cubic ZrO2/(cubic ZrO2 ⫹ cubic YO1.5) boundary. Their data are
higher in mole fraction of YO1.5 than the data of Stubican et
al.31–34 The measurements of Jayaratna et al.41 for the cubic
ZrO2/(cubic ZrO2 ⫹ cubic YO1.5) boundary show good agreement
with those of Stubican et al.31–34 The data of Stubican et al.31–34
are used in this present modeling study.
There are less data on the YO1.5-rich side of the diagram. It is
dominated by the C-type YO1.5 phase, which transforms to the
hexagonal YO1.5 phase at high temperatures. The liquidus data in
this region and the phase boundary data are from Stubican et
al.31–34 However, their melting point for pure YO1.5 is 2782 K,
whereas the accepted melting point is 2712 K18. Therefore the
YO1.5-rich liquidus data of Stubican et al.31–34 are given less
weight in this modeling.
There is one confirmed intermediate compound in this system—
Y4Zr3O12 or the delta phase.31–34 This phase decomposes to the
cubic ZrO2 solution on heating. There is some controversy over its
decomposition temperature—we shall take the more recent results
of Stubican,32–34 which place it at 1655 K. Other investigators
have reported a pyrochlore-type compound of the form Zr2Y2O7.36
However the existence of this compound is controversial,42 since
many investigators have not observed it. Therefore it is not
considered in the present study.
There are five invariant points in the experimental phase
diagram. These are listed in Table III. The low-temperature
eutectoids cannot be placed with any certainty due to long
equilibration times. The most controversial and technologically
important of these is the monoclinic–tetragonal– cubic ZrO2 eu-
tectoid. This has been reported at temperatures ranging from ⬃750
to ⬃1350 K and with xYO1.5 ⬃ 0.03– 0.08.22 We use the value of
1273 K and xYO1.5 ⫽ 0.05, recommended by Yashima et al.22 The
lowest temperature euctectoid—monoclinic– cubic– delta—is at a
very low temperature and therefore cannot be measured.
Yokokawa et al. show the cubic phase is not stable at temperatures
below about 500 K.8 Stubican et al.31–34 have proposed this
low-temperature eutectoid at xYO1.5 ⬃ 0.4 and T ⬃ 500 K. We
include this eutectoid in our calculations but recognize it cannot be
placed with certainty.
There are also some partial molar thermodynamic data. Vintoyak
et al.43 have used a solid-state electrochemical cell at 1300 K to
measure the activity of Y2O3 in both tetragonal and cubic
solutions. As noted, equilibrium at this low temperature is difficult
to attain. The data for the tetragonal phase were not used in this
study; the data for the cubic phase were given less weight than the
higher temperature data discussed below. These data of Vintoyak
et al.43 are listed in Table IV.
Belov and Semenov44 used a vapor pressure method to measure
Y2O3 and ZrO2 activities at 2773 K across the entire composition
range. Their data indicate a single phase, whereas the accepted
liquidus measurements indicate that at 2773 K with increasing
x(YO1.5) there would be a region of cubic ZrO2, coexistence of
ZrO2 and liquid, and at high xYO1.5 only liquid. For this reason Du
et al.5,6 use only the first three data points for the cubic phase field;
we shall do the same. It is important to recognize the relationship
between the activity of YO1.5 and the activity of Y2O3.45 A simple
equilibrium can be written as follows:
2YO1.5 ⫽ Y2O3 (3a)
a YO1.5 ⫽ 冑aY2O3 (3b)
The vapor pressure data were taken with a Knudsen cell mass
spectrometer, which operates in a vacuum. Hence, it is not directly
comparable to the other data used in this study, which were taken
in air. We give it a lower weight than the other thermodynamic
data.
Lee et al.13 have measured the enthalpy of formation of the
intermediate compound delta phase as ⫺5.38 ⫾ 1.8 kJ/mol for
0.5714YO1.5(C-type) ⫹ 0.4286ZrO2(monoclinic)
⫽ Y0.5714Zr0.4286O1.7142 (4)
This shows very good agreement with first principles calculations
of ⫺5.4 kJ/mol.46
III. Results
(1) Neutral Species Model and Results
Each of the solutions are modeled with the reference Gibbs
energies, a random mixing term, and a Redlich–Kister polynomial1,47

