New or Improved Manufacture of Smokeless Powder and High Explosives.
Year: 1892

page_text: Date of Application, 14th Apr., 1892
Complete Specification Left, 16th Jan., 1893-Accepted, 14th Apr., 1893
PROVISIONAL SPECIFICATION.
New or Improved Manufacture of Smokeless Powder and High
Explosives.
We, JOSEF Kallivoda Vox FALKENSTEIN, of Vinkovce, Croatia, Austria,
Pharmaceutical Chemist, and ARNOLD MICHAEL BÖHM of Rathhausstrasse 2
Vienna I, Austria, Gentleman, do hereby declare the nature of this invention to be
as follows:-
This invention has reference to the manufacture of smokeless powder and high
explosives. According thereto natural fibrous, but preferably amorphous cellulose,
is nitrated, and then placed in a solution of potassium permanganate in order to
obtain a uniform product not liable to decompose. Nitric acid is then added to the
mixture for the purpose of neutralising the alkali formed, the nitro-cellulose mixed
with hydrated oxide of manganese is allowed to settle, and by further addition of
nitric acid and application of heat the hydrated oxide of manganese is converted
into nitrate of manganese. The residual nitro-cellulose is washed, ground and
dried, and then pressed. For the manufacture of a smokeless powder the nitro-
cellulose thus obtained is granulated and polished. For the manufacture of a high
explosive the nitro-cellulose after being ground and dried, is mixed with bichromate
of potassium, and the mixture after being either granulated or pressed into suitably
shaped blocks and dried, is saturated with nitro-glycerine.
In carrying out the invention natural fibrous cellulose, such as cotton, soda-cellulose,
sulphite-cellulose, hemp and flax fibres, are before nitration preferably brought
into an amorphous condition, whereby a very complete nitration is facilitated, and
comparatively small quantities of nitrating mixture are required, and the production
of too high a temperature during the reaction is obviated.
The amorphous cellulose can be made by dissolving one part by weight of
permanganate of potassium in ten parts by weight of water, and gradually intro-
ducing into the solution, after the same has been cooled to 12-14° C., two to four
parts by weight of the comminuted cellulose. The paste like mass thus produced
being continually stirred by means of a suitable mixing apparatus. The reaction
which takes place with the simultaneous generation of heat, is terminated as soon
as the generation of gas ceases, the amorphous cellulose mixed with hydrated oxide
of manganese separating out as a brown mass. The product, which has an alkaline
reaction, is washed until it has a neutral reaction, and is then well mixed with one
part by weight of nitric acid of 1-3 specific gravity, and allowed to stand for
about 12 hours, sufficient water being present, to render the nitric acid suitably
dilute.
The mixture is then heated in a water bath to about 40 to 70° C. until the
separated oxide of manganese is entirely converted into nitrate of manganese and
the amorphous cellulose separates in the form of a pure white sediment.
The solution of nitrate of manganese is separated by pressure from the
cellulose, and is subsequently treated for the recovery of the manganese in the form
of a permanganate. The residual cake of cellulose is crushed under water, washed
until entirely deprived of acid, and the water allowed to drain therefrom. The
thick mass thus obtained is then ground in a mill to the greatest practicablo degree
of fineness, and pressed by means of an ordinary hand press, until it contains only
about 30 to 40% of water; it is then passed through sieves or pressed and dried.
The drying operation is commenced at the ordinary atmospheric temperature and
the heat slowly increased up to about 70° C. as a maximum, after which the horn-like
amorphous cellulose is again ground to as fine a condition as practicable.
The powdered amorphous cellulose thus obtained is then introduced into a

page_text: nitrating mixture made by introducing into a vessel which is provided with a mixing
apparatus and must be well closed during the nitrating process, 1.5 to 2.1 parts by
weight of chemically pure nitric acid of 1-4 to 1-55 specific gravity, and injecting
into the latter in a thin jet, 4-5 to 6-3 parts by weight of pure sulphuric acid o
1.85 specific gravity, the mixture being constantly stirred and kept cool.
