J. Am. Ceram. Soc.
, 87 [12] 2268 –2274 (2004)
journal
Experimental Determination and Thermodynamic Calculation of the
Zirconia–Calcia–Magnesia System at 1600°, 1700°, and 1750°C
Sara Serena, Maria Antonia Sainz, and Angel Caballero*
Instituto de Cerámica y Vidrio, CSIC, Campus de Cantoblanco, 28049 Madrid, Spain
Phase relations in the ternary system ZrO2–CaO–MgO were
experimentally established at 1600°, 1700°, and 1750°C. The
investigation was based on powder X-ray diffractometry,
scanning electron microscopy– energy dispersive spectroscopy,
and electron probe microanalysis, on 24 ternary compositions.
The compositions were prepared using attrition milling of
respective oxides and carbonates as raw materials. The results
obtained allowed construction of the corresponding isothermal
sections, which verified the existence of the cubic-ZrO2–
CaZrO3 phase compatibility field at the three temperatures.
Finally, experimental results also were compared with the
thermodynamic assessment previously reported of the system
ZrO2–CaO–MgO.
I. Introduction
V ARIOUS ceramic materials with advanced and traditional appli-
cations can be formulated in the system ZrO2–CaO–MgO.
These materials include porous MgO–CaZrO3,1,2 cubic- (c-) and
partially-stabilized-ZrO2,3–5 and refractory MgO–CaZrO3 or c-
ZrO2.6 –9
The ZrO2–CaO–MgO phase diagram is of fundamental impor-
tance to efficiently define the processing conditions for obtaining
the mentioned materials and the subsequent treatments to obtain
optimal engineering properties. However, the experimental infor-
mation in the phase diagram is scant.
There are numerous studies on the MgO or CaO solid solutions
in ZrO2 stable polymorph, i.e., c-ZrO2, tetragonal-ZrO2 (t-ZrO2),
and monoclinic-ZrO2 (m-ZrO2), especially in c-ZrO2. The size of
the various ions (0.072 nm for Zr4⫹, 0.099 nm for Ca2⫹, and 0.072
nm for Mg2⫹) allows their substitution in the c-ZrO2 lattice in a
wide range of composition (⬍22 mol% CaO,10,11 or ⬍19 mol%
MgO12,13). However, the maximum solid-solution values typically
reported for t-ZrO2 are ⬍5 mol% CaO or MgO, whereas solid
solutions of the m-ZrO2 are usually insignificant.11,12 Also, CaO
and MgO present solid solutions in a considerable range of
compositions (⬍22 mol% MgO in CaO and ⬍5 mol% of CaO in
MgO);14 however, the solid solution of ZrO2 in both compounds is
usually considered to be negligible. No conclusive/quantitative
data exist on the presence of solid solutions in CaZrO3; therefore,
they are normally considered as pure compounds.
In 1978, Longo and Podda15 proposed a first version of the
phase diagram for the system in the 1200°–1700°C temperature
range. The principal conclusions of this study were that no ternary
compound was formed in the system and that there was a relatively
extensive area of ternary solid solution (c-ZrO2 with solid solution
of CaO and MgO simultaneously). The latter conclusion meant
J. R. Hellmann Jr.—contributing editor
Manuscript No. 10508. Received January 19, 2004; approved June 30, 2004.
Supported by CICYT, Spain, under Project No. MAT-2000–0941 and by CAM
under Project No. CAM 07N/0038/2001.
*Member, American Ceramic Society.
2268
that CaO and MgO may have replaced each other in ZrO2 with no
structural variation taking place in the material. The isothermal
sections at 1220° and 1420°C were determined in detail by
Hellmann and Stubican.16 These authors considered the stability of
the ␾1 (CaZr4O9) and ␾2 (Ca6Zr19O44) phases in the system
ZrO2–CaO and included these phases in the isothermal section at
1220°C of the ZrO2–CaO–MgO system.
There is only one piece of experimental research on the liquidus
surface of the system; it was conducted by de Aza et al.17 as a part
of an experimental study on the quaternary system CaO–MgO–
ZrO2–SiO2. In this work, data on the liquidus surface and the
eutectic point of the system MgO–CaZrO3 were reported.
