Materials Letters 61 (2007) 3466 – 3468

www.elsevier.com/locate/matlet

Phase relations and microwave dielectric properties

of vanadium modified Ba5Nb4O15 ceramics
Fei Zhao, Hao Zhuang, Zhenxing Yue ⁎, Jing Pei, Zhilun Gui, Longtu Li
State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering,
Tsinghua University, Beijing 100084, P. R. China
Received 23 September 2006; accepted 17 November 2006
Available online 8 December 2006

Abstract

Microwave dielectric ceramics of Ba5Nb4−xVxO15 (x = 0–1) were prepared by a solid-state reaction method. Vanadium substitution can
markedly lower the sintering temperature of Ba5Nb4O15 from 1450 to 1100 °C. The X-ray powder diffraction analysis reveals the multiphase
nature of this system. A hexagonal-to-orthorhombic phase transition was also observed for the BaNb2O6 secondary phase. The microwave
dielectric properties, such as τf, εr and Q × f value, decreased with increasing vanadium content for samples sintered at 1100 °C. There was an
apparent increase in τf and Q × f value for samples (x ≥ 0.5) sintered at 1200 °C due to the hexagonal-to-orthorhombic phase transition of the
BaNb2O6 phase. These results suggested that the microwave dielectric properties of multiphase ceramics strongly depended on the phase
compositions and the phase transitions.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Dielectrics; Electroceramics; Perovskites; X-ray techniques