Into this nitrating mixture which is cooled to about 5 to 8° C., is gradually
introduced with constant stirring, 1 part by weight of dry amorphous cellulose, care
being taken that the temperature does not rise above 30° C. After the introduction
of the cellulose, the cooling apparatus is, used, until a temperature of 16° C. is
reached and kept constant. Then after removal of the cooling apparatus, the
nitrating process is continued at about 18 to 20° C. and is completed in from
about 48 to 72 hours.
The nitrating liquid is then removed by pressure and collected for further use,
and the nitro-cellulose cakes are crushed, washed with a plentiful quantity of
water and allowed to drip. The paste or mass thus obtained is then placed in a
solution of 1 to 2 parts by weight of potassium permanganate in water in which it is
allowed to remain for about 10 to 12 hours, the mass being frequently stirred.
Then a quantity of nitric acid of 1-3 specific gravity equal to about one fourth of
the weight of the potassium permanganate is then added, and the mixture is allowed
to again stand for about six hours. After the expiration of this period the mixture
is placed on a water bath, and the temperature increased to about 70° C., the mixture
being thus left until the generation of gas ceases. The vessel employed for this
purpose should only be about half filled in order to prevent overflowing of the
mixture through effervescence.
The use of potassium permanganate has for object to disintegrate any portion
of the nitro-cellulose that may not have been nitrated or only slightly nitrated, and
thereby of producing a uniform product that shall not be liable to spontaneous
decomposition.
By acidifying the solution of potassium permanganate when acting upon the
nitro-cellulose, the alkali formed in the reaction, which might when heated, have
a decomposing action upon the nitro-cellulose, is neutralised.
The nitro-cellulose mixed with hydrated oxide of manganese is allowed to settle
from the mixture thus treated, and is deposited as a dark colored powder. A
quantity of nitric acid of 1.45 specific gravity equal to about three fourths of the
weight of the potassium permanganate is then poured into the mixture, half of
the supernatant liquid being preferably poured off, so as to previously allow the
nitric acid to act in a more concentrated state. The mixture is then heated in a
water bath at a temperature of about 70 to 80° C., until the whole of the hydrated
oxide of manganese has been converted into nitrate of manganese which dissolves
in the mixture. The solution is then poured off and collected for the purpose of
recovering the manganese.
As soon as the nitro-cellulose is completely deprived of color, the heating is
stopped to prevent decomposition, and the nitro-cellulose is washed with hot water
and then with cold water, or is digested with a solution of potassium carbonate.
After the paste or mass has been thus well washed, it is finely ground and
pressed, and then mixed with 1 to 3% of its weight (calculated for the dry
preparation) of tragacanth and made into a thick paste or dough in a powder-
stamping apparatus wherein it is formed by pressure into cakes which are crushed
between rolls, the disintegrated product being then sorted by means of sieves into
various sizes of grains. The grains thus produced are highly polished in a
granulating apparatus, and then carefully dried in order that they shall not
become cracked. The smokeless gunpowder thus obtained can also be made into
the form of prisms or other suitably shaped blocks for use in ordnance.
When the nitro-cellulose is to be made into a high explosive, the ground and
pressed paste or mass is intimately mixed with from about 3 to 4% of its weight of
powdered tragacanth and 5 to 10% of its weight of bichromate or neutral chromate
of potash or chromate of ammonia, (these proportions having reference to dry

page_text: nitro-cellulose) and worked, with a very small addition of water, into a thick
homogeneous paste or dough.
This paste or dough is subjected to hydraulic pressure, and the pressed cake
thus obtained is crushed by means of rolls, the disintegrated product sorted into
grains of various sizes by sieves, and the grains highly polished in a granulating
apparatus, that may be of ordinary construction, during which operation some
ethylic alcohol may advantageously be poured or sprinkled upon them.
In this manner there is produced in granular form, a high explosive which is
preferably packed in metallic or pasteboard cases for use.
