Manufacture or Production of Substances of Extreme Hardness.
Year: 1893

page_text: Date of Application, 14th Aug., 1893
Complete Specification Left, 15th May, 1894-Accepted, 14th Aug., 1894
PROVISIONAL SPECIFICATION.
Manufacture or Production of Substances of Extreme Hardness.
I, FRÉDÉRIC CHAPLET, of 15 Rue des Halles, Paris France, Electrician, do
hereby declare the nature of this invention to be as follows:-
This invention relates to the manufacture or production of certain new hard
substance capable of scratching chrome-steel, the ruby and the diamond, and
suitable for cutting, polishing and abrading purposes, either in a powdered or
divided form, or in the form of a grind-stone, or applied to material such as paper
or cloth.
The new substances or compounds produced according to this invention
comprise silicide of titanium, boride of titanium, and silicide of carbon, boride
of carbon, boride of silicon, and other varieties of silicides and borides, silicic-
carbides and silicic-borides of titanium, and boric-carbide of aluminium.
These compounds are obtained in the crystallized state, but they may also
be obtained in the form of an uncrystallized melted mass, by operating in the
presence of one of the constituents when the said constituent is fusible.
To produce, for instance silicide of titanium, I proceed as follows:-
I mix about 82 parts of rutile in coarse powder with about 60 parts of sand or
crushed quartz and about 48 parts of powdered coke or carbon. The dry mixture
is pressed into a carbon crucible placed in an electric furnace provided with movable
electrodes, such for example as the electric furnace employed by Mr. Moissan in
the artificial production of diamonds. The furnace after being closed is heated
for a longer or shorter period of time, according to the strength of the
electric arc.
In this manner there is obtained a melted grey mass having a bright fracture, of
great hardness, and of a density of about 4-8, and which, according to the duration
of the heating operation may contain in addition to the titanium and silicon,
about 20 to 25% of carbon, and also varying amounts of nitrogen. The same
substance can be obtained in a crystallized state by using a metal, in a state
of fusion, as a solvent, and afterwards removing the metal by means of a
suitable acid. Boride of titanium, carbides of silicon, and borides of silicon,
are also obtained by the same process, either in the crystallized or uncrystallized
state.
The process described may also be employed for producing different varieties of
borides and silicides, which have in common with boride of titanium or of silicide of
titanium the character of being formed by an igneous process at a very high
temperature, and of possessing the extreme hardness sought for.
To obtain, for example boride of carbon in the crystallized state, I proceed as
follows:-
1. By direct union of boron and carbon, the mixture prepared as above described,
being heated in an electric furnace. After the process has been completed the
current stopped and the mass allowed to cool, there is found at the bottom of the
crucible, a crystalline substance which, after being washed with hydrochloric acid,
and decanting the same, consists of boride of carbon which is a perfectly new and
clearly defined substance.
2. By directly uniting boron and carbon as before and then melting the resulting
compound in a fusible metal, such as iron, capable of dissolving boride of carbon.
After cooling, there is obtained a metallic residuum from which the boride of

page_text: carbon (which is insoluble in acids) is obtained by dissolving the solvent metal by
the action of hydrochloric acid.
3. By forming boride of carbon by means of a borate and then dissolving the
resulting boride in a metal or in a compound thereof. For this purpose a mixture
is made of borate of lime, carbon, and pieces or powder of malleable iron or cast
iron. The crucible containing the mixture is placed in the electric furnace and
heated for a longer or shorter period, according to the strength of the arc,
say for 15 to 20 minutes with a current of 40 amperes and 100 volts. After
cooling treating the mass with acid, washing and decanting, there is obtained
crystallized boride of carbon. The hereinbefore described method allows of
obtaining very hard borides and carbides of boron, and even the boric-carbide of
aluminium of Henri Saint-Claire-Deville, and also boride of silicon in crystals,
either transparent when in the pure state, or colored when they contain a small
quantity of metal, or for producing melted masses when the mixture employed
contains silicon in excess. Boride of silicon may however be obtained also in the
crystallized state or in the form of an uncrystallized melted mass, by heating in
the crucible of the electric furnace, a mixture of borate of lime, silica and carbon, the
carbon acting to reduce the silica. This latter mixture may also be heated in
the presence of iron or other metal acting as a solvent.
