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A history of niobium

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Metall-Magazin
A History of Niobium
Habashi, F. (1)
Niobium is a member of the group known as re- years, about 460 mil-
fractory metals composed of the ten metals tung- lion tons. The mining
sten, molybdenum, niobium, tantalum, titanium, of weathered ore,
zirconium, hafnium, vanadium, rhenium, and running between 2.5
chromium, located near each other in the Peri- and 3.0 % Nb2O5, is
odic Table (Fig. 1). All these metals have high conducted by simp-
melting points. For example, tungsten melts at le open pit mining
3380 °C and niobium at 2487 °C. They are without the need for
mainly used as alloying elements in steel but also drilling and explosi-
in the elemental form. Some resist high tempera- ves.
The other pyrochlo-
ture without oxidation, and some are very hard,
re mine in Brazil is
having excellent wear and abrasion resistance.
owned and operated
Information about the history and technology of by Anglo American
this group of metals is available in a number of Brasil Mineração
monographs and review articles [1-15]. Catalão and contains
18 million tonnes
Occurence and relative at 1.34 % niobium oxide. The third
Abundance major deposit of pyrochlore being
actively mined is the Niobec Mine in
The most important niobi- Quebec, Canada, owned by Cambior,
um mineral is pyrochlore, with reserves of 18,000 tonnes. In all
(Ca,Na)2-mNb2O6(O,OH,F)1-n.xH2O dis- three facilities, the pyrochlore mineral
covered in 1826. The lattice positions is processed by primarily physical pro-
of Na and Ca can also be occupied cessing technology to give a concen-
by Ba, Sr, rare earths, Th, and U. The trate ranging from 55 to about 60 %
latter two elements are responsible for niobium oxide. These three companies
the radioactivity of some pyrochlore produce about 85 % of the world‘s
concentrates. The name comes from demand for niobium products, with
the Greek πυρ, fire, and χλωρος, most of that output being in the form
green in allusion to the fact that the of ferro-niobium with a nominal 60 %
mineral usually turns green on igniti- niobium oxide content, for making
on. Two types of niobium ore deposits high-strength, low-alloy steel.
are known. In primary deposits, e.g., The second most important niobium
the Canadian deposits at Saint Honoré mineral is columbite, (Fe,Mn)(Nb,Ta)2O6,
and Oka both in Quebec Province, the in which niobium is always present
calciopyrochlore is interstratified in with tantalum. These ores are referred
dolomite. The ore contains 0.5-0.7 % to as columbites if the Nb2O5 content
Nb2O5. In the secondary Brazilian is greater than that of Ta2O5, otherwi-
deposits at Araxá and Catalão both se as tantalites. Columbites and tan-
in Minas Gerais State, the niobium talites contain at least 60 % combined
content of the carbonate minerals pentoxides. These minerals occur as
has been considerably enriched by primary deposits in granites and peg-
weathering. The ore contains about matits, or in alluvial secondary depo-
3 % Nb2O5, 46 % Fe2O3, 17-18 % BaO sits. It was in these minerals that both
as barite, and 1.5 % P as apatite. The niobium and tantalum were disco-
world‘s largest deposit is located in vered.An important potential reserve
Araxá and is owned by Companhia lies in a belt stretching from China to
Brasileira de Metalurgia e Mineração. Indonesia via Thailand and Malaysia,
The reserves are enough to supply and consists of cassiterite, SnO2, that
current world demand for about 500 contains some tantalum and niobium.
804
During tin smelting, the tantalum and
niobium become concentrated in the
slag.
Discovery and isolation
Discovery of a new metal is a great
honor to the discoverer and a great
prestige to his country. The anci-
ent people knew only seven metals:
gold, silver, copper, lead, mercury,
tin, and iron. During the Middle Ages
arsenic, antimony, bismuth, and zinc
became known. It was in the eigh-
teenth century that more metals were
discovered and only towards the end
of that century and the beginning of
the next, that most of the refractory
metals were discovered.
