J. Am. Ceram. Soc.
, 84 [2] 435– 41 (2001)
journal
Zinc Vanadates in Vanadium Oxide-Doped Zinc Oxide Varistors
School of Materials Engineering, Nanyang Technological University, Singapore 639798
Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB2 3QZ, United Kingdom
Convergent-beam electron diffraction has been used to deter-
mine the space groups of ␤- and ␥-Zn3(VO4)2 particles in
vanadium oxide-doped zinc oxide varistors. The crystal struc-
ture of ␤-Zn3(VO4)2 has been determined to be monoclinic
with space group P21 and lattice parameters of a ⴝ 9.80 Å, b ⴝ
8.34 Å, c ⴝ 10.27 Å, and ␤ ⴝ 115.8°, whereas that of
␥-Zn3(VO4)2 is monoclinic with space group Cm and a ⴝ
10.40 Å, b ⴝ 8.59 Å, c ⴝ 9.44 Å, and ␤ ⴝ 98.8°. Energy-
dispersive X-ray microanalysis of these two phases shows
significant deviations from their expected stoichiometry. It is
apparent that the ␤-phase is, in fact, the metastable Zn4V2O9
phase, whereas the ␥-phase either is a new oxide that consists
of zinc, vanadium, and manganese or, more likely, is a zinc
vanadate phase with a Zn:V atomic ratio of 1:1 that has the
ability to go into solid solution with manganese.
I. Introduction
Z INC ORTHOVANADATE (Zn3(VO4)2) has been detected as a minor
secondary phase in V2O5-doped ZnO varistors, using X-ray
diffractometry (XRD).1– 4 Not much information about this phase
can be found in the literature, other than it occurs in three
polymorphs: ␣-, ␤-, and ␥-phases, as suggested by Brown and
Hummel.5 Although the ␣-phase is known to be orthorhombic,6 no
definitive crystal structures are quoted in the JCPDS† files for the
␤- and ␥-phases, although interplanar spacings and relative peak
intensities are available.5 In a recent brief and initial report, we
used analyses of the selected-area electron diffraction (SAED)
patterns from the ␤- and ␥-phases to propose lattice parameters
and Bravais lattices for the ␤- and ␥-phases that are found in
V2O5-doped ZnO varistors.3
In the current work, we extend our previous analyses of these
phases to report the space groups of the submicrometer-sized
grains of the ␤- and ␥-phases in these ZnO varistors, as determined
using convergent-beam electron diffraction (CBED), together with
a refinement of the lattice parameters of the ␤-phase. Composi-
tional analyses of these two phases obtained using energy-
dispersive X-ray (EDX) analysis are inconsistent with the poly-
morphism of Zn3(VO4)2 that was recorded by Brown and
Hummel;5 instead, the analyses support the conclusions of
Makarov et al.,7 that polymorphism does not occur. However, to
avoid confusion, this report generally will conform to the notation
T. E. Mitchell—contributing editor
Manuscript No. 188736. Received February 16, 2000; approved August 31, 2000.
Author HHH was supported by Nanyang Technological University, Singapore.
Based in part on the thesis submitted by author HHH for the Ph.D. degree in the
Dept. of Materials Science and Metallurgy, University of Cambridge, 1999.
*Member, American Ceramic Society.
†
Joint Committee for Powder Diffraction Standards, Swarthmore, PA (now
International Centre for Diffraction Data, Newtown Square, PA).
435
Huey-Hoon Hng
Kevin M. Knowles* and Paul A. Midgley
given by Brown and Hummel;5 i.e., we will designate the phases
as either ␤- and ␥-Zn3(VO4)2 or as the ␤- and ␥-phases.
II. Zinc Vanadates
Brown and Hummel5 were the first to study the ZnO–V2O5
system. They reported the existence of only three compounds:
Zn3(VO4)2, Zn2V2O7, and Zn(VO3)2. Two polymorphic transfor-
mations were proposed for Zn3(VO4)2:
795⬚C 815⬚C
␣-Zn3共VO4兲2 ¢
O ¡ ␤-Zn3共VO4兲2 O
¢¡ ␥-Zn3共VO4兲2 (1)
The transition at 795°C was reported to be sluggish but reversible,
whereas that at 815°C was reported to be rapid and reversible. The
low-temperature polymorph (␣-Zn3(VO4)2) and the intermediate-
temperature polymorph (␤-Zn3(VO4)2) both were reported to
be light yellow, whereas the high-temperature polymorph
(␥-Zn3(VO4)2) had a dull-red color. A rapid and distinct color
change was reported visually as Zn3(VO4)2 was cooled through the
inversion temperatures.5 Gopal and Calvo6 also observed a slug-
gish transformation when they heated an ␣-Zn3(VO4)2 single
crystal. However, Makarov et al.7 did not record the existence of
any polymorphism when they produced a phase diagram for the
ZnO–V2O5 system. In addition to the three compounds that were
observed by Brown and Hummel,5 Makarov et al.7 detected a
fourth compound: Zn4V2O9. The X-ray characteristics determined
by Makarov et al.7 for Zn2V2O7 and Zn(VO3)2 were consistent
with those obtained by Brown and Hummel.5 The interplanar
spacings for the Zn3(VO4)2 phase that was recorded by Makarov et
al.7 also were analogous to those of ␣-Zn3(VO4)2 that was
observed by Brown and Hummel.5 Makarov et al.7 hypothesized
that the ␤-Zn3(VO4)2 phase that was observed by Brown and
Hummel5 actually consisted of a mixture of the ␣-Zn2V2O7 and
Zn4V2O9 phases; they also noted that the interplanar spacings of
the ␥-Zn3(VO4)2 phase that was observed by Brown and Hummel5
matched those of Zn4V2O9 very well.
The crystal structures of some of these zinc vanadates were
deduced later from single-crystal X-ray methods and powder
XRD. The ␣-Zn2V2O7 phase was deduced to be monoclinic, with
space group C2/c and lattice parameters of a ⫽ 7.429 Å, b ⫽
8.340 Å, c ⫽ 10.098 Å, and ␤ ⫽ 111.37°.8 Similarly, the crystal
structure of the low-temperature ␣-Zn3(VO4)2 phase was reported
by Gopal and Calvo6 and Morris et al.9 Gopal and Calvo6 deduced
the crystal structure from single crystals of ␣-Zn3(VO4)2 that were
prepared from a melt that was slowly cooled in a platinum crucible
containing stoichiometric amounts of ZnO and V2O5. They found
that ␣-Zn3(VO4)2 crystallizes in the orthorhombic structure, with
space group Cmca and a ⫽ 6.088 Å, b ⫽ 11.489 Å, c ⫽ 8.280 Å,
and Z ⫽ 4. The crystal structure is based on a pseudo-cubic
arrangement of closed-packed layers of O atoms. The oxygen
layers alternate between pairs of layers that contain tetrahedrally
coordinated V5⫹ ions. The Zn2⫹ ions reside in two types of
octahedral sites. Their attempts to convert a single crystal to the
436 Journal of the American Ceramic Society—Hng et al. Vol. 84, No. 2

