Journal of Physics and Chemistry of Solids 66 (2005) 466–470

www.elsevier.com/locate/jpcs

Tantalum and niobium powder preparation from their oxides by

calciothermic reduction in the molten CaCl2
Masahiko Baba1, Youhei Ono2, Ryosuke O. Suzuki*
Department of Energy Science and Technology, Kyoto University, Yoshida-Honmachi, Sakyo-ku, Kyoto 606-8501, Japan
Accepted 4 June 2004

Abstract
Calciothermic reductions of Ta2O5 and Nb2O5 are proposed aiming at the fine powder preparation for the larger capacitance of condensers.
Because the molten CaCl2 can coexist stably with metallic Ca, and because it can dissolve a few mol%Ca and about 20 mol%CaO, the
reductant Ca can be supplied to the oxide via molten CaCl2, and the reaction by-product CaO can be in situ eliminated from the reaction
interface. The metallic powder was obtained after an hour at 1173 K. In the prolonged time the particles sintered together, but oxygen was
gradually removed to the level of a few thousands ppm.
q 2004 Elsevier Ltd. All rights reserved.

Keywords: Electronic materials; Chemical synthesis; Crystal growth

1. Introduction Calcium is thermodynamically reactive both with Ta2O5

Fine Ta particles are mainly used for the electric
condensers in the mobile devices, because the thin oxide
layer on Ta surface has the excellent dielectronic properties
for condensers. Due to small natural abundance of Ta ores,
Nb is expected as a material alternative or a supplement to
Ta. Their finer particles give the larger surface area, which
leads to the larger capacitance.
One of the current preparation methods of Ta powder
consists of the production of K2TaF7 from Ta oxide ores
and the subsequent reduction by molten Na at high
temperatures. A more compact process is requested for
energy saving and waste management without fluoride.
Here we propose the calciothermic reduction of Ta2O5
and Nb2O5 aiming at their fine powder preparation in one
step.
* Corresponding author. Tel: C81 75 753 5453; fax: C81 75 753
5432/4754.
E-mail address: suzuki@energy.kyoto-u.ac.jp (R.O. Suzuki).
1
Guest researcher of Kyoto University, currently at Cabot Supermetals
K.K.
2
Graduate Student of Kyoto University, currently at Ricoh Company,
Ltd.
0022-3697/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2004.06.042
and Nb2O5 [1–6].
Ta2 O5 ðor Nb2 O5 Þ C 5 Ca Z 2 Taðor NbÞ C 5 CaO (1)
However, the strong exothermal heat sintered the
metallic particles tightly and the by-product CaO was
often caught within the sintered lumps [7–9]. The existence
of CaO between the oxide and Ca prohibits the invasion of
Ca into the oxide and delays the complete reduction.
The addition of CaCl2 could solve these problems: the
molten CaCl2 can coexist stably with metallic Ca, and it
dissolves a few mol%Ca [10–12] and about 20 mol%CaO
[13,14] at 1223 K. Ca, CaO and CaCl2 react neither with Ta
nor Nb [3,4]. Therefore, the reductant Ca is supplied to the
oxide via molten salt, and the reaction by-product CaO is
eliminated from the reaction interface between the oxide
and Ca into the molten salt, as showed in Fig. 1 [15–18]. The
residual oxygen in the reduced metals is also removed by
the dissolved Ca [4,19–21]. Additionally, it is expected that
the exothermal reaction becomes mild and homogeneous
due to the solvent CaCl2.
The purpose of this work is to propose the direct
reduction of Ta2O5 and Nb2O5 using the dissolved Ca in the
molten CaCl2 in order to obtain the particles with the finer
surface structure and better purity for capacitor application.
 M. Baba et al. / Journal of Physics and Chemistry of Solids 66 (2005) 466–470 467

Fig. 1. Schematic illustration of calciothermic reduction in the molten

CaCl2.

