VOI. 42 NO.

1 SCIENCE IN CHINA (Series A) January 1999

Crystal structure of zirconia by Rietveld refinement
WANG Daning ( Ek?? 1, GUO Yongquan
LIANG Kaiming ( $@R
and TAO Kun (I@ 3%)
(Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China)
Received June 25, 1998
Abstract The crystal structures and phase transformation of zirconia ceramics have been investigated by means of
X-ray powder diffraction and Rietveld powder diffraction profile fitting technique. A structural transition from mono-
clinic to tetragonal occurs when Yz03 and Ce02 are doped into zirconia. The space group of the tetragonal structure is
P42/nrnc, Z= 2. The lattice parameters are a = 0.362 6(5)nm, c =0. 522 6(3)nm for Ce02 doped zirconia and a =
0. 360 2(8)nm, c ~ 0 . 5 1 7 9( l ) nm for Y2O3 doped zirconia, respectively. In each unit cell, there are two kinds of
equivalent positions, i. e. 2b and 4d, which are occupied by Zr4+ , M( M= Y3+, Ce4+ ) cations and 0'- anions, re-
spectively. The crystallographic correlation among the cubic, tetragonal and monoclinic structures of Z Q is discussed.
Ke ~ o r d s :
zirconin, crystal structure, Rietveld refinement, phase transformation.
Zirconia has three different polymorphs under general conditions, that is, monoclinic at room
temperature, tetragonal between 1 440-2 640 K and cubic at higher temperature. The tetrago-
nal and cubic phases of pure zirconia can be stabilized at room temperature by the addition of suit-
able oxides, such as CaO, MgO, Y203, Ce02, etc. These partially or fully stabilized zirconia al-
loys have optimized electric, optical and mechanical properties, so they have commercial applica-
tions in fuel cells, oxygen sensors, structural and wear components. These applications have in
turn motivated further studies on crystal structure and mechanism of transformation of zirconia
polymorphs.
McCullough and rueb blood"] first derermined the crystal structure of monoclinic zirconia by
using X-ray single-crystal methods on natural baddleleyite. Smith and ~ewki rk"] reconfirmed the
results of McCullough and Trueblood using new X-ray data collected from a synthetic single crys-
tal. Cubic Zr(Ca, Y)@-, solid solutions have been investigated at various temperatures from both
X-ray and neutron data by Carter and ~ o t h ' ~ ' , Steele and ~e n d e r ' ~] , Morinaga and ohe en'^].
The tetragonal cell with a = 0.364 nm, c = 0. 527 nm of zirconia, which was first reported by
~ e u f e r ' ~ ] using X-ray powder diffraction intensities collected at 1 470 to 2 230 K, has been ac-
cepted by a number of investigators. However, some portrayals with different crystal structures of
tetragonal phase have been proposed in recent years. chengE7] reported a large tetragonal cell with
lattice parameters of a = 0. 510 2 nm, c = 0. 517 8 nm for nitrogen-containing zirconia. Li et
al. ['I presented data on the structure of Y2O3 stabilized tetragonal 21-9, which were very close to
Cheng's result. Sanchez-Bajo et al. 191 suggested that there are two kinds of tetragonal structure,
namely t and t', in Yz03 stabilized zirconia by refinement of the X-ray diffraction data.
The present study gives refinement results on the crystal structure of three zirconia poly-
morphs. The correlation among them has also been discussed.
No. 1 CRYSTAL STRUCTURE OF ZIRCONIA BY RIETVELD REFINEMENT 81
1 Experiment
The samples used for data collection were pure ZrOz, CeOz and Y20s-doped zirconia. Pure
Zr02 powder was a commercial superfine zirconia powder (Dahua Ceramic Corp., Beijing). The
powders of Ce02- and Y203-doped zirconia were prepared by co-precipitated method with the ad-
dition of 12mol% and 3mol% Y2O3, respectively. After cold-pressing, the samples were sintered
in air at 1 873 K for 4 h.
