IMPROVEMENTS IN THE TREATMENT OF CAOUTCHOUC, GUTTA PERCHA, AND ANALOGOUS GUMS FOR THE PRODUCTION THEREFROM OF ARTICLES OF UTILITY AND ORNAMENT
Year: 1869

page_text: LETTERS PATENT to John Henry Johnson, of 47, Lincoln's Inn
Fields, in the County of Middlesex, Gentleman, for the Invention
of "IMPROVEMENTS IN THE TREATMENT OF CAOUTCHOUC, GUTTA PERCHA, AND
ANALOGOUS GUMS FOR THE PRODUCTION THEREFROM OF ARTICLES OF UTILITY AND
ORNAMENT." A communication from abroad by John Ballon New-
brough and Edward Fagan, both of the City, County, and State of
New York, United States of America.
Sealed the 25th January 1870, and dated the 11th November 1869.
PROVISIONAL SPECIFICATION left by the said John Henry Johnson
at the Office of the Commissioners of Patents, with his Petition,
on the 11th November 1869.
I, JOHN HENRY JOHNSON, of 47, Lincoln's Inn Fields, in the County
of Middlesex, Gentleman, do hereby declare the nature of the said
Invention for "IMPROVEMENTS IN THE TREATMENT OF CAOUTCHOUC, GUTTA
PERCHA, AND ANALOGOUS GUMS FOR THE PRODUCTION THEREFROM OF ARTICLES OP
UTILITY AND ORNAMENT," a communication to me from abroad by John
Ballon Newbrough and Edward Fagan, both of the City, County, and
State of New York, United States of America, to be as follows:-
This Invention relates to a new mode of producing what is known as
hard or vulcanized rubber, and consists in combining iodine with

page_text: caoutchouc or analogous gum, so as to form a composition whereof to
mould or otherwise shape articles of utility or ornament prior to the
same being hardened by vulcanizing, the said composition being in some
cases mixed with clay, kaolin, or other mineral substance so as to vary
its consistency, and wolfram or tungsten oxide being used if desired
in combination with the composition so as to prevent the same from
being over vulcanized during the process of incorporating the gum with
the iodine by heat and pressure.
The Invention further consists in the application of bromine to the
above composition through the medium of any of the preparations
described hereafter, also in the manufacture of articles of utility and
ornament, by first shaping the same of unprepared caoutchouc or
analogous gum and then treating them with a solution of bromine in
chloroform as herein-after described.
The Invention also relates to a composition for coating metal and
other material, the said composition consisting of caoutchouc or other
analogous gum 'dissolved in a solution of bromine and chloroform.
Caoutchouc, gutta percha, or analogous gum is rolled or otherwise
worked into sheets, which are placed one above the other with inter-
vening layers of powdered iodine, thus forming a "pack," which is so
worked between heated rollers or by other suitable appliances, that a
thorough incorporation of the gum with the iodine is effected. Instead
of applying the iodine in the form of a powder the gum may be worked
in the presence of iodine vapor until thoroughly incorporated with it,
or the iodine may be first melted with linseed oil and then worked into
the gum. Clay or other mineral substances may be mixed with the
composition to vary its consistency or for other purposes. In preparing
articles of utility and ornament from this composition, or when it is
desired to harden or partly harden a mass of the same by the process of
"vulcanization," the composition is reduced to any desired shape by
moulding or otherwise, and is then baked for from about 30 minutes to
3 hours at a temperature of from 230° to 330° Fahrenheit, this tempera-
ture being varied as the. character of the composition or of the article
to be formed may suggest. Either an elastic, semi-elastic, or nearly
inflexible substance may be produced by varying the proportions of the
ingredients and the character of the heat employed. For instance, about
15 ounces of gutta percha (or 8 ounces of caoutchouc) combined with two
ounces of iodine will form a semi-elastic substance if heated in steam
and a solid and nearly non-elastic substance if baked by dry heat or

