Improvements in Alloys of Titanium and Processes for Producing same,
Year: 1898

page_text: Date of Application, 23rd Aug., 1898-Accepted, 29th Oct., 1898
COMPLETE SPECIFICATION.
Improvements in Alloys of Titanium and Processes for Producing
same,
We, AUGUSTE JACQUES ROSSI, Metallurgist, of 134, West 83rd Street, JAMES
MACNAUGHTON, Engineer, of 1, West 30th Street, and WALTER DUMAUX EDMONDS,
Lawyer, of 31-33, Nassau Street, all of the City, County, and State of New York,
United States of America, do hereby declare the nature of this invention and in
what manner the same is to be performed to be particularly described and ascer-
tained in and by the following statement, that is to say:-
-
The object of our invention is to produce in an economical and effective manner
an alloy or compound of titanium and iron, associated with as small a quantity
of carbon as can be conveniently and practically effected, and in which the
titanium is contained in industrially important quantities, that is to say, not less
than five per centum of the mass, and the iron also enters into the compound in
substantially important quantities, constituting, say for instance, not less than
ten per centum of the mass, and which iron thus serves as a vehicle for the
titanium of the compound. Such a compound may be fitly termed a ferro-titanium
alloy, and in the production of this novel article we make use of our new
processes hereinafter described.
It has long been known that iron, cast iron, steel and the like, derived from
titaniferous iron ores, possessed in a remarkable degree the qualities of strength
and toughness. But the expense and difficulties of treating such titaniferous
ores had proved practically insurmountable until our invention, of the process
for reducing such ores, secured to us by Letters Patent of Great Britain, No. 21761,
dated November 29th, 1892. By means of the process last mentioned it has been
rendered possible to obtain iron from such titaniferous ores and such iron has
contained, accidentally, or incidentally, to its great advantage, a very small
inherent quantity of titanium, exceptionally one per centum of the entire mass, or
possibly a little more than that. Notwithstanding the small quantity of titanium
thus combined incidentally with the iron thus reduced from such titaniferous
ores, the special qualities of resistance and hardness have been so noticeable in
such iron as to render it desirable to produce, if possible, an article containing
titanium in industrially important quantities that is to say not less than five per
centum of the weight of the mass so as to insure its utilization in the treatment on
an industrial scale of large bodies of ordinary iron and steel not containing
titanium.
Until recently it has proved substantially impossible to produce metallic
titanium to any extent whatever; now, however, as is well understood, small
quantities of that metal have been produced in the laboratory by subjecting rutile
in the presence of carbon to the intense heat of an electric arc of extremely high
amperage, but at an expense entirely prohibitory, as far as commercial production
for use in the industrial arts and manufactures was concerned.
I, the said Auguste Jacques Rossi, have discovered that so far as the application
of titanium in the improvement of iron and steel is concerned, the same advantages

page_text: may be secured by producing preliminarily, instead of separate metallic
titanium, a combination of iron and titanium, containing incidentally though not
designedly more or less carbon, the titanium being present in such industrially
important quantities, say not less than five per centum of the entire mass, as to
justify the designation of such combination as an alloy of titanium,. and I have
also discovered that such combination or alloy may be economically and success-
fully produced by subjecting to an intense heat, say at or above the melting
point of platinum, in the presence of carbon, a mixture of molten iron and some
highly titaniferous compound, not necessarily containing iron, such as titanium
dioxide, or a highly titaniferous slag, not necessarily containing iron, with metallic
iron or iron in ore, or with a highly titaniferous iron ore containing both iron and
titanium and in which the oxide of iron being first reduced by carbon to the state
of iron may form the vehicle or support for titanium without the addition of, pig
iron, provided the said elements are during the exposure to the said heat so long
and so supported in relation to each other as to ensure the reduction of the
titaniferous compound while surrounded by and in a bath of the molten iron,
so as to ensure the combination with the iron of the titanium reduced from the,
titanic compound by the action of the carbon under said heat.
森
Metallurgists, will, of course, understand that it is impossible to prescribe any
absolute rule or ratio of proportion for the various elements used in the production
of my novel alloy, containing titanium in industrially important quantities,,,by
the processes which I have discovered. Such proportions and ratios will, of
course, vary more or less, according to the special conditions of each particular
case. It seems enough for me to state that the alloy in question may be success-
fully produced as follows:
+i
First One way of producing my novel manufacture or alloy is to mix together
carbon and some one of the titaniferous or well known ilmenite ores containing
a large amount, say 35 to 60 per centum and more of iron in the form of iron
oxides, and some 10 to 20 and even 48 per centum of titanic acid; and to subject
continuously the aforesaid mixture to any very high temperature, say at or above
the melting point of platinum, or, say not less than 3500 degrees Fahrenheit,
such as may be attained for instance by the use of an electric current or other
means; from which treatment and process it is possible to secure a compound
of iron and titanium containing from 8 to nearly 30 per centum of titanium,―
ferro titanium.
To illustrate with even greater definiteness the principles involved in my
improvements, I call attention to the following specific combinations of elements
and ingredients which I have found successful in producing my desired novel
alloy. I have, for instance, found it useful to intimately mix together ilmeno-
rutile, a mineral containing some 10 per centum of oxide of iron and 90 per
centum of titanic acid, with powdered charcoal and molten iron in about the
following proportions, viz:
Ilmeno rutile
Charcoal
Cast iron
and the balance silicon and carbon.
:
16 containing 8.64 titanium
5
100 containing about 95% iron,
I support this mixture so that the constituents 'may be retained in contact with
k athan while ented unan
11