X-ray diffraction (XRD) intensity data, which were used for crystal structure analysis, were
collected at ambient temperature by a Rigaku automatic diffractometer with a rotating anode and a
12 kW X-ray generator. CuKal radiation ( A = 0. 154 05 nm) and a graphic monochrometer for
diffracted beams were used. A step scanning mode was adopted with a scanning step of 0.02'
( 20) . The positions of diffraction peaks were corrected by using high purity Si as the inner stan-
dard. After normalization, the TREOR program[101 is used to index the XRD pattern. The
diffraction data were analyzed by using the Rietveld ' s powder diffraction profile- fitting tech-
nique["] to determine the crystal structural parameters.
2 Results and discussion
2. 1 Crystal structure of monoclinic Zr02
The XRD pattern for pure ZrOz powder which was refined by Rietveld method is shown in
fig. 1. Rietveld analysis standard agreement indices are the residual factor R, = 3. 07%, the
weighted residual factor R , = 4.09 % and the goodness of fit factor s = 2. 1. Table 1 shows the
refined structural parameters and ionic positions. The ionic coordination number and bond length
are listed in table 2.
28/ ( ' )
Fig. 1. The refined XRD pattern of m-ZQ. + , Experimental; - , calculated. The lowest trace indicates the difference
between the calculated and experimental patterns. The middle vertical line indicates the peak positions of monoclinic
phase.
The structure of pure Zr02 is monoclinic, which has the space group symmetry P21/c with
four ZQ in the unit cell. The 2r4+ cations and 02- anions all occupy the nonequivalent 4e posi-
82 SCIENCE IN CHINA (Series A) Vol. 42
tions in the lattice. The Zr is seven-fold coordination surrounded by three OI anions and four 011
anions. The present refinement is in agreement with the results of ~ c ~ u l l o u ~ h [ ' ~ and smith[".
Table 1 Refined structure parameters of ZrOz polymorphs
Space Lattice parameter Ionic position and coordinate
Phase
P UP /nm ion site x Y z g/nm2 N
a=0. 5146( 7) Zr4+ 4e 0. 2728(2) 0. 0337(2) 0. 2088(4) 0. 0078 4. 0
Pure Zr02 P21/c b =0. 520 5(1)
c=0. 5313( 6) 0:- 4e 0.077 3(9) 0.313 3(8) 0.304 6(3) 0.003 6 4.0
(monoclinic) 2 = 4 P=99. 1(8)'
V=0. 1405nm3 0:; 4e 0. 4619(1) 0. 7882(5) 0. 4362(3) 0. 0305 4. 0
-
Ce02 doped P4z/nmc a = 0.362 6(5) Zr4* 2b 0. 7500 0. 2500 0. 2500 0. 0028 1. 76
(tetragonal) Z = 2 V=0. 0687nm3 0' - 4d 0. 2500 0. 2500 0. 0482(6) 0. 0097 4. 0
Y203 doped P42/nmc a = 0.360 2(8) Zr4+ 2b 0. 7500 0. 2500 0. 2500 0. 0030 1.88
zrO2 c=0. 5179( 1) Y3+ 2b 0. 7500 0, 2500 0. 2500 0. 0006 0.12
(tetragonal) 2 = 2 V=0. 0672nm3 0'- 4d 0. 2500 0. 2500 0. 0493(8) 0. 0092 3.76
Yz4doped Fm3m a=0. 5135( 9) Zr4+ 4a 0. 0000 0. 0000 0. 0000 0. 0072 4.0
zaz
(cubic) 2 = 4 V=0. 1354nm3 d- 8c 0. 2500 0. 2500 0. 2500 0. 0157 8. 0
Table 2 Ionic coordination number and bond length in m - Z a
Ion Zr4 + 0l2 - 01: -
Coordination number 7 10 10
Zr-O1 0.188 5 01-201 0. 2738 011 - 2011 0.268 6
Bond length/nm - 011 0.191 4 - 011
- 01 0.286 8 0.286 8
- 0 1 1 0. 2133 - 011 - 01 0.287 2 0.287 2
2. 2 Crystal structure of C e q doped ZIQ
The analysis of XRD reveals that a structural transition from monoclinic to tetragonal occurs
after CeG doping in Zr 02. The refined X-ray diffraction pattern is displayed in fig. 2. In fig. 2,
the selected profile function is Pseudo-Voigt function. The residual factor Rp, the weighted resid-
ual factor R,, and goodness of fit factor s are 9. 61 % , 11. 5 % and 1. 48, respectively. The
structural parameters are listed in table 1 . Table 3 shows the data of ionic coordination number,
bond lengths and the 0-Zr-0 bond angles.
