Article No : a17_251

Niobium and Niobium Compounds

JOACHIM ECKERT, Hermann C. Starck Berlin, Werk Goslar, Goslar, Germany

1.
2.
2.1.
2.2.
3.
4.
4.1.
4.2.
4.3.
4.3.1.
4.3.2.
5.
5.1.
5.2.

Introduction. . . . . . . . . . . . . . . . . . . . . . .
Properties . . . . . . . . . . . . . . . . . . . . . . . .
Physical Properties . . . . . . . . . . . . . . . . .
Chemical Properties . . . . . . . . . . . . . . . .
Occurrence . . . . . . . . . . . . . . . . . . . . . . .
Processing of Niobium Ores. . . . . . . . . . .
Winning of Pyrochlore Concentrates . . . .
Treatment of Pyrochlore Concentrates . .
Production of Niobium Oxide from
Columbites and Tantalites . . . . . . . . . . . .
Extraction Processes . . . . . . . . . . . . . . . . .
Chlorination . . . . . . . . . . . . . . . . . . . . . . .
Niobium Compounds . . . . . . . . . . . . . . . .
Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . .
Halides. . . . . . . . . . . . . . . . . . . . . . . . . . .

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133
133
133
134
134
135
135
135

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135
135
136
138
138
138

1. Introduction
Niobium [7440-03-1], Nb, atomic number 41,
Ar 92.91, is also known as columbium, Cb, in
the United States. There are many artificial
radionuclides, but only one known natural nonradioactive isotope, 93Nb. The electronic configuration of the ground state is 4s2p6d3 5s2,
which explains the existence of the oxidation
states 2 to 5.
Niobium was discovered by HATCHETT in 1801
in the mineral columbite and was named columbium. In 1844 the name niobium was proposed
by ROSE.

2. Properties
2.1. Physical Properties
Some important physical properties of niobium
metal are as follows [13]:

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a17_251.pub2

5.3.
6.
6.1.
6.2.
6.3.
6.4.
7.
7.1.
7.2.
8.
9.

Carbides and Hard Materials . . . .

Niobium Metal. . . . . . . . . . . . . . . .
Reduction of Niobium Pentoxide . .
Reduction of Halides . . . . . . . . . . .
Refining . . . . . . . . . . . . . . . . . . . . .
Uses . . . . . . . . . . . . . . . . . . . . . . . .
Ferroniobium. . . . . . . . . . . . . . . . .
Production . . . . . . . . . . . . . . . . . . .
Uses of Ferroniobium . . . . . . . . . .
Analysis . . . . . . . . . . . . . . . . . . . . .
Economic Aspects . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . .

Density at 20
C
Crystal structure
mp
bp
Linear coefficient of thermal
expansion
Specific heat
Latent heat of fusion
Latent heat of vaporization
Thermal conductivity at 0
C
Electrical resistivity at 0
C
Temperature coefficient
0 600
C
Electrochemical equivalent
Standard electrode potential
E
Nb/Nb5
Magnetic susceptibility
at 25
C
Superconductivity TC
Spectral emissivity at
6501010 m (at 2003 K)
Ionisation potential
Work function

.....
.....
.....
.....
.....
.....
.....
.....
.....
.....
.....
.....

.
.
.
.
.
.
.
.
.
.
.
.

139
141
141
141
141
142
143
143
144
144
145
145

8.57 g/cm3
body-centered cubic
(a 3.31010 m)
2468  10
C
4927
C
6.892106 K1
0.26 kJ kg1 K1
290 kJ/kg
7490 kJ/kg
0.533 Wcm1 K1
15.22 mW  cm
0.0396 K1
0.19256 mg/C
0.96 V
2.28106
9.13 K
2.28106
6.67 eV
4.01 eV

134

Niobium and Niobium Compounds

Vol. 24

crust at 24 mg/g. It is thus more common than

cobalt, molybdenum, or tantalum.
The most important niobium mineral is pyrochlore, a compound with the general formula
(Ca,Na)2mNb2O6 (O,OH,F)1n  x H2O. The
lattice positions of Na and Ca can also be
occupied by Ba, Sr, rare earths, Th, and U. The
latter two elements are responsible for the
radioactivity of some pyrochlore concentrates.
Two types of niobium ore deposits are known.
In primary deposits, the pyrochlore is always
interstratified in carbonatites. This is so in the
Canadian deposits at Niobec and Oka, in which
calciopyrochlore is interstratified in dolomite.
The ore contains 0.5 0.7 % niobium pentoxide.
In the important secondary Brazilian deposits at
Araxa and Catalao, the niobium content of
the carbonate minerals has been considerably
enriched by weathering. Here, the ore is present
in combination with apatite, iron oxide, and
barite and contains about 3 % Nb2O5, 46 %
Fe2O3, 17 18 % BaO, and 1.5 % P as apatite
[5]. Table 1 shows the average Nb2O5 capacity,
the production, and the reserves of various
deposits [6]. In addition to the sources listed in
Table 1, other, potential sources exist in Canada,
Africa, Brazil, China, the United States, and the
former Soviet Union.
The most commercially important deposits
are in Brazil, Canada, Nigeria, and Zaire. World
reserves are estimated to be 4.1106 t Nb, of
which 78 % are in Brazil. The Canadian reserves
are estimated at 0.12106t.
The second most important niobium mineral
is columbite, (Fe,Mn)(Nb,Ta)2O6, in which
niobium is nearly always present with tantalum.
These ores are referred to as columbites if the
Nb2O5 content is greater than that of Ta2O5,
otherwise as tantalites. Columbites and tantalites
contain at least 60 % combined pentoxides.
These minerals occur as primary deposits in
granites and pegmatites, or in alluvial secondary

