\;,

. ..c. .-.., ,...,I

,./'I' ,.--.:
,:-'?"I;,
/, ~ . ,.
A,& .I i
,;.

J. Am. Cerum Sac., 78 [81 2225-28 (1995)

Tetragonal-Monoclinic Phase Transition Enthalpy and Temperature of

Zr0,-CeO, Solid Solutions
Masatomo Yashima,',' Takefumi Mitsuhashi,*Hiroyuki Takashina, Masato Kakihana,+
Takayasu Ikegami,*and Masahiro Yoshimura',t
Research Laboratory of Engineering Materials, Tokyo Institute of Technology, Yokohama, 226, Japan
National Institute for Research in Inorganic Materials (NIRIM), Ibaraki, 305 Japan

DSC (differential scanning calorimeter) measurements 11. Experimental Procedure

were performed to investigate the tetragonal-monoclinic
(t-m) transition enthalpy of the compositionally homoge- ( I ) Sample Preparation
neous Zi-0,-X mol% CeO, solid solution of X = 0, 4, 8, All samples of Zr0,-X mol% CeO, solid solutions ( X = 0,
and 12. The transition enthalpy decreases linearly with an 4, 8, and 12) were prepared by the same procedure, because
increase of CeO, content. The m + t transition enthalpy on the t-rn transition behavior strongly depends on the heat treat-
heating agreed well with the inverse t -+ m one obtained ment, thermal cycling, and microstructures. High-purity zirconia
during cooling. With increasing X , the DSC peak broadens (Zr0,,$99.9%, Tosoh, Tokyo, Japan) and ceria (CeO,, 99.9%,
and the transition temperature distribution of each sample Shin-Etsu Chemical, Tokyo, Japan) powders were mixed manu-
increases, while the thermal hysteresis is almost indepen- ally as dried powders and methanol slurries for 3 h with a
dent of X . pestle in an agate mortar. The mixed powders were isostatically
pressed at 200 MPa for 3 min into pellets 20 mm in diameter,
I. Introduction 5 mm in height. These pellets were calcined at 1400°C in air for
5 h in an electric furnace (Type Super-Mini, Marusho-Denki,
Himeji, Japan) and then crushed and ground in a tungsten
HE high toughness of zirconia ceramics is caused mainly by carbide mortar. This calcined powder was isostatically pressed
T the stress-induced tetragonal-to-monoclinic (t-to-rn) phase
transition.' The Ce-TZP (tetragonal zirconia polycrystals)
again at the same pressure and then fired in air at 1650°C for
5 h in an electric furnace (Type Super-Kanthal, Nishimura-
exhibit outstanding high fracture toughness in the range of Kogyo, Tokyo, Japan) in the stable tetragonal region of the
12-18 (MPa--\if;;) due to a pronounced transformation plas- Zr0,-CeO, phase diagram,', where the heating and cooling
ticity.'-' The enthalpy change between the tetragonal and mono- rates were about 10"C/min. The fired pellet was crushed and
clinic phases is one of the most important parameters for ground into a fine powder in the tungsten carbide mortar,
thermodynamic considerations of the energy required to propa- because the powdered sample does not show the sudden bursts
gate a crack in a transformation-toughened ceramic6 of the t-rn transformation,'",'' which might not be preferable for
Nevertheless, little data on the enthalpy change have been quantitative DSC measurements. At temperatures as high as
reported in the literature. On07.8 investigated the transition 1650"C, zirconia-ceria solid solutions exhibit an oxygen defi-
enthalpy AH"" of Zr0,-X mol% CeO, in a narrow composi- ciency due to partial reduction of Ce4+into Ce3+.However, they
tional range of 8 i X 5 10. However the AH'"' did not absorb oxygen during cooling, and all samples obtained are
stoichi~metric.'~.'~The compositional homogeneity of the pale-
change systematically with CeO, content. The phase transition
yellow powder thus obtained was confirmed using X-ray pow-
behavior in zirconia ceramics strongly depends on transition
der diffraction (40 kV-40 mA, CuKa radiation, Type MXP3VA,
cycles, grain size (sintered material or powders), impurity con-
MAC Science, Tokyo, Japan) with a Ni filter and graphite
tents, and heat treatments because of the heterogeneous nucle- monochromator. The scan rate was O.S"/min in 28. The powders
ation of the martensitic phase transition.'."'' The measured were heated up to 1300°C and then cooled down to room
enthalpy change was influenced by the annealing temperature, temperature in air in the furnace, where the heating and cooling
which was interpreted to be ascribed to a difference in some rates were about 3"C/min. This heat treatment up to 1300°C
lattice imperfection among sample^.^,^ was performed a total of three times, because the dependence
The aim of the present study is to determine the dependence of transformation behavior on the thermal cycles is known to
of AH"" and transition temperature on CeO, concentration in a become negligible after repeated thermal cycles.'",'','5
wider compositional region of 0 5 X 5 12 mol% CeO,. Care-
fully prepared powdered samples were used for DSC (differen- (2) DSC and X-ray Diffraction Measurements and Data
tial scanning calorimeter) measurements to obtain a systematic Analysis
change of the transition enthalpy with X . Transition enthalpy determination was carried out using a
Setaram multi-detector high-temperature calorimeteri6 and a
Perkin-Elmer DSC (Perkin-Elmer 7 Series thermal analysis
A. V. Virkar-i-ontributing editor system). For sample compositions of X = 0, 4, and 8, the
Setaram multi-detector high-temperature calorimeter was used
as a heatflux DSC detector, which is designed for studying
Manuscript No. 193146. Received October 13,1994; approved June 2,1995. enthalpy changes in materials on the basis of a surrounding heat
Presented in part at the 6th Fall Meeting of The Ceramic Society of Japan, Kita- flux principle.I6Samples were studied by continuous scan mode
Kyusyu, Japan, Oct. 6 8 , 1 9 9 3 (Paper No. 2-3Dl4).
Supported in part by the Kanagawa Academy of Science and Technology; Iketani through heating and cooling rates of 5"C/min under a flowing
Science and Technology Foundation; and Grant-in-Aid ShBrei-kenkyu 07750744 for
Fundamental Research from the Ministry of Education, Science and Culture of Japan.
'Member, American Ceramic Society.
+TokyoInstitute of Technology. Themica1 analysis showed the zirconia powder contains 1.1 mol% IlfO,. The
*National Institute for Research in Inorganic Materials. molar weight was calibrated using this value.