On the other hand, two groups, Du et al.18 and Yin and Argen,19
published thermodynamic assessments of the ZrO2–CaO–MgO
phase-equilibrium diagram and its binary systems MgO–CaO,
ZrO2–CaO, and ZrO2–MgO.
In 1992, Du et al.18 published the first thermodynamic evalu-
ation of the ZrO2–CaO–MgO system by extrapolating the binary
systems they had previously calculated. This work showed the
calculated isothermal sections at 1220°, 1420°, and 1700°C, and
the liquidus surface of the system. The calculation was consistent
with the experimental data reported by Hellmann and Stubican16 at
1420°C in the rich-ZrO2 zone of the system. However, there were
discrepancies with the data of Hellmann and Stubican16 at 1220°C
and with the data obtained by Longo and Podda15 at 1700°C
because of the sizes of the c-ZrO2, MgO–CaO, and c-ZrO2–
CaZrO3 fields. The liquidus surface calculated by Du et al.18 was
not in agreement with the data of the liquidus of the subsystem
MgO–CaZrO3 published by de Aza et al.17
The latest thermodynamic calculation of the system ZrO2–
CaO–MgO was reported by Yin and Argen.19 This work included
an experimental study on the ZrO2-rich region of the ternary
system at 1250°, 1300°, 1420°, and 1500°C. The authors extrap-
olated their own binary systems and calculated isothermal sections
from 1250° to 1500°C, the MgO–CaZrO3 subsystem, and the
liquidus surface of the system. The isothermal sections published
were consistent with their own experimental data, and the liquidus
surface of the MgO–CaZrO3 system was in agreement with the
experimental data of de Aza et al.17 However, there were discrep-
ancies with the experimental data at 1420°C of Hellmann and
Stubican16 related to the extension of the c-ZrO2–CaZrO3 com-
patibility field.
II. Thermodynamic Calculation
CALPHAD methodology20 was followed to calculate the phase
diagrams of the ZrO2–CaO–MgO system from the existing ther-
modynamic assessment. The isothermal sections were calculated
using THERMO-CALC software. Thermodynamic functions for the
system proposed by Du et al.18 and Yin and Argen19 were used in
the calculations.
In the Du et al.18 assessment, the lattice stabilities for the stable
forms of CaO and MgO, were taken from the OXUNARY
databank.21 The lattice stabilities of the metastable forms were
taken from Kaufman,22 and the lattice stabilities of the stable
forms of ZrO2 were estimated by Du et al.18 The CaZrO3,
CaZr4O9, and Ca6Zr19O44 phases were treated as stoichiometric
December 2004 Experimental Determination and Thermodynamic Calculation of the ZrO2–CaO–MgO System
compounds, and their heat capacities were calculated by the
mentioned authors. The solid solution of MgO in CaO and CaO in
MgO was described as a unique phase, called Halite. The binary
liquid and solution phases were described according to a simple
substitutional solution model, with the excess Gibbs free energy of
the solution phases given by the Redlich–Kister expression.20 The
Gibbs free energy of the ternary phases was extrapolated from
binary phases based on the Bonniers equation,23 which is suitable
for the estimation of thermodynamic properties of ternary systems
in which two components are similar to each other (MgO and
CaO) but markedly different from the third (ZrO2).
The lattice stabilities of the constituent oxides used by Yin and
Argen19 also were taken from the OXUNARY databank,21
whereas those that corresponded to the metastable structure of the
constituent oxides and CaZrO3 and Ca6Zr19O44 pure compounds
were estimated by the authors. The solid solution of MgO in CaO
and CaO in MgO was described as a single phase, halite. For
liquid- and solid-solution phases, a substitutional solution model
was used. In this assessment, the excess Gibbs free energy of the
ternary system was extrapolated from the binary systems in terms
of a symmetrical model, according to the Muggianu24 equation. A
ternary interaction parameter was necessary for the c-ZrO2 solid-
solution description.