The mechanical properties, like those of most

refractory metals, are influenced by the purity
of the metal, the production method, and the
mechanical treatment. Even small amounts of
interstitial impurities increase the hardness and
strength but reduce the ductility. Some important
mechanical properties of commercial niobium
are as follows [4]:
Annealed niobium
Ultimate tensile strength
Yield strength
Elongation
Reduction in area
Hardness
Poissons ratio
Strain hardening exponent
Elastic modulus
tension
shear
Ductile brittle
transition temperature
Recrystallization temperature
Cold worked niobium
Ultimate tensile strength
Elongation
Hardness

195 MPa
105 MPa
30 %
80 %
60 HV
0.38
0.24
103 GPa
17.5 GPa
< 147 K
800 1000
C
585 MPa
5%
150 HV

2.2. Chemical Properties

Niobium is very resistant to most organic and
inorganic acids, with the exception of HF, at
temperatures up to 100
C [1]. Concentrated
sulfuric acid above 150
C causes embrittlement.
The resistance towards alkaline solutions is
lower. Because niobium has a marked tendency
to form oxides, hydrides, nitrides, and carbides,
its use in air is limited to temperatures up to ca.
200
C.

3. Occurrence
Niobium occupies the 33rd place in order of
natural abundance, being present in the earths
Table 1. Niobium deposits [6]

Location

Capacity,
106 kg Nb2O5

Araxa, Brazil
St. Honore, Quebec
Catalao, Brazil
Nigeria
Thailand
Zaire

24.75
3.15
2.48
0.9
0.45 0.9
pilot scale

Ore grade

Reserves,
106 t Nb2O5

Production,
106 kg Nb2O5

3.0
0.7
1.5

500
11
50

9.45
3.15
2.48

23

extensive

0.23

Vol. 24

Niobium and Niobium Compounds

135

Table 2. Chemical composition of the principal niobium-bearing minerals, % [7]

Mineral

Nb2O5

Ta2O5

TiO2

Fe

MnO

SnO2

Pyrochlore, NaCaNb2O6F
Columbite, (Fe,Mn)(Nb,Ta)2O6
Tantalo-columbite, (Fe,Mn)(Nb,Ta)2O6
Tantalite, (Fe,Mn)(Ta,Nb)2O6
Microlite, Ca2(Ta,Nb)2O6(OH,F)

40
40
25
2

2
1
20
42
60

16
0.5 3
0.5 3
0.5 3

2
10 20
10 20
10 20

2.6
2.6
2.6

2
2
2

65
75
60
40

deposits. Table 2 lists the chemical compositions

of various niobium and tantalum minerals [7].
Columbites are mined in Australia, Brazil,
Nigeria, Malaysia, and Zaire. Since the discovery
of the enormous deposits of pyrochlore in Brazil,
world production of columbite has decreased
considerably. This trend could change when the
extraction of columbite as a byproduct of tin
extraction is started with the Pitinga deposits in
Brazil [8]. The discovery of large deposits of
pyrochlore in South Greenland (Motzfeld
Center) was reported in 1986.
A further source of niobium is provided by
tantalum niobium slags from tin production,
since columbites and tantalites are often associated with cassiterite; niobium and tantalum concentrate in the slags as oxides. The niobium and
tantalum pentoxide content of various tin slags is
given in Table 3 [9]. Niobium and tantalum are
also found in rare minerals such as stibiocolumbites (Sb,Nb)TaO4, fergusonites (Re3 )NbO4,
and euxenite Y(Nb,Ti)2O6. The last two of these,
however, are of no commercial significance.

40
50
84
70

ation processes such as crushing, grinding,

magnetic separation, and flotation. Brazilian
concentrates (Araxa) are also treated chemically
to remove lead, phosphorus, and sulfur. The raw
concentrate is roasted in the presence of calcium
chloride and calcium oxide in a rotary furnace at
800 900
C, and the product is leached with
hydrochloric acid. In the case of Brazilian pyrochlore, this procedure also leads to replacement
of barium by calcium [10].

4.2. Treatment of Pyrochlore

Concentrates

4.1. Winning of Pyrochlore

Concentrates

Whereas pyrochlore from Araxa can be converted directly to ferroniobium, pyrochlore

concentrates from other sources must first be
chemically pretreated before niobium can be
obtained. Some well-known processes are treatment with concentrated sulfuric acid or with
molten soda. Reductive chlorination of pyrochlore at ca. 1000
C produces volatile chlorides of niobium and other metals. These
processes are, however, generally regarded as
uneconomical. This is also true of the process in
which digestion of pyrochlore with mixtures of
hydrofluoric and sulfuric acids is followed by
solvent extraction [11].