page_text: Second: I have likewise found it useful to make an intimate mixture of highly
titaniferous iron ore, containing 20 per centum titanic acid, and some 60 per
centum of metallic iron, with powdered charcoal in substantially the proportions
of 100 parts of said ore to 25 parts of such charcoal; and, as aforesaid, supporting
and submitting same to heat or electric current of similar intensity as in the
previous treatment described, it will be found that almost instantly the iron-
oxide will be reduced and run off in globules, forming a metallic bath or support
of molten iron and that, after some ten minutes of further action, there will be
obtained a clean, well melted mass of iron of fine grain, very hard, analysing as
follows:-
Carbon
25
Pig iron 100, containing about 3.50 to 4 per centum carbon, some three
per centum of silicon, the balance, about 93 per centum being iron.
Subjecting this again to the aforesaid heat or action of the electric current
specified as used in the previous cases there may be obtained, in less than ten
minutes, large, well melted globules of the alloy, clean from slag, and showing
a silvery fracture which, analyzed, will contain substantially as follows, viz.:
Titanium
Silicon
Iron
Carbon
27.53
2.30
59.15
10.41
The silicon appearing in the resultant alloy, is, in this instance, supplied by the
pig iron:
Fourth I have also found it useful in producing my desired compound, to
still further vary the treatment as follows, viz: Taking the aforesaid highly.
titanic slag as the main source of the supply of titanic acid and intimately mixing
the same, together with the proper amount of carbon, and adding the aforesaid
titaniferous ores as an ingredient (instead of the pig iron last aforesaid said ore
containing say 20 per centum of titanic acid and say 60 per centum of iron, in
the proportions of approximately 125 parts of said slag to 160 parts of said ore
intended to supply, by its reduction to iron by charcoal, the iron necessary to form
the titanium alloy, and, as aforesaid, supporting and subjecting such mixture to
the aforesaid heat of an electric current as aforesaid equally satisfactory results
will be obtained, as in the previous treatment.
Further instances might doubtless be multiplied, but the foregoing I deem amply
sufficient to instruct persons, skilled in metallurgy, in methods whereby can be
produced my novel manufacture or compound of iron and titanium in industrially

page_text: important quantities. It should be observed generally, that in every case the
quantity of titanium in my novel article will depend upon the proportional
amount of the titaniferous ores, slag, molten iron, or ilmeno-rutile added, and that
the production of the titanium can be consequently varied, within wide limits,
to suit each particular case it being understood that the object of my invention
is to produce the alloy referred to containing such a proportion of titanium as
to be of industrial importance; that is to say, not less than five per centum of the
mass in any case.
Care will, however, he observed to so regulate the proportions and support the
mixture that a sufficient amount of molten iron as a bath may be retained con-
tinuously present to serve as the vehicle or inducement for the otherwise indus-
trially impracticable reduction, melting or fusing of the titanium, and care will
also be taken to regulate the amount of carbon by experiment, to meet the varying
requirements of different ores, slags, irons, or other ingredients which may be
involved in each instance.
For the purpose of producing the bath of molten iron referred to any con-
venient iron may be employed, as for instance, cast iron may be used providing
it is low in silicon, such for instance, as the cast iron produced from titaniferous
ores through my patented process referred to, and in such case cast iron will be
of advantage as contributing, to the mixture, part of the carbon requisite for
the reduction of the oxide of titanium; or, on the other hand, where such cast
iron is not available any form of wrought iron with added carbon may be
employed. In other cases the bath will be furnished or produced by the iron
derived from the reduction of the iron oxide of the ore by carbon as aforesaid,
but I prefer, so far as my experience has gone, to use in every instance, a bath
or vehicle produced, or at least partly produced, by the direct addition of some
iron, to the mixture.
I prefer to produce this novel manufacture of mine to-wit, my ferro-titanium,
by treatment with an electric current as aforesaid. As I have intimated, however,
I believe that the temperature required in these conditions of treatment is below
that generated by electricity, and that my process may be successfully applied by
the use of temperatures sufficiently high otherwise derived; such as, for instance,
by the use of the oxhydric flame or in an open hearth furnace, utilizing a producer
gas, or otherwise, in any other well known way for securing temperatures as
high at least as the melting point of platinum or say not less than 3500 degrees
Fahrenheit.
The utility of the novel product of my process will be manifest. My ferro-
titanium incorporates in itself, and in such constituent combination and quantity
with other metals as to be readily utilized in the manufacture of iron and steel,
the much desired titanium. The accompanying iron is in no way detrimental
in such application, and the compound thus economically and readily produced
will enable the iron and steel worker to conveniently and economically incorporate
into his molten metals and their resultant products such proportion of titanium
as is required in order to impart the desirable qualities resulting from the
incorporation of this particular metal.
It will of course be understood that as convenience or other conditions may
dictate the iron to be utilized as the supporting bath when molten, may be either
preliminarily reduced to the molten condition, after which the other ingredients
are added, or may be, in the first instances, introduced cold as pig or other iron in
the charge simultaneously with the other ingredients, it being of course more readily
affected by the heat than the others and reduced to molten condition before any
of the subsequent re-actions take place. My invention does, however, involve
the continuous support of the ingredients and constituents referred to in operative.
relation to each other while exposed to the aforesaid heat, until the re-actions
shall have been duly accomplished, since without such support and retention, the
production of the alloy in question containing titanium in industrially important
quantities would be impracticable.