(3) Thermodynamic Data for Solution Phases Table IV. Measured43 and Calculated Activities of YO1.5 in
Cubic YO1.5–ZrO2 at 1300 K
Thermodynamic data on the YO1.5–ZrO2 system are limited.
Calculated
Enthalpies of mixing for oxides tend to be very small. Lee et al.13
Neutral Charged
have recently reported heats of formation for YO1.5-stabilized xYO1.5 Measured 43
species model species model
cubic ZrO2. Extreme care was taken in their measurements to
ensure the presence of the cubic phase. Their data are reported with 0.165 4.47 ⫻ 10⫺3 8.11 ⫻ 10⫺3 2.34 ⫻ 10⫺2
respect to YO1.5 (C-type) and ZrO2 (monoclinic). 0.261 2.81 ⫻ 10⫺2 2.50 ⫻ 10⫺2 5.28 ⫻ 10⫺2
0.400 0.148 0.110 0.160
xYO1.5共C-type兲 ⫹ 共1⫺x兲ZrO2共monoclinic兲 0.462 0.286 0.207 0.263
0.519 0.583 0.359 0.414
⫽ xYO1.5䡠共1⫺x兲ZrO2共cubic solid solution兲 (2)
1562 Journal of the American Ceramic Society—Jacobson et al. Vol. 87, No. 8

Table V. Interaction Parameters for the YO1.5–ZrO2 fields. The smaller phase regions were added by fine-tuning the
System with the Neutral Species Model parameters.
Table V lists the model parameters thus obtained. Figure 1 is the
Phase Parameter Value (J/mol)
calculated phase diagram. The data points are for the experimental
Liquid L 0
⫺106150 ⫹ 2.5T data indicated. The invariants are reproduced, and the phase
YO1.5,ZrO2
L 1
⫺31600 boundaries show agreement with the experimental phase bound-
YO1.5,ZrO2
aries within experimental uncertainties. It should be noted that the
Cubic ZrO2 L 0
YO1.5,ZrO2 ⫺77000 ⫺ 4T
1 YO1.5-rich side of the diagram is less certain than the ZrO2-rich
L YO1.5,ZrO2 20000 side, due to the lack of experimental data input to the model
Tetragonal ZrO2 L 0
YO1.5,ZrO2 ⫺52000 ⫹ 3T parameters. Experimentally, the eutectic is uncertain and very
Monoclinic ZrO2 L 0
YO1.5,ZrO2 ⫺20000 close to the melting point of YO1.5. This is, of course, true for the
Hexagonal YO1.5 L 0
YO1.5,ZrO2 ⫺42000 calculated diagram as well. The delta/cubic ZrO2/C-type YO1.5
C-type YO1.5 L 0
YO1.5,ZrO2 ⫺35000 ⫺ 11T eutectoid is similarly uncertain. Figure 2 is a calculation of the heat
L 1
YO1.5,ZrO2 ⫺22000 of formation for the cubic ZrO2 solution. Figure 3 is a plot of
Y0.5714Zr0.4286O1.7142 C ⫹ DT ⫺8898 ⫺ 6T activity of YO1.5 and activity of ZrO2 at 2773 K compared with the
experimental data of Belov and Semenov.44 Agreement is reason-
able, and the calculated data indicate the expected two-phase
region. Table IV compares the calculated activity values of YO1.5
to describe the excess free energy: at 1300 K to those measured by Vintoyak et al.,43 and agreement
is good. The enthalpy of formation for the intermediate delta phase