2225
2226 Communications of the American Ceramic Society Vol. 78, No. 8

Table I. Volume Fraction of Monoclinic Phase in the Sample for DSC Measurements
Coniposition (mol% CeO,) 0 4 8 12

Before DSC measurement 1.o 1.o 0.996 0.892

After DSC measurement 1 .o 1.o 0.993* 0.823
0.992+
*After first DSC measurement 'After second DSC measurement usmg the same sample as first one

dry Ar atmosphere. The instrument was calibrated by means of 111. Results and Discussion
the heats of fusion of zinc and gold and of the enthalpy changes
of NBS alumina at the temperature intervals of 200°C. Three The samples were prepared by the solid-state reactions which
runs for each standard material were carried out to obtain tem- yield compositional homogeneityn in a wide compositional
perature-dependent mean values for the calibration, where the range of 0-15 mol% Ce0,.18 X-ray diffraction (XRD) patterns
calibration curve was approximated by the following equation: of ZrO-X mol% CeO, powders indicated monoclinic single
+
phase for X = 0 and 4 and (monoclinic tetragonal) mixture
Q = C.S (1) for X = 8 and 12 (Table I). These samples were tetragonal
where S, Q , and C are the observed DSC peak area, the enthalpy single phase at the sintering temperature of 16SOoC,where a
change, and the calibration coqstant. The constant C has a part or all of the tetragonal phase transformed diffusionlessly
temperature dependence of C = 2 a;T', where T is temperature into the monoclinic phase during cooling or crushinglgrinding
to prepare the powders.
in degrees Celsius and a , is a tg:perature-independent coeffi-
The DSC curve of each sample shows both a single endother-
cient. The a, values for heating experiments and those for cool-
ing ones were determined independently. For the Zr02-12 mic peak on heating and a single exothermic peak on cooling
mol% CeO, sample, DSC measurements were made with the (Fig. l), also suggesting the compositional homogeneity. The
Perkin-Elmer DSC-7 series thermal analysis system, because endothermic and exothermic peaks are ascribed to the martens-
the transformation of the 12 mol% sample occurs at a relatively itic monoclinic-to-tetragonal ( m + t ) and the reverse t + m
low temperature region where the DSC-7 has higher sensitivity. phase transitions, respectively.
Samples were measured by a continuous scan mode through a (1) Monoclinic-Tetragonal Phase Transition Enthalpy
heating rate of S"C/min under a dry nitrogen atmosphere. The
instrument was calibrated by means of the heats of fusion The XRD indicates that the volume fraction of monoclinic
of indium. phase V,, decreases with an increase of CeOLcontent X (Table I).
X-ray diffraction patterns showed that each sample was The DSC peak area S decreases with increasing X as seen in
monoclinic single-phase or (monoclinic +
tetragonal) two- Fig. 1. Using the V , and the enthalpy change Q obtained from
phase mixture. The volume fraction of monoclinic phase V, in S, the molar transition enthalpy AH"+' on heating and AH""
each sample was determined by X-ray diffraction measure- on cooling were estimated as shown in Table I1 and Fig. 2. The
ments (scan rate = O.S"/min) before and after each DSC AH"" on heating agreed well with AH' +n' on cooling. The
measurement to estimate the molar transition enthalpy from the transition enthalpy decreases linearly with an increase of X :
measured values. The V, value was calculated using a cali-
bration curve17 from the integrated intensities of 117 and 111
reflection peaks of monoclinic phase and 101 reflection peak of
The homogeneity was strongly suggested by the variation of structural parameters
tetragonal phase, which were calculated by a profile-fitting with CeO, content obtained by the Rietveld refinement of high-resolution neutron
program attached to the MXP system. diffraction data.'8