Table I. Comparison of Observed Interplanar Spacings of 8.299 Å, b ⫽ 11.5284 Å, c ⫽ 6.1116 Å, and Z ⫽ 4 was obtained
the Zn4V2O9 Phase (by Makarov et al.7) with Those (JCPDS Powder Diffraction File Card No. 34-0378, in which the
Calculated Using the Crystal Structure Deduced by Waburg space group is quoted erroneously as Abam). These two crystal
and Müller-Buschbaum10 structures for ␣-Zn3(VO4)2 are, in essence, exactly the same,
except for the assignment of the unit-cell parameters.
Calculated
Observed (Makarov et al.7) (Waburg and Müller-Buschbaum10) More recently, Waburg and Müller-Buschbaum10 reported the
d-spacing (Å) Intensity d-spacings (Å) hkl existence of a metastable Zn4V2O9 phase between a CO2-laser-
generated flux and a solid ZnO–V2O5 material. The crystal
3.189 Very weak 3.189 3៮ 11, 203៮ structure of this phase was determined to be monoclinic, using
3.119 Medium 3.117 312៮ single-crystal X-ray methods, with space group P21 and a ⫽
3.052 Very strong 3.062, 3.061 112, 220 10.488 Å, b ⫽ 8.198 Å, c ⫽ 9.682 Å, and ␤ ⫽ 118.66°. This phase
2.826 Strong 2.832 003 has a framework of polyhedra in which the Zn2⫹ ions are in
2.592 Very weak 2.601 1៮ 31, 031 fourfold, fivefold, or sixfold oxygen coordination polyhedra with
2.514 Medium 2.517 223៮
2.445 Weak 2.450 4៮ 03, 212 V5⫹ ions that have been incorporated into tetrahedral coordination
2.404 Weak 2.402 103 sites. The interplanar spacings of the Zn4V2O9 phase that was
⫹ other reflections observed by Makarov et al.7 can be indexed with this crystal
structure, as shown in Table I.