The herein described processes allow of producing silicide of carbon under the best
conditions. It is merely necessary to heat in the crucible of the electric furnace a
mixture of silica and carbon in the presence of iron or other metal acting (as above
stated) as a solvent. The said processes also allow of obtaining certain metallic
silicides, particularly those of zirconium, chromium, iron, nickel, cobalt, manganese,
molybdenum, tungsten, uranium, and vanadium, which may have in admixture
varying amounts of carbon and nitrogen.
Dated this 14th day of August 1893.
F. CHAPLET,
By L. W., per F. B.
COMPLETE SPECIFICATION.
Manufacture or Production of Substances of Extreme Hardness.
I, FRÉDÉRIC CHAPLET, of 15 Rue des Halles, Paris, France, Electrician, do
nereby 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:-
This invention relates to the manufacture or production of certain new hard
substances capable of scratching chrome-steel, the ruby, and the diamond (some of
the said substances being capable of even cutting the last two of the said bodies),
and suitable for cutting, polishing and abrading purposes either in a powdered or
divided form, or in the form of a grindstone; or applied to material such as paper
or cloth. The new substances or compounds produced according to this invention
comprise silicide of titanium, boride of titanium, silicide of carbon, boride of carbon,
boride of silicon, and other varieties of silicides and borides, silicic-carbides and
silicic-borides of titanium, and the silicides, boro-silicides and silico-carbides of
other metals and metalloids.
To produce for instance silicide of titanium I proceed as follows:-I mix about
82 parts of rutile in coarse powder with about 60 parts of sand or crushed quartz,
and about 48 parts of a reducing agent, for example powdered coke or carbon.
The dry mixture is pressed into a carbon crucible which is then placed in an
electric furnace provided with movable electrodes, such for example as the electric
furnace employed by M. Moissan in the artificial production of diamonds. The
furnace, after being closed, is heated for a longer or shorter period of time,
according to the temperature of the electric arc employed. In this manner there

page_text: is obtained an amorphous grey mass which possesses a bright fracture, great.
hardness, and a density of about 4-8 and which, according to the duration of the
heating operation, may contain in addition to the titanium and silicon, about 20 to.
25% of carbon and also a variable amount of nitrogen.
The same substance can be obtained in a crystallized state by using a metali
in a state of fusion, as a solvent or medium in which the substance can assume a.
crystalline forn, and afterwards removing the said metal by means of a suitable
acid.
Boride of titanium, carbides of silicon, and borides of silicon, can also be obtained:
by the same process, either in the crystallized or the amorphous state. Thus,
boride of titanium is produced by the direct union of about 90 parts of boron and.
about 260 parts of rutile.
The processes described may also be employed for producing different varieties.
of borides and silicides, which have, in common with boride of titanium and silicide
of titanium, the character of being formed by an igneous process at a very high
temperature, and of possessing the extreme hardness sought for.
To obtain, for example, boride of carbon in the crystallized state, I proceed as.
follows:-
1. By the direct and simple union of boron and carbon say in the proportion of
44 parts of boron to 40 parts of carbon, the mixture being prepared as hereinbefore
described and heated in an electric furnace. After the process has been completed,.
the current stopped and the mass allowed to cool, there will be found at the
bottom of the crucible, a crystalline substance which, after being washed with
hydro-chloric acid and the acid decanted consists of boride of carbon, which is a
perfectly new and clearly defined substance.
2. By directly uniting boron and carbon as before, and then melting the resulting
compound in a fusible metal, such as iron, capable of dissolving boride of carbon..
After cooling, there is obtained a metallic product from which the boride of carbon,.
which is insoluble in acids, is obtained by dissolving the solvent metal by the action.
of hydrochloric acid.
3. By forming boride of carbon by means of a borate and dissolving the resulting
boride in a metal or in a compound thereof. For this purpose a mixture may be
made consisting of about 70 parts of borate of lime, about 50 parts of carbon and
pieces or powder of malleable iron or cast iron. The crucible containing the
mixture is placed in an electric furnace and heated for a longer or shorter period,
according to the strength of the arc, say for 15 to 20 minutes with a current of
40 amperes and 100 volts. After cooling, treating the mass with acid, washing,
and decanting, there is obtained crystallized boride of carbon.
