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ELSEVIER
Wolf-Dieter Schubert
Institute for Chemical Technology of Inorganic Materials, Vienna University of Technology, A- 1060 Vienna,
Austria
Abstract: Tungsten blue oxide (TBO), currently the most important highly pure
intermediate for reduction to tungsten metal powder, is described from various
viewpoints, such as chemical composition, physical constitution and homogeneity. Tungsten blue oxide is not a well defined product, with varying
chemical and physical properties which depend on production conditions and
the equipment used. The different industrial production methods are discussed
and proposals for a meaningful characterization of the TE30 are made.
residual
ammonia
as ammonium
tungsten
bronzes.
The above mentioned change was remarkable
not only because it favored the use of a chemically
undefined
product with varying composition,
depending on calcination conditions, but also
because no particular advantage of TBO over
tungsten trioxide can be named. To produce WO,
instead of TBO from APT is neither more expensive, nor does it require a special type of furnace.
The reduction behavior of both oxides is comparable, especially with respect to tungsten powder of
average grain sizes between 1 and 10 ,um. In that
case most of the tungsten is transported as the
volatile tungsten oxide hydrate via the gas phase.
Therefore
any significant influence from the
chemistry of the solid oxide can be neglected.
The non-sag tungsten industry joined the
others and also switched to TBO. No clear advantage of TBO over the formerly used raw materials
with respect to the subsequent dopant incorporation has so far been given, although the ammonium tungsten bronze with its ion exchange
112
2 INDUSTRIAL
PRODUCTION
OF TBO
compartment
or tube. Both temperatures
can
differ considerably, due to the overall endothermic behavior of the APT*TBO
decomposition
reaction.
In order to produce a highly reactive TBO with
a large specific surface area, the optimal decomposition temperature is approximately 400C. In
addition to the temperature and the decomposition atmosphere, the heating time plays a crucial
role in determining the oxide quality. The exposure time in a rotary kiln is usually much shorter
than in the pushers. Therefore higher temperatures are applied in the kilns to increase the
decomposition rate and produce an oxide with a
comparable
degree of decomposition.
With
longer annealing times, especially above 5OOC,
grain growth occurs, significantly lowering the
specific surface area of the oxide (Fig. 1; compare
also Fig. 2(a) and (b)).8
Normally NS producers aim for a product
which contains considerable amounts of residual
ammonia, present as an ammonium
tungsten
bronze. Such a TBO is chemically highly reactive
with respect to the subsequent rapid ion exchange
in aqueous dopant-containing
solutions.2,3 On the
other hand, the producer of undoped tungsten
metal powder is calzining the APT at higher temperatures ( 2 500C) in order to release most or
even all of the ammonia. Due to the authors own
experience such kinds of TBO can also be used to
produce a high quality non-sagging tungsten wire.
Taking into consideration that during industrial
scale production the many influencing parameters
which determine the TBO quality are always subject to a certain amount of fluctuation, it is obvious that inhomogeneous TBO quality will be the
consequence. In this respect the comment made at
the conclusion of Ref. 9 is particularly important:
$~12_
$ Z
m otota,
;s
0.1!6
r6UP
PE 4;%
wf
2-
#yellow oxide
oxide
q blue
APT
mm
0
100
1
200
>
300
I
400
Decomposition
1
500
I
600
temperature
I
700
PC
I
800
Fig. 1. Changes in BET surface area of oxides with variation in decomposition temperature (same APT). Exposure
time varied at 400 and 500C.
113
3 CHEMICAL. COMPOSITION
In the literature there are many contradictory
reports about the chemical composition of TBO
and its dependency on the calcination conditions.
This subject has been critically reviewed and
summarized by van Put and Zegers.6 A major
reason for this diversity in observations and opinions originates no doubt from the fact that laboratory investigations were performed using widely
different conditions with respect to atmosphere,
amount of APT, etc. As already pointed out, not
only does the temperature influence the calcination process, but also the time of heating and the
partial pressure of the gases involved in the
respective reactions play an important role. The
mass of APT itself is responsible for producing a
certain amount of ammonia and water vapor and
consequently hydrogen and nitrogen. It is easy to
understand that in a boat of comparable size, 100
or 1000 g will produce different atmospheres,
especiahy inside the powder layers whose heights
are also quite different.
It must be stressed from the very beginning that
technical TBO is in any case a mixture of different
compounds, such as:
hexagonal ammonium tungsten bronze;
tetragonal
hexagonal
hydrogen
tungsten
bronze;
0 temperature;
l heating time;
l composition and pressure of atmosphere;
l mass of APT flow with time;
0 gas flow;
0 layer height in the boat (push-type furnace);
l slope and rotation rate (rotary furnace).
The oxygen index (molar ratio O/W) is commonly used to characterize the degree of reduction of TB0.6 However, since TBO contains NH,
and H,O in addition to W and 0, this value is not
sufficient for an overall description of the degree
of decomposition. The formula proposed by Lurk
et ~1.~is more complete in this respect:
-x(NH,).y(H,O).WO.
Analyzing
various
industrial
samples
these
authors found the following values for the three
factors:
x= 0.02-0.09
y= O-02-0.14
n = 2+32-2.99
In general, the higher the calcination temperature and the longer the exposure time, the lower x
and y will be. A higher hydrogen partial pressure
decreases n, but also retards the release of ammonia.O
Lunk et aL5 also analyzed the samples in question with qualitative and quantitative
X-ray
powder diffraction and found a remarkable variation in composition:
tungsten bronze
WO,
WQ.9
WO,.,,
amorphous
O-45%
O-45%
5-20%
O-25%
30-55%
Amorphous in this context means X-ray amorphous; the exact composition is still unknown.
The tungsten and oxygen atoms are arranged in
114
Fig. 3.
5 HOMOGENEITY
As already pointed out, TBO is composed of
different chemical compounds. Consequently the
following questions about their distribution arise:
Do all particles have the same properties and
composition, or do they differ?
0 Are there any gradients in composition
within the particle itself?
115
6 TBO CHARACTERIZATION
The obvious question at this point is how to
characterize a product of variable chemical and
physical constitution not knowing exactly which
properties and which compounds or constituents
are more determinative and crucial for the sub-
116
REFERENCES
1. Lassner, E., Int. J. Refract. Metals and Hard Mater. (in
press).
2. Bartha, L., Kiss, A., Neugebauer, J. & Nemeth, T., High
Temperatures - High Pressures, Vol. 14, 1982, pp.
l-10.
117