III. Experimental Procedures
The starting materials were high-purity powders of m-ZrO2
(99.9 wt%, TZ-0, Tosoh Corp., Tokyo, Japan) with an average
size, d50, of ⬍0.47 ␮m; CaCO3 (⬎99 wt%, Fluka Chemical Corp.,
Ronkonkoma, NY) with d50 ⬍ 4 ␮m; and Mg5(CO3)4䡠(OH)䡠4H2O
(⬎99 wt%, Merck, Darmstadt, Germany) with d50 ⬍ 1 ␮m. Phase
relations in the ternary system ZrO2–CaO–MgO were experimen-
tally established at 1600°, 1700°, and 1750°C, for the composi-
tions shown in Table I.
The processing route proposed was as follows: the powders of
each composition were homogenized by attrition milling (1300
rpm) in isopropyl alcohol media for 2 h using ZrO2 balls as milling
media, dried at 60°C, sieved through a 60 ␮m screen, and cold
isostatically pressed at 200 MPa to obtain the green compact. The
samples were fired in a bottom-loading elevator furnace to 1800°C
(Ceram-Aix) at temperatures in the range of 1600°–1750°C. The
2269
⫺1 ⫺1
heating rate was 5°C䡠min to 800°C, 2°C䡠min to 900°C, where
they remained for 1 h, and 5°C䡠min⫺1 to final temperature, where
they remained for 16 h. After thermal treatment was completed,
the samples were air-quenched. To ensure equilibrium, the sam-
ples were reground and reheated for 16 h at the corresponding
temperature until no variations in the X-ray diffractometry (XRD)
patterns and microstructures were observed.
For phase identification, all the samples were examined using
XRD and scanning electron microscopy– energy dispersive spec-
troscopy SEM-EDS. Lattice parameter studies and phase compo-
sition determination using electron probe microanalysis (EPMA-
WDS) also were conducted on selected samples.
Phase identification and lattice parameter studies were per-
formed using a conventional diffractometer (Model D-500 Kristal-
loflex, Siemens, Karlsruhe, Germany) with Ni-filtered CuK␣
radiation, operated at 50 kV and 30 mA. Silicon powder was used
as an internal standard in the calculations of the precise lattice
parameters of the c-ZrO2 phase.
Microstructural analysis and phase identification were con-
ducted using SEM-EDS (Model DMS 950, Carl Zeiss,
Oberkochen, Germany) with sputtered gold coating on the pol-
ished surfaces of selected samples.
The measurement of phase composition in the CaO–MgO–
CaZrO3 and c-ZrO2–CaZrO3–MgO compatibility triangles was
performed using EPMA-WDS (Model Superprobe JXA-8900H-
WD/ED combined microanalyzer, JEOL, Tokyo, Japan) on pol-
ished surfaces. Quantitative point microanalysis of the various
phases for zirconium, calcium, magnesium, and oxygen was
conducted using microprobe standards. The corresponding com-
pound percentages were calculated considering ZrO2, CaO, and
MgO.