1. Introduction [7,8] modified its τf toward 0 ppm/°C with BaNb2O6 additions.

In the past decades, microwave dielectric ceramics have
received much attention because of the rapid growth of the
wireless communication industry. A large number of ceramic
dielectric materials have been developed over the years. There
are three key requirements for microwave resonator materials,
which are a high dielectric constant (εr), a high quality factor (Q
value) and a low-temperature coefficient of resonant frequency
(τf) [1].
Recently, the dielectric properties of some hexagonal
perovskite-like oxides have been investigated and they have
been found to be the candidate materials for dielectric
resonators in the base station of telecommunication systems
[2–10]. The Ba5Nb4O15 can be sintered at 1400–1450 °C and
can characterize a dielectric constant of 39–40, a Q × f value of
26,000–50,000 GHz and a τf of ∼ 78 ppm/°C [9,10]. Kim et al.
⁎ Corresponding author. Tel.: +86 10 62784579; fax: +86 10 62771160.
E-mail addresses: zfei99@mails.tsinghua.edu.cn (F. Zhao),
zhuangh_83@sohu.com (H. Zhuang), yuezhx@tsinghua.edu.cn (Z. Yue),
pj04@mails.tsinghua.edu.cn (J. Pei), figuline@126.com (Z. Gui),
llt-dms@tsinghua.edu.cn (L. Li).
0167-577X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.11.095
And the B2O3 doped Ba5Nb4O15–BaNb2O6 ceramics could be a
candidate for low-temperature cofired ceramic (LTCC) [7,8].
However, the literatures on modified Ba5Nb4O15 are still
minimal. We have investigated the Ta5+ substituted Ba5Nb4O15
ceramics, and a homogenous solid solution was obtained [4].
The sintering temperature was not lowered and the dielectric
properties were improved to a certain extent but still not
satisfactory.
In this work, V2O5, generally added to the ceramic matrix as
sintering aids, was used to modify the Ba5Nb4O15. The phase
relations and microwave dielectric properties of the Ba5Nb4−xVxO15
(x=0–1) ceramics were investigated as a function of vanadium
content and sintering temperature.
2. Experimental procedure
Samples of Ba5Nb4−xVxO15 with x = 0–1 were synthesized
from high-purity (more than 99.9%) powders of BaCO3, Nb2O5
and V2O5, using the conventional solid-state reaction method.
The oxides and carbonate were weighed according to the
desired molar ratio. The mixtures were ball milled for 5 h using
zirconia balls in an alcohol medium. The slurries were dried and
 F. Zhao et al. / Materials Letters 61 (2007) 3466–3468
Fig. 1. XRD patterns of Ba5Nb4−xVxO15 ceramic powders with x = 0–1 calcined
at 1000 °C and sintered at 1150 °C for 4 h.
then calcined at 1000 °C for 4 h. The calcined powders were
remilled, dried, mixed with an appropriate amount of PVA
(5 wt.%) as a binder, and then pressed into cylindrical disks of
diameter 10 mm and height about 5 mm at a pressure of about
2000 kg/cm2. These pellets were preheated at 600 °C for 3 h to
expel the binder and then sintered at temperatures from 1050 to
1200 °C for 4 h in air.
The bulk densities of the samples were measured by the
Archimedes method. The crystalline phases of the sintered
samples were determined by X-ray diffraction (XRD) techni-
ques. The microwave dielectric properties were measured at 6–
8 GHz at room temperature using Hakki–Coleman method and
cavity method [11–13]. The temperature coefficients of
resonant frequency were obtained in the temperature range
from 20 to 80 °C.
3. Results and discussions
Fig. 1 shows the XRD patterns of Ba5Nb4−xVxO15 ceramic powders
with x = 0–1, sintered at 1150 °C. For samples with x = 0.0625, all the
peaks were indexed in terms of the Ba5Nb4O15 and no secondary
phases were observed. With increasing vanadium content, however, the
Fig. 2. XRD patterns of Ba5Nb4−xVxO15 ceramic powders with x = 0.75 and 1,
calcined at 1000 °C and sintered (a) at 1100 °C and (b) 1200 °C for 4 h, showing
the crystal structures of BaNb2O6 secondary phase (H: hexagonal, O:
orthorhombic).
3467
Fig. 3. SEM micrograph of the polished and etched surface for the ceramics
sintered at 1150 °C for 4 h in air.
peaks for the Ba3(VO4)2 indicated by the filled arrowhead were found
in samples with compositions of x ≥ 0.125, and the intensity of the
peaks increased with increasing vanadium content. These suggest that
majority of the V5+ ions hardly substituted the Nb5+ ions at the B-site of
the hexagonal perovskite structure, instead, they preferred forming
another compound, Ba3(VO4)2. Additionally, some weak peaks
corresponding to the BaNb2O6 secondary phase were also observed
in samples with composition of x ≥ 0.5. Therefore, the solid-state
reaction of the initial oxides and carbonate powders can be expressed
by the following equation:
5BaCO3 þ ð2−x=2ÞNb2 O5 þ x=2V2 O5 →ð1−x=3ÞBa5 Nb4 O15
þ x=6BaNb2 O6 þ x=2Ba3 ðVO4 Þ2 þ 5CO2 ↑: ð1Þ
Accordingly, the Ba5Nb4O15 main phase decreased with increasing
vanadium content (x), whereas the Ba3(VO4)2 and the BaNb2O6
secondary phases increased. The secondary phases can be detected in
the XRD patterns when they have enough volume fractions.
Moreover, the BaNb2O6 has two polymorphic phases: hexagonal
and orthorhombic [14]. Recent literature [14] revealed that the