冘 冘 (reaction (4)) was calculated to be ⫺8.9 kJ/mol, which is a little

2 2

G mix共x, T兲 ⫽ xiG⬚i 共T兲 ⫹ RT xi ln xi ⫹ Gmix

excess
(5a) higher than the measured value of ⫺5.38 kJ/mol.
i⫽1 i⫽1

冘
n (2) Charged Species Model and Results
excess
G mix ⫽ x1x2 L j共x1 ⫺ x2兲 j (5b) The second solution model uses cation and anion sublattices.
j⫽0 Consider a two-component solution with two sublattices, written
(A⫹,B⫹)p(C⫺,D⫺)q, where p and q indicate the number of sites in
Here xi is the mole fraction of component i, °Gi(T) the lattice each sublattice. Consider first the liquid solution. The ionic model
stability of that component (Table II), L j are the interaction (within ThermoCalc) was used for the liquid phase.48,49 This is the
parameters, R is the gas constant, and T is the absolute tempera- Temkin model50 which assumes ideal mixing within the cation
ture. In this assessment, only the first two terms of the Redlich– “sublattice” and ideal mixing within the anion “sublattice”. Since we
Kister polynomials (regular and subregular solution parameters) are examining a cut in the Y–Zr–O ternary, we need only consider the
were used: two cations. Following Hillert et al.48 we may consider the liquid as
composed of two sublattices and write the liquid as follows:
excess
G mix ⫽ x1x2L0 ⫹ x1x2L1共x1 ⫺ x2兲 (6)
共Y3⫹,Zr4⫹兲p共O2⫺兲q (8a)
Each interaction parameter is expressed as
L ⫽ A ⫹ BT (7) Here p and q are defined as

These interaction parameters were evaluated from the experimen- p ⫽ 2y O2⫺ ⫽ 2 (8b)
tal data via the optimizing code Parrot in ThermoCalc†. First the
rough YO1.5–ZrO2 diagram was obtained by fitting the liquidus q ⫽ 3y Y3⫹ ⫹ 4yZr4⫹ (8c)
and the approximate boundaries of the large cubic ZrO2 phase
The two reference points are thus Y2O3 and Zr2O4, and the
reference energy for this system is

† G⬚ ⫽ y°Y3⫹GY2O3 ⫹ 2yZr4⫹G°ZrO2 (9)

ThermoCalc, Ver. P., ThomoCalc Software, Stockholm, Sweden.

Fig. 1. Phase diagram calculated from neutral species model.

August 2004 Thermodynamic Modeling of YO1.5–ZrO2 1563

This covers the entire composition range from ZrO2 to YO1.5. Now
the compound energy formalism1,49 must be used to obtain the
reference energy for this phase as follows. The reference state is
G⬚ ⫽ y YI 3⫹yOIII2⫺G°YO2 ⫹ yZr
I III
ZrO2 ⫹ yY3⫹yVaG°
4⫹yO2⫺G°
I III
YO1.5

⫹ y Zr
I III
4⫹yVaG°ZrO1.5 (13)

We need to define the Gibbs energies for each of the pure

compounds listed. This is clear for the stable compounds YO1.5
and ZrO2, but not clear for the fictive compounds YO2 and ZrO1.5.
Since the compounds YO2 and ZrO1.5 are unstable, their Gibbs
energies have been derived by adding a positive number to the
stable compound of YO1.5 and ZrO2, respectively. This positive
number can be optimized using experimental data if such data are
available. In this study, a reasonable number is selected by trying
three positive numbers of different magnitude, as given below:
G°ZrO1.5 ⫽ G°ZrO2⫺cubic ⫹ 2000, 20000, 200000 (14a)

G°YO2 ⫽ G°YO1.5⫺C-type ⫹ 2000, 20000, 200000 (14b)

This variation had a dramatic effect on the required parameters for

Fig. 2. Heat of mixing for cubic YO1.5–ZrO2 from C-type YO1.5 and
monoclinic ZrO2 from the neutral species model. Data points are from Lee
et al.13
As noted, the ionic model determines the configurational entropy
by assuming random mixing in both the cation and the anion
sublattices:
the cubic phase. Using 20 000 J/mol for both fictive compounds
led to reasonable magnitudes of the model parameters developed
for the cubic phase.
The ideal Gibbs energy of mixing is calculated for each
sublattice. It is important to note that this is not strictly correct, as
strong experimental and theoretical evidence46 indicates a degree
of order in these sublattices. However, the additional temperature
dependence terms in the excess free energy term permit compen-
sation for the overestimate of entropy.