page_text: I have spoken in this specification of my preference for utilizing the electric
current as the source of the high temperatures to which I have referred. This
may be done in any of the numerous well-known ways which may prove most
convenient according to circumstances. For instance, there may be employed a
form of "electric furnace" so-called consisting broadly of bottom, walls, and a
removable cover of refractory material, enclosing a central cavity or chamber
containing a covered pot or crucible, within which crucible are charged the
materials to be treated. Electrical insulation of the furnace having been secured
in any convenient manner, the electrodes are introduced through proper openings
into said chamber through the walls of the furnace, and, intermediate between
said walls and the inner crucible, is packed a quantity of coarsely broken frag-
ments of charcoal. The electric current being now supplied, the crucible and
its contents will be raised to the high temperature necessary for the latter's
reduction. Such an apparatus as I have described may be used to melt one
charge after another, or preferably in any convenient way, adapted to operate in
a continuous manner as by providing a proper inlet for the materials and a
suitable outlet for the melted products. By the use of such contrivance I have
succeeded in obtaining as the result of one charge from fifty to one hundred
pounds of my ferro-titanium alloy, containing fifteen per centum of metallic
titanium.
The accompanying drawing will serve to illustrate one form of such an
apparatus, whereby the heat of the electric current may be utilized as aforesaid.
The drawing in question illustrates a central vertical cross-section, the transverse
cross-section at right angles to this one being substantially similar, except that
it does not show the carbon electrodes. A represents a graphite crucible; B the
removable cover; C the furnace proper, constructed preferably of refractory
material, such as magnesia brick, or, less refractory material might be employed
and provided with a refractory lining; D D are electrodes, connected with proper
source of electrical current and so arranged as to be movable and adjustable,
such arrangement, as is well understood, being necessary in order to initiate the
arc. Loosely packed between the exterior walls of the crucible and the interior
of the furnace proper and the electrodes, is a quantity of small pieces of char-
coal, EE, .tending to produce a multiplicity of sub-arcs. F is the cover of the
furnace, likewise constructed of some highly refractory material. The furnace
and crucible being uncovered, the elements of the charge are placed in the latter
as aforesaid, the covers are restored to position, the electric current turned on,
and the electrodes properly adjusted until the arc has been started inside of the
furnace, whereby the crucible and its contents are raised to the high temperature
required for the operation of my process and the production of my novel product
as aforesaid. After the requisite temperature has been sufficiently maintained
the covers are removed, the crucible lifted out, and the product cast in an ordinary
mould, and a new charge inserted. By the use of such apparatus I have succeeded
in obtaining in a ferro-titanium alloy 43 per centum of titanium, and some 49
or 50 per centum of iron; and by using apparatus slightly varying in details
there has been obtained by the application of my said process, and as the result
of a single charge, between 50 and 100 pounds of my ferro-titanium alloy.
I am aware that it has been sought to produce an alloy of titanium and iron by
mixing with molten pig iron while cooling titaniferous iron sand to produce a
species of briquettes, and thereafter charging a blast furnace or cupola in part
with such briquettes, the oxide of titanium being in such case unable, to a great
extent, if not entirely, to be reduced by the carbon while in the furnace, until, at
least if at all, after the pig iron forming the briquette has melted, at which point,
owing to its specific gravity and condition of non-support in the blast furnace or
cupola, the said pig iron will immediately drop into the hearth, leaving the
titaniferous sand by itself in the same condition as any other ore charged directly
in the furnace with the fuel and fluxes.
I am also aware that it has been asserted that a so-called "ferro-titanium"

