Manufacture or Production of Titanium and Alloys thereof.
Year: 1895

page_text: Date of Application, 12th Feb., 1895
Complete Specification Left, 24th July, 1895-Accepted, 7th Sept., 1895
PROVISIONAL SPECIFICATION.
Manufacture or Production of Titanium and Alloys thereof.
"
I, HENRI MOISSAN, of 15, Rue des Halles, Paris, France, do hereby declare the
nature of this invention to be as follows:-
Heretofore titanium has been merely a laboratory curiosity, indeed it may even
be said that pure titanium has never hitherto been produced. The reason for this
lies in the very strong affinity of titanium for nitrogen. Furthermore it has not yet
been possible to obtain molten titanium.
Berzelius, in attacking the fluo-titanate of potassium, or the chloride of titanium,
with potassium, obtained a dark powder which on trituration turned to a red color.
This powder, which Berzelius supposed to be titanium, was however, for the greater
part, nitride of titanium. Wahler and Deville, in employing the same reaction in a
current of hydrogen, produced a grey powder which decomposed water at 100° C.,
and which they supposed to be titanium, without, however, giving any analysis.
Kern roduced in a porcelain tube by the action of vapour of titanium upon
sodium contained in a small dish, a grey powder which did not decompose water
below 500° C.
These various samples of titanium are impure. In fact the metals of the
alkalies, have alone, up to the present, yielded by reduction of the compounds of
titanium, a grey powder which does not show any trace of fusion, is rendered
impure by an admixture of sodium, or of potassium, nitrogen, and often other
impurities. Titanic acid has heretofore been supposed to be incapable of reduction
by means of carbon. But this is not the case.
I have already shown by numerous experiments that the oxides of uranium, of
vanadium, and of zirconium, and also silica, which was supposed to be irreducible,
could be reduced by means of carbon if the temperature were sufficiently high.
Similarly, titanic acid, whether such as occurs in Nature or such as can be prepared
in the pure state, can be reduced by means of carbon under the conditions herein-
after set forth.
If in the electric furnace which I have invented ("Comptes Rendus de l'Academie
des Sciences," 1892), or in any other suitable electric furnace, there be melted
down by means of an electric arc of about 400 ampères and 80 volts, a mixture
of rutile or pure titanic acid and carbon in the proportions indicated by the
formula TiO,+2C there is obtained a very bard fused mass which will readily
scratch the ruby, has a yellow fracture, and is of a reddish brown colour; it
consists of nitride of titanium, containing 79 to 80% of titanium, and having a
specific gravity of from about 5-02 to 5-15. This compound is analogous to the
nitride known by the formula Ti,N, of Friesel and Guérin. This nitride will
contain impurities consisting of carbon, and small amounts of silicon and iron, if
produced by treating rutile or natural oxide of titanium.
With an engine of 45 horse power, it has hitherto been found possible to produce
only a fused nitride of titanium. In order to produce the real fused titanium, it is
absolutely necessary that the temperature produced by the electric arc shall exceed
the temperature of decomposition by heat of the nitride of titanium. To produce
this result, there is required an arc of 1000 to 2000 ampères and of 60 to 70 volts.
Under these conditions the aforesaid mixture of 330 parts by weight of rutile and
96 parts by weight of carbon heated in a carbon crucible yields after a period of

page_text: 10 minutes, a mass the upper part only of which is fused, and which has the following
characteristics:-A fused mass covered with a yellowish layer of oxide, having a
white fracture bright or shiny and having "a metallic appearance.
Under the
hammer it becomes reduced to powder, it is acted on by dilute hydrochloric acid,
whilst the carbide TiC, and the nitride Ti,N, are not acted upon thereby.
This titanium produced by direct reduction of titanic acid by means of carbon,
contains varying percentages of carbon which may amount to from 2% to 6%
according to the care given to the process. The product containing 2% of carbon
is sufficiently pure for industrial purposes.
Titanium of still greater purity can be produced by remelting this titanium, in a
crushed state and in the presence of titanic acid by means of an arc of the same
intensity as last herein mentioned.
If the amount of carbon added to the titanic acid be increased, there will be
obtained, according to the formula TiO, + 3 C = TiC + 2 CO, a definite carbide,
which is found by analysis to be expressed by the formula TiC. This compound
is crystalline; it has the colour of galena, and possesses a specific gravity of
about 4.3.
The fused carbide, as also the fused nitride hereinbefore referred to, may be
applied to industrial purposes which will readily suggest themselves.
In these reactions I may substitute for titanic acid, an oxide of titanium, or any
salt natural product, or other compound containing titanium. Titanium thus
produced may be melted in the electric furnace or by other means, in the presence
of iron or of any other metal, so as to produce alloys having new properties.
An alloy of titanium and iron, or of titanium and nickel, is soluble in molten
iron, cast iron, or steel. Thus I have been able to produce with ease titanium
steels.
I may modify this mode of preparation as follows:-
I place in the crucible in the electric furnace the whole or a part of the amount
of metal which it is desired to alloy with titanium, and I melt it down gently.
I then add to it gently, an agglomerate of oxide of titanium or of rutile, and carbon
or other suitable reducing agent, in proportions determined by the richness or
percentage of the alloy it is desired to produce.
These agglomerates are composed of oxide of titanium, rutile, or other ore of
titanium, and carbon, mixed with any suitable agglutinant or binding agent, in
order that the same may be moulded or formed into small pieces, cakes or cylinders
of any desired shape and which are then carefully dried. The alloys thus obtained
over or on a metallic bath, are very homogeneous, of constant or uniform composition,
and can be cast.
Dated shin 10th J
100%
Manufacture or Production of Titanium and Carbide thereof.
I, HENRI MOISSAN, of 15 Rue des Halles, Paris, France, do hereby declare the
nature of this invention and in what manner the same is to be performed to be
particularly described and ascertained in and by the following statement :-
Heretofore, titanium has been merely a laboratory curiosity, indeed it may even
be said that pure titanium has never hitherto been produced. The reason for this
lies in the very strong affinity of titanium for nitrogen. Furthermore, it has not
heretofore been possible to obtain fused titanium.
Berzelius, in attacking the fluo-titanate of potassium, and the chloride of
titanium, with potassium, obtained a dark powder which, on trituration, turned to