high-temperature phase resulted in diffraction rings, and no crystal III. Experimental Procedures
structure determinations were made. Subsequently, Morris et al.9
used powder XRD to deduce the crystal structure of ␣-Zn3(VO4)2. ZnO– 0.25-mol%-V2O5 (ZV), ZnO– 0.25-mol%-V2O5–1-
The sample was prepared by heating a 3:1 (molar ratio) mixture of mol%-MnO2 (ZVM), and ZnO– 0.25-mol%-V2O5–1-mol%-Co3O4
ZnO and V2O5 at 780°C for three days, with several regrindings. (ZVC) ceramic varistors were prepared from high-purity oxide
An orthorhombic structure with space group Acam and a ⫽ powder starting materials. The powder mixtures of the selected

Fig. 1. (a) Spot pattern, (b) zero-order Laue zone (ZOLZ) pattern, and (c) whole pattern including the first-order Laue zone (FOLZ) layer of ␤-Zn3(VO4)2
at the [100]o zone axis or the [01៮ 0]m zone axis when assuming an orthorhombic lattice (noted with a subscript “o”) or a monoclinic lattice (noted with a
subscript “m”), respectively.
February 2001 Zinc Vanadates in Vanadium Oxide-Doped Zinc Oxide Varistors 437

Fig. 2. CBED patterns of ␤-Zn3(VO4)2 along the [010]o or [101]m zone axis ((a) zero-order Laue zone (ZOLZ) pattern and (b) [010]o zone axis tilted toward
the FOLZ–a*o direction or the [101]m zone axis tilted toward the FOLZ–b*o direction). Arrows indicate the disks lying on either side of the a*o-axis, showing
the break in mirror symmetry.

compositions were ball-milled for 24 h using ZrO2 beads in zero-order Laue zone (ZOLZ) is known as “projection” whole
deionized water. The mixtures then were dried and pressed into pattern (W-P) symmetry11 and discounts the effects of any
pellets, sintered in an atmosphere of ambient air for 4 h at 900°C, higher-order Laue zone (HOLZ) reflections. The ZOLZ in Fig.
and cooled at a rate of 5°C/min. 1(b) shows only twofold symmetry parallel to the [100] axis, and
X-ray analyses of the sintered samples were conducted using no evidence of mirror symmetry along the b*o- and c*o-axes is
CuK␣ radiation on a vertical powder diffractometer (Model observed. The full whole pattern (Fig. 1(c)) that was obtained
PW1710, Philips, Eindhoven, The Netherlands). Specimens for using a short camera-length pattern (to include HOLZ reflections)
transmission electron microscopy (TEM) were prepared using confirmed the presence of a twofold axis parallel to the [100] axis
standard ion-beam-thinning methods and examined using a TEM and the absence of mirror planes. The full W-P symmetry refers to
system (Model 2000FX, JEOL, Tokyo, Japan) at an accelerating the symmetry of the complete pattern (including the HOLZ) and
voltage of 200 kV; this TEM system had an ultrathin beryllium yields three-dimensional information about the crystal. If the
window that was attached to an analyzer (Model 6284, Link crystal is orthorhombic, then the minimum symmetry that is
Systems, High Wycombe, Buckinghamshire, U.K.) for EDX observed in the ZOLZ (from point group 222) should be 2mm,
analysis. Quantitative microanalyses were performed using a because a twofold axis appears as a mirror in projection. The
computer program (RTS-2/FLS, Link Systems). absence of mirrors in the ZOLZ (or HOLZ) excludes an orthor-
hombic lattice; thus, the crystal must be monoclinic, with point
group 2 or 2/m. Careful examination of the spot pattern obtained
IV. Results from the [100] zone axis (Fig. 1(a)) showed that the angle between
the b*o-axis and the c*o-axis was not exactly 90°. Although this
Other than the major ZnO phase, Zn3(VO4)2 was the only
secondary phase that was detected via powder XRD in the ZV,
ZVM, and ZVC materials. Using the X-ray data reported by
Brown and Hummel,5 the phases in the various varistor composi-
tions were identified as ␤-Zn3(VO4)2 (JCPDS Powder Diffraction
File Card No. 19-1468), ␥-Zn3(VO4)2 (JCPDS Powder Diffraction
File Card No. 19-1470), and ␣-Zn3(VO4)2 (JCPDS Powder Dif-
fraction File Card No. 34-378) in the ZV, ZVM, and ZVC
materials, respectively.4
In our previous report,3 ␤-Zn3(VO4)2 had an orthorhombic A
lattice, with a ⫽ 8.34 Å, b ⫽ 10.68 Å, and c ⫽ 17.0 Å, whereas
␥-Zn3(VO4)2 had a monoclinic C lattice, with a ⫽ 10.4 Å, b ⫽
8.59 Å, c ⫽ 9.44 Å, and ␤ ⫽ 98.8°, based on the indexing of
SAED patterns from grains that were typically 0.5–1 ␮m in size.
This procedure allows TEM identification of secondary zinc
vanadate phases in other vanadium-doped ZnO varistor composi-
tions but lacks the fuller description, in terms of a space group, that
CBED can achieve readily from such grains.11 Hence, CBED was
used to determine the space group of these two phases.

