Journal of Materials Processing Technology 170 (2005) 187–191

Cold consolidation of ATR-niobium powder under high pressure

G.S. Bobrovnitchii, J.N.F. Holanda ∗
Laboratory of Advanced Materials, State University of Northern Fluminense, Campos dos Goytacazes, RJ 28013-602, Brazil

Received 10 December 2003; received in revised form 12 March 2005; accepted 28 April 2005

Abstract

This paper presents the results of a study concerning the consolidation of aluminothermic niobium powder under high-pressure conditions at
room temperature. The method of cold powder consolidation consists of two steps: initial die-compaction followed by high-pressure treatment
in almost hydrostatic conditions. The densification behaviour of the aluminothermic niobium powder during compaction was evaluated by
using the compaction response diagram. The microstructure of highly dense parts was evaluated by SEM. The influence of the precompacting
pressure and the high pressure on the final density was investigated. Successful compaction was obtained for precompacting pressure of up to
700 MPa and high pressure of up to 4 GPa. The niobium powder compaction is governed, at the applied high-pressure range, by mechanisms
such as axial and radial plastic deformation. In addition, the experimental results showed that porosity lower than 2% can be attained under
high-pressure compaction conditions, without external heat supply.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Compaction; Niobium powder; High pressure

1. Introduction
Niobium, which belongs to group Vb of the Periodic Table
of Elements, is classified as a refractory metal because of its
elevated melting point of 2468 ◦ C. Furthermore, niobium has
particular properties, such as good resistance to corrosion by
acids, wear resistance and a very stable oxide film of high rel-
ative dielectric constant. This leads to the main application in
the chemical and metallurgical industry, medical field, super-
conductivity, and electronic devices [1–3].
Niobium is mainly processed by powder metallurgy (P/M)
techniques [4,5], which consists basically of the powder com-
paction in a rigid die and/or cold isostatic pressing, followed
by high vacuum sintering at high temperatures. For producing
highly dense parts it is necessary to use very high sinter-
ing temperatures above 1800 ◦ C, however, at considerable
expenses. Moreover, at high temperatures grain growth takes
place intensely and causes a decreasing in properties with
prolonged sintering [5].
The cold powder compaction in rigid dies at high pres-
sures of some metals has been investigated [6,7]. For stainless
∗ Corresponding author. Tel.: +55 22 2726 1623; fax: +55 22 2726 1533.
E-mail address: holanda@uenf.br (J.N.F. Holanda).
steel powder, pressures of the order of 3–4 GPa have been
employed to attain a density of over 95% of theoretical den-
sity. This pressure range is approximately four to five times
higher than that normally required for compaction in rigid
dies. The major difficulty in die-compaction at high pressure
is related to the fact that the compaction tools in service are
submitted to high stresses and excessive wear occurs. As a
consequence, the life of the compaction tools become very
critical. Moreover, very little research has been conducted
in this field, leaving significant opportunities for investiga-
tion and study, particularly in the topical area of new powder
consolidation methods, which is the main topic of this paper.
This paper reports the densification behaviour of alu-
minothermic niobium powder under high-pressure cold com-
paction conditions up to 6 GPa. The main objective is to
demonstrate that niobium powder can be consolidated to
highly dense parts (near theoretical density) without external
heating supply, eliminating the sintering step. In addition, it
was determined the influence of the key process variables like
precompacting pressure and high pressure on the densifica-
tion of this powder. This work belongs to a major research
programme which comprises the analysis of physical and
mechanical properties of metallic and ceramic powder com-
pacts obtained under high pressure conditions, as well as