The pressed nitro-cellulose may also be advantageously mixed with from about
1 to 15% of its weight of powdered tragacanth and from 5 to 10% of its
weight of powdered bichromate of potash (calculated for dry nitro-cellulose) and
compressed in a suitable press into cylindrical shaped porous blocks which, when
dried are placed in nitro-glycerine which they will absorb.
These cylinders are also packed in cases and ignition thereof is effected by means
of ordinary igniting caps.
The uitrating process may also be effected directly with natural fibrous cellulose,
and the latter may be converted, subsequently to nitration, into amorphous nitro-
cellulose by the use of potassium permanganate. It is however considered more
advantageous to treat the natural cellulose in the manner hereinbefore described.
Smokeless powder and high explosives produced as described, have an igniting
temperature of 180° C. and can be stored for a long period without danger of
spontaneous decomposition and without becoming hygroscopic.
Dated this 14th day of April 1892.
JOSEF KALLIVODA VON FALKENSTEIN,
By L. W., per F. B.
ARNOLD M. BÖHM,
By L. W., per F. B.
COMPLETE SPECIFICATION.
New or Improved Manufacture of Smokeless Powder and High
Explosives.
We, JOSEF KALLI VODA VON FALKENSTEIN, of Vinkovce, Croatia, Austria,
Pharmaceutical Chemist, and ARNOLD MICHAEL BÖHM, of Rathhausstrasse 2
Vienna 1, Austria, Gentleman, 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 :—
This invention has reference to the manufacture of smokeless powder and high
explosives. According thereto natural fibrous, but preferably amorphous, cellulose,
is nitrated, and then placed in a solution of potassium permanganate in order to
obtain a uniform product not liable to decompose. Nitric acid is afterwards added
to the mixture for the purpose of neutralising the alkali formed, the nitro-cellulose
mixed with hydrated oxide of manganese is allowed to settle and by further addition
of nitric acid and application of heat the hydrated oxide of manganese is converted
into nitrate of manganese. The residual nitro-cellulose is washed, ground and
dried, and then pressed. For the manufacture of a smokeless powder the nitro-
cellulose thus obtained is granulated and polished. For the manufacture of a high
explosive the nitro-cellulose after being ground and dried, is mixed with bichromate
of potassium, and the mixture after being either granulated or pressed into suitably
shaped blocks and dried, is or may be saturated with nitro-glycerine.
In carrying out the invention natural fibrous cellulose, such as cotton, soda-
cellulose, sulphite cellulose, hemp and flax fibres, are, before nitration, preferably
brought into an amorphous condition, whereby a very complete nitration is facilitated,
and comparatively small quantities of nitrating mixture are required, and the
production of too high a temperature during the reaction is obviated.

page_text: The amorphous cellulose can be made by dissolving one part by weight o
potassium permanganate in about ten parts by weight of water, and gradually
introducing into the solution, after the same has been cooled to 12-14° C., two to
four parts by weight of the comminuted cellulose, the paste-like mass thus produced
being continually stirred by means of a suitable mixing apparatus. The reaction
which takes place with the simultaneous generation of heat, is terminated as soon as
the generation of gas ceases, the amorphous cellulose, mixed with hydrated oxide o
manganese, separating out as a brown mass. The product, which has an alkaline
reaction, is washed until it has a neutral reaction, and is well mixed with one part
by weight of nitric acid of 1-3 specific gravity, and allowed to stand for about
12 hours, sufficient water being present, to render the nitric acid suitably dilute.
The mixture is then heated in a water bath to about 40° to 70° C. until the
separated oxide of manganese is entirely converted into nitrate of manganese and
the amorphous cellulose separates in the form of a pure white sediment.
The solution of nitrate of manganese is separated by pressure from the cellulose,
and is subsequently treated for the recovery of the manganese in the form of a
permanganate. The residual cake of cellulose is crushed under water, washed until
entirely deprived of acid, and the water allowed to drain therefrom. The thick
mass thus obtained is then ground in a mill to the greatest practicable degree of
fineness, and pressed by means of an ordinary hand press, until it contains only
about 30 to 40% of water; it is then passed or pressed through sieves and dried.