(1) ␤-Zn3(VO4)2
Assuming an orthorhombic A lattice for ␤-Zn3(VO4)2, the spot
diffraction pattern and the CBED patterns that have been obtained
along the [100] zone axis are shown in Fig. 1. The symmetry of the
Fig. 3. Schematic diagram showing how the crystal structure of
␤-Zn3(VO4)2 is reduced from a pseudo-orthorhombic A lattice to a
monoclinic P lattice. (␣ ⫽ 93°, a ⫽ 8.34 Å, b ⫽ 10.68 Å, c ⫽ 17.0 Å, ␣⬘ ⫽
116°, a⬘ ⫽ 8.34 Å, b⬘ ⫽ 10.27 Å, and c⬘ ⫽ 9.80 Å.)
438 Journal of the American Ceramic Society—Hng et al.
discrepancy could be due to distortions that are introduced by the
lenses in the TEM apparatus, repeated measurements of several
such spot patterns from many grains showed that this angle is
93° ⫾ 1°, which further indicates that this phase is indeed
monoclinic, rather than orthorhombic.
Additional symmetry analysis along the [010]o zone axis,
keeping the pseudo-orthorhombic notation, was performed. The
ZOLZ pattern (see Fig. 2(a)) showed mirror symmetry along the
a*o-axis only and confirmed that there is a twofold axis parallel to
the [100]o zone axis. A 2/m point group is a possible point group
that can be deduced from the pattern symmetries along the [100]o
zone axis. For such a point group, we should observe mirror
symmetry along the c*o-axis; this feature was not observed in the
ZOLZ pattern (Fig. 2(a)), which suggests that the point group
should actually be 2.
Gjønnes–Moodie (G-M) lines also were observed in the ZOLZ
pattern (Fig. 2(a)). G-M lines appear because of the dynamical
nature of electron diffraction. Reflections that are forbidden in
kinematical diffraction occur because of double diffraction in
CBED patterns. The appearance of G-M lines indicates either the
presence of twofold screw axes (21) and/or glide planes in the
crystal structure. The symmetry in the HOLZ rings near the a*o-axis
was observed from a pattern that was obtained by tilting slightly
Fig. 4. CBED patterns of ␥-Zn3(VO4)2 along the [001] zone axis ((a) zero-order Laue zone (ZOLZ) pattern, (b) [001] zone axis tilted toward the HOLZ–a*
direction, and (c) [001] zone axis tilted toward the HOLZ–b* direction).
Vol. 84, No. 2
away from the zone axis (see Fig. 2(b)). There was no mirror
symmetry in the HOLZ layer; therefore, the G-M lines must be due
to the presence of a 21 axis, rather than glide planes.
An A21 monoclinic lattice is not possible. However, by consid-
ering the (100)o plane of the crystal lattice in the pseudo-
orthorhombic indexing system shown in Fig. 3, the crystal lattice
can be reduced from an A lattice to a primitive P lattice without
losing the 21 screw axis along the a-axis. Using simple geometry
and considering the a-axis to be the unique axis, the new monoclinic
P lattice has lattice parameters of a ⫽ 8.34 Å, b ⫽ 10.27 Å, c ⫽
9.80 Å, and ␣ ⫽ 116°. To conform to the conventional way of
defining a monoclinic lattice, the crystal lattice parameters were
redefined as a ⫽ 9.80 Å, b ⫽ 8.34 Å, c ⫽ 10.27 Å, and ␤ ⫽ 116°.
Therefore, by assuming a monoclinic P lattice, the CBED
patterns that are shown in Figs. 1 and 2 can now be re-indexed as
the [01៮ 0]m and [101]m zone axes, as denoted by the subscript “m.”
Hence, the space group for ␤-Zn3(VO4)2 was identified as P21
(No. 4).
(2) ␥-Zn3(VO4)2
CBED patterns along the [001] zone axis of ␥-Zn3(VO4)2 are
shown in Fig. 4. Mirror symmetry was observed along the a*-axis
February 2001 Zinc Vanadates in Vanadium Oxide-Doped Zinc Oxide Varistors
in the ZOLZ pattern (see Fig. 4(a)). The intensity of the HOLZ
rings in the zone-axis pattern was very weak. Additional patterns
were obtained by tilting away from the zone axis to observe the
symmetry in the HOLZ rings along the a*- and b*-axes more
clearly, as shown in Figs. 4(b) and (c), respectively. Mirror
symmetry was observed along the a*-axis but not along the
b*-axis. Hence, the results showed that the possible point group is