page_text: by steaming a combination of 18 ounces of gutta percha or 9 ounces
of caoutchouc with 4 ounces of iodine. The composition may be colored
by mixing with the ingredients vermillion or other coloring substance,
and by immersing the articles produced from the composition in liquid
ammonia all unpleasant odors may be removed. Sulphur may be
combined with the iodine and superheated steam may be employed for
baking the composition, or it may be heated in oil or other materia!
which will not dissolve the gum. The composition will be partially
vulcanized during the amalgamation of the ingredients by heat and
pressure, but care should be exercised to so incorporate the ingredients
that the preliminary vulcanizing will not impair the composition as
regards its proper consistency for being moulded or otherwise shaped
prior to the final vulcanizing process. As a means of preventing the
complete vulcanization of the composition during the incorporation of
the ingredients wolfram or tungsten oxide may be added, and although
various proportions of the different substances may be employed 12
parts of gum, 6 parts of wolfram or tungsten oxide, and one part of
iodine have been found in practice to be advantageous proportions. A
superior product for many purposes may be obtained by the addition of
The wolfram or
6 parts of clay, or kaolin, or equivalent substance.
tungsten oxide, with or without the clay, is ground in water with the
iodine prior to being incorporated with the gum.
The application of bromine in the treatment of rubber or other gum is
effected by first producing one of the following preparations:-One
preparation consists of a solution of from 1 to 5 parts by weight of
bromine in about 20 parts of chloroform; other proportions of the
materials may however be used. A second preparation is made by
dissolving in turpentine one part of iodine and two parts. of bromine,
proportions however which may be greatly varied. To make a third
preparation sulphur is boiled in turpentine until the sulphur is decom-
posed and settles with part of the oil to the bottom of the vessel in
which the materials are treated; the oil is then poured off and the
residuum generally dried by moderate heat after being washed. if
necessary with sulphuric acid. A fourth preparation is formed by:
treating iodine in the same manner as sulphur is treated in making the.
third preparation, except that the turpentine need not be boiled, and refuse.
oil from the manufacture of the third preparation may be employed.
In order to prevent explosions which are apt to result from treating*
bromine, iodine, or sulphur directly with turpentine, the latter is first

page_text: mixed with about one-fourth its weight of sulphuric acid or is boiled
with a small quantity of sulphur. Caoutchouc or other gum is worked
with iodine as before described, or the gum may be incorporated with
the second preparation (before referred to) of bromine and iodine, the
materials being in some cases combined in the proportion of 1 pound of
gum and 1 ounces of the preparation, the proportion of gum may
however be increased if a more elastic product is desired. To produce
useful or ornamental articles from this composition it is moulded or
otherwise reduced to the desired shape and subjected to a dry heat of
such a degree and for such a length of time as may be found desirable.
In practice tho subjection of the articles to a heat of from 200° to 320°
Fahrenheit for from ten minutes to one hour has been found suitable,
the toughness of the product increasing with the duration of the appli-
cation of heat. Any desired color may be imparted by combining with
the material before hardening suitable coloring matter. A third com-
position may be made by combining caoutchouc or other analogous gum
with the third and fourth preparations before described, the two pre-
parations being first melted together and then added to the gum in
proportions of about three ounces of the mixture to one pound of gum.
This composition may be moulded or otherwise formed of any desired
shape, and articles thus produced may be hardened by baking them in an
oven the temperature of which during the first 30 minutes is raised to
320° Fahrenheit, and is then maintained at this temperature for about
an hour, or until the desired change has been effected.
"
Instead of preparing the gum as above described articles of utility
and ornament may be made of unprepared gum (previously reduced to
the desired shape) by immercing the articles in the first preparation,
where it should remain until thoroughly impregnated with the same.
After removal from the preparation and the evaporation of the chloro-
form the gum will be found to have become hardened or "changed
and possessed of properties differing from those of the gum in its natural
state. A solution of the gum in the first preparation may be made, and
this solution may be applied to objects of iron or other material to form
a coating which is "changed" as the chloroform evaporates, or it may be
deposited on the interior of moulds to form hollow articles. Wherever
iodine and bromine have been referred to a mixture of sulpherand the
bromine or iodine may be employed, the materials being used in pro-
portions to be varied in accordance with the result desired.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said John Henry Johnson in the Great Seal Patent
Office on the 10th May 1870..
TO ALL TO WHOM THESE PRESENTS SHALL, COME, I, JOHN
HENRY JOHNSON, of 47, Lincoln's Inn Fields, in the County of
Middlesex, Gentleman, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Eleventh day of November, in the year
of our Lord One thousand cight hundred and sixty-nine, in the thirty-
third year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto me, the said John Henry Johnson, Her special
license that I, the said John Henry Johnson, my executors, adminis-
trators, and assigns, or such others as I, the said John Henry Johnson,
time
my executors, administrators, or assigns, should at any
agree with,
and no others, from time to time and at all times thereafter during the
term therein expressed, should and lawfully might make, use, exercise,
and vend, 'within the United Kingdom of Great Britain and Ireland,
the Channel Islands, and Isle of Man, an Invention for "IMPROVE-
MENTS IN THE TREATMENT OF CAOUTCHOUC, GUTTA PERCHA, AND ANALOGOUS GUNS
FOR THE PRODUCTION THEREFROM OF ARTICLES OF UTILITY AND ORNAMENT,"
a communication to me from abroad by John Ballon Newbrough
and Edward Fagan, both of the City, County, and State of New York,
United States of America, upon thic condition (amongst others) that I,
the said John Henry Johnson, my executors or administrators, by an
instrument in writing under my hand and seal, should particularly
describe and ascertain the nature of the said Invention, and in what
manner the same was to be performed, and cause the same to be
filed in the Great Seal Patent Office within six calendar months next
and immediately after the date of the said Letters Patent...
NOW KNOW YE, that I, the said John Henry Johnson, do hereby
declare the nature of the said Invention, and in what manner the
same is to be performed, to be particularly described and ascertained
in and by the following statement :-
The said Invention relates to a new mode of producing what is known
as hard or vulcanized rubber, and consists in combining. iodine with
caoutchouc or analogous gum so as to form.a composition whereof to
mould or otherwise shape articles of utility or ornament prior to the