IV. Results and Discussion
(1) Thermodynamic Calculation
Figure 1 shows the calculated isothermal section at 1700°C,
which has been obtained in the present work using the thermody-
namic functions proposed by Yin and Argen.19 The compatibility
fields emerging from this assessment are the same as those
proposed by Du et al.,18 but differences are observed in the
location of phase boundaries. In this sense, CaO and c-ZrO2

Table I. Composition Formulated in the System ZrO2–CaO–MgO and Phase Assemblage in Each Composition at
1600°, 1700°, and 1750°C
Composition (mol%) Phase assemblage†
Specimen ZrO2 CaO MgO 1600°C 1700°C 1750°C

C1 7.64 87.74 4.62 Ca*, CZ, Mg2 Ca*, CZ Ca*, CZ

C2 2.50 48.75 48.75 Ca*, Mg, CZ Ca*, Mg, CZ Ca*, Mg, CZ
C3 4.50 47.75 47.75 Ca*, Mg, CZ Ca*, Mg, CZ Ca*, Mg, CZ
C4 32.34 33.83 33.83 CZ*, Mg, Ca2 CZ*, Mg, Ca2 CZ*, Mg, Ca2
C5 33.34 33.33 33.33 CZ*, Mg CZ*, Mg CZ*, Mg
C6 34.34 32.83 32.83 CZ*, Mg, c-Z2 CZ*, Mg, c-Z2 CZ*, Mg, c-Z2
C7 45.76 27.12 27.12 c-Z*, Mg, CZ c-Z*, Mg, CZ c-Z*, Mg, CZ
C8 64.38 17.81 17.81 c-Z*, Mg, CZ c-Z*, Mg, CZ c-Z*, Mg, CZ
C9 65.38 17.31 17.31 c-Z*, Mg, CZ c-Z*, Mg, CZ c-Z*, Mg, CZ
C10 66.38 16.81 16.81 c-Z*, Mg, CZ2 c-Z*, Mg, CZ2 c-Z*, Mg, CZ2
C11 69.38 15.31 15.31 c-Z*, Mg c-Z*, Mg c-Z*, Mg
C12 65.38 30.77 3.86 c-Z*, CZ, Mg2 c-Z*, CZ, Mg2 c-Z*, CZ, Mg2
C13 65.38 33.63 1.00 c-Z*, CZ c-Z*, CZ c-Z*, CZ
C14 73.20 13.40 13.40 c-Z*, Mg c-Z*, Mg c-Z*, Mg
C15 74.20 12.90 12.90 c-Z*, Mg c-Z*, Mg c-Z*, Mg
C16 75.20 12.40 12.40 c-Z*, Mg c-Z*, Mg c-Z*, Mg
C17 78.20 10.90 10.90 c-Z*, Mg2 c-Z*, Mg2 c-Z*, Mg2
C18 82.20 8.90 8.90 c-Z c-Z c-Z
C19 84.20 7.90 7.90 c-Z c-Z c-Z
C20 86.20 6.90 6.90 c-Z c-Z c-Z
C21 88.20 5.90 5.90 c-Z c-Z c-Z
C22 90.20 4.90 4.90 c-Z, t-Z c-Z, t-Z c-Z, t-Z
C23 91.82 4.09 4.09 c-Z, t-Z c-Z, t-Z c-Z, t-Z
C24 93.82 3.09 3.09 c-Z, t-Z c-Z, t-Z c-Z, t-Z
†
Ca is CaO, Mg is MgO, c-Z is c-ZrO2, t-Z is t-ZrO2, and CZ is CaZrO3; * is majority and 2 is minority.
2270 Journal of the American Ceramic Society—Serena et al. Vol. 87, No. 12

Fig. 1. Isothermal section at 1700°C of the ZrO2–CaO–MgO system calculated in the present work from Yin and Argen19 thermodynamic assessment (CZ
is CaZrO3).

stability fields are smaller than those that result from the Du et The isothermal sections at 1600° and 1750°C are not depicted
al.18 assessment. As a consequence, there are significant differ- here because they do not differ substantially from the isotherm at
ences in the CaO–MgO–CaZrO3 and c-ZrO2–MgO–CaZrO3 com- 1700°C, except for the compositional limits of the various com-
patibility triangles phase composition. The compositions of the patibility fields. The differences can be observed in terms of the
phases in both compatibility triangles calculated from Yin and composition of the phases in the compatibility triangles collected
Argen19 thermodynamic assessment have been collected in Table in Table II.
II at the three studied temperatures. The basic differences with the
Du et al.18 results are related to the composition of CaO and
c-ZrO2 phases in the corresponding compatibility triangles. The
(2) Experimental Investigation
composition of CaO in the CaO–MgO–CaZrO3 compatibility
triangle is ⬃14 mol% higher in ZrO2 and 13 mol% lower in CaO. (A) Experimental Determination of Phase Assemblage: The
The composition of c-ZrO2 in the compatibility triangle c-ZrO2– determination of the phase assemblages in the analyzed composi-
MgO–CaZrO3 is ⬃6 mol% lower in ZrO2 and 3 mol% higher in tions is based on complementary observations of the samples using
CaO in the Du et al.18 calculation. XRD and SEM. The characterization using XRD is decisive in
determining the presence of c-ZrO2 and CaZrO3 in the samples
because of the high intensity observed in their principal diffraction
Table II. System ZrO2–CaO–MgO Composition of the peaks compared with the other phases. On the other hand, the
Phases in the Compatibility Triangles CaO–MgO–CaZrO3 darkness of the grains of the MgO phase in SEM observation
and c-ZrO2–MgO–CaZrO3 at 1600°, 1700°, and 1750°C† makes it possible to detect them using this technique. The volume
expansion associated with the hydration process of the CaO phase
Phase composition (wt%) produces a dusting effect on the polished surfaces of the samples
Temperature (°C) Phase ZrO2 CaO MgO that is decisive in establishing its presence using SEM observa-
CaO–MgO–CaZrO3
tions, even in small quantities.