m, with (010) being the mirror plane. Additional symmetry
analysis at the [100] zone axis was performed (see Fig. 5). Only
one mirror symmetry was observed in projection (Fig. 5(a)) and for
the whole pattern (Fig. 5(b)). Hence, the point group for
␥-Zn3(VO4)2 was confirmed to be m. No G-M lines were ob-
served; therefore, the space group for ␥-Zn3(VO4)2 was Cm (No.
8).
(3) Energy-Dispersive X-ray Microanalysis
Only the ␣-phase that was detected in the ZVC material gave
the correct Zn:V atomic ratio of 3:2 for Zn3(VO4)2. This determi-
nation served as an internal calibration for the EDX analyses of the
␤- and ␥-phases. The composition of the ␤-phase in the ZV
material was 75.7 wt% zinc and 24.3 wt% vanadium, which
corresponds to 70.8 at.% zinc and 29.2 at.% vanadium and gives a
Zn:V atomic ratio of ⬃2:1. The ␥-phase had a composition of 44.9
wt% zinc, 41.9 wt% vanadium, and 13.3 wt% manganese, which
corresponds to 39.2 at.% zinc, 47.0 at.% vanadium, and 13.8 at.%
manganese and gives a (Zn ⫹ Mn):V atomic ratio of ⬃1:1.
V. Discussion
In this investigation, all three polymorphs of Zn3(VO4)2—i.e.,
the ␣-, ␤-, and ␥-phases, as suggested by Brown and Hummel5—
were detected in our samples via powder XRD. However, TEM/
EDX microanalysis clearly questions the chemistry of the ␤- and
␥-phases. Of course, deviation from the correct proportion of ␤-
and ␥-phases in EDX could be due to contributions from the
Fig. 5. CBED patterns of ␥-Zn3(VO4)2 along the [100] zone axis ((a) zero-order Laue zone (ZOLZ) pattern and (b) whole pattern including the first-order
Laue zone (FOLZ) layer).
439
surrounding ZnO grains to the Zn peak, as well as complications
from the dissolved manganese. Another obvious possibility is that
Zn3(VO4)2 polymorphism does not exist, as suggested by Makarov
et al.7
The crystal structures of the different zinc vanadates that have
been determined in this study, as well as those reported in the
literature, are summarized in Table II. The results show that the
Zn4V2O9 phase10 apparently has the same space group as the
␤-phase that has been detected in this investigation. In addition, if
the values of the lattice parameters a and c are interchanged, the
unit-cell parameters for the two crystals are essentially the same,
within experimental error, given that we have proposed unit-cell
parameters for the ␤-phase from measurements on electron dif-
fraction patterns, rather than from single-crystal XRD. In fact, the
SAED patterns that have been obtained for the ␤-phase in the ZV
material could be indexed consistently using the cell parameters of
Zn4V2O9. Makarov et al.7 instead suggested, as an alternative
explanation, that the interplanar spacings of ␤-Zn3(VO4)2 ob-
served by Brown and Hummel5 could be interpreted in terms of a
mixture of ␣-Zn2V2O7 and Zn4V2O9. It is apparent from Table III
that the interplanar spacings and relative intensities of
␤-Zn3(VO4)2 that were reported by Brown and Hummel5 can be
indexed reasonably satisfactorily in terms of an equimolar mixture
of ␣-Zn2V2O7 and Zn4V2O9, in agreement with the interpretation
of Makarov et al.7 A re-examination of the powder XRD data
shown by us previously4 as evidence of ␤-Zn3(VO4)2 in sample
ZV in the light of the work in this paper shows that there is no
evidence for ␣-Zn2V2O7 in sample ZV, and that the second phase
in sample ZV is simply the metastable Zn4V2O9 first reported by
Waburg and Müller-Buschbaum.10 Thus, the sluggishness reported
by Brown and Hummel in the ␣3␤ transformation of Zn3(VO4)2
can be understood straightforwardly in terms of the necessary
microstructural changes to enable ␣-Zn3(VO4)2 to decompose to
␣-Zn2V2O7 and Zn4V2O9.
In regard to the ␥-phase, this “polymorph” also may possibly be
another zinc vanadate phase with a composition that is different
440 Journal of the American Ceramic Society—Hng et al. Vol. 84, No. 2

