Improved Manufacture of celluloiu.
Year: 1898

page_text: Date of Application, 20th May, 1898
Complete Specification Left, 18th Feb., 1899-Accepted, 15th Apr., 1899
Improved Manufacture of celluloiu.
We, CARL GUSTAV HAGEMANN, of 13, Moltkestrasse, Ludwigshafen, a/Rhine,
Germany, Engineer, and DR. FRIEDRICH OTTO CORNELIUS ZIMMERMANN, of An der
Leimfabrik No. 1, Ludwigshafen aforesaid, Manufacturer, do hereby declare the
nature of this invention to be as follows:-
Ordinary celluloid consists essentially of nitro-cellulose and camphor, the latter
constituent imparting to celluloid the property of becoming plastic when heated.
Such celluloid is extremely inflammable and burns with great violence. Now the
present invention has for object mainly to obviate this violent inflammability, and it
effects this purpose by molecular combination of the nitro-cellulose with alumina
hydrate, or other hydrated metallic oxides and metallic oxides by chemical transforma-
tion.
For the purpose of making celluloid in accordance with this invention nitro-
cellulose, which may contain about 50 per cent. of water and therefore need only
be pressed, but not dried, is dissolved in acetone or other suitable solvents or is
worked up with such solvents, so as to form a viscid mass.
Then a concentrated aqueous solution of sulphate of alumina is added by stirring
or kneading, the said solution combining with the solution of nitro-cellulose to form
a homogeneous translucent kneadable mass. Into this mass there is gradually intro-
duced, with constant stirring or kneading, concentrated soda lye, until neutrality is
effected, which is indicated by the mass becoming converted almost suddenly into a
more crumbly or friable condition. The alumina hydrate is precipitated quantita-
tively, and in molecular subdivision, according to the following formula:-
A24)3 +
The mass thus obtained contains nitro-cellulose alumina hydrate, Glauber's salt,
and acetone, or such other solvent as may have been employed. The two last con-
stituents must be removed and this readily effected by stirring up the mass in
water, whereby the nitro-cellulose remains behind in intimate combination with
alumina hydrate as a fine granulated mass, which may be subjected to centrifugal
action or to pressure whilst the acetone and the Glauber's salt pass into the water
and can be entirely removed from the mass by washing several times. The acetone
is recovered from the washing water by distillation, whilst the Glauber's salt separates
in the form of pure crystals from the residue of distillation.
The compound of nitro-cellulose with alumina hydrate thus produced is dried and
gelatinized in a usual manner, for example, with acetone or with camphor containing
acetone, or camphor containing alcohol, etc., and is formed by the ordinary process
by strong pressure into blocks or is moulded directly into articles for use.
The more camphor there is incorporated with the mass, the softer and more
plastic is the final product, whilst, if there is an entire absence of camphor, there is
produced a very hard celluloid which has very little plasticity when heated.

page_text: Castor oil also can be readily worked into it if the castor oil is mixed from the
beginning with the solution of nitro-cellulose. This addition imparts greater supple-
ness to the new celluloid.
The following are some examples of advantageous proportions of mixture for the
manufacture of celluloid in accordance with this invention.
Сътриог
Castor oil
Total
C
10
"
- 100
The amounts of the respective concentrated solutions of sulphate of alumina and
caustic soda are determined according to the known stëchiometric rules with relation
to the degree of purity of the raw materials employed.
Celluloid manufactured as herein before described can be readily dyed in the same
manner as ordinary celluloid, alumina hydrate being suitable for fixing dye-stuffs.
In preparing celluloid according to the above-described process, other hydrated
metallic oxides and non-hydrated metallic oxides can be brought into intimate
combination with nitro-cellulose if the salts employed instead of the alumina sulphate
form readily soluble, thin, water solutions that will not combine with the solutions
of nitro-cellulose.
From the above description, it will be obvious that celluloid prepared according to
this invention has considerable advantages a s mpared with the ordinary celluloid,
such as its extremely small inflammability and the possibility of varying the hardness
of the product within wide limits. Furthermore, the manufacture of the celluloid
herein before 'described can be effected entirely without danger, because the nitro-
cellulose is, worked in such a moist state that it does not even burn, and much less