0924-0136/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2005.04.102
188 G.S. Bobrovnitchii, J.N.F. Holanda / Journal of Materials Processing Technology 170 (2005) 187–191
Table 1
Characteristics of the ATR-niobium powder used in the experiments
Theoretical density (g cm−3 ) 5.99
Apparent density (g cm−3 ) 1.79
Particle size (␮m) <38
Specific surface area (m2 g−1 ) 0.56
Fabrication route Chemical reductiona
a Chemical reduction followed by comminution.
other procedures adopted for the production of high density
parts.
2. Experimental procedure
The aluminothermic niobium powder (ATR-niobium) of
high purity obtained by aluminothermic reduction of the
oxide Nb2 O5 with subsequent comminution was supplied
by FAENQUIL-DEMAR (Lorena-SP, Brazil). The ATR-
powders processing have been described elsewhere [8]. The
ATR-niobium powder consists of angular-shaped particles,
whose main characteristics are summarized in Table 1. This
morphology results from cleavage of brittle ATR-niobium
particles during comminution. The identification of the
phases present in the powder was done by X-ray diffraction
(Seifert, URD 65 model) using Cu K␣ radiation.
The ATR-niobium powder initially was submitted to a sin-
gle action die-compaction step in a cylindrical 7 mm diameter
steel die without lubricants under the following pressures:
500, 700 and 1000 MPa. As a result, different sample densi-
ties were obtained, resulting in different heights depending
on the compaction pressure. After uniaxial compaction, the
consolidated samples were pressed under high pressure.
The high-pressure compaction needs an apparatus that can
stably generate a pressure of more than 1 GPa. A toroidal
type high-pressure device [9] with concavity of 13.5 mm
Fig. 1. Anvil type high-pressure device with toroidal concavity for press of 630 tonnes. This device is constituted of anvil of WC–Co (1), supported by the
multi-rings (2); and a calcite based gasket (3); into the gasket cavity is put the sample of ATR-Nb (4).
fabricated by DURIT was used in the experiments. Fig. 1
shows a typical drawing of the high-pressure device. This
device allows the compaction tests in cylindrical powder
samples until 7 mm of diameter and 9 mm of height. The high-
pressure tests were carried out in a special hydraulic press
(Ryazantyashpressmash, DO 138B model) with capacity up
to 630 tonnes. The tests were carried out as follows: the pre-
compacted ATR-niobium powder sample was placed without
slackness into the central aperture of the deformable capsule
(Fig. 1). The deformable capsule is made of a calcite based
powder compact (95% CaCO3 + 5% (SiO2 , Al2 O3 , Fe2 O3 )).
The calcite-based material is a solid pressure medium well
known in the field of ultrahigh pressure technology [10]. A
high-pressure anvil made of hard metal was used as mould,
where the capsule was fixed in its concavity, and then sealed
with the other side of the mould. Finally, the complete device
was axialmente placed in the mobile table of the press. When
the force is applied, the capsule is deformed with concomitant
formation of a gasket and the generation of a high pres-
sure. The following confining high pressure of 2.00 ± 0.05,
4.00 ± 0.08, and 6.00 ± 0.10 GPa were applied to the samples
during 5 s. The high pressure into the compression chamber
was transmitted to the ATR-niobium powder sample by the
capsule. After the high-pressure process, the density of the
powder compacts was measured by picnometry tests. The
microstructure of the dense powder compacts was evaluated
by scanning electron microscopy (Zeiss, DSM 962 model).
3. Results and discussion
The variation of the green density and the relative density
of die-pressed ATR-niobium powder compacts as a function
of the applied pressure is shown in Table 2. It is observed that
densification is enhanced with increasing of pressure. How-
ever, the ATR-niobium powder is still far of attaining high
 G.S. Bobrovnitchii, J.N.F. Holanda / Journal of Materials Processing Technology 170 (2005) 187–191 189

Table 2 Table 3
Results of die-compaction of the ATR-niobium powder Results of high-pressure compaction of ATR-niobium powder
Samples Precompacting Green density Relative Samples Precompacting High pressure Final density
(MPa) (g cm−3 ) density (%) (MPa) (GPa) (g cm−3 )
A 500 4.60 76.8 A1 500 2.0 5.69
B 700 4.77 79.6 A2 500 4.0 5.72
C 1000 4.83 80.6 A3 500 6.0 5.88
B1 700 2.0 5.57
B2 700 4.0 5.81
B3 700 6.0 5.25
C1 1000 2.0 5.82
C2 1000 4.0 5.87
C3 1000 6.0 5.52

that transmits the pressure to the sample is in a state of

Fig. 2. X-ray diffraction pattern for the ATR-Nb powder.
density under die-compaction up to 1000 MPa. The samples
reached density values ranging between 76.8 and 80.6% of
the theoretical density. The reason for this may be related to
the ATR-powder particles that are very hard and difficult to
compact [11]. X-ray diffraction analysis of the ATR-niobium
powder sample, as shown in Fig. 2, indicated the presence of
the following phases Nbss , Nb2 Al (␴) and NbAl3 according
to Nb–Al system phase diagram [12]. These hard intermetal-
lic phases are formed due to the excess aluminum used in the
aluminothermic reduction processing step. Thus, a new incre-
ment of densification with continuous pressurization beyond
that level is of little benefit and very difficult by using die-
compaction technique.
The high-pressure treatments can be done using differ-
ent designs of the high-pressure device [13]. In this work,
a device was used that applies almost hydrostatic pressures
on cylindrical samples, as shown in Fig. 1. The solid phase
complex tension. The value of the effective pressure in the
analyzed point is determined by the arithmetical