Table II. Summary of Reported Crystal Structures of Zinc Vanadates

Cell parameters
Space ␤
group a (Å) b (Å) c (Å) (degrees) Reference

␣-Zn3(VO4)2, orthorhombic
Acam 8.299 11.528 6.112 Morris et al.9 (JCPDS 34-0378)
Cmca 6.088 11.489 8.280 Gopal and Calvo6
␤-Zn3(VO4)2, monoclinic
P21 9.80 8.34 10.27 116 Present study
␥-Zn3(VO4)2, monoclinic
Cm 10.40 8.59 9.44 98.8 Present study
Zn4V2O9, monoclinic
P21 10.488 8.198 9.682 118.66 Waburg and Müller–Buschbaum10
␣-Zn2V2O7, monoclinic
C2/c 7.429 8.340 10.098 111.37 Gopal and Calvo8 (JCPDS 29-1396)

Table III. Indexing of Interplanar Spacings of the ␤-Zn3(VO4)2 Observed by Brown and Hummel5 in Terms of the Zn4V2O9
Metastable Phase Determined by Waburg and Müller-Buschbaum10 and the ␣-Zn2V2O7 Phase Determined by
Gopal and Calvo6
␤-Zn3(VO4)2, Brown and Hummel5 ␣-Zn2V2O7, JCPDS File Card No. 38-0251† Zn4V2O9, Waburg and Müller-Buschbaum10‡
d-spacing Relative d-spacing Relative d-spacing Relative
(Å) intensity (Å) intensity (Å) hkl intensity

8.50 15 8.496 001 51

5.30 30 5.321 40
4.25 25 4.248 002 52
4.17 20 4.165 10 4.168 112៮ 84
3.45 60 3.454 47
3.18 15 3.191, 3.189 3៮ 11, 203៮ 116
3.12 85 3.1189 100 3.117 312៮ 380
3.07 55 3.062, 3.061 112, 220 999
2.95 30 2.954, 2.950 113៮ , 022 67
2.84 100 2.832 003 498
2.78 20 2.7748 12
2.67 20 2.6648 24
2.58 15 2.5772 21 2.605, 2.601 131៮ , 031 80
2.52 20 2.517 223៮ 319
2.36 15 2.3952 11 2.380 132៮ 58
2.243 30 2.2204 17 2.240 114៮ 107
2.076 25 2.0747 13
1.957 10
1.903 15 1.9043 8
1.810 1.811 4៮ 15, 223 70
1.778 1.776 9
1.684 15
1.664 25 1.664 015 198
1.631 15 1.6304 18
1.573 20 1.571 534៮ 40
† ‡
Also see JCPDS File Card Nos. 29-1396 and 70-1532. Also see JCPDS File Card No. 77-1757. Relative intensities in this data set are calculated relative intensities in JCPDS
File Card No. 77-1757.