No. 1 CRYSTAL STRUCTURE OF ZIRCONIA BY R1ETVEI.D REFINEMENT 83
Fig. 2. The refined XRD pattern of Ce02 doped zirconia. The meaning of the marked symbols is similar to that in
figure 1 .
Table 3 Ionic coordination number, bond length and bond angle in Y203 and Ce02 doped zirconia
Ce02 doped zirconia Y203 doped zirconia
coordination
Ion bond length/nm
number
coordination
ion bond length/nm
number
( Zr 4 +, Ce4+ ) 8 (Zr, Ce)-40 0. 209 8 ( Zr 4 +, Y4+ ) 8 ( Zr , Y) - 40 0 . 2 0 8 0
4 0 0. 239 1 4 0 0. 237 7
@- 10 0--2(Zr, Ce) 0. 209 8 0 - 10 0- - 2( Zr , Y) 0 . 2 0 8 0
2( Zr , Ce) 0. 239 1 2( Zr , Y) 0 . 2 3 7 7
6 0 0. 261 3 2 0 0. 259 0
4 0 0. 259 8
0 - Zr - 0 bond angle
135. 94"
( t Z r - 0 bond angle
135. 92"
By comparison with Teufer' s results, the space group of tetragonal phase is also P42/nmc
with two Zr02 in the unit cell. Each 2r 4+ cation is surrounded by 8 d- anions, 4 of them with
a shorter-length Zr-0 bond forming a flattened tetrahedron and 4 with a longer-length Zr-0
bond forming a elongated tetrahedron. However, there is a little difference on the descriptions of
ionic positions. Teufer suggested that 2 2r4 + and 4 d - occupy 2a position with ( x = 0, y = 0, z
= 0) , and 4d position with (x = 0, y = 0. 5, z = 0. 185), respectively. In our results, 22r4+ and
4 d prefer to occupy the 2b and 4d crystal position, respectively. The reason for this difference
accounts for the different choices of the cell origins. There are two origin choices for P42/nmc in
the international table for crystallography. Teufer selected choice I with the origin at Tm2/n.
However, choice I1 with origin at i seems to fit our XRD patterns. When the origin shifs from
to Tm2, the coordinates of zr4 + and d - given in table 1 transform to 2b ( x = 0, y = 0, z = 0 . 5 )
and 4d (x = 0, y = 0. 5, z = constant). If 2r4+ moves by 1/ 2 in c axis, then our results become
identical with Teufer ' s descriptions.
84 SCIENCE IN CHINA (Series A) Vol. 42
According to crystallography, the choice of crystal unit cell should make the cell volume
smaller and smaller, so the crystal structure is more stable. Based on Li' s and Cheng's
if their lattice parameter a (about 0. 51-0. 52 nm) is divided by &, the abtained value
(-0.36 nm) would be very close to the data reported by Teufer. It seems that the volume of the
tetragonal cell selected by Li and ~ h e n g " . ~ ~ is twice the minimum cell volume. Sanchez-Bajo et
al. suggest that there are two kinds of tetragonal structures in Y2O3 ( 3 mol% )-doped zirconia,
but in our experimental results, there are not any other tetragonal phases having been found by
XRD analysis.
2. 3 Crystal structure of Y203 doped zirconia
The XRD results of the samples show that two phases, tetragonal and cubic, coexist in the
Yz03-doped zirconia. The refined XRD pattern of the sample is presented in fig. 3. The selected
peak profile function is also the Pseudo-Voigt function. The residual factor R,, the weighted
residual factor R,, and the goodness of fit factor s are 8. 53 % , 10.5 % abd 1. 56, respectively.