By the herein before described processes firstly there may be obtained very hard
borides, and carbides of boron, and even the boric-carbide of aluminium of
Henri Saint Claire-Deville, and also boride of silicon or silicide of boron in
crystals, either transparent when in the pure state, or coloured when they contain
a small quantity of a colouring metal; and, secondly when the mixture employed
contains silicon in excess, there may be produced amorphous masses. Boride of
silicon may however be obtained also in the crystallized state or in the form of an
amorphous mass, by heating in the crucible of an electric furnace, a mixture of
borate of lime, silica and carbon, the carbon acting to reduce the silica. This latter
mixture may also be heated in the presence of iron or other metal acting as a solvent
or vehicle in which the boride can assume the crystalline form.
To obtain silicide of boron by direct union, a mixture is made of about 45 parts
of boron and about 80 parts of silicon. To obtain it by means of silica and boron,
about 90 parts of boron are mixed with about 180 parts of silica.
The herein described processes enable also silicide of carbon to be produced under
the best conditions. For this purpose it is merely necessary to heat in the crucible
of the electric furnace a mixture of silica and carbon in the presence of iron or
other metal acting, as above stated as a solvent or vehicle for the silicide.
To obtain silicide of carbon by direct union, a mixture of about 28 parts of

page_text: silicon and about 15 parts of carbon is employed, the mixture being heated in an
electric furnace in the manner herein before explained. It may also be obtained by
means of silicon and carbon with the addition of siliconized iron, the mixture then
consisting of about 28 parts of silicon, 15 parts of carbon, and about 50 parts of
siliconized iron. Silicide of carbon may also be produced by means of silica,
carbon, and siliconized iron; in this case the mixture consists of about 60 parts
of silica, about 40 parts of carbon, and about 100 parts of siliconized iron.
By the said processes there may also be obtained certain metallic silicides,
particularly those of zirconium, chromium, iron, nickel, cobalt, manganese,
molybdenum, tungsten, uranium, and vanadium, which may be mixed with variable
amounts of carbon and nitrogen.
It should be noted that the hereinbefore described substances can be produced in
the presence of an excess of one or other of their constituents.
Although rutile is the only form of titanic oxide herein referred to and is in
most cases the most suitable, being the most abundant and the cheapest, it will
of course be understood that anatase, brookite, or other form of titanic oxide may be
substituted for the rutile used according to this invention.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture or production of hard substances capable of scratching
chrome-steel and of scratching or cutting the ruby and diamond, by subjecting a
mixture composed of the component materials to form the required substance, with
or without a reducing agent, as may be required, and whilst within a crucible,
to the heat of an electric furnace in such a manner as to obtain the desired
substance in a pure crystallized state, or in an amorphous state, or in a melted state
in a metal capable of acting as a solvent or vehicle in which the said substance can
crystallize and from which it is obtained in the form of hard crystals by removing
the metal by an acid, the process being effected (a) by the direct and simple union
of the mixed materials; (b) by the direct union of the mixed materials in the
presence of an excess of metal which is subsequently removed by means of an acid;
or (c) by forming the substance by reduction of an oxide or salt of one of its
constituents and dissolving the resulting compound or substance in a metal from
which it is subsequently obtained by removal of the metal all substantially as
hereinbefore set forth.
2. The several new hard substances produced by the hereinbefore described
processes viz. the silicide and the boride of titanium and other varieties of silicides
and borides, the silico-carbides and the silico-borides of titanium, and the silicides,
boro-silicides and silico-carbides of other metals and metalloids the said substances
being capable of scratching chrome steel, and of scratching or cutting the ruby and
diamond and being suitable in the form of powder, a grindstone, or applied to paper
or cloth, for use as a cutting, polishing or abrading agent.
Dated thie 15th day of May 1891
Deted thie 15th day of May 1801
For the Applicant,
W. LLOYD WISE,
46, Lincoln's Inn Fields, London, W.C., Chartered Patent Agent.