mean of the
components of the tensor Pef = 1/3 τ ii . Deformation pre-
dominates in the axial direction. In addition, the shape of
the compact depends on the density of the material of the
deformable capsule and on the density of the precompacted
sample. It is recommended for the precompacted samples a
density between 70 and 80% of the theoretical density. In
addition, the axial deformation should be accompanied by a
radial support. The possible configurations for the precom-
pacted cylindrical samples treated under high-pressure, are
shown in Fig. 3. Thus, when the value of density of the pre-
compacted sample is lower than that of the recommended
range, the height of the compact decreases and the lateral
surface becomes concave (Fig. 3a). Otherwise, the lateral
surface becomes convex (Fig. 3b). If the precompacted sam-
ple has the density between 70 and 80% of the theoretical
density, the height of the compact decreases and its diameter
increases (Fig. 3c).
The results of compaction under high pressure are shown
in Table 3. The correlation between the values of precompact-
ing pressure, high pressure, and final density is well estab-
lished. For most metal powders the compaction behaviour
during pressing has been evaluated by using plots of rela-
tive density after compaction versus applied pressure [14].
As it can be observed both applied precompacting pres-
sure and high pressure positively influenced the final density
(Fig. 4) of the samples. However, high densification levels
were achieved only under high-pressure conditions. Under

Fig. 3. Typical configurations for the sample into compression chamber of the high-pressure device.
190 G.S. Bobrovnitchii, J.N.F. Holanda / Journal of Materials Processing Technology 170 (2005) 187–191
Fig. 4. Compaction response diagram for the ATR-Nb powder.
these conditions extensive plastic deformation occurred. A
combination of axial and radial deformation, with predom-
inance of axial deformation, is the mechanism that controls
the compaction.
Some important changes in the final density occurred for
high pressures above 4 GPa, as shown in Fig. 4. A decrease
of the final density for some samples is observed. This effect
is related to the influence of the residual shear stress on each
grain caused by a new increase of axial plastic deforma-
tion. The axial tensions increased much more than the radial
ones, mainly in the extremities (Fig. 3c). As a consequence,
micro-cracks are formed in the particles and also in the dense
transverse sections. For the studied conditions we suggest that
the optimum value of the precompacting pressure is between
500 and 700 MPa. On the other hand, the optimum value of
the high pressure is up to 4 GPa. Above of these values the
compaction operation is very critical. Decrease of the final
density and structural defects in the highly dense parts were
observed.
The fractional porosity (P) of a powder is defined by the
expression [15]: P = 1 − PF, where PF is the packing fac-
tor. As PF approaches unity, the apparent density approaches
the theoretical value for the bulk material. The values of P,
as shown in Fig. 5, are between 1.8 and 12.3%. This rep-
resents the maximum porosity that can be achieved for the
packing state of the ATR-niobium powder for the given test-
Fig. 5. Porosity of the ATR-Nb compacts obtained under high pressure.
Fig. 6. SEM micrograph of ATR-Nb compact (sample B2) pressed under
high pressure.
ing conditions. The micrograph shown in Fig. 6 (sample B2)
provides a perspective of the densification behaviour under
high pressure. Note that the microstructure is characterized
by a small amount of narrow flat pores well dispersed in the
metallic matrix. In addition, the structure is completely com-
pact, revealing that cold welding among the ATR-niobium
powder particles due to the fresh in-situ formed surfaces dur-
ing compaction occurred. These surfaces are free of oxide
and other contamination, which facilitates the approach of
surfaces up to atomic distances. As a consequence, strong
bondings are achieved at room temperature. Moreover, it
is possible that the fragmentation of the ATR-niobium par-
ticles contributes to densification. Thus, it seems reason-
able that the high-pressure compaction at room temperature
used in this work can be considered as a “cold sintering
process”.
4. Conclusions
From the results presented above, the following conclu-
sions can be drawn. The ATR-niobium powder was success-
fully compacted under high-pressure conditions. The method
used can be an alternative for Nb dense parts processing, with-
out external heat supply. High final densities near theoretical
density have been obtained. Extensive plastic deformation
occurred during compaction. Only small flat pores are left. In
the high-pressure zone, the combined axial and radial plastic
deformation of the particles controls the compaction. It was
also verified that the high final density obtained is dependent
on the applied precompacting and high pressure. Although
high densification has been achieved, structural defects in
dense parts at some studied conditions were observed. Thus,
this study suggests a precompacting value of up to 700 MPa
and high pressure of up to 4 GPa for the cold consolidation
of ATR-niobium powder.
 G.S. Bobrovnitchii, J.N.F. Holanda / Journal of Materials Processing Technology 170 (2005) 187–191
Acknowledgement
The authors would like to thank FAENQUIL-DEMAR
(Lorena-SP) by the supply of the ATR-niobium powder.
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