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Materials Letters 61 (2007) 2127 2129

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A coprecipitation technique to prepare CoTa2O6 and CoNb2O6


I.S. Mulla a , N. Natarajan a , A.B. Gaikwad b , V. Samuel c , U.N. Guptha c , V. Ravi a,
a

Physical and Materials Chemistry Division, National Chemical Laboratory, Pune 411008, India
b
Center for Materials Characterization, National Chemical Laboratory, Pune 411008, India
c
Catalysis division, National Chemical Laboratory, Pune 411008, India
Received 2 July 2006; accepted 10 August 2006
Available online 28 August 2006

Abstract
An aqueous solution of sodium hydroxide was used to coprecipitate cobalt and tantalum (or niobium) ions from their precursors as hydroxides
under basic conditions. This precipitate yielded CoTa2O6 (CT) or CoNb2O6 (CN) ceramics on calcining at 700 C, i.e. at a temperature much
lower than 900 C, reported for the formation of these powders prepared by the traditional solid state method. The X-ray diffraction (XRD) studies
were employed to investigate phase contents and lattice parameters. The morphology of the synthesized powders was investigated by transmission
electron microscopy (TEM).
2006 Elsevier B.V. All rights reserved.
Keywords: Chemical synthesis; X-ray methods; Electronic materials; Oxides

1. Introduction
Niobate or tantalite based compounds (AB2O6), (A = Ba, Sr,
Mg and Zn, B = Nb and Ta) with either coulombite (orthorhombic) or trirutile (tetragonal) type structure have excellent electrooptic, pyroelectric, photo-refractive and microwave dielectric
applications[17]. Generally, these compounds were formed by
conventional ceramic processing at high temperatures. Since wet
chemical techniques have several advantages over traditional
solid state methods for the preparation of functional ceramics,
we have investigated low temperature synthesis of this Series of
compounds by wet chemical methods such as coprecipitation
and citrate gel methods [17]. As an extension of this work, we
report here a simple coprecipitation technique to produce
CoTa2O6 (CT) or CoNb2O6 (CN) powders using water soluble
salts. The compound, CoTa2O6 was investigated for its
interesting magnetic properties. It has a complex helical magnetic structure (antiferromagnetic) with Neel temperature of
4 K [811]. The compound CoNb2O6 is a quasi-one
dimensional Ising magnet with a Neel temperature of
2.95 K. The compound CN was also reported to be a potential

Corresponding author. Tel.: +91 020 25902295; fax: +91 020 25893044.
E-mail address: r.venkat@ncl.res.in (V. Ravi).
0167-577X/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.08.024

microwave dielectric resonator material [1214]. The requirements of ceramic resonators used at microwave frequencies are
high dielectric constant, a high Q value (reciprocal of dielectric
loss) and a low temperature coefficient of resonant frequency.

Fig. 1. XRD of CoTa2O6, precipitate powders calcined at (a) 300 C and


(c) 700 C for 6 h. (+ Co3O4 and Ta2O5 peaks).

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I.S. Mulla et al. / Materials Letters 61 (2007) 21272129

Fig. 4. TEM image of CoTa2O6 powders.


Fig. 2. XRD of CoNb2O6, precipitate powders calcined at (a) 150 C, (b) 300 C,
(c) 600 for 6 h.

The coprecipitation process can avoid complex steps such as


refluxing of alkoxides, resulting in less time consumption
compared to other techniques. The limitation of this process is
that cations should have similar solubility. This method is not
reported for the preparation of CT (or CN) in the literature.
2. Experimental
For preparing CoTa2O6 and CoNb2O6, tantalum (V) oxide,
niobium (V) oxide cobalt nitrate and sodium hydroxide were
used as the starting materials (Loba Chemie, AR grade). Ta2O5
(or Nb2O5) was dissolved in HF acid (40%) after heating in a hot
water bath for 10 h. To this TaF5 solution, the required quantity
of Co(NO)39H2O was added and mixed thoroughly. An
aqueous sodium hydroxide was added dropwise to precipitate
tantalum (or niobium) and cobalt as hydroxides under basic
conditions. The pH was maintained 9 to ensure completion of

Fig. 3. (a) Ideal XRD pattern of CoNb2O6, (b) XRD of precipitate powders
calcined at 700 C.

the reaction. At higher pH, cobalt ions again dissolve in solution.


Hence, precaution should be taken for the proper control of pH.
Then, the precipitated precursor powder was filtered and oven
dried, then calcined at different temperatures from 400 to 900 C
for 6 h. The XRD (Philips PW 1710 Diffractometer) studies were
used to investigate the phase contents and lattice parameters of
these samples. For lattice parameter and interplanar distance (d)
calculation, the samples were scanned in the 2 range of 1060
for a period of 5 s in the step scan mode. Silicon was used as an
internal standard. Least squares method was employed to determine the lattice parameters. For comparison, cobalt tantalite and
niobate samples were also prepared by the ceramic method. The
corresponding oxides are taken in stoichiometric ratio and
mixed, ground several times and heated at 900 C for 72 h.
3. Results and discussion
Fig. 1 shows the XRD pattern of the CoTa2O6 precursor calcined at
different temperatures. At 300 C, lines corresponding to Co3O4
(JCPDS-9-418) and Ta2O5 (JCPDS-18-1304) were observed indicating
the reaction path. The reaction is complete at 700 C and CT phase was

Fig. 5. TEM image of CoNb2O6 powders.

I.S. Mulla et al. / Materials Letters 61 (2007) 21272129

found to be formed as shown in Fig. 1. This is the lowest temperature


reported so far for the formation of CoTa2O6 by the coprecipitation
technique. The crystal structure of CoTa2O6 is tetragonal (trirutile type)
and all the d-lines match with reported values (JCPDS: 32-314). The
calculated lattice parameters by least squares fit are a = 4.737 , and
c = 9.171 .
Fig. 2 shows the XRD pattern of the CoNb2O6 powder formed after
calcining the powders at different temperatures. It is observed that CN
phase was formed only at 700 C. At lower temperatures cobalt and
niobium oxides are found by XRD peaks. Fig. 3 depicts the XRD of
ideal pattern and that of coprecipitation derived CN samples The
crystal structure of CoNb2O6 is orthorhombic and all the d-lines match
with reported values (JCPDS: 31-426). The calculated lattice
parameters by least square fit (two decimal accurate) are
a = 15.023 , b = 5.715 and c = 5.242 . This temperature (700 C)
is the lowest temperature reported so far for the formation of CoNb2O6
by the coprecipitation technique. Few extra lines (low intensity) may
arise from unknown impurities present or intermediate phase formed in
the samples. The TEM images of both coprecipitated powders
(CoTa2O6 and CoNb2O6) were given in Figs. 4 and 5. The conventional
solid state method also forms the CoTa2O6 or CoNb2O6 phase at
900 C after prolonged heating (72 h) with intermittent grinding.

4. Conclusions
A simple coprecipitation process was used for the preparation of ultrafine powders of CoTa2O6 and CoNb2O6 at 700 C.

2129

This is the lowest temperature reported for the formation of CT


(or CN) phase.
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