Concentrates containing 50 60 % Nb2O5 are

obtained from pyrochlore-containing carbonatites or weathered ores by conventional benefici-

4.3. Production of Niobium Oxide

from Columbites and Tantalites

4. Processing of Niobium Ores

Table 3. Niobium and tantalum pentoxide content of various tin slags,

% [9]
Country

Nb2O5

Ta2O5

Malaysia
Nigeria
Portugal
Singapore
Thailand
Zaire

4
14
7
3
8
5

4
4
7
2
12
9

4.3.1. Extraction Processes

Niobium and tantalum always occur together in
columbites and tantalites and must be separated
not only from the other elements present but also
from each other. The industrial separation of
tantalum from niobium has long been carried
out by the Marignac process of fractional
crystallization of potassium heptafluorotantalate

136

Niobium and Niobium Compounds

and potassium heptafluoroniobate [12]. This expensive process of precipitation and crystallization, which is also environmentally unacceptable, has been abandoned, together with the long
established Fansteel process [12], in favor of
processes based on solvent extraction.
Tantalite and columbite, either naturally
occurring or synthetically produced as concentrates from tin slags [13, 14], are digested with
hydrofluoric and sulfuric acids at elevated
temperature. The accompanying elements are
dissolved along with the tantalum and niobium,
which form the complex heptafluorides H2TaF7
and H2NbOF5 or H2NbF7. After filtering off
the insoluble residue (fluorides of alkaline earth
and rare earth metals), the aqueous solution of
Ta Nb in hydrofluoric acid is extracted in
several continuously operated mixer-settlers
with an organic solvent, e.g., methyl isobutyl
ketone (MIBK) [1517]. The complex fluorides
of niobium and tantalum are extracted by the
organic phase, whereas most of the impurities
and other elements, such as iron, manganese,
titanium, etc., remain in the aqueous phase. In
practice, Nb2O5 Ta2O5 concentrations of
150 200 g/L in the organic phase are used.
The organic phase is washed with 6 15 N
sulfuric acid and then reextracted with water or
dilute sulfuric acid to obtain the niobium. The
aqueous phase takes up the complex fluoroniobate and free hydrofluoric acid, while the complex fluorotantalate remains dissolved in the
organic phase. The aqueous niobium solution is
reextracted with a small amount of MIBK
to remove traces of tantalum. The resulting
organic phase is returned to the combined
tantalum niobium extraction stage. Gaseous
or aqueous ammonia is added to the aqueous
niobium solution to precipitate niobium oxide
hydrate. Crystallization of K2NbF7 can only
be achieved in strong hydrofluoric acid solution;
therefore, it is only carried out on a small scale
because of the high costs arising from the
increased consumption of hydrofluoric acid.
The tantalum is reextracted from the organic
phase with water or dilute ammonia solution, and
tantalum oxide hydrate is precipitated by ammonia, or potassium salts are added to produce
K2TaF7, which is used in the production of
tantalum metal.
The oxide hydrates are collected by filtration,
dried, and calcined at up to 1100
C. Variation of

Vol. 24

the conditions of precipitation, drying and calcination produces different particle sizes, giving
oxides suitable for various applications. Depending on the quality requirements, the calcination is
carried out in directly or indirectly heated chamber or rotary furnaces. The nature of the furnace
lining has considerable influence on purity.
Sophisticated process control and optimization enable niobium and tantalum to be produced with high yield (> 95 %) and purity
(> 99.9 %).
A number of alternative extraction media
have been reported in the literature, most of
which have never been used in industry, except
for tributyl phosphate (TBP) [18] and tri-noctylphosphine oxide (TOPO) [19].
Figure 1 shows the flow diagram of an industrial installation for the processing of tantalum
niobium raw materials [20].
4.3.2. Chlorination
The chlorination process is a modern alternative
to the extraction process. There are two versions:
reductive chlorination of natural and synthetic
raw materials, and chlorination of tantalum
niobium ferroalloys.
In reductive chlorination, the ore or concentrate is pelletized with coal/coke and pitch, dried,
and reacted in a stream of chlorine at 900
C. The
nonvolatile alkaline earth metal chlorides remain
behind, while the readily volatilized tetrachlorides of silicon, tin, titanium, the pentachlorides
NbCl5 and TaCl5, and WOCl4 are distilled off
and fractionated. The waste gas, which contains
large amounts of phosgene and chlorine, must be
rigorously purified.
The chlorination of ferroalloys is much simpler and more economical [21, 22]. Ferroniobium
or ferroniobium tantalum are produced by the
aluminothermic or electrothermic process, size
reduced, and fed together with sodium chloride
into a NaCl FeCl3 melt. The chlorinating agent
is NaFeCl4. Chlorine is passed into the melt,
continuously regenerating NaFeCl4. The following overall reactions take place:
FeTaNbNaCl7 NaFeCl4 !Ta=NbCl5 8 NaFeCl3
8 NaFeCl3 4 Cl2 !8 NaFeCl4

The reaction temperature of 500 600
C is

much lower than that required for reductive

Vol. 24

Niobium and Niobium Compounds

137

Figure 1. Flow diagram for the processing of tantalum niobium raw materials [20]

chlorination. The volatile chlorides are evolved

from the molten salt bath. The boiling points
of NbCl5, TaCl5, and WOCl4 lie between 228
and 248
C, and these compounds must therefore be separated by means of a distillation
column.