1600 CaO 0.801 96.654 2.2545 The extent of the c-ZrO2 phase field has been determined
MgO 0.002 0.887 99.111 using lattice parameter (LP) measurement. The change in the
CaZrO3 68.723 31.277 slope of the LP versus concentration (mol%, X) (LP–X) curve
1700 CaO 1.181 95.408 3.411 makes it possible to establish the boundary of the c-ZrO2 and
MgO 0.005 1.285 98.710 t-ZrO2 compatibility field and the c-ZrO2 field in the ZrO2-rich
CaZrO3 68.723 31.277 compositions.
1750 CaO 1.410 94.679 3.911 Phase compositions in the compatibility triangles CaO–MgO–
MgO 0.007 1.528 98.465
CaZrO3 68.723 31.277 CaZrO3 and c-ZrO2–MgO–CaZrO3 have been specifically deter-
mined using EPMA-WDS. These results are compared with the tie
c-ZrO2–MgO–CaZrO3 triangle estimated from the established phase boundaries to eval-
1600 c-ZrO2 89.091 8.725 2.184 uate the consistency of the various experimental results.
MgO 0.023 0.073 99.904
CaZrO3 68.723 31.277 Established phase assemblages at 1600°, 1700°, and 1750°C in
1700 c-ZrO2 88.965 8.523 2.512 the formulated compositions are given in Table I. Table III shows
MgO 0.042 0.121 99.837 the composition of phases in the compatibility triangles deter-
CaZrO3 68.723 31.277 mined using EPMA-WDS. The results show the average and the
1750 c-ZrO2 88.903 8.407 2.690 standard deviation calculated for n measurements (n ⱖ 5) of each
MgO 0.056 0.153 99.791 phase composition. The standard deviation is, in most cases, lower
CaZrO3 68.723 31.277 than 0.5 wt%; therefore, the established compatibility triangles are
†
Calculated from Yin and Argen19 thermodynamic assessment. sound.
December 2004 Experimental Determination and Thermodynamic Calculation of the ZrO2–CaO–MgO System 2271

Table III. System ZrO2–CaO–MgO Composition of the Phases in the

Compatibility Triangles CaO–MgO–CaZrO3 and c-ZrO2–MgO–CaZrO3 at
1600°, 1700°, and 1750°C Determined Using EPMA-WDS
Phase composition (wt%)†
Temperature (°C) Phase ZrO2 (SD) CaO (SD) MgO (SD)

CaO–MgO–CaZrO3
1600 CaO 0.16 (0.09) 97.45 (0.49) 2.39 (0.45)
MgO ⬍0.1 1.52 (0.37) 98.46 (0.62)
CaZrO3 66.51 (0.10) 33.21 (0.51) 0.28 (0.19)
1700 CaO 0.17 (0.03) 96.39 (0.05) 3.44 (0.06)
MgO ⬍0.1 1.52 (0.18) 98.47 (0.18)
CaZrO3 66.72 (0.32) 33.01 (0.33) 0.28 (0.16)
1750 CaO 0.17 (0.04) 95.33 (0.32) 4.50 (0.34)
MgO 0.08 (0.02) 1.77 (0.54) 98.15 (0.51)
CaZrO3 66.22 (0.38) 33.06 (0.56) 0.72 (0.17)
c-ZrO2–MgO–CaZrO3
1600 c-ZrO2 87.90 (0.76) 9.38 (0.17) 2.72 (0.85)
MgO 1.00 (0.54) 0.85 (0.46) 98.15 (0.49)
CaZrO3 67.09 (0.36) 32.55 (0.37) 0.35 (0.05)
1700 c-ZrO2 88.13 (0.84) 9.47 (0.09) 2.40 (0.31)
MgO 0.82 (0.39) 0.32 (0.14) 98.86 (0.48)
CaZrO3 66.85 (0.56) 32.47 (0.22) 0.68 (0.51)
1750 c-ZrO2 88.74 (0.64) 9.20 (0.22) 2.33 (0.60)
MgO 1.32 (0.65) 0.59 (0.29) 98.08 (0.83)
CaZrO3 66.90 (0.54) 32.49 (0.28) 0.62 (0.31)
†
SD is standard deviation.