冘 冘
ideal
S mix The full excess Gibbs energy term becomes quite complex for
⫽ ⫺p yi ln yi ⫺ q yj ln yj (10) a three-sublattice model. It is written as follows with only zero-
R
i j and first-order interaction parameters:
Now we need the excess free energy. As in the neutral species excess
G mix ⫽ yYI 3⫹yZr
I
4⫹yO2⫺共L
III
Y3⫹,Zr4⫹:O2⫺:O2⫺
model, we take only the regular and subregular solution terms:
⫹ L Y1 3⫹,Zr4⫹:O2⫺:O2⫺共 yYI 3⫹ ⫺ yZr
I
4⫹兲)
excess
G mix ⫽ yY3⫹yZr4⫹共LY0 3⫹:Zr4⫹ ⫹ LY1 3⫹:Zr4⫹共 yY3⫹ ⫺ yZr4⫹兲兲 (11)
⫹ y YI 3⫹yZr
I
4⫹yVa共LY3⫹,Zr4⫹:O2⫺:Va
III 0
As in expression (7), each interaction parameter is given a
temperature-dependent and temperature-independent term. ⫹ L Y1 3⫹,Zr4⫹:O2⫺:Va共 yYI 3⫹ ⫺ yZr
I
4⫹兲)
Consider next the cubic ZrO2 phase, which we describe with
three sublattices: ⫹ y Va yY3⫹yOIII2⫺共LY0 3⫹:O2⫺:O2⫺,Va
III I

共Y ,Zr 兲1共O 兲1.5共O ,Va兲0.5

3⫹ 4⫹ 2⫺ 2⫺
(12)
⫹ L Y1 3⫹:O2⫺:O2⫺,Va共 yOIII2⫺ ⫺ yVa
III
兲)

⫹ y OIII2⫺yVa yZr4⫹共LZr
III I 0
4⫹:O2⫺:O2⫺,Va

⫹ L Zr
1
4⫹:O2⫺:O2⫺,Va共 yO2⫺ ⫺ yVa兲)
III III

⫹ y YI 3⫹yZr
I
4⫹yVayO2⫺共LY3⫹,Zr4⫹:O2⫺:O2⫺,Va兲
III III 0
(15)

To attain our goal of describing this system with as few parameters

as possible, we must simplify this expression. It is reasonable to

Table VI. Interaction Parameters for the YO1.5–ZrO2

System from the Charged Species Model
Phase Parameter Value (J/mol)

Liquid L 0
Y3⫹,Zr4⫹:O2⫺ ⫺83720 ⫹ 17T
L 1
Y3⫹,Zr4⫹:O2⫺ ⫺82140
Cubic ZrO2 L 0
3⫹ 4⫹ 2⫺
Y ,Zr :O :O
2⫺ ⫺72000 ⫹ 14T
L 1
Y3⫹,Zr4⫹:O2⫺:O2⫺ ⫺7000 ⫺ 14.5T
Tetragonal ZrO2 L 0
Y3⫹,Zr4⫹:O2⫺:O2⫺ ⫺34000 ⫹ 17T
0
Monoclinic ZrO2 L 3⫹ 4⫹ 2⫺
Y ,Zr :O :O
2⫺ 1000
C-type YO1.5 L 0
Y3⫹,Zr4⫹:O2⫺:O2⫺ 15000 ⫺ 10T
Hexagonal YO1.5 L 0
3⫹ 4⫹ 2⫺
Y ,Zr :O :O
2⫺ ⫺8000
Fig. 3. Activities at 2773 K calculated from the neutral species model. Zr1.5Y2O6 C ⫹ DT ⫺27000 ⫺ 16.4T
Data points are from Belov and Semenov.44
1564 Journal of the American Ceramic Society—Jacobson et al. Vol. 87, No. 8

Fig. 4. Calculated phase diagram from the charged species model.