The drying operation is commenced at the ordinary atmospheric temperature and
the heat slowly increased up to about 70° C. as a maximum, after which the horn-
like amorphous cellulose is again ground to as fine a condition as practicable.
The powdered amorphous cellulose thus obtained is then introduced into a
nitrating mixture made by introducing into a vessel which is provided with a mixing
apparatus and which must be well closed during the nitrating process 1-5 to
21 parts by weight of chemically pure nitric acid of 14 to 1.55 specific gravity, and
injecting into the latter in a thin jet, 4-5 to 6-3 parts by weight of pure sulphuric
acid of 1-85 specific gravity, the mixture being constantly stirred and kept cool.
Into this nitrating mixture, which is cooled to about 5 to 8° C., is gradually
introduced with constant stirring, 1 part by weight of dry amorphous cellulose care
being taken that the temperature does not rise above 30° C. After the introduction
of the cellulose a cooling apparatus is used, until a temperature of 16° C. is reached,
which temperature is kept constant. Then after removal of the cooling apparatus
the nitrating process is continued at about 18 to 20º C., and is completed in from
about 48 to 72 hours.
The nitrating liquid is then removed by pressure and collected for further use,
and the nitro-cellulose cakes are crushed, washed with a plentiful quantity of water
and allowed to drip. The paste or mass thus obtained is then placed in a solution
of 1 to 2 parts by weight of potassium permanganate in about 10 parts by weight
of cold water in which it is allowed to remain for about 10 to 12 hours, the mass being
frequently stirred. Then a quantity of nitric acid of 1-3 specific gravity equal to
about one fourth of the weight of the potassium permanganate is then added, and
the mixture is allowed to again stand for about six hours. After the expiration of
this period the mixture is placed on a water bath, and the temperature increased to
about 70° C., the mixture being thus left until the generation of gas ceases.
vessel employed for this purpose should only be about half filled in order to prevent
overflowing of the mixture through effervescence.
The
The use of potassium permanganate has for object to disintegrate any portion of
the nitro-cellulose that may not have been nitrated or only slightly nitrated, and
thereby of producing a uniform product that shall not be liable to spontaneous
decomposition.
By acidifying the solution of potassium permanganate when acting upon the
nitro-cellulose, the alkali formed in the reaction, which might when heated have a
decomposing action upon the nitro-cellulose is neutralised.
The nitro-cellulose mixed with hydrated oxide of manganese is allowed to settle

page_text: from the mixture thus treated, and is deposited as a dark colored powder. A
quantity of nitric acid of 1-45 specific gravity equal to about three fourths of the
weight of the potassium permanganate is then poured into the mixture, half of the
supernatant liquid being preferably poured off previously so as to allow the nitric
acid to act in a more concentrated state. The mixture is then heated in a water
bath at a temperature of about 70 to 80° C., until the whole of the hydrated oxide
of manganese has been converted into nitrate of manganese which dissolves in
the mixture. The solution is then poured off and collected for the purpose of
recovering the manganese.
As soon as the nitro-cellulose is completely deprived of color, the heating is
stopped to prevent decomposition, and the nitro-cellulose is washed in hot water
and then with cold water, or is digested with a solution of potassium carbonate.
After the paste or mass has been thus well washed, it is finely ground and pressed,
and then mixed with 1 to 3% of its weight (calculated for the dry preparation) of
tragacanth and made into a thick paste or dough in a powder-stamping apparatus
wherein it is formed by pressure into cakes which are crushed between rolls, the
disintegrated product being then sorted by means of sieves into various sizes of
grains. The grains thus produced are highly polished in a granulating apparatus,
and then carefully dried in order that they shall not become cracked. The
smokeless gunpowder thus obtained can also be made into the form of prisms or
other suitably shaped blocks for use in ordnance.