The data obtained are summarized in the proposed isothermal
section at 1700°C (Fig. 2) and are described in detail below.
Because of the mentioned resemblance between the isothermal
sections of the ZrO2–CaO–MgO system between 1600° and
1750°C, only a detailed discussion of the results at 1700°C is
conducted. The results for the other isothermal sections are
summarized.
(B) Phase Boundaries: The XRD patterns of the composi-
tions C1, C2, and C3 treated at 1700°C show the presence of MgO,
CaO, and CaZrO3 in all the samples. The intensity of the
characteristic reflections of CaZrO3 evidences the presence of a
considerable quantity of this phase in these samples. The phase
assemblage for the composition C2 limits the MgO–CaO compat-
ibility field up to compositions ⬍2.5 mol% ZrO2. This result
suggests that the CaO solid-solution phase field is smaller than that
calculated by Du et al.18 The solubility of ZrO2 in this phase must
be ⬍2.5 mol%, closer to that resulting from the Yin and Argen19
assessment. The same effect also is observed at 1600° and 1750°C.
The narrowness of the MgO–CaZrO3 compatibility field (32.3
mol% ⬍ ZrO2 ⬍ 34.33 mol% for MgO:CaO ⫽ 1:1) is evident
when the phase assemblage determined for the compositions C4 to
C6 (Table I) is observed. This is in agreement with the extension
of the compatibility field that results from both thermodynamic
assessments considered and confirms the solid solutions of ZrO2,

Fig. 2. Experimental isothermal section at 1700°C of the ZrO2–CaO–MgO system established in the present work (open symbols represent experimental
compositions, solid symbols represent phase composition of the tie triangles determined using EPMA, and CZ is CaZrO3).
2272 Journal of the American Ceramic Society—Serena et al. Vol. 87, No. 12

(a) (b)

Fig. 3. SEM micrograph of the samples C12 and C13 heat-treated at 1700°C: (bright phase) c-ZrO2, (gray phase) CaZrO3, and (dark phase) MgO.

CaO, and MgO that exists in the MgO and CaZrO3 phases. This As expected, in both cases, the equilibrium microstructure shows
supports the treatment of CaZrO3 phase as a stoichiometric three phases at the three temperatures.
compound in a first approximation, as considered by Du et al.18 The microstructure of the sample C3 treated at 1700°C (Fig.
and Yin and Argen.19 Again, the same effect is observed at 1600° 5(a)) is composed of bright grains of CaZrO3 phase (grain size of
and 1750°C. 1–3 ␮m), gray grains of CaO phase (grain size of ⬃3 ␮m) phase,
The phase boundary between the CaZrO3–MgO–c-ZrO2 and and darker grains of MgO phase (grain size of ⬃3 ␮m). The grains
MgO–c-ZrO2 compatibility fields has been established using XRD of the main phases (CaO and MgO) are homogeneously distrib-
between the compositions C10 and C11 at 1700°C (66.38 mol% ⬍ uted, whereas the CaZrO3 grains are located in grain boundaries.
ZrO2 ⬍ 69.38 mol% for MgO:CaO ⫽ 1:1). These experimental Very similar microstructures are observed at 1600° and 1750°C for
data are ⬃2 mol% lower in ZrO2 than that calculated by Yin and this composition.
