ht. J.

of Refmctory Metals &Hard Materials 13 (1995) 11 l-l 11

0 1995 Elsevier Science Limited
Printed in Great Britain. All rights reserved
0263-4368/95/$9.50
0263-4368(95)00005-4

ELSEVIER

Tungsten Blue Oxide

Erik Lassner
Sandgasse 23A, A-SO 10 Graz, Austria
&

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.

1 INTRODUCTION AND HISTORY

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

In the 1950s the tungsten powder producing

industry made a remarkable change in the highly
pure starting oxide material. The traditional tungstic acid (H2WO4) or yellow tungsten oxide (WO,)
was replaced by tungsten blue oxide (TBO).
Today nobody seems to know for sure why this
was done. To a certain extent there is a direct relationship with the transition in tungsten hydrometallurgy from tungstic acid to APT. The
advantages of that modification are outlined in
detail in Ref. 1. Calcination of tungstic acid always
leads to the yellow tungsten trioxide, while the
calcination of APT depends on the atmosphere
and can result in yellow oxide, if sufficient air is
supplied. Under exclusion of air, however, part of
the ammonia released during APT decomposition
is cracked, leading to a slightly reducing atmosphere. The product of this type of calcination is
greenish blue to flashing dark blue in color and is
called TBO. Especially at low decomposition temperatures it can contain considerable amounts of
111

112

E. Lassner. W.-D. Schubert

capacity is often regarded

the dopant uptake.*-5

2 INDUSTRIAL

as being essential for

PRODUCTION

OF TBO

The conversion of APT to TBO is performed

either in push-type kilns or in rotary furnaces. In
the push-type kiln a static powder layer in a boat
moves through the furnace, whereas in a rotary
kiln the powder is constantly being mixed by the
turning motion so that it flows, providing more
equal conditions for each individual particle than
is the case in a static powder bed. Regarding
homogeneity, the rotary furnace is therefore more
advantageous. For a powder layer in a boat, of
course, the conditions for the particles at or near
the top of the layer are completely different from
those in the interior or at the bottom, due to the
gradients in the immediate reaction atmosphere.
The porosity of the powder layer determines the
diffusion of gases out of and into the layer. That
means that gases such as ammonia, water vapor,
nitrogen and hydrogen (stemming from ammonia
cracking) which are released during reaction are
contained inside the powder layer in a higher
concentration (or partial pressure) than outside or
at the surface. On the other hand, if additional
gases are applied (e.g. hydrogen or hydrogennitrogen mixtures), their concentration is higher
outside the layer or at its surface. After calcination a cross-section through the layer of powder in
the boat reveals different colors and TBO compositions depending on depth. Consequently the
final product contains a mixture of differently
composed particles.
The product from a rotary furnace is more
homogeneous, although different compounds are
also found but only within a particle itself;
between the individual particles there are no
major differences.
Various atmospheres
are commonly
used.
Sometimes, mostly in rotary furnaces, the released
gases themselves are used as the reducing atmosphere. Sometimes, usually in push-type furnaces,
an additional constant flow of hydrogen or a
hydrogen-nitrogen
mixture is supplied.
Temperature
may vary between 400 and
900C.3Jj,7 Literature values can be misleading
because some are related to the real temperature
of the powder layer, while others are furnace temperatures measured at the wall of the heating

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

Tungsten blue oxide

tungsten trioxide (WO,);

tungsten /I-oxide (WO,., or W,,O,,);
tungsten y-oxide (W02.72 or W,s04&
Small amounts of WO, and even a- or p-tungsten
can also be present under more reductive decomposition conditions.6
The relative amounts of the various compounds in the TBO depend on the calcination
parameters:

Fig. 2. AIV resp. TBO particles, obtained from APT

decomposed at 400 and 650C. TBO particles are pseudomorphous to the APT, (SEMx 600); (a) APT used for
decomposition, (b) TBO obtained at 4OoC, (c) at 650C.

Especially at low formation temperatures,

the
slight energy differences between the possible
oxide structures enable the simultaneous formation of a variety of metastable compounds.