page_text: has been heretofore exhibited in small irregular lumps up to, say one inch cube,
and said to contain twenty-two per centum titanium, but I am not aware that any dis-
closure has been made respecting the composition of, or possibility of producing,
such article, nor that it has even been utilized except as a metallurgical curiosity.
I am aware that a so called alloy of titanium and iron has been heretofore
directed to be produced by smelting in a blast furnace iserine, which is a
naturally pulverized titaniferous iron ore consisting essentially of titanic acid
and oxide of iron, and that as aforesaid a pig metal containing but a very small
quantity of titanium has resulted from the application of my process of reducing
titaniferous iron ores described in my said Letters Patent No. 486,941, but I do
not know that in either of these cases it has been possible to produce a mixture
which could be properly termed an "alloy," that is containing titanium in
commercially important proportions, nor indeed in any more than merely inci-
dental quantity, say, exceptionally even, not to exceed one to two per centum of
the entire mass of the mixture or resulting pig metal, and thus entirely insufficient
to be useful for the purpose of seasoning with its surplus titanium other non-
titaniferous iron, nor, should it prove that in some cases the smelting of iserine
has produced an alloy containing titanium in greater proportion, am
aware that
such useful result has been heretofore accomplished or been possible prior to my
invention, by the use of any other materials or elements than those specifically
constituting such iserine and in their specific natural physical condition and
arrangement. I am also aware that it has hitherto been suggested that the
reduction of titanium might be possibly accomplished by subjecting some refrac-
tory metallic compound containing it, comingled with subdivided carbon, but
without the presence of molten iron, to the electrolytic action of an arc whose
electrodes are separated one above the other.
"
I am also aware that "minute residues" containing a large proportion of so-
called "carbide of titanium are asserted to have been separated from their
containing pig iron, but only in quantities so insignificant as to be "barely
sufficient for a microscopic slide." It is also asserted that the quantitative analysis
of such carbides has disclosed the presence of iron, but the proportion of this
has been so minute, less than four per centum of the mass, as to preclude its
practical operation in any sense as a vehicle in the way in which I use it, and to
justify its being regarded merely as one of the number of impurities associated
with the carbide. I do not therefore now wish to be understood as claiming any
of these prior matters as constituting any part of my invention.
Having now particularly described and ascertained the nature of our said inven-
tion, and in what manner the same is to be performed, we declare that what we
claim is
1. The process of producing a new compound or alloy of titanium and iron,
containing some carbon, and titanium in industrially important proportions, that
is. to say in excess of five per centum of titanium, which consists in supporting
in a bath of molten iron and while subjected to intense heat, say not less than
3500 degrees Fahrenheit, a mixture of carbon and of titanic acid, substantially
as, and for the purposes described.
2. The process of producing a new compound or alloy of titanium and iron,
containing some carbon, and titanium in industrially important proportions, that
is to say in excess of five per centum of titanium, which consists in supporting
in a bath of molten iron and while subjected to intense heat, say not less than
3500 degrees Fahrenheit, a mixture of carbon and of a compound, containing
titanic acid as one of its important constituents, substantially as and for the
purposes described.
3. The process of producing a new compound or alloy of titanium and iron,
containing some carbon, and titanium in industrially important proportions, that
is to say in excess of five per centum of titanium, which consists in supporting
in a bath of molten iron and while subjected to intense heat, say not less than

page_text: 3500 degrees Fahrenheit, a mixture of carbon and titaniferous iron ore, substan-
tially as and for the purposes described.
4. As a new article of manufacture, a new compound containing an important
quantity of iron, say not less than ten per centum of the mass, some carbon, and
titanium in industrially important proportions, that is to say, not less than five
per centum of the mass, substantially as and for the purposes described.
5. The process of producing a new compound or alloy of titanium and iron,
containing some carbon and titanium in industrially important proportions, that
is to say, in excess of five per contum of titanium, which consists in supporting
in a bath of molten iron and while subjected to intense heat, say not less than
3500 degrees Fahrenheit, a mixture of carbon and highly titaniferous slag, sub-
stantially as and for the purposes described.
Dated this 23rd day of August 1898.
EDWARDS AND Co.,
65 and 66, Chancery Lane, London, Agents for the Applicants.