Argen19 and ⬃2.5 mol% higher in ZrO2 than that calculated by Du The compositions of the phases at the three studied tempera-
et al.18 at the three temperatures. tures measured using EPMA-WDS (C2 and C3 samples) are
The characterization using XRD of the compositions C12 and shown in the Table III. MgO is the main solid solution in CaO
C13 treated at 1700°C shows that CaZrO3 and c-ZrO2 are the main (⬍4.5 wt% MgO) phase, and ⬍0.17 wt% ZrO2 is dissolved. The
crystalline phases in both samples. However, SEM analysis (Fig. solid solutions measured in CaO phase are as expected according
3) permits the detection of the presence of MgO in the sample C12. to the ZrO2–CaO10,11 and MgO–CaO14,25 phase-equilibrium dia-
Figures 3(a) and (b) show the microstructure of the samples C12 grams. The very low solid solution in the MgO (⬍0.1 wt% ZrO2)
and C13, respectively, at 1700°C. Both samples are composed of phase is evident at the three temperatures, as expected from the
bright grains of ZrO2 phase and gray grains of CaZrO3 phase, with ZrO2–MgO12,13 and MgO–CaO14,25 binary systems. The CaZrO3
close porosity inside the largest grains of both phases. Only a small phase presents a small quantity of CaO and MgO solid solution
quantity of MgO (dark phase) is found in sample C12, and it is (⬍2 wt% CaO and ⬍1 wt% MgO). The experimental values are
located in the grain boundaries of ZrO2 and CaZrO3 phases. This closer to those calculated by Yin and Argen19 and differ from
shows experimentally the existence of the CaZrO3 and c-ZrO2 those calculated by Du et al.,18 especially in the compositions of
binary compatibility field for first time. The existence of this CaO phase (⬃14 wt% ZrO2 and ⬃3 wt% MgO).
compatibility field had been predicted in both thermodynamic The microstructure of the sample C7 treated at 1700°C (Fig.
calculations of the system, but not experimentally confirmed 5(b)) is composed of bright grains of ZrO2 phase (grain size of
before the present work. The same has been demonstrated in the
isothermal sections at 1600° and 1750°C.
SEM analysis of the samples was decisive in establishing the
phase boundary between the MgO–c-ZrO2 and c-ZrO2 compati-
bility fields, between compositions C17 and C18, at 1700°C (78.2
mol% ⬍ ZrO2 ⬍ 82.2 mol% for MgO:CaO ⫽ 1:1). Once more,
these experimental data are very similar to the thermodynamic
assessments considered at the three temperatures.
The lattice parameter measurements for the c-ZrO2 in the
samples C20 –C24 treated at 1700°C as a function of ZrO2 content
are shown in Fig. 4. The change observed in the slope of the LP–X
curve between compositions C21 and C22 makes it possible to
establish the boundary between the c-ZrO2 and t-ZrO2 compati-
bility field and the c-ZrO2 phase field in 88.2 mol% ⬍ ZrO2 ⬍
90.2 mol% for MgO:CaO ⫽ 1:1. The phase-boundary locations at
1600° and 1750°C are between the same compositions. The results
seem to be consistent with those experimentally determined by Yin
and Argen19 at lower temperatures. The determined extension of
the c-ZrO2 phase field is better fitted to the one calculated using
the thermodynamic functions proposed by Yin and Argen.19
(C) Compatibility Triangles CaO–MgO–CaZrO3 and c-ZrO2–
MgO–CaZrO3: Figures 5(a) and (b) show the microstructure Fig. 4. Lattice parameter of the c-ZrO2 phase in the ZrO2–CaO–MgO
using SEM of the samples C3 on the CaO–MgO–CaZrO3 and C7 system along the CaO:MgO ⫽ 1:1 line for the compositions C20 to C24
on the c-ZrO2–MgO–CaZrO3 compatibility triangles at 1700°C. heat-treated at 1700°C.