hexagonal BaNb2O6 was a low-temperature phase, and could be
transformed to the orthorhombic phase over a broad temperature range
above 1150 °C. In the present system, although only a few BaNb2O6
phases existed, the hexagonal-to-orthorhombic phase transition was
still clearly observed, as shown in Fig. 2. It is evident that the
diffraction lines for the powders sintered at 1100 °C were indexed as
the hexagonal structure, whereas those for the powders sintered at
1200 °C represented the orthorhombic structure. These observations
are consistent with previous reports [14].
The relative densities for samples sintered at 1100–1150 °C for 4 h
in air could reach 95% or above, implying that the sintering
temperatures were effectively decreased from 1450 °C to 1100 °C.
The densification temperatures and microstructure were not markedly
changed with increasing vanadium content. The typical SEM
micrograph of the polished and etched surface is shown in Fig. 3. It
Table 1
Densities and microwave dielectric properties of Ba3(VO4)2 ceramics sintered at
different temperatures
Sintering temperature Relative density (%) εr Q × f (GHz) τf (ppm/°C)
1100 94.1 13.5 34,900 +17.8
1150 97.2 13.1 46,700 +16.9
1200 96.5 13.0 45,600 +16.8
3468 F. Zhao et al. / Materials Letters 61 (2007) 3466–3468
Fig. 4. Variations of relative densities and microwave dielectric properties with
vanadium content (x) for Ba5Nb4−xVxO15 ceramics sintered at 1100 °C and
1200 °C for 4 h: (a) relative density; (b) temperature coefficient of resonant
frequency, τf; (c) dielectric constant, εr; and (d) quality factor, Q × f.
exhibits minimal porosity and is comprised of uniform, platelet-shaped
grains. According to the literatures [7,8] and our previous experiments,
the sintering temperature of which the 0.84Ba5Nb4O15–0.16BaNb2O6
system can be sintered into dense is about 1150–1200 °C; dense Ba3
(VO4)2 was obtained at about 1100–1150 °C. Therefore, the
improvement of sinterability in this system was attributed to the
coexistence of the Ba3(VO4)2 and the BaNb2O6 secondary phases with
the Ba5Nb4O15 main phase.
Due to the multiphase nature of the present system, the porosities
and the phase compositions, including the hexagonal-to-orthorhombic
phase transition of BaNb2O6, were dominant factors affecting the
microwave dielectric properties. To our knowledge, no reports have
been made on the microwave dielectric properties of Ba3(VO4)2, one of
the key secondary phases in this system. Thus, the Ba3(VO4)2
compound was synthesized by the same method described above.
Pure phase was achieved and the microwave properties were
characterized. The results are summarized in Table 1. The other
secondary phase, BaNb2O6, showed significantly different dielectric
properties for different structures, which are Q × f ∼ 4000 GHz, εr ∼ 42
and τf ∼ −800 ppm/°C for hexagonal and Q × f ∼ 43,000 GHz, εr ∼ 30
and τf ∼ −45 ppm/°C for orthorhombic [14].
Fig. 4 demonstrates the variations of relative densities and
microwave dielectric properties with vanadium content for the
Ba5Nb4−xVxO15 ceramics sintered at 1100 °C and 1200 °C for 4 h.
For the samples sintered at 1100 °C, the relative densities were N 95%,
implying that the relative density did not markedly affect the
microwave dielectric properties. It can be seen from Fig. 4(b)–(d)
that all samples sintered at 1100 °C exhibited similar behaviors in τf, εr
and Q × f value, decreasing with increasing x. These were ascribed to
the secondary phases present. As indicated above, the hexagonal
BaNb2O6 phase had a large-negative τf and a lower Q × f value, and the
Ba3(VO4)2 phase had lower τf and εr, compared with those of undoped
Ba5Nb4O15. Interestingly, the microwave dielectric properties of the
samples sintered at 1200 °C show different tendencies with those
sintered at 1100 °C. The reductions of εr and Q × f value for
compositions of x ≤ 0.25 were attributed to the low relative densities,
as shown in Fig. 4(a). The increases of τf and Q × f value for
compositions of x ≥ 0.5 were ascribed to the hexagonal-to-orthorhom-
bic phase transition, since the τf and the Q × f value of the orthorhombic
BaNb2O6 phase were much higher than those of the hexagonal
BaNb2O6 phase [7,14].
4. Conclusions
Microwave dielectric ceramics of Ba5Nb4−xVxO15 (x = 0–1)
were prepared by a solid-state reaction method. The sintering
temperature was reduced from 1450 to 1100 °C through
vanadium substitution. Ba3(VO4)2 and BaNb2O6 were formed
as secondary phases. A hexagonal-to-orthorhombic phase
transition was confirmed for the BaNb2O6 secondary phase.
The phase transition and the phase compositions had great
influence on the microwave dielectric properties of this system.
In addition, the microwave dielectric properties of Ba3(VO4)2
were primarily characterized, showing a εr of 13.1, a Q × f value
of 46,700 GHz and a τf of + 16.9 ppm/°C.
Acknowledgements
This work was supported by the Ministry of Science and
Technology of China through 973-Project under 2002CB613307,
the Natural Science Foundation of China (NSFC No. 50672043
and No. 50632030), and SRFDP (No. 20040003003).
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