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

E. Lassner, W.-D. Schubert

114

locally ordered structures, but their coherent

diffracting areas are too small to yield an X-ray
pattern. During early calcination, after losing a
certain amount of water and ammonia, the crystalline APT converts to an amorphous substance.
During further heating, crystallized binary tungsten oxides and tungsten bronzes are formed from
the amorphous material. Since the recrystallization process proceeds so slowly, at the end of a
technically acceptable heating period a considerable percentage of amorphous
oxide can still
remain. The amount of amorphous oxide was
reported to be higher in TBO produced in rotary
furnaces than in TBO produced in push-type
kilns. This can be explained by the much shorter
reaction time in the case of the rotary furnace.
The constitution of this part of the TBO should
be the reason for its high reactivity. It is however
still not clear which of the compounds formed
during APT decomposition are the most influential for a homogeneous dopant uptake during subsequent doping and annealing (formation of K,
Al-tungsten bronzes).
For a complete chemical characterization
of
TBO it is by no means sufficient to analyze only
for oxygen, ammonia and water; the ratios of the
various other compounds contained must also be
determined.
X-ray investigations, as done by
Lunk et al, are much too tedious and expensive
for routine work. It is therefore of utmost importance in industrial practice to keep all the calcination parameters as constant as possible, in order
to assure a constant TBO quality. Moreover when
comparing products from different producers, the
quality can only be the same, if comparable APT
and the same type of equipment are used under
the same conditions.
Although most TBO producers work under
similar conditions, small differences in one or
more of the numerous parameters exist. It is
therefore easy to understand why NS tungsten
producers always say: We have to do the blueing
ourselves! That standpoint is quite right since
even slight variations in APT quality or, more
likely, in calcination parameters or in equipment
may cause different TBO properties, which then
change the doping and subsequent reduction
behavior.
4 PHYSICAL CONSTITUTION:
MORPHOLOGY OF TBO
The behavior of TBO during the subsequent steps
of NS tungsten production are influenced not only

by its chemical constitution, but also by several

important physical properties:
0 The particle size and particle size distribution - both parameters are being related to
the crystal size and crystal size distribution of
the starting APT as a consequence of the
crystallization process.
l The internal porosity of the particles caused when the reaction gases are released,
leading to an increase in density, both
occurring during the blueing process.
4.1 Macromorphology
There are still inconsistencies in the current literature regarding the macromorphology
of TBO.
During the conversion of APT to TBO:
water vapor and ammonia are evolved;
due to the elevated temperature, part of the
ammonia is cracked;
hydrogen thus formed (plus added) partially
reduces the oxide;
the APT crystal lattice breaks down, amorphous compounds
form and partially recrystallize to lower oxides and tungsten
bronzes;
by the gas release and the increase in density
the former APT particles become porous
and may show cracks although the original
shape of the APT is retained;
due to mechanical forces, some particles can
be broken (seldom occurs).
In principle, after calcination the blue oxide
particles, independently of the Cal&ration parameters, exhibit the same shape as the starting APT
crystals (Fig. 3). Only the chemical compositions
and internal porosities may vary from particle to
particle or even within the particle itself.
The macromorphology
of TBO is an important
property which influences the reduction behavior.
It is directly related to the respective APT properties of average crystal size, and crystal size distribution and agglomeration.
Together with the microporosity of the particles (see below) these properties determined the
permeability and thus the diffusion resistance of
the powder layer, which is a determining factor for
the material exchange (H20*H2) during reduction.
4.2 Micromorphology: porosity of the TBO
particles
The micromorphology
of TBO is important for
the further processing (doping and reduction). As

Tungsten blue oxide

Fig. 3.

Surface of TBO particles obained from AFT decomposed

already discussed, TBO particles reveal a certain

porosity, which is generated by the release of
gaseous compound and an increase in density.
The degree of porosity is infIuenced by the calcination parameters (time, temperature, degree of
decomposition
and reduction, etc.). The former
APT crystal turns into a porous, sponge-like
macroparticle. The sizes of the microparticles, of
which a macroparticle is composed, are very small
for short heating times and increase with calcination time and temperature (Fig. 2).
It is obvious that the microporosity (which is
directly related to the specific surface area of the
oxide) influences the uptake of dopants for NS
tungsten and the transformation of /3- or y-oxide
to wo*.

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?

In connection with the first question, results

reported by van Put et aZ.ll are of great importance. They observed a BET surface area dependof the
TBO
particle
size under
ency
industrial-scale conditions: the larger the particle
size (separation by screening) the greater was the
specific surface area. Furthermore they found a

115

at: (a) 400C and (b) 650C (SEM X 10 000).

large spread in the specific surface area values

between samples taken from the bottoms of the
boats (4 m*/g) and from the tops (6.5 m*/g).
These results indicate a significant variance in
the oxide quality of individual particles. From the
viewpoint of product homogeneity, such marked
differences in the physical (and most probably
also chemical) constitution cannot be regarded as
an advantage; these findings are for TBO prepared in a push-type furnace. On the other hand,
TBO produced in a rotary furnace would be
expected to exhibit more homogeneity among the
particles. But here we come to the second question - the homogeneity within the particle itself.
The heating time in rotary furnaces is much
shorter, and in connection with the microporosity
of the particles, we can assume quite different
conditions between the interior and the surface of
a particle.
Nevertheless, both types of equipment are in
use today for the industrial production of TBO,
although from the viewpoint of product homogeneity a fhtidized bed reactor would be more
appropriate. This reactor type has, however, still
not found its way into industrial TBO production.

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

E. Lassner, W.-D. Schubert

sequent processing steps of doping and reduction.