from Zn3(VO4)2; a possible candidate is Zn2V2O7. However, its
crystal structure, as deduced by Gopal and Calvo,8 does not match
that which has been determined in this study. Makarov et al.7
suggested that the interplanar spacings of ␥-Zn3(VO4)2 that was
observed by Brown and Hummel5 were similar to those of
Zn4V2O9. However, we cannot find any evidence to support this
hypothesis. Instead, our results for the ␥-phase, whose presence we
inferred initially from powder XRD from the occurrence of
relatively few peaks in comparison with the intense peaks from the
ZnO matrix,4 can be explained two ways. First, one can assume
that the ␥-phase that has been detected in this study is not the
␥-Zn3(VO4)2 that was observed by Brown and Hummel,5 despite
the agreement with the powder XRD data; instead, it is a new
oxide compound that is composed of zinc, vanadium, and manga-
nese and exhibits XRD characteristics that are similar to those of
the ␥-phase. The second, and more likely, possibility is to consider
the ␥-Zn3(VO4)2 that was observed by Brown and Hummel5 to be
likely to be more than one compound, one of which is essentially
the same as the phase designated as ␥-phase in this study, with an
atomic ratio of Zn:V of 1:1 instead of 3:2, and with the ability to
form a solid solution with manganese, primarily at the expense of
zinc. More research is required to distinguish between these two
possibilities.
The fact that the zinc vanadates exist as minor micrometer-sized
phases in our ZnO varistor samples makes full structural charac-
terization of these phases difficult. In principle, one should be able
to determine the atom positions within an unknown structure using
CBED intensity data, as has been done for the relatively simple
case of the tetragonal ␶-AuSn phase, which is closely related to the
equilibrium AuSn4 phase.12 Such analyses require intensity data
from CBED patterns of sufficient quality, as a recent study has
emphasized.13 The technique that has been used to acquire and
interpret such data from CBED patterns is not yet sufficiently well
developed that it is now practicable to use for phases with
February 2001 Zinc Vanadates in Vanadium Oxide-Doped Zinc Oxide Varistors
relatively large unit cells and a complex chemistry, such as the
␤- and ␥-phases in our ZnO varistor materials. More realistically,
a detailed study of these phases, which involves the preparation of
single crystals and accurate XRD and chemical analyses, is
required. This observation highlights the need for a thorough
re-examination of the ZnO–V2O5 binary system and related
ternary systems (such as ZnO–V2O5–MnO2) via solid-state chem-
istry. V2O5 has been shown to have great potential in replacing
Bi2O3 as the varistor-forming ingredient in ZnO varistors;4 thus, a
complete characterization of the secondary phases that have been
developed during processing will help in the understanding of this
family of electronic ceramics.
VI. Conclusions
All three forms of zinc orthovanadate (Zn3(VO4)2)—i.e., the ␣-,
␤-, and ␥-phases, as suggested by Brown and Hummel5— have
been detected in vanadium-doped zinc oxide varistor materials
samples via powder X-ray diffractometry. The crystal structure of
the ␤-phase was determined to be monoclinic, with space group
P21 and lattice parameters of a ⫽ 9.80 Å, b ⫽ 8.34 Å, c ⫽
10.27 Å, and ␤ ⫽ 116°. Energy-dispersive X-ray (EDX) and
crystallographic analysis suggested that the ␤-phase actually was
the metastable Zn4V2O9 phase that was determined by Waburg
and Müller-Buschbaum.10 The crystal structure of the ␥-phase was
determined to be monoclinic, with space group Cm and a ⫽
10.40 Å, b ⫽ 8.59 Å, c ⫽ 9.44 Å, and ␤ ⫽ 98.8°. EDX analysis
suggested that the ␥-phase either was an oxide that was composed
of zinc, vanadium, and manganese or was a zinc vanadate phase
with a Zn:V atomic ratio of 1:1 that could form a solid solution
with manganese.
441
Acknowledgment
The authors thank Prof. A. H. Windle, F.R.S., for providing the laboratory
facilities.
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