During the eighteenth century mine-
ralogists and chemists were actively
collecting, analyzing, and arranging
minerals for display and study. Some-
times the analysis of a mineral was a
few per cent short to account for its
full composition. In these cases, the
presence of a new metal was suspec-
ted and attempts were made to isolate
it. Once a grain of metallic character
was obtained from an earth (oxide),
the discovery of a metal was confir-
med and the work was extended to
prepare a large amount of this metal
in a pure form to study its proper-
Fig. 1: Position of the refractory
metals in the Periodic Table
· 61. Jahrgang · 1-2/2007

Fig. 2: Charles Hatchett (1765-
1847) discoverer of niobium. A
medal given annually in his honor
to noted chemists since 1979
by the Institute of Materials in
London. The award is given to the
author of the best paper on the
science and technology of niobium
and its alloys.
ties. This, however, was not enough
for two closely related metals like
niobium and tantalum. In this case,
separation of compounds of the indi-
vidual metals must first be achieved.
It may take a century or more from
the time a metal was discovered until
it was isolated in a pure form.
The melting point is one of the
most important criteria for the purity
of a substance. Chemists, physicists,
and metallurgists made great effort
to determine the melting points of
metals. This is particularly difficult
for the high-melting metals. A Table
Fig. 3: Swedish chemist Anders
Gustaf Ekeberg (1767-1813)
· 61. Jahrgang · 1-2/2007
Historische Metallurgie
published by the famous German che-
mist and Nobel Prize winner Walther
Nernst (1864-1941) at the end of
the last century shows that the mel-
ting points of most of the refractory
metals were still unknown (Table 1).
The close similarity between niobium
and tantalum and their occurrence
together in minerals caused a con-
fusion among chemists for about
half a century. In 1801 in London,
the English chemist Charles Hat-
chett (1765-1847) (Fig. 2) announced
the discovery of a new earth which
implied the discovery of a new metal.
He called it columbium because he
found it in a specimen of a heavy Fig. 4: English chemist William H.
black mineral called columbite from Wollaston (1766-1828)
New England in the North Ame-
rican colony, in honor of Christo- resolved the confusion regarding the
pher Columbus because it was first two metals (Fig. 7). He was then able
discovered in North America. The to isolate tantalum after repeated
mineral was supplied to the British crystallization of double fluorides
Museum by the Governor of Con- followed by reduction. Today, sol-
necticut, John Winthrop, who was vent extraction methods are used to
a manufacturing chemist, physician, separate niobium from tantalum, for
and mineral collector. A year later example, using Hexone.
in 1802, the Swedish chemist Anders Niobium was isolated in 1864 by the
Gustaf Ekeberg (1767-1813) (Fig. 3) Swedish chemist Christian Wilhelm
in Uppsala analyzed a specimen of Blomstrand (1826-1897) (Fig. 8) by
a mineral from Kimitom in Finland reduction of NbCl5 in hydrogen but
and another from Ytterby quarry in the metal still contained tantalum.
Sweden and found that both contain The first pure samples of both nio-
a hitherto unknown metal which he bium and tantalum were not made
called tantalum because it had been a until 1907 when the German chemist
tantalizing task to trace it down.
In 1809, another English chemist Wil-
Metal Melting point (°C)
liam H. Wollaston (1766-1828) (Fig. 4)
analyzed the same mineral studied by Nernst Today
Hatchett and came to the conclusion Ti not fused 1677
that Hatchett‘s columbium must be Zr >Si 1852
the same as Ekeberg‘s tantalum. This
Cr >1957 1900
erroneous opinion was held by the
greatest chemists in Europe for forty V not fused 1917
years until proved wrong by Heinrich Hf 2222
Rose (1795-1864) (Fig. 5) in Germany Nb not fused 2487
who in 1844 analyzed a large number Mo very high 2610
of minerals from America and Europe
Ta not fused 2997
and came to the conclusion that what
was thought to be an oxide of tanta- Re 3180
lum is in fact the oxide of new metal W very high 3380
which he called niobium. It was the
Swiss chemist Jean-Charles Marignac Table 1. Melting points of the refrac-
(1817-1894) (Fig. 6) in 1866 who tory metals as given by Nernst (Theo-
was able to make the separation of retical Chemistry, MacMillan, London)
niobium oxide from tantalum oxide in 1895 and today. Hafnium and
by utilizing differences in solubilities rhenium were not discovered yet.
of their complex fluorides and have
805
Metall-Magazin
Fig. 5: German chemist Heinrich
Rose (1795-1864)
Werner von Bolton (1868-1912) (Fig.
9) at Siemens - Halske laboratories in
Berlin reduced K2NbOF5 and K2TaOF5
with aluminum powder. It had taken
over 100 years to go from the disco-
very to the isolation of niobium.