page_text: a red colour. This powder, which Berzelius supposed to be titanium, was, however,
for the greater part nitride of titanium. Wahler and Deville, in employing the
same reaction in a current of hydrogen, produced a grey powder which decomposed
water at 100° C., and which they supposed to be titanium, without, however, giving
any analysis. Kern produced in a porcelain tube by the action of vapour of
titanium upon sodium contained in a small dish, a grey powder which did not
decompose water below 500° C.
These various samples of titanium were however impure. In fact the alkaline
metals have up to the present time only yielded, by the reduction of compounds of
titanium, a grey powder which does not show any trace of fusion, and contains
sodium or potassium, nitrogen, and often other impurities.
Titanic acid has heretofore been supposed to be incapable of reduction by means
of carbon. But-this is not the case.
I have already shown, by numerous experiments, that the oxides of uranium,
vanadium, and zirconium, and also silica, which was supposed to be irreducible,
could be reduced by means of carbon if the temperature were sufficiently high.
Similarly, titanic acid, whether such as occurs in nature, or such as
prepared in the pure state, can be reduced by means of carbon under the conditions
hereinafter set forth.
can be
If in the electric furnace that I have invented (see "Comptes Rendus de
l'Academie des Sciences," 1892), or in any other suitable electric furnace, there be
melted down by means of an electric arc of about 400 ampères and 80 volts, a
mixture of pure titanic acid and carbon in the proportions indicated by the formula
TiO2 + 2 C, there will be obtained a very hard fused mass which will readily
scratch the ruby, has a yellow fracture, and is of a reddish brown colour; it consists
of nitride of titanium, containing 79 to 80% of titanium and having a specific
gravity of from about 5.02 to 5.15. This compound is analogous to the nitride
known by the formula Ti,N, of Friesel and Guérin. If produced by treating rutile
or natural oxide of titanium (instead of the pure oxide) the nitride will coutain
impurities consisting of carbon and small amounts of silicon and iron.
With an engine of 45 horse power, it has hitherto been found possible to produce
only a fused nitride of titanium. In order to produce fused titanium itself it is
essential that the temperature produced by the electric arc shall exceed the
temperature necessary for the decomposition by heat of the nitride of titanium.
To produce this result, there is required an arc of 1000 to 2000 ampères and of
60 to 70 volts. Under these conditions a mixture of 330 parts by weight of rutile
and 96 parts by weight of carbon, heated in a carbon crucible, yields, after a period
of 10 minutes, a mass the upper part only of which is fused, and which has the
following characteristics :-A fused mass covered with a yellowish layer of oxide;
having a white fracture, bright or shiny, and having a metallic appearance. Under
the hammer it becomes reduced to powder, and is acted upon by dilute hydrochloric
acid, whilst the carbide, T₁C, and the nitride Ti,N,, are not acted upon thereby.
Titanium thus produced by the direct reduction of titanic acid by means of
carbon contains varying percentages of carbon, which may amount to from 2 to 6%,
according to the care given to the process. The product containing 2% of carbon
is sufficiently pure for industrial purposes.
Titanium of still greater purity can be produced by remelting the said titanium
in a crushed state and in the presence of titanic acid by means of an arc of the
same intensity as last herein mentioned.
If the amount of carbon added to the titanic acid be increased, there will be
obtained, according to the formula TiO, +3 C: TiC + 2 CO, a definite carbide,
which is found by analysis to be expressed by formula TiC. This compound is
crystalline, has the colour of galena, and possesses a specific gravity of about 4.3.
The fused carbide, as also the fused nitride berein before referred to, may be
applied to various industrial purposes, which will readily suggest themselves.
In the above reactions, I may substitute for titanic acid, another oxide of
titanium, or any salt, natural product, or other compound containing titanium.

page_text: Titanium produced as described, may be melted in the electric furnace or by
other means, in the presence of iron or of any other metal, so as to produce alloys
therewith having new properties.
An alloy of titanium and iron, or of titanium and nickel, is soluble in molten
iron, cast-iron, or steel. Thus I have been able to produce, with ease, titanium
steels.
I may modify this mode of preparation as follows:-I place in the crucible in
the electric furnace, the whole or a part of the amount of metal which it is desired
to alloy with titanium, and I melt it down gently. I then add to it gently, an
agglomerate of oxide of titanium, or rutile, and carbon (or other suitable reducing
agent), in proportions determined by the richness or percentage of the alloy it is
desired to produce. The agglomerates are composed of oxide of titanium, rutile,
or other ore of titanium, and carbon mixed with any suitable agglutinant or binding
agent in order that the same may be moulded or formed into small pieces, cakes, or
cylinders of any desired shape, which are then carefully dried. The alloys thus
obtained over or on a metallic bath, are very homogeneous, of constant or uniform
composition, and can be cast.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed I declare that what
I claim is :-
The manufacture or production of fused titanium (whether pure or in the form
of a carbide) by reducing an oxide or other compound of titanium, by means of
carbon with the aid of an electric arc producing a temperature exceeding the
temperature necessary for the decomposition of nitride of titanium, substantially
as herein described.
Dated this 24th day of July 1895
F. WISE HOWORTH,
46, Lincoln's Inn Fields, London, W.C., Agent for the Applicant.