The previous study of Nb2O5 reported the electrochemical

contribution to the Ca reduction accompanied with the
thermochemical reaction [6]. We will focus here on the
mechanism of oxygen removal and pulverization.
2. Experimental
Granular Ca (99.8% metallic purity), dehydrated CaCl2
powder (99.9%), Ta2O5 powder (99.9%) or Nb2O5 powder
(99.9%) were used for the reactions. About 220 g of the raw
materials were set in a Ta or Nb crucible to avoid the
contamination, and they were heated and cooled in an Ar
atmosphere. The solidified CaCl2 and residual Ca and CaO
were dissolved in distilled water and a dilute HCl acid, and
the black powder was recovered from the bottom of the
crucible. The obtained powder was identified by X-ray
diffraction (XRD) measurement. The residual oxygen was
analyzed by an inert gas fusion-infrared absorption method.
The morphology was observed using a scanning electron
microscopy (SEM), and the size distribution was counted by
the particle size analyzer using laser diffraction and
scattering.
Fig. 2. Initial and final compositions of the molten salt, assuming that all the
oxygen in the oxide transferred to the salt after the reduction.
small leakage of Ca vapor. The other samples were
identified as the metallic form by XRD. When the ratio
was 1:10:150 (#2, twice amount of Ca to stoichiometry was
used), the oxygen contents both for Ta and Nb were
the lowest. The residual oxygen was high for samples
#4 and 5. When the larger amount of the by-product CaO
was produced in their mixing ratio as shown in Fig. 2, it
could not dissolve completely in the molten salt within the
experimental time, because the dissolution of CaO at
the higher CaO concentration is slower [13,14]. Because
the thermochemical activity of CaO was very high, nearly 1,
in the cases of #4 and 5, the deoxidation was incomplete.
When the large amounts of Ca were used (#3–5), a
significant evolution of the hydrogen gas bubbles was
observed in leaching, and the surface may be oxidized in
water by the reaction heat. Therefore, the mixing ratio of
1:10:150 (#2) was taken below.
4. Reduction of Ta2O5

3. Desired mixing ratio Fig. 3 shows the oxygen content in the samples after
reduction at 1153 and 1223 K, which are above the melting
The mixing ratio of NOxide, NCa and NCaCl2 (in molar points of Ca and CaCl2. The reduction from the oxides was
fraction) affected the stable phases in the salt and the so quick that it completed within 3.6 ks. The lower oxygen
residual oxygen level in the obtained samples. Table 1 concentration both for Ta and Nb was obtained at the higher
shows the analytical results after the reduction at 1223 K for temperature, where the reduction and deoxidation were
7.2 ks. When the stoichometric amount of Ca for reduction enhanced by the dissolution of Ca and CaO.
was applied (#1), the reduction was not complete because of The oxygen content in Ta decreased gradually in the
prolonged reaction time, and approached to a value higher
Table 1
than the equilibrium oxygen concentration (!ppm level
Oxygen concentration for the samples reduced at 1223 K for 7.2 ks
[1,2]). A characteristic morphology of the primary Ta
Run Mixing molar ratio Oxygen (mass ppm) particles is shown in Fig. 4. Many primary fine particles
oxide:Ca:CaCl2 in Nb in Ta (!1 mm in diameter) congregated together to form the
#1 1:5:100 88 710 25 540 larger secondary grains. Fig. 5 shows the particle distri-
#2 1:10:150 5200 5060 butions of the samples reduced at 1223 K. Note that the
#3 1:20:300 6400 7380 optical particle analyzer counts the secondary particles as
#4 1:30:60 6700 7540
well as the isolated primary particles. The grain size of the
#5 1:40:80 8600 7310
powder was larger than the raw oxide, as shown in Fig. 5.
468 M. Baba et al. / Journal of Physics and Chemistry of Solids 66 (2005) 466–470

Fig. 5. Particle distributions of the reduced Ta samples at 1223 K.