The chlorination of ferroalloys produces very

pure niobium pentachloride and tantalum pentachloride in tonnage quantities. The NbCl5
contains less than 30 mg/g Ta, and other metallic
impurities only amount to 1 2 mg/g. Niobium
pentachloride is an intermediate in the production

138

Niobium and Niobium Compounds

of oxides and organometallic compounds, and is

the starting material for production of niobium
powder and for chemical vapor deposition (CVD)
of niobium coatings.

5. Niobium Compounds
5.1. Oxides
Niobium pentoxide [1313-96-8], niobic acid,
Nb2O5, mp 265
C, bp 1495
C, is a colorless
powder that can only be dissolved by fusion with
acidic or alkaline fluxes such as NaOH or
KHSO4, or in hydrofluoric acid. It is prepared
by hydrolyzing solutions of alkali-metal niobates, niobium alkoxides (e.g., Nb(OC2H5 )5 ),
or niobium pentachloride, or by precipitation
from hydrofluoric acid solutions with alkalimetal hydroxides or ammonia. Depending
on the method used, the oxide hydrate formed
is either a gel that is difficult to filter or is
flocculent. The oxide hydrate is filtered,
washed, and calcined at 800 1100
C. The
temperature and treatment time determine
which of the various crystalline modifications
is formed. Nearly all the phase changes are
irreversible [2325].
Uses. Niobium pentoxide is used in metallurgy, for the production of hard materials, in
optics, and in electronics. Hydrated Nb2O5,
which can be regarded as an isopolyacid, has a
high surface acidity, and catalyzes the polymerization of alkenes, e.g., propylene [26].
Various applications require different qualities of Nb2O5. For the electrothermic and
metallothermic manufacture of niobium metal
or its alloys, technical quality niobium pentoxide
(> 98 99 %) is suitable. For higher quality
requirements, chemically pure niobium pentoxide (> 99.7 %) is used.
In optics, niobium pentoxide is used as an
additive to molten glass to prevent devitrification
and to control properties such as refractive index
and light absorption [27]. Optical grade niobium
pentoxide, with a purity of > 99.9 %, must be
free from colored impurities such as chromium,
nickel, iron, manganese, etc.
Extremely stringent purity requirements apply
to Nb2O5 used in the manufacture of LiNbO3
[12031-63-9] or KNbO3 [12030-85-2] single

Vol. 24

crystals (Nb2O5 ultra pure grade, > 99.995 %).

These compounds are used for electroacoustic
and electrooptical components such as modulators, frequency doublers, and wave filters [28, 29].
Ceramic grade niobium pentoxide, used for
making dielectric materials, must be manufactured with a special particle size distribution.
This market sector will demand greatly
increased quantities of niobium pentoxide if the
development of the new class of ferroelectric
perovskites (relaxors) is successful, e.g., Pb
(Mg1/3 Nb2/3)O3 for the manufacture of ceramic
capacitors [3032].
Details of the various commercial qualities of
niobium pentoxide are given in Table 4 [20].

5.2. Halides
Niobium pentachloride [10026-12-7], NbCl5, Mr
270.2, mp 209.5
C, bp 249
C, is now produced
exclusively by chlorination of ferroniobium,
niobium metal, or niobium scrap (see Section
4.3.2.).
Niobium pentachloride forms strongly hygroscopic yellow crystals that react with water to
form NbOCl3 or Nb2O5x H2O. The pentachloride
is very soluble in dry ethanol, tetrahydrofuran,
and benzene. Alcoholic solutions of niobium
pentachloride are used in the production of
niobium alkoxides such as the pentaethoxide,
Nb(OC2H5 )5, from which micronized niobium
pentoxide is produced [33]. Pure niobium
pentachloride is used for large scale production
of niobium pentoxide and niobium metal.
Niobium tetrachloride [13569-70-5], NbCl4,
sublimes between 350 and 400
C. Niobium
trichloride [13569-59-0], NbCl3, disproportionates between 900 and 1000
C. Niobium
trichloride and niobium dichloride [13777-098], NbCl2, are formed by reduction of NbCl5
with hydrogen, but are of no industrial
importance.
Niobium oxychloride [13597-20-1], NbOCl3,
Mr 215.28, is a colorless, crystalline compound
that sublimes at 400
C and partly decomposes
into niobium pentoxide and niobium pentachloride on further heating.
Niobium pentafluoride [7783-68-8], NbF5,
Mr 187.91, mp 72
C, bp 236
C, can be prepared by fluorination of niobium pentachloride
or niobium metal with fluorine or anhydrous HF.