In the United States the metal disco-
vered by Hatchett used to be known
as columbium, but in Europe the
name niobium given by Rose is used.
The International Union of Pure and
Applied Chemistry recommended in
1949 the use of the name niobium. In
mythology Niobe was the daughter of
Tantalus. Tantalum was named from
Greek mythology after King Tanta-
lus son of Zeus. The English verb
to tantalize recalls the unsuccessful
attempts of Tantalus that was so near
and desirable. The discoverer found
difficulty in dissolving the earth of
that metal.
The major use of niobium is an
alloying element for steel. Because
of its lower density and low thermal
neutron cross section compared to
other refractory metals, niobium is
useful in atomic reactors. At ordina-
ry temperatures niobium will resist
attack by all mineral acids, with the
exception of hydrofluoric, and it is
not affected by mixed acids such as
aqua regia. In 1999 the world mine
production of niobium was 18,500
tons with Brazil (16,000 tons) and
Canada (2,300 tons) being the major
sources. World mine production of
tantalum is much smaller at 473 tons
in 1999, Australia (350 tons), Brazil
806
(60 tons) and Canada (60 tons) being
the major sources.
Epilogue
The refractory metals form part of
the so-called transition metals. They
are characterized by having the same
number of electrons in their outer-
most shell and a progressively greater
number of electrons in the next
inner shell. There are, however, some
apparent irregularities in the num-
ber of electrons in the outermost
electron shells. This is due to energy
levels which are determined from
spectroscopic measurements. As their
name implies the transition metals
have properties between the typical
and less typical metals. They are Fig. 6: Swiss chemist Jean-Char-
less reactive than the typical metals les Marignac (1817-1894)
because they will not achieve the
inert gas structure when they lose chromium, molybdenum and
their outermost electrons, but they tungsten.
are nevertheless more reactive than They mostly form borides, car-
the less typical metals. They share bides, nitrides, and hydrides
the following properties: which have mostly metallic
They resemble each other quite character except rhenium which
closely besides showing the usu- does not form carbides.
al group relationships because They have the lowest solubility
they have the same number of in mercury.
the outermost electrons. The metals between lanthanum and
They may lose additional elec- hafnium, namely cerium to lutetium,
trons from the next lower shell known as the lanthanides, are known
to form ions with higher char- as inner transition metals because
ges. As a result they show a they have the same number of elec-
variable valence. For example, trons in the two outermost shells and
vanadium exists in +2, +3, +4, a progressively greater number of
and +5 oxidation states, and
titanium in +2, +3, and +4.
The atomic radius of the succes-
sive metals in a certain horizon-
tal period decreases slightly as
the atomic number rises because
when an electron is added to an
inner shell it decreases slightly
the size of the atom as a result
of increased electrostatic attrac-
tion.
Most of them form colored ions
in solution due to electronic
transition with the exception
of the group Sc, Y, La and Ac
which form only colorless com-
pounds. Fig. 7: Separation of niobium from
They form many covalent com- tantalum by Marignac’s method based
pounds, e.g., the chlorides of on solubility differences
titanium, and the oxyacids of
· 61. Jahrgang · 1-2/2007

Fig. 8: Swedish chemist Christian
Wilhelm Blomstrand (1826-1897)
electrons in the next inner shell. As
in typical and transition metals, the
atomic radius in the lanthanides gra-
dually decreases from lanthanum to
lutetium with the result that although
the atomic radius of lanthanum is
larger than that of yttrium, which
is above it in the Table, the atomic
radius of lutetium is smaller than
that of yttrium, i.e., La >Y >Lu. This
is known as the „lanthanide contrac-
tion“ and is responsible for the fact
that the atomic radius of hafnium
equals that of zirconium, and that
of tantalum to niobium, and that of
tungsten to molybdenum. Two facts
emerge as a result:
Isomorphous substitution. Haf-
nium is always associated with
zirconium in their minerals,
niobium with tantalum, and
molybdenum with tungsten.