The solution can only be a compromise.
IndustrialIy produced TBO is characterized by
measuring the residual ammonia ( *the presence
of ammonium tungsten bronze), the oxygen index
( *the
degree of reduction), the specific surface
area ( *the surface area for dopant adsorption)
and the average particle size (*the apparent
density).
The individual NS producers of course have
their own ideas about the importance of the
various parameters as well as their optimal range.
With respect to the chemical composition a
more rigid specification does not even seem
meaningful for industrial practice. If it is still not
known which of the constituents or how many of
them are important, how can a design be made?
Moreover, as already mentioned, NS tungsten
powder can also be produced in the same way but
starting from tungstic acid or tungsten trioxide.,
This obviously leads to the conclusion that chemical composition alone is not of major relevance
for the dopant incorporation.
On the contrary, the physical properties seem
to be much more important, and their determination and specification should be discussed.
The particle size and size distribution are
predetermined by the respective APT properties.
A suitable method for evaluating both properties
is laser diffraction. A partial disintegration can
however occur during measurement due to the
constant application of ultrasonic energy, which is
used for deagglomeration purposes. In this case,
for example for TBO decomposed at low temperatures of about 300C where the resulting
particles are more brittle, the measured values are
deceptive. Particle size measurement by FSSS, as
sometimes mentioned in the related literature, is
misleading, because of the porosity of the TBO
particles. The porosity permits a certain gas flow
through the particles and not only between them,
resulting in an incorrectly small average particle
size. An empirical relationship between FSSS and
particle size measured by laser scattering can
however be detected if the microporosity of the
samples is uniform (constant blueing conditions).
The specific surface area of the oxide, which is
influenced mainly by its microporosity,
is of
utmost importance for the doping process as well
as for the subsequent reduction (tungsten bronze
formation). The porosity is a direct consequence
of the blueing conditions. It is responsible for the
even dopant uptake and distribution and finally, in

combination with the reduction conditions for the

homogeneous distribution of the K, Al, Si inclusions in the tungsten powder. The specific surface
area measurement is performed using the BET
method.
7 CONCLUSION
(1) Tungsten blue oxide (TBO) is not a well
defined tungsten compound;
its overall
chemical composition and physical characteristics vary.
(2) TBO is a designation for an industrially
manufactured product which is produced
by the calcination of APT under exclusion
of air or hydrogen or hydrogen-nitrogen
atmospheres.
(3) APT-related properties are particle size,
particle size distribution and purity.
(4) Properties which depend on the calcination
conditions are chemical composition, the
ratio of crystalline/amorphous
material and
the internal porosity of the particles.
(5) Individual oxide particles themselves also
differ in their chemical and physical constitution. This spread in properties is a result
of the decomposition
process, which is
carried out in push-type furnaces or in
rotary kilns. From the viewpoint of product
homogeneity, a fluidized bed reactor would
be the more appropriate calcination equipment.
(6) Non-sag tungsten production aims at producing a highly reactive oxide, which provides a homogeneous
distribution of the
dopants in the final tungsten metal powder.
This is achieved by a low temperature
calcination of the APT to form TBO containing ammonium tungsten bronzes (crystalline and amorphous) and having a high
specific surface area.
(7) Every NS producer has his own ideas
about the importance of the respective
physical and chemical properties of the
TBO as well as their optimal range.
(8) Industrial experience is however more or
less empirical and based on a certain
procedure
for obtaining a final doped
metal powder of reproducible
quality.
Sometimes though, due to a lack of knowledge about the specific processes and
reactions
involved,
this goal is not
achieved.

Tungsten blue oxide

(9) Although the chemical reactivity of the

ammonium tungsten bronzes is said to be
of crucial importance
for the dopant
uptake, their presence does not seem to be
a prerequisite: high quality non-sag tungsten can also be produced based on tungstic acid as well as tungsten trioxide.

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

3. Pink, E. & Bartha, L. (eds), The Metallurgy of Doped/

Non-sag Tungsten. Elsevier Science Publishers Ltd.,
London, 1989.
4. Szalay, T., Ludanyi, A. & Kiss, B. A., J. Mater. Sci., 22
(1987) 3543-6.
5. Lunk, H. J., Ziemer, B., Salmen, M. & Heidemann, D.,
Int. J. Refract. Metals and Hard Mater., 12 ( 1993-1994)
17-26.
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HardMater., lO(1991) 115-22.
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Bildstein & R. Eck. Metallwerk Plansee, Reutte, Austria,
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Hard Mater., 10 (1991) 171-83.
9. Tilley, R. D., Int. J. Refract. Metals and Hard Mater., 13
(1995) 93-109.
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Seminar 1985, Vol. 1, eds H. Bildstein & H. M. Ortner.
Metallwerk Plansee, Reutte, Austria, pp. 337-48.
11. van Put, J. W., Zegers, T. W. & Liu, H., Znt.J. Refract.
MetalsandHardMater., 10 (1991) 123-31.