When the nitro-cellulose is to be made into a high explosive, for blasting
purposes the ground and pressed paste or mass is intimately mixed with from
about 3 to 4% of its weight of powdered tragacanth and 5 to 10% of its weight
of bichromate or neutral chromate of potash or chromate of ammonia, (these pro-
portions having reference to the dry nitro-cellulose) and worked, with a very small
addition of water, into a thick homogeneous paste or dough.
This paste or dough is subjected to hydraulic pressure, and the pressed cake thus
obtained is crushed by means of rolls, the disintegrated product sorted into grains
of various sizes by sieves, and the grains highly polished in a granulating apparatus
that may be of ordinary construction, during which operation some ethylic alcohol
may advantageously be poured or sprinkled upon them.
In this manner there is produced in granular form, a high explosive suitable for
blasting purposes and which is preferably packed in metallic or pasteboard cases
for use.
The pressed nitro-cellulose may also be advantageously mixed with from about
1 to 1.5% of its weight of powdered tragacanth and from 5 to 10% of its weight of
powdered bichromate of potash (calculated for dry nitro-cellulose) and compressed
in a suitable press into cylindrical shaped porous blocks which, when dried and
then placed in nitro-glycerine will absorb the same.
These cylinders are also packed in cases and ignition thereof is effected by means
of ordinary igniting caps.
The nitrating process may also be effected directly with natural fibrous cellulose,
and the latter may be converted, subsequently to nitration, into amorphous nitro-
cellulose by the use of potassium permanganate. It is however considered more
advantageous to treat the natural cellulose in the manner herein before described.
Smokeless powder and high explosives for blasting produced as described, have
an igniting temperature of 180° C. and can be stored for a long period without
danger of spontaneous decomposition and without becoming hygroscopic.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed we declare that what we
claim is :-
1. The manufacture of the herein described new or improved explosive, consisting
of nitro-cellulose produced by nitrating natural fibrous or amorphous cellulose,
treating the nitrated cellulose with potassium permanganate and afterward with
nitric acid as set forth, and either pressed and granulated for use as smokeless

page_text: powder; or mixed with bichromate of potash, or chromate of potash, or chromate
of ammonium, and granulated, or mixed with bichromate of potash and pressed into
blocks, which may be impregnated with nitro-glycerine for use as a high explosive,
substantially as described.
2. The manufacture or production of an explosive capable of being used as
smokeless powder, by nitrating natural fibrous or amorphous cellulose substantially
in the proportions by weight specified subjecting the nitrated cellulose to the action
of a solution of permanganate of potash, then adding nitric acid to the mixture for
the purpose of neutralising the alkali formed, separating the nitro-cellulose with
intermixed hydrated oxide of manganese; dissolving out the hydrated oxide of
manganese as nitrate of manganese washing the residual nitro-cellulose grinding it
to a fine state and afterwards subjecting it to pressure and forming it into grains or
blocks and drying the same substantially as described.
3. For increasing the explosive or blasting power of the explosive produced
according to the process specified in the preceding claim, mixing the ground and
pressed nitro-cellulose with bichromate of potash, chromate of potash, or chromate
of ammonium, and compressing and granulating the mixture or mixing the said
nitro-cellulose with bichromate of potassium and compressing the mixture into
blocks substantially as described.
4. For the manufacture of the explosive specified in Claim 1, the production of
amorphous cellulose by introducing comminuted natural fibrous cellulose, sub-
stantially in the proportions specified, into an aqueous solution of potassium
permanganate and constantly stirring the mixture, separating the amorphous
cellulose mixed with hydrated oxide of manganese heating the mixture with nitric
acid until the whole of the oxide of manganese is dissolved out as nitrate of 2
manganese and separating the resulting white amorphous cellulose which is then
pressed, ground and sifted, and then dried at an increased temperature and again
ground, substantially as described.
Dated this 16th day of January 1893.
J. KALLIVODA VON
FALKENSTEIN, 3
By L. W., per F. B.
J. KALLIVODA VON FALKENSTEIN,
By L. W., per F. B.
A. M. DORM,
RL W nor FR