at 1153 K. A fairly large Nb oxide grains were reduced within

7.2 ks and pulverized by the cracks due to shrinkage of the
crystal lattice, as illustrated in Fig. 8(B) and (C). Due to
the density difference of Nb2O5, NbO2, NbO and Nb, the
interfaces among the Nb lower oxides may initiate the cracks.
Fig. 3. Oxygen content residual in the reduced samples.
It is assumed that Nb2O5 is reduced through the Nb lower
Fig. 6 shows a model that explains the decrease of oxides, NbO2 and NbO, although they were not observed
oxygen content and the increase of particle size, summar- experimentally because of the quick reduction.
izing the above-mentioned results. Fine powder of Ta2O5 is
separately reduced within 3.6 ks by Ca dissolved in the Nb2 O5 þ Ca ¼ 2 NbO2 þ CaO
molten CaCl2, as shown in Fig. 6(B). Its local exothermic (2)
ðDH8 ¼ K319:4 kJ=mol at 1223 KÞ
heat of reduction sintered the formed metallic particles, and
the un-reacted oxide and the un-dissolved CaO are also
caught in the secondary grains, as shown in Fig. 6(C). It 2 NbO2 C 2 Ca Z 2 NbO C 2 CaO
becomes difficult that we remove perfectly the CaO phase (3)
existing inside the congregated grains (Fig. 6(D)) by the ðDH8 Z K563:7 kJ=mol at 1223 KÞ
acid leaching. This CaO delayed the deoxidation of Ta
particles after 14.4 ks. The dissolution speed of the captured 2 NbO C 2 Ca Z 2 Nb C 2 CaO
CaO seems a key to obtain the lower oxygen content. (4)
ðDH8 Z K455:12 kJ=mol at 1223 KÞ

5. Reduction of Nb2O5

Nb2O5 was also reduced in a short time, however, the

oxygen content increased after 7.2 ks, then decreased. Fig. 7
shows that the particle size of the sample reduced for 7.2 ks
was significantly smaller than the others and much smaller
than that of the raw oxide. It was similar in the samples reduced

Fig. 4. SEM image of the Ta powder reduced at 1223 K for 28.8 ks. Fig. 6. A model of Ca reduction of Ta2O5.
 M. Baba et al. / Journal of Physics and Chemistry of Solids 66 (2005) 466–470
Fig. 7. Particle distributions of the reduced Ta samples at 1223 K.
These sequential reactions evolve the exothermic heat
gradually, and the adiabatic temperature increase is
suppressed. However, there is no intermediate oxide in the
Ta–O binary system, and Ta2O5 is directly reduced to Ta as,
Ta2 O5 C 5 Ca Z 2 Ta C 5 CaO
(5)
ðDH8 Z K1196 kJ=mol at 1223 KÞ
Although the exothermic heat of this reaction is smaller
than the total heat of Eqs. (2)–(4), the localized heat
enhances the sintering of Ta powder. In this discussion, the
possible existence of the intermediate phases such as
CaNb2O7 [6] was neglected because we could not observe
their precipitation.
After 7.2 ks, the reduced and dispersed Nb powder
sintered together, and the secondary grains grow coarser
(Fig. 8(D)), similar to the Ta powder. The captured CaO
inside the secondary grains disturbs the efficient
Fig. 8. A model of Ca reduction of Ta2O5.
469
deoxidation. Therefore, the best condition both for fine
powder formation and low oxygen level to match the
industrial demand for condensers was the reaction for 7.2 ks
in our studied conditions.
The proposed mechanism via electron [6] could not be
justified in this study, because the used metallic crucible was
electron conductive that might work as the external circuit.
All the powders obtained in this work were homogeneous in
the crucible and no significant difference in powder
morphology was found in the sequence of reduction time,
although it was reported that the electronically mediated
reaction occupied 3–15% in the whole reaction [6].
6. Conclusion
Ca dissolved in the molten CaCl2 could reduce success-
fully Ta2O5 and Nb2O5 powder. CaCl2 could dissolve the
by-product CaO, but some portion of CaO was caught inside
the secondary grains. The difference between the reductions
of Ta2O5 and Nb2O5 was found at the particle size and
oxygen content in the early stage. It reflects the existence of
the Nb lower oxides and the sudden exothermal heat for
reduction.
Acknowledgements
The author thanks Ms K. Iwamoto (Cabot Supermetals
K.K.) for analysis. This work was supported in part by
Cabot Supermetals K.K. and Grants-in-Aid for Scientific
Research under Contract No. 14205109.
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