/HEAT FLOW ( m ~ ' 1

I Ii40

--20
20
0
i
: 4Ce
4

- 60
- 80

Heating 4Ce
-160
-180

Fig. 1. DSC curves of ZrO,X mol% CeO, where XCe denotes Zr0,-X mol% CeO,.
August 1995 Communications of the American Ceramic Society 2227

Table 11. Measured Transformation Enthalpy Values of Zr02-Ce0,

Composition (molW CeO,) 0 4 8 12

Ahm4'
heating (kJ/mol of cation) 5.87 t 0.29" 4.24 t 0.03 2.84 t 0.02 1.37
AH"" cooling (kJ/mol of cation) 5.54 2 0.29 3.97 +- 0.15 2.57 ? 0.04
AH'-'*' (kJ/mol of cation) 5.71 4.10 2.70
TFm(K)* 1399.7 1132.4 854.I
AS""§ (J/mol of cation/K) 4.07 3.62 3.16
*The error bar was estimated from the uncertainty in drawing the baseline and/or from the reproducibility. +AH'-"' = (AH"" + AH"'")/2. Th* =
( A , + M , ) / 2 . aAS'-"'= AH' "/Th".

71
(2) Transition Temperature and Its Distribution in Each
I 0
X
Heating
Cooling
I Sample
Four kinds of transition temperatures were estimated for each
sample from Fig. 1: the starting point of the m -+ t transition on
heating ( A s ) ,that of the t -+ m transition on cooling ( M J , and
the peak points during heating (A,) and during cooling ( M J .
These transition temperatures decrease linearly with an increase
of X as shown in Fig. 3. The thermal hysteresis, A , - M, is
almost independent of X.
The DSC curves of undoped ZrO, show sharp peaks, while
broad peaks are observed for Ce0,-doped ZrO,. The peak width
and M , - M, increase with an increase of X as shown in Figs. 1
and 3. This broadening with X should be caused by the increase
of the distribution of nonchemical energy accompanying the
tetragonal-monoclinic nucleation/growth.'-' ','' As a result of
this broadening, the starting point difference A, - M , decreases
with an increase of X. Such decrease of A, - M , with X is
observed in other dopant systems as Zr0,-YO, q.24

't
01
0
I I
2 4
I I
6
I I I
8 1 0 1 2 1 4
The equilibrium temperature between tetragonal and mono-
clinic phases To is thermodynamically defined to be the
temperature where their free energies are equal for a given
composition. Although it is difficult to estimate exactly the To
value, it has often been assumed or approximated to be
Zr02 mol% C e 0 2
To = (A, + MJ2 (Refs. 25-28) (3)
Fig. 2. Variation of the transition enthalpy between monoclinic and Yoshikawa and S ~ t oassumed
,~ the following equation:
tetragonal phases in the Zr02-Ce0, solid solutions. 0: on heating; To = (A, + M,)/2
X: on cooling. (4)
The present DSC data show that both To have almost the same

AH'-" = 5.64 - 0.363.X (2)