focus on only the Y3⫹:Zr4⫹ interaction parameters, since they
change with composition. So we have the following simplification:
L Y0 3⫹,Zr4⫹:O2⫺:O2⫺ ⫽ LY0 3⫹,Zr4⫹:O2⫺:Va
L Y1 3⫹,Zr4⫹:O2⫺:O2⫺ ⫽ LY1 3⫹,Zr4⫹:O2⫺:Va
L 0
Y3⫹:O2⫺:Va,O2⫺ ⫽L0
Zr4⫹:O2⫺:Va,O2⫺ ⫽0
L 1
⫽L1
⫽0
Y3⫹:O2⫺:Va,O2⫺ Zr4⫹:O2⫺:Va,O2⫺
L Y0 3⫹,Zr4⫹:O2⫺:Va,O2⫺ ⫽ 0
In summary, we use three sublattices to model cubic ZrO2. Two
interaction parameters, which focus on the cation interactions, are
used in the excess energy description.
The remaining solid solution phases—tetragonal ZrO2, mono-
clinic ZrO2, C-type YO1.5, and hexagonal YO1.5—were also
modeled with three sublattices. The fictive compounds in the
compound energy formalism were defined in a manner analogous
to that described for the cubic phase. These solid solution phases
exhibit a much more narrow range of solubility than the cubic
ZrO2.
As with the neutral species model, interaction parameters were
(16a) evaluated from the experimental data via the optimizing code
Parrot in ThermoCalc. First the YO1.5–ZrO2 diagram was obtained
(16b) by fitting the liquidus and the approximate boundaries of the large
cubic and C-type phase fields. The smaller phase regions were
(16c)
added by fine-tuning the parameters.
(16d) The model parameters for the YO1.5–ZrO2 system with the
charged species model are given in Table VI. In most cases the L0
(16e) and L1 parameters are needed; however, in some cases only the L0
parameter is needed. The complete calculated phase diagram is
shown in Fig. 4 with experimental data shown as symbols. Nearly
all features of the experimental diagram are reproduced. As with
the previous model, there is more uncertainty with the YO1.5 side
of the diagram than the ZrO2 side.
The calculated heats of formation for the cubic phase are
compared with experimental values in Fig. 5. As noted, these were
weighted more heavily than the phase-boundary data in the model
parameter determination. Figure 6 is a plot of calculated activity of
YO1.5 and ZrO2 at 2773 K compared with the experimental data of

Fig. 5. Heat of formation for cubic YO1.5–ZrO2 from C-type YO1.5 and
monoclinic ZrO2 from the charged species model. Data points are from Lee Fig. 6. Activities at 2773 K calculated from the charged species model.
et al.13 Data points are from Belov and Semenov.44
August 2004 Thermodynamic Modeling of YO1.5–ZrO2 1565
44 4
Belov and Semenov. Agreement is very good, and the calculated S. A. Degtyarev and G. F. Voronin, “Solution of ‘Incorrect’ Problems in the
Thermodynamics of Phase Equilibria. II. Calculation of the ZrO2–Y2O3 Phase
data show the two-phase region. Table IV compares the calculated Diagram,” Russ. J. Phys. Chem., 61 [3] 320 –23 (1987).
activity values of YO1.5 at 1300 K to those measured by Vintoyak 5
Y. Du, Z. Jin, and P. Huang, “Thermodynamic Assessment of the ZrO2–YO1.5
et al.,43 and agreement is reasonable. The enthalpy of formation System,” J. Am. Ceram. Soc., 74 [7] 1569 –77 (1991).
for the intermediate phase was calculated to be ⫺7.7 kJ/mol, 6
Y. Du, Z. Jin, and P. Huang, “Thermodynamic Calculation of the ZrO2–YO1.5–
which is a little higher than the measured value of ⫺5.38 kJ/mol. MgO System,” J. Am. Ceram. Soc., 74 [9] 2107–12 (1993).
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M. Chen, B. Hallstedt, and L. J. Gauckler, “Thermodynamic Modeling of the
pound. Two solution models are used to develop two different ZrO2–YO1.5 System”; presented at CALPHAD XXXII, Quebec, Canada, May 25–30,
descriptions of the system. In both descriptions regular and 2003.
11
L. V. Gurvich, V. S. Iorish, D. V. Chekhovskoi, and V. S. Yungman,
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15
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