Detailed refinement data are listed in tables 1 and 3.
Fig. 3 . The refined XRD pattern of Y2O3 doped zirconia.
For tetragonal phase, the space group is Pd2/nmc, the same as the previous description.
Table 1 shows that y3+ and Zr4+ cations occupy the 2b crystal position, and d- anions occupy
the 4d crystal position with some oxygen vacancies in Y203-doped zirconia. That is, the lower-
valence y3+ cations substitute zirconium randomly in tetragonal lattice and generate a certain
amount of oxygen vacancies to keep the charge in balance, which is in agreement with the results
of ~ i [ ' ~ ] , Kountouros and ~e t z ow[ l ~] .
According to Wiles and Young's formula[141, the content of tetragonal and cubic phase in
Yz03-doped Z a solid solution can be calculated to be 76wt% and 24wt%, respectively. The
space group of cubic phase is Fm3m with four Zr02 in the unit cell. The lattice parameter and ion-
ic positions of cubic ZIQ are shown in table 1. As in fluorite, the Zr and 0 ions of cubic zirconia
are in the special positions 4a and 8c, respectively.
No. 1 CRYSTAL STRUCTURE OF ZIRCONIA BY RIETVELD REFINEMENT 85
2. 4 Correlation of polymorphs of ZrOz
The crystallographic correlation among three polymorphs (cubic, tetragonal, monoclinic) of
Zr02 is shown in table 4. The cubic phase has a fluorite structure. The monoclinic cell can be ob-
tained from cubic cell through a sample distortion without significant change of the unit cell vol-
ume. The transition from cubic to tetragonal is a displacive transition. When this transition oc-
curs, four Zr4+ cations at 4a position of cubic form have split into two groups to occupy the 2b po-
sition in tetragonal form individually, and the d- anions at 8c site of cubic form have also slipt
into two groups which occupied 4d site of t-Zr02, respectively. Based on the calculated results,
the lattice parameter a , of tetragonal phase is as long as 1/& of a C of cubic phase, and the unit
cell volume of tetragonal phase is about one half of the cubic phase. Therefore, it can be demon-
strated that one unit cell of cubic phase has split into two unit cells of tetragonal phase during the
c+t transition.
Table 4 Crystallographic correlation among three polymorphs of Zr02
Phase Cubic Tetragonal Monoclinic
Space group Fm3m P42/nmc P21/c
Reflection conditions hkl : h + k , k + l , L + h = 2n h k O : h + k = 2 n hO1:h + 1 = 271
OkL:k,L = 2n hhl:l = 2n 0kO:k = 2n
hhl:h+ I = 2n 00L:L = 271 hO0:h = 271
hO0:h = 2 hO0:h = 271 001:L = 2 n
z 4 2 .4
Lattice parameter a c a , = b,%a,/./2 a,#b,-a,
c,%a, c,>a,
Unit cell volume V,= a: V,% V,/2 V,*2 V,
Ionic position Zr4 + 4a 2b 4e
02- 8c 4d O1 4e
011 4e
In the course of t +m transition, two groups of Zr4+ at 2b site in the tetragonal cell have
combined to one group to occupy 4e position of monoclinic phase, and two groups of d- at 4d
site in tetragonal cell have transformed into 401 and 4011 which have occupied two nonequivalent
4e positions of monoclinic phase, respectively. That is, two unit cells with tetragonal symmetry
combine to one monoclinic cell, which can be seen from the change of the unit cell volume. The
t+m transition is derived from a structure-rebuilding transformation with significant change of
the coordination number of Zr. In tetragonal phase, each zr4 + is surrounded by 8 d - anions
with two kinds of nonequivalent Zr-0 bond. However, in monoclinic zirconia, each Zr4+ is sur-
rounded by 3 OI and 4 011 anions, and all the bond length of 2-0 is nonequivalent.
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