Coughlin and King" measured the heat contents of zirco-
nium oxide ( X = 0) by a dropping method and obtained the 1200
transition enthalpy value of 5.94 kJ/lmol, which agrees well
with the present data. Although the previous data of AH'-"
showed a scatter to some extent even for undoped Zr02,'9-2'the
present data are precise enough to discuss the compositional
dependence of the transition enthalpy and temperature. 1000
The present data clearly show the decrease of AH'-" with
increasing X . This indicates that the apparent cohesive energy
difference between t and rn phases decreases with X. This
J
interpretation is consistent with recent structural information Y

that the monoclinic structure approaches that of the tetragonal 2

Q)
800
one with increasing X:'*(1) the length of a , approaches that of a
E
b, with an increase of X , (2) the pm angle decreases with X, +a.,
(3) all positional parameters of the monoclinic phase approach
those of the tetragonal structure with X .
As shown in Table 11, the transition entropy AS"" decreases 600
with an increase of CeO, content. The present AS'" of undoped
zirconia (4.07 J.mol-'-K-') shows a fairly good agreement with
that after Coughlin and King" (4.0 J.mol-'.K-'). Becher et aL2,
suggested a AS'-" value of MgO-PSZ (3.2 J.mo1-l.K-I) from
the relationship between the transformation toughening contri-
bution and the temperature difference T-M,. This valuez2in
MgO-doped ZrO, is smaller than that in pure ZrO, (4.07 CeO, mol%
J.mol-'.K-'), which is consistent with the present result that
AS'-"' decreases by the CeO, doping. The smaller ASr-, value Fig. 3. Variation of the tetragonal-monoclinic transition tempera-
of MgO-PSZ than that of undoped zirconia is probably due to tures in the ZrO-CeO, solid solutions with CeO, content. 0: A,;
the MgO doping. 0:A,, 0:M,; and A: M,.
2228 Communications of the American Ceramic Society Vol. 78, No. 8
2K. Tsukuma and M. Shimada, “Strength, Fracture Toughness and Vickers
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U ’P. E. Reyes-Morel and I-W. Chen, “Transformation Plasticity of Ce0,-Stabi-
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‘ 1000 Cerum. Soc., 71 151 343-53 (1988).
4P. E. Reyes-Morel, J.-S. Chemg, and I-W. Chen, “Transformation Plasticity
of Ce0,-Stabilized Zirconia Polycrystals: 11, Pseudoelasticity and Shape Mem-
ory Effect,”J. Am. Cerum. Soc., 71 [8] 648-57 (1988).
5L.R. F. Rose and M. V. Swain, “Transformation Zone Shape in Ceria-
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493-502 (1992).
’A. Ono, “Phase Transformation in the System ZrO,-CeO,,” Mineral. J., 7 [ I ]
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‘A. Ono, “Phase Transformation of (Zr,Ce)O, and Measurements of the
0 2 4 6 8 10
Enthalpy Changes,” Mineral. J . , 7 121 228-31 (1973).
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tion of Metastable Tetragonal ZrO,,”J. Am. Ceram. Soc., 57 [2] 97-101 (1974).
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”M. Yashima, H. Takashina, M. Kakihana, and M. Yoshimura, “Low-Temper-
,u 1100
2‘ 000
-
-6-Ono’72
Duwez’50
ature Phase Equilibria in the System ZrO,-CeO, by Flux Method,” J. Am.
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15M. Yashima, N. Ishizawa, T. Noma, and M. Yoshimura, “Tetragonal
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0 2 4 6 8 10 12 14 “H. Toraya, M. Yoshimura, and S. Szmiya, “Calibration Curve for Quantita-
mol% G O p tive Analysis of the Monoclinic-Tetragonal ZrO, System by X-ray Diffraction,”
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InM. Yashima, T. Hirose, S. Katano, Y. Suzuki, M. Kakihana, and
Fig. 5. Comparison of Tkmdata obtained in the present work with M. Yoshimura, “Structural Changes of Zr0,-CeO, Solid Solutions around the
those in the l i t e r a t ~ r e . ~ ~ ~ ~ ’ ” ~ ~ ’ Monoclinic-Tetragonal Phase Boundary,”Phys. Rev. B , 51 [I318018-25 (1995).
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X 5 10 agreed well with the present data (Fig. 5 ) , although Teplofiz. Vys. Temp., 17 [4]754-58 (1979).
’,P. F. Becher, M. V. Swain, and M. K. Ferber, “Relation of Transformation
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VI. Conclusion 16 (1991).
2dM. Yashima and M. Yoshimura, “Distribution of Tetragonal-Monoclinic
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