Vol. 24

Niobium and Niobium Compounds

139

Table 4. Commercially available niobium oxides [20]

Specification
Composition
Nb2O5
Ta
Al
B
Bi
Ca
Cl
Co
Cr
Cu
F
Fe
K
Mg
Mn
Mo
Na
Ni
Pb
Rare earths
S
Si
Sn
Ti
V
W
Zr
Alkali
Loss on ignition
Average particle
size (FSSS)
Tap density
Apparent density
(Scott)
Microtac analysis

Technically
pure grade

Chemically
pure grade

Ceramic grade

min. 99 %
max. 1600 ppm

min. 99.7 %
max. 800 ppm

min. 99.8 %
max. 500 ppm

max. 700 ppm

max. 200 ppm

min. 99.95 %
max. 100 ppm
max. 2 ppm

max. 10 ppm
max. 2 ppm
max. 2 ppm
max. 2 ppm

max. 1000 ppm

max. 200 ppm

max. 100 ppm

max. 10 ppm

max. 2 ppm
max. 400 ppm

max. 200 ppm

max. 100 ppm

max. 2 ppm

max. 50 ppm

max. 1000 ppm

max. 250 ppm

max. 30 ppm
max. 50 ppm

max. 300 ppm

max. 100 ppm

max. 100 ppm

max. 0.5 %
0.5 10 mm

max. 50 ppm
max. 50 ppm
max. 200 ppm
max. 0.4 %
0.7 0.8 mm

max. 2 ppm

max. 1 %
1 10 mm

max. 0.2 %
max. 5 mm

0.8 1 g/cm3
0.5 0.7 g/cm3
90 % < 1.2 mm
50 % 0.7 0.8 mm
10 % < 0.5 mm

Grain size

Crystal structure

Grade HPO
(high purity optical)

orthorhombic
(T-phase)

The reaction of Nb2O5 with aqueous HF yields

fluoroniobic acids of various compositions (e.g.,
H2NbF7 or H2NbOF5 ), depending on the acid
concentration. They are soluble in organic solvents and consequently play an important part in
the separation of tantalum from niobium by
solvent extraction.

Grade UP (ultra pure)

min. 99.997 %
max. 8 ppm
max. 0.5 ppm
max. 0.2 ppm
max. 0.5 ppm
max. 1 ppm
max. 10 ppm
max. 0.2 ppm
max. 0.2 ppm
max. 0.2 ppm
max. 1 ppm
max. 1 ppm
max. 1 ppm
max. 0.5 ppm
max. 0.2 ppm
max. 2 ppm
max. 1 ppm
max. 0.2 ppm
max. 0.5 ppm
max. 1 ppm
max. 1 ppm
max. 1 ppm
max. 0.5 ppm
max. 1 ppm
max. 0.5 ppm
max. 1 ppm
max. 1 ppm
max. 0.005 %
1 3 mm
0. 8 1.25 g/cm3

1. < 600 mm
HPO 600
2. < 400 mm
HPO 400
3. < 150 mm
HPO 150
monoclinic
(H-phase)

< 255 mm

monoclinic (H-phase)
orthorhombic (T-phase)

5.3. Carbides and Hard Materials

The carbides, borides, silicides, and nitrides
of niobium are metallic hard materials [34].
Some of their physical properties are listed in
Table 5. Only the carbides are commercially
important.

1.2
1.27
15.2
9.5

40
10

7.74
550
1950
(decomp.)

12/34

1.27

64.5

8.25
**

Vickers hardness at 0.5 N loading.

Mohs hardness

1.27
*

Electrical
resistivity,
mWcm
Superconductivity
transition
temperature, K

8.0
2060
1860
(decomp.)

2200
2280

2290
2700
(decomp.)

6.6
2600
3000

9.18

7.83
2123
3100
(decomp.)

35

8.33
2123

60

5.45
700
1950
6.26
600
2480

[12060-34-3]
a-tetragonal
b-tetragonal
[12164-59-9]
hexagonal,
ZrSi4 type

[24621-21-4]
face-centered
cubic,
NaCl type
8.2
8**
[12033-43-1]
hexagonal,
W2C type

[12069-94-2]
face-centered
cubic,
NaCl type
7.78
2400
3600
[12011-99-3]
hexagonal
[12007-29-3]
hexagonal,
AlB2 type
[12045-19-1]
orthorhombic,
CrB type
[12045-55-5]
tetragonal,
U3Si2 type

Nb5Si3
Nb4Si
NbN
Nb2N
NbC
Nb2C
NbB2
Nb3B4

[12045-89-5]
orthorhombic,
Ta3B4 type

Density, g/cm3
Hardness*
mp,
C

Niobium Hydrides. On heating niobium in

a pure hydrogen atmosphere to 350 500
C,

CAS registry
number
Crystal structure

Niobium Nitrides. Various nitride phases,

with regions of homogeneity varying in distinctness, are obtained by heating niobium metal or
mixtures of niobium oxide and carbon in a stream
of ammonia or nitrogen [39]. Niobium metal can
be produced by thermal decomposition of NbN in
high vacuum. The pure nitrides have not as yet
found any industrial application. Table 5 lists
some of the physical properties of niobium
nitrides.

NbB

Niobium Silicides, Nb4Si, Nb5Si3, and

NbSi2, are produced by the silicothermic reduction of Nb2O5 or from the elements by sintering,
pressure sintering, or fusion in an electric arc
furnace. Some physical data are given in Table 5.
These compounds are not used industrially.