December 2004 Experimental Determination and Thermodynamic Calculation of the ZrO2–CaO–MgO System
(a) a)
Fig. 5. SEM micrograph of the samples (a) C3 ((bright phase) CaZrO3, (gray phase) CaO, and (dark phase) MgO) and (b) C7 ((bright phase) c-ZrO2, (gray
phase) CaZrO3, and (dark phase) MgO) heat-treated at 1700°C.
⬃6 ␮m), gray grains of CaZrO3 phase (grain size of ⬃6 ␮m),
and darker grains of MgO phase (grain size of ⬃5 ␮m). Some
grains of c-ZrO2 phase have grown by coalescence, which
entraps the grains of a smaller size (⬍1 ␮m) of other phases.
Very similar microstructures are observed at 1600° and 1750°C
for this composition.
The compositions of the three phases at the three studied
temperatures measured using EPMA-WDS (C7 and C9 samples)
are shown in Table III. The c-ZrO2 solid solution is close, but the
⬃1 wt% CaO is higher than the value calculated from the Yin and
Argen19 assessment and differs from that calculated by Du et al.18
(⬃86 wt% ZrO2, ⬃10 wt% CaO, and ⬃4 wt% MgO). The very
low solid solution in the MgO phase (⬍1 wt% CaO and ⬍1.5 wt%
ZrO2) is again in good agreement with the ZrO2–MgO12,13 and
MgO–CaO25 binary systems at the three temperatures. Once more,
a little solid solution of CaO and MgO is found in the CaZrO3
phase (⬍2 wt% CaO and ⬍1 wt% MgO).
The measurement using EPMA-WDS of both compatibility
triangles reveals that CaZrO3 phase can dissolve a small quantity
of CaO and MgO (⬍2 wt% CaO and ⬍1 wt% MgO). The presence
of certain elements as solid solutions in CaZrO3 has been previ-
ously reported.26 –28
The phase composition determined using EPMA-WDS agrees
with the phase boundaries experimentally observed for the CaO–
MgO–CaZrO3 and the c-ZrO2–MgO–CaZrO3 compatibility fields
at 1600°, 1700°, and 1750°C. This increases the confidence in the
experimental results obtained in the present work at the three
temperatures.
Experimental data seem to be in good agreement with the
results of the assessment provided by Yin and Argen19 at the three
temperatures. The main differences observed are related to the
detection of CaZrO3 solid solutions and the extension of the
CaZrO3–c-ZrO2 compatibility field, which especially affects the
c-ZrO2 compositions of the c-ZrO2–MgO–CaZrO3 tie triangle.
In general, the agreement of the experimental data with the
result of the thermodynamic evaluation proposed by Yin and
Argen19 is reasonable in the whole system and is better than that
obtained using the Du et al.18 calculation. The basic difference
between the calculations is the model used to extrapolate the
binary systems to the ternary system. The agreement of the present
experimental data with the Yin and Argen19 calculation supports
the idea that a symmetrical model is suitable for describing the
contribution of the binary system to the ZrO2–CaO–MgO ternary
system.
V. Conclusions
The isothermal sections of the ZrO2–CaZrO3–MgO system at
1600°, 1700°, and 1750°C have been experimentally established.
2273
(b)
The existence of the c-ZrO2 and CaZrO3 phase compatibility field,
thermodynamically predicted, but not previously experimentally
observed, is confirmed at the three temperatures.
The field boundaries established using XRD and SEM analysis
are consistent with the composition of the phases, determined
using EPMA, of the tie triangles CaO–MgO–CaZrO3 and c-ZrO2–
CaZrO3–MgO. This provides data of the necessary confidence to
establish the isothermal sections and to use in future thermody-
namic assessments of the ZrO2–CaO–MgO ternary system.
The experimental isothermal sections show a reasonable agree-
ment with those that result from the thermodynamic assessment of
Yin and Argen,19 and differ from that proposed by Du et al.18 The
comparison of experimental and theoretical isothermal sections
indicates that a symmetric model is more suitable for describing
the excess Gibbs free energy of ternary phases in the system
ZrO2–CaO–MgO.
The isothermal sections determined from 1600° to 1750°C do
not differ substantially from each other. Consequently, materials
based on ZrO2 and CaZrO3–MgO show good thermochemical
stability in the temperature range studied.
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