Refractory character. Since
the atomic weights of metals in
European Aluminium Materials
European standardization has also
led to serious changes within the alu-
minium domain. In a relative short
period the German Industrial Stand-
ards (DIN) had to be replaced by
European Standards. At a combined
meeting of the International and
European Standardization committee
(AGIE) of the ANP advisory council
(ANPIE) for DIN, held 1996 in Heidel-
berg, a majority of the people present
regretted the problems involved in
· 61. Jahrgang · 1-2/2007
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the lower row are nearly double
those above them in the Periodic
Table, it follows that the densi-
ties of the metals in the lower
row are also nearly double those
above them.
The atoms of those metals in the
lower row are hence so compact, i.e.,
high density and this renders them
difficult to melt, i.e., refractory.
References
[1] C.K. Gupta, editor, Chemistry and Me-
tallurgy of Refractory and Reactive Me-
tals and Materials: Extraction and Pro-
cessing, 2 volumes, Freund Publishing
House, Tel-Aviv, Israel 1991-92.
[2] F. Habashi, editor, Handbook of Extracti-
ve Metallurgy, 4 volumes, WILEY-VCH,
Weinheim and New York 1997[3]
F. Habashi, editor, A History of Me-
tallurgy, Métallurgie Extractive Québec,
Sainte Foy, Québec 1994. Distributed by
Laval University Bookstore.
[4] F. Habashi, „Discovery of Metals“, Bull.
Can. Inst. Min. & Met. 87 (979), 69-74
(1994), and 87 (980), 112-117 (1994)
[5] F. Habashi, „Mining, Metallurgy and My-
thology“, Bull. Can. Inst. Min. & Met. 85
(956), 79-83 (1992)
[6] F. Habashi, “A New Look at the Peri-
odic Table,” Interdiscipl. Science Rev. 22
(1), 53–60 (1997)
[7] R. Kieffer, G. Jangg, and P. Ettmayer,
Sondermetalle, Springer Verlag, Vienna
1971
[8] P. Kumar and R.L. Ammon, editors, Re-
fractory Metals. State of the Art, The
Minerals, Metals, and Materials Society,
Warrendale, Pennsylvania 1988
[9] K.C. Liddell, D.R. Sadoway, and R.G.
Bautista, editors, Refractory Metals.
Extraction Processing and Applications,
The Minerals, Metals and Materials So-
ciety, Warrendale, Pennsylvania 1991
[10] A.G. Quarrell, editor, Niobium, Tanta-
lum, Molybdenum, and Tungsten, Else-
vier, Amsterdam 1971
[11] W. Schreiter, Seltene Metalle, 3 volu-
mes, VEB Deutscher Verlag für Grunst-
converting the DIN Standards for Al
and its alloys into European Stand-
ards. Beyond that, it showed that
in practice there is generally little
knowledge concerning the alloy des-
ignation system, the material temper
designations and the old/new recod-
ing for aluminium and its alloys.
Therefore the task-forte AGIE10 „EN
conversion non-ferrous metals - alu-
minium/copper“ was formed, which
was aimed at compiling a simple aid
Historische Metallurgie
Fig. 9: German chemist Werner
von Bolton (1868-1912) was the
first to prepare pure niobium and
tantalum in 1907
offindustrie, Leipzig 1961
[12] H.Y. Sohn, O.N. Carlson, and J.T. Smith,
editors, Extractive Metallurgy of Re-
fractory Metals, The Metallurgical So-
ciety of AIME, Warrendale, Pennsylva-
nia 1981
[13] V. Tafel, editor, Lehrbuch der Metall-
hüttenkunde, Volume 3, Hirzel Verlag,
Leipzig 1954
[14] M.E. Weeks, Discovery of the Elements,
Journal of Chemical Education, Easton,
Pennsylvania 1960
[15] A.N. Zelikman, O.E. Krein, and G.V.
Samsonov, Metallurgy of Rare Metals,
Izdatel‘stvo Metallurgiya, Moscow
1964, English translation by Israel Pro-
gram for Scientific Translations, Jerusa-
lem 1966
(1) F. Habashi, Department of Min-
ing, Metallurgical, and Materi-
als Engineering, Laval University,
Quebec City, Canada G1K 7P4,
for the practical man. The result is
this pocket book. It is arranged in
an application oriented manner and
can always be present „on site“ due
to its size. The cited Standards and
the Standards for areas which are not
treated are obtainable from the Beuth
publishing house.
From H.-W. Wenglorz, Beuth-Verlag,
Berlin, 2006, 294 p., Softcover, EUR
29,80, ISBN 3-410-16287-9
807