Table 5. Physical properties of borides, carbides, nitrides, and silicides of niobium [34]

Niobium Borides. The niobium boron

phase diagram [38] shows the existence of
Nb3B2, NbB, Nb3B4, and NbB2. However, these
high-melting, very hard materials, have no
industrial uses. Table 5 lists their physical
properties.

NbSi2

Niobium Carbides (! Carbides). The

niobium carbon phase diagram [35] indicates
the existence of a face-centered cubic compound,
NbC, which melts without decomposition at
3600
C with a broad region of homogeneity,
and of Nb2C, which has a peritectic melting
point. Only NbC has practical applications. In
addition to its original use as a grain growth
inhibitor in tungsten carbide cobalt hard
materials, it is now used mainly as solid solutions
with titanium carbide, tantalum carbide, and
tungsten carbide for cutting tools. The precise
effect of niobium on the composition, microstructure, and properties of these hard materials
is not yet fully understood [36]. In practice, up
to 50 % of the more expensive TaC can be
replaced by NbC without appreciably affecting
the hardness or fracture strength [37].
Production, like that of TaC, is by carburizing
the oxide, hydride, or metal at 1500
C in a
carbon tube furnace, vacuum furnace, or in the
presence of a molten metallic menstruum such as
iron or aluminum. Some of the physical properties of niobium carbides are given in Table 5.

50.4

Vol. 24
[12034-80-9]
hexagonal,
CrSi2 type

Niobium and Niobium Compounds

Nb3B2

140

Vol. 24

hydrogen (ca. 44 atom %) is absorbed, causing

expansion of the lattice and embrittlement. Apart
from the NbH0.9 [13981-86-7] thus formed, the
hydride Nb4H3 [56941-03-8] [40, 41] and the
unstable dihydride NbH2 [13981-96-9] [42] are
also known.
The reversible uptake and release of hydrogen by NbH is used in industry as a means
of producing niobium powder from compact
niobium, e.g., scrap or ingots. The metal is first
hydrogenated, then ground, and finally dehydrogenated in a vacuum furnace or under an
inert gas.

6. Niobium Metal
The industrial production of niobium is usually
carried out by the reduction of the pentoxide or
halides. The crude metal is then refined
electrothermally.

6.1. Reduction of Niobium Pentoxide

Niobium pentoxide is reacted with carbon,
aluminum, or silicon at high temperature. In the
carbothermic process, niobium pentoxide is
mixed with carbon black, and the mixture is
pelletized and reduced in a vacuum furnace in
a two-stage process at 1950
C:
Nb2 O5 7 C!2 NbC5 CO
Nb2 O5 7 C!2 NbC5 CO

The reaction takes place with the formation of

NbC, Nb2C, NbO2 and NbO [43, 44]. A crude
product containing oxygen and carbon is produced, which must be refined in further hightemperature processes.
The following one-stage carbonitrothermic
reduction of niobium pentoxide has been successfully carried out on the pilot-plant scale. A
pelletized mixture of niobium pentoxide and
carbon black is reacted in a stream of ammonia
in an induction furnace at 1570  20
C to form
niobium nitride, NbN, which is then thermally
decomposed in high vacuum at 2000
2100
C. However, the process does not yet
appear to have been used on an industrial scale
[45, 46].

Niobium and Niobium Compounds

141

Over 90 % of niobium metal is produced by

aluminothermic reduction:
5 NbCNb2 O5 !7 Nb5 CO

Niobium metal produced by this process is

designated ATR niobium. In general, an excess
of aluminum is used, producing a niobium
aluminum alloy which is melted in a vacuum,
electric arc, or electron beam furnace to produce
low-oxygen, carbon-free niobium [47, 48]. The
amount of excess aluminum determines the yield
of niobium and its oxygen content [49].
The silicothermic reduction of niobium
pentoxide can lead to silicide formation, and
the thermodynamics of this reaction are less
favorable. This process is therefore not in
regular use.

6.2. Reduction of Halides

The reduction of niobium pentachloride can be
achieved with hydrogen at 600 650
C [50].
Alternatively, niobium pentachloride vapor is
reduced with hydrogen in a fluidized bed furnace
at 750 1050
C [51] or in a hydrogen plasma
above 2000
C [52]. Metallothermic reduction
with sodium or magnesium has also been
reported [53]. The company TOHO Titanium
Corporation has commissioned a plant with a
capacity of 30 t/a niobium in which niobium
pentachloride is reduced by magnesium [54].
A reduction process with zinc using the auxiliary
metal bath technique is also known [55]. In
contrast to the production of tantalum, the reduction of the fluoroniobates K2NbF7 and K2NbOF5
has not become industrially significant.
Very pure niobium can be obtained by electrowinning from oxygen-free molten salt systems
with double fluorides or chlorides as the source of
metal [56]. These molten salts are very corrosive
and the current efficiencies are low. For these
reasons, molten salt electrowinning of metallic
niobium is not carried out commercially.

6.3. Refining
Crude niobium must be refined in order to
remove impurities introduced either from the
raw materials or during the treatment stages.