page_text: explode—also the drying process is effected only after-the nitro-cellulose has been
combined with the alumina hydrate, and therefore this drying process can be effected
without danger.
It will be obvious that this improved manufacture of celluloid is a highly important
technical improvement which is rendered still more striking by the low cost of
production..
1630
F. WISE HOWORTH,
46, Lincoln's Inn Fields, London, W.C., Agent for the Applicants.
Improved Manufacture of Celluloid.
We, CARL GUSTAV HAGEMANN, of 13, Moltkestrasse, Ludwigshafen a/Rhine,
Germany, Engineer, and DR. FRIEDRICH OTTO CORNELIUS ZIMMERMANN, of An der
Leimfabrik No. 1, Ludwigshafen aforesaid, Manufacturer, 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 :-
Ordinary celluloid consists essentially of nitro-cellulose and camphor, the latter of
which imparts to celluloid the property of becoming plastic when heated. Such
celluloid is extremely inflammable and burns with great violence.
Now the present invention has for its principal object to obviate this violent
inflammability, and it effects this purpose by molecular combination of the nitro-
cellulose with alumina hydrate, or other hydrated metallic oxides or non-hydrated
metallic oxides, by chemical transformation.
For the purpose of making celluloid in accordance with this invention, nitro-
cellulose, which may contain about 50. per cent. of water and therefore need only be
pressed, but not dried, is dissolved in acetone or other suitable solvents or is worked
up with such solvents, so as to form a viscid mass. Then a concentrated aqueous
solution of sulphate of alumina is added whilst stirring or kneading, the said solution
combining with the solution of nitro-cellulose to form a homogeneous translucent
mass capable of being kneaded. Into this mass there is gradually introduced with
constant stirring or kneading, concentrated soda, lye, until neutrality is effected,
which is indicated by the almost sudden conversion of the mass into a more
crumbly.or friable condition.
-
The alumina hydrate is precipitated quantitatively and in molecular subdivision, .
11
The mass thus obtained contains nitro-cellulose, alumina hydrate, Glauber's salt,
and acetone, or such other solvent as may have been employed. The last two
constituents must be removed, and this is easily effected by stirring up the mass.in.
water; the nitro-cellulose then remains behind in intimate combination with alumina
hydrate as a fine granulated mass, which may be subjected to centrifugal action or to
pressure, whilst the acetone and the Glauber's salt pass into the water and can be
entirely removed from the mass by washing several times. The acetone is recovered
from the washing water by distillation, whilst the Glauber's salt separates in the form
of pure crystals from the residue of distillation.
The compound of nitro-cellulose with alumina hydrate thus produced is dried and
gelatinized in a usual manner-for example, with acetone, or with camphor-con-
taining acetone, camphor-containing alcohol, etc.-and is formed by the ordinary
...... 675

page_text: process by strong pressure into blocks or is moulded directly into articles for use.
The more camphor there is incorporated with the mass, the softer and more plastic is
the final product, whilst, if there is an entire absence of camphor, there is produced a
very hard celluloid which has very little plasticity when heated.
Castor oil also can be easily worked in if the castor oil is mixed from the beginning
with the solution of nitro-cellulose. This addition imparts greater suppleness to the
new celluloid.
The following are some examples of advantageous proportions of mixture for the
manufacture of celluloid in accordance with this invention :-
The amounts of the respective concentrated solutions of sulphate of alumina and
caustic soda are determined according to the known stoichiometrical rules with rela-
tion to the degree of purity of the raw materials employed.
Celluloid manufactured as herein before described can be easily dyed in the same
manner as ordinary celluloid, because alumina hydrate is suitable for fixing dye-
stuffs.
In preparing celluloid according to the process herein before described, other
hydrated metallic oxides and non-hydrated metallic oxides can be brought into
intimate combination with nitro-cellulose if the salts employed instead of the sulphate
of alumina are also readily soluble, but thin, watery solutions do not combine with
the solution of nitro-cellulose.
From what has been said, it will be obvious that celluloid prepared according to
this invention has considerable advantages as compared with the ordinary celluloid,
such as its extremely small inflammability and the possibility of varying the hardness
of the product within wide limits. Furthermore, the manufacture of the celluloid
hereinbefore described can be effected entirely without danger, because the nitro-
cellulose is worked in such a moist state that it does not even burn, and much less
explode; whilst the drying process is effected only after the nitro-cellulose has been

page_text: combined with the alumina hydrate, and therefore this drying process can be
effected without danger.
It will be obvious that this improved manufacture of celluloid is a highly important
technical improvement, which is rendered still more striking by the low cost of
production.
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 a new kind of celluloid, by precipitating metallic hydrated
oxides, or non-hydrated metallic oxides, from concentrated solutions of the respective
salts, whilst they are in intimate mixture with solutions of nitro-cellulose, and then
lixiviating the mass with water, whereupon the raw celluloid of the new kind, which
remains behind, is, either alone or with an addition of camphor, gelatinized by means
of a solvent, and then moulded into shape.
2. A kind of celluloid of small inflammability produced by combining the solutions
of nitro-cellulose and metallic salts, and precipitating the corresponding hydrated
metallic oxides or non-hydrated oxides in molecular contact with the nitro-cellulose,
as hereinbefore described.
3. A kind of celluloid of small inflammability which consists essentially of nitro-
cellulose and alumina hydrate, and which may contain also other additions, as
camphor and castor oil, substantially as described.
Dated this 18th day of Februaro 1800
F. WISE HOWORTH,
46, Lincoln's Inn Fields, London, W.C., Agent for the Applicants.