142

Niobium and Niobium Compounds

Vol. 24

Purification can be achieved by high-temperature treatment because the melting point of

niobium (2497
C) is so high that most other
elements can be removed by vaporization. Niobium is extremely reactive towards all but the
inert gases [57], and melting must therefore
always be carried out in a high or ultra-high
vacuum or under a pure inert gas to minimize
the concentration of harmful interstitial foreign
atoms.
In comparison to the classical sintering and
electric arc melting processes, electron beam
melting (EBM) has considerable technical advantages for the production of pure metal.
The vaporization of the impurities can be
controlled in each melting cycle by[58, 59]:
1. Optimizing the melting rate,
2. Maintaining the bath in a liquid state for a
long period, and
3. Controlled superheating of the molten metal.
Sufficient refinement cannot be achieved with
one melting cycle only, so that in practice the
solid ingot produced must be remelted. The
melting rate (kg/h Nb) for the first melt (main
refining step) depends on the raw material and is
lower for ATR niobium because of the high
content of aluminum and NbO that must be
evaporated compared with compacted granular
niobium. Further development of the plasma
melting technique would enable a simple plasma
furnace to be used for the first melting operation
[60, 61]. In the second and third melting cycles,
the melting rate can be increased by a factor of
3 4, depending on the specification of the
material.
Optimization of the equipment used in the
electron beam melting process, leading to reduction in residual gas pressure and leakage rate, has
enabled standard quality niobium to be produced
from ATR niobium on a large scale with only two
melting cycles [62].
The electron beam melting and remelting
technique enables niobium metal with less than
50 mg/g interstitial impurities to be produced for
high-frequency superconductors. Figure 2 shows
the concentration of interstitial impurities (O, N,
and C) as a function of the number of melting
cycles [63].
Ultra-high purity niobium can be obtained
from metal melted by the EBM method by a

Figure 2. Contents of interstitial impurities (O, N, and C) of

an electron beam melted niobium ingot as a function of the
number of melting cycles [63]

series of additional sophisticated process steps,

including electrorefining and electron beam zone
melting, followed by high-temperature treatment
in high vacuum. By these methods, niobium
metal can be prepared with metallic impurities
in the parts per billion range and with interstitial
impurities < 1 ppm [64].

6.4. Uses
Niobium has good resistance towards corrosive
chemicals [4, 65] even at high temperatures, and
is therefore used in the construction of chemical
equipment, though it is not quite so resistant as
tantalum. The process of oxide dispersion hardening of niobium with titanium dioxide gives a
material which can be used both for chemical
equipment and for medical implants subjected to
high mechanical loading [66]. High-niobium
alloys such as KBI 40/41 [67] can also be used
under these conditions, for which formerly the
more expensive metal tantalum had to be used.
Because niobium has a low neutron capture
cross-section and is unusually resistant towards
corrosion by liquid sodium, it is used in the pure
state or as the alloy NbZr1 in the nuclear industry
for the production of fuel element cans. This
alloy is also used for the sealing caps of sodium
vapor lamps.

Vol. 24

World consumption of niobium for the production of superconducting materials, such as

Nb3Sn and NbTi is estimated to be 60 70 t/a.
The addition of niobium to titanium
aluminum alloys imparts the ductility needed
to fabricate this material for the aircraft and
space industry [68].
Other newly developed alloys C 103
(NbHf10Ti1) and Nb 752 (NbW10Zr25) combined with a special coating technique enable
niobium to be used in the manufacture of
nozzles and combustion chambers for rocket
propulsion [69].

7. Ferroniobium
Approximately 85 90 % of the total niobium
production is used in the steel industry in the
form of iron niobium alloy (ferroniobium)
containing 40 70 % niobium. Depending on
the application, the alloy can also contain
small amounts of Ta (ferroniobium tantalum), e.g., FeNb65Ta2, which contains 65 %
Nb and 2 % Ta. Other alloy specifications are
given in [70].

7.1. Production
Ferroniobium is usually produced by aluminothermic reduction of niobium oxide ores, with
the addition of iron oxides if the niobium ore
used contains insufficient iron. The starting
materials are mainly columbites and pyrochlore
concentrates.
The enthalpy of the reaction between Nb2O5
and Al is 276.1 kJ/mol Al, which is lower than
the threshold value for self-sustaining aluminothermic reactions. The mixture must therefore
either be preheated or mixed with oxygenreleasing compounds such as BaO2, CaO2, KClO4,
KClO3 or NaNO3 .
Concentrates with lower percentages of niobium (ca. 40 %) can also be treated by the aluminothermic process in an electric arc furnace. Also,
a two-stage electroaluminothermic process for
the production of ferroniobium from columbite
has been developed [71].
The method of operation is to charge the
mixture of niobium concentrate with the additives to refractory lined reaction vessels. Either

Niobium and Niobium Compounds

143

the whole mixture is reacted, or a small amount is

set aside, ignited with a special exothermic mixture, and added to the bulk mixture. The molten
reaction product is allowed to solidify in the
furnace, and the block of metal separates from
the slag. After cooling, it is broken into pieces of
the required size.
In the aluminothermic process operated at
Araxa, Fe Nb blocks of metal up to 11 t in
weight are produced. The yield of niobium metal
is 96 97 %. The typical composition of a reaction charge is as follows:
Pyrochlore concentrate
Iron oxide
Aluminum powder
Fluorspar
Lime

18 000kg (60 % Nb2O5 )

4000 kg (68 % Fe)
6000 kg
750 kg
500 kg

The reaction gives ca. 11 000 kg of ferroniobium

of composition:
Nb
Fe
Si
Al
Ti
P
S
C
Pb

66.0 %
30.5 %
1.5 %
0.5 %
0.1 %
0.1 %
0.04 %
0.08 %
0.02 %

and ca. 20 000 kg of slag containing:

Al2O3
CaO
TiO2
BaO
Re2O3
Nb2O5
ThO2
U3O8

48.0 %
25.0 %
4.0 %
2.0 %
4.0 %
trace
2.0 %
0.05 %

Special niobium alloys, e.g., nickel niobium,

cobalt niobium, aluminum niobium and
chromium niobium, are also manufactured
by the aluminothermic process. For these
alloys, which have various niobium contents
[72], niobium oxide is the only raw material
used.

144

Niobium and Niobium Compounds

7.2. Uses of Ferroniobium

Niobium has very marked carbide and nitride
forming properties and is therefore mainly used
in the production of steels and gray iron [73].
The addition of niobium prevents intercrystalline corrosion in stainless austenitic chromium nickel steels and improves corrosion resistance, weldability, ductility, and toughness
in ferritic chromium steels [74]. Ferroniobium
is also used as a trace additive in large quantities for the production of high-strength lowalloy (HSLA) steels used in automobile body
manufacture, structural steels, concrete reinforcing steel, and pipelines. Superalloys containing up to 5 % niobium are used for gas
turbine components. These materials have
high hot strength [75, 76], and mostly have a
nickel or copper base. The niobium is added in
the form of nickel niobium or cobalt niobium.

8. Analysis
Extensive literature on the analytical determination of niobium is available in handbooks and
monographs [7780].
The determination of niobium in raw materials is carried out by X-ray fluorescence [8183].
For this purpose, test pieces in tablet form are
produced by reacting the niobium-containing
material with borate to produce a melt, or by
compressing it with binders such as wax or boric
acid.
For ferroniobium, X-ray fluorescence analysis of HF solutions [84] or borate tablets is
used. For umpire assay, it is usual to separate
the niobium from the other material using ionexchange resins with HF solutions, followed by
gravimetric determination [85]. Small niobium
contents in steels are determined photometrically [86].
Metallic impurities in niobium pentoxide
or niobium metal are determined by atomic
absorption spectrometry (AAS) or atomic
emission spectrometry (ICP-OES, DCP-OES)
in HF solution [87]. Emission spectrum analysis in a d.c. current plasma arc is also used.
The nonmetals oxygen, nitrogen, hydrogen,

Vol. 24

carbon, and sulfur are determined by extraction at high temperature either with a carrier
gas or under vacuum, or by combustion analysis in a stream of oxygen [88]. The hydrideforming elements arsenic, antimony, bismuth,
selenium, and tellurium can be converted to
their hydrides and detected with high sensitivity by the AAS method. The anions Cl and
F are separated by distillation and determined
photometrically, by ion-selective electrodes, or
by ion chromatography.
In all the above-mentioned methods, the usual
limits of detection are from the low mg/g
region down to the ng/g region in routine quality
testing. For the analysis of ng/g trace impurities
it is necessary to separate and concentrate the
material [89, 90]. The final determination is
carried out using AAS with a graphite furnace,
ICP-OES, DCP-OES, or voltammetry. Recently,
ICP mass spectrometry has become a powerful
additional method for many metallic impurities.
Niobium metal is analyzed simply and quickly
for metallic and nonmetallic impurities down
to the lower ng/g region by glow discharge
mass spectrometry (GDMS) [91]. The additional
techniques of neutron activation analysis [92, 93]
or proton activation analysis [94] are used for
verification.

Figure 3. World niobium consumption compared to world

crude steel production from 1972 1988 [95]

Vol. 24

Niobium and Niobium Compounds

9. Economic Aspects
The world consumption of niobium has, since
1980, reached 16 20106 kg Nb2O5. The
annual rate of increase is ca. 2 %. More than
90 % of total niobium production goes to the
steel industry in the form of ferroniobium or
niobium alloys, and therefore the demand for
niobium is determined by the world market for
iron and steel [95]. Figure 3 shows the clear
relationship between steel production and
niobium demand. Between 1984 and 1988,
technical quality niobium pentoxide was marketed in the price range 14.3 15.2 $/kg. The
price of standard grade ferroniobium was
14.5 $/kg Nb. In mid 1987, the price of niobium concentrate (> 65 % Nb2O5 Ta2O5,
10 : 1) was 5.5 6.4 $/kg Nb2O5 CIF Europe.
Canadian pyrochlore concentrate was quoted at
5.9 $/kg Nb2O5 FOB.

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Further Reading
A. Agulyansky: The chemistry of tantalum and niobium
fluoride compounds, 1st ed., Elsevier, Amsterdam 2004.
J. E. Schlewitz: Niobium and Niobium Compounds, Kirk
Othmer Encyclopedia of Chemical Technology, 5th
edition, vol. 17, p. 132157, John Wiley & Sons, Hoboken,
NJ, 2006, online: DOI: 10.1002/0471238961.
1409150219030812.a01.pub2.