page_text: same being hardened by vulcanizing, the said composition being in some
cases mixed with clay, kaolin, or other mineral substance so as to vary
its consistency, and wolfram or tungsten oxide being used if desired in
combination with the composition so as to prevent the same from being
over vulcanized during the process of incorporating the gum with the
iodine by heat and pressure.
The Invention further consists in the application of bromine to the
above composition through the medium of any of the preparations
described hereafter. Also in the manufacture of articles of utility and
ornament by first shaping the same of unprepared caoutchouc or
analogous gum, and then treating them with a solution of bromine in
chloroform, as hercin-after described.
The Invention also relates to a composition for coating metal and other
material, the said composition consisting of caoutchouc or other analogous
gum dissolved in a solution of bromine and chloroform. Caoutchouc,
gutta percha, or analogous gum is rolled or otherwise worked into sheets,
which are placed one above the other with intervening layers of powdered
iodine, thus farming a "pack," which is so worked between heated
rollers or by other suitable appliances that a thorough incorporation of
the gum with the iodine is effected. Instead of applying the iodine in
the form of powder the gum may be worked in the presence of iodine
vapor until thoroughly incorporated with it, or the iodine may be first
melted with linseed oil and then worked into the gum. Clay or other
mineral substances may be mixed with the composition to vary its
consistency or for other purposes. In preparing articles of utility and
ornament from this composition, or when it is desired to harden or partly
harden a mass of the same by the process of "vulcanization," the
composition is reduced to any desired shape by moulding or otherwise,
and is then baked for from about thirty minutes to three hours at a
temperature of from about 230° to 330° Fahrenheit, this temperature being
varied as the character of the composition or of the article to be formed
may suggest. Either an elastic, semi-elastic, or nearly inflexible substance
may be produced by varying the proportions of the ingredients and the
character of the heat employed. For instance, about sixteen ounces of
gutta percha (or eight ounces of caoutchouc combined with two ounces
of iodine will form a semi-clastic substance if heated in steam, and a
solid and nearly non-elastic substance if baked by dry heat, or by

page_text: steaming a combination of about eighteen ounces of gutta percha or
nine ounces of caoutchouc with about four ounces of iodine. The com-
position may be colored by mixing with the ingredients vermillion or
other coloring substance, and by immersing the articles produced from
the composition in liquid ammonia all unpleasant odors may be
removed. Sulphur may be combined with the iodine, and superheated
steam may be employed for baking the composition, or it may be heated
in oil or other material which will not dissolve the gum. The com-
position will be partially vulcanized during the amalgamation of the
ingredients by heat and pressure, but care should be exercised to so
incorporate the ingredients that the preliminary vulcanizing will not
impair the composition as regards its proper consistency for being
moulded or otherwise shaped prior to the final vulcanizing process.
As a means of preventing the complete vulcanization of the composition
during the incorporation of the ingredients wolfram or tungsten oxide
may be added, and although various proportions of the different substances
may be employed twelve parts of gum, six parts of wolfram or tungsten
oxide, and one part of iodinc have been found in practice to be
advantageous proportions. A supcrior product for many purposes may
be obtained by the addition of about six parts of clay or kaolin or
equivalent substance. The wolfram or tungsten oxide with or without
the clay is ground in water with the iodine prior to being incorporated
with the gum.
The application of bromine in the treatment of rubber or other gum
is effected by first producing one of the following preparations:-One
preparation consists of a solution of from one to five parts by weight of
bromine in about twenty parts of chloroform; other proportions of the
materials may however be used. A second preparation is. made by
dissolving in turpentine one part of iodine and two parts of bromine,
proportions, however, which may be greatly varied. To make a third
preparation sulphur is boiled in turpentine until the sulphur is decom-
posed and settles with part of the oil to the bottom of the vessel in
which the materials are treated; the oil is then poured off and the
residuum gradually dried by moderate heat after being washed if
necessary with sulphuric acid. A fourth preparation is formed by
treating iodine in the same manner as sulphur is treated in making the
third preparation, except that the turpentine need not be boiled, and
refuse oil from the manufacture of the third preparation may be,
employed.

page_text: In order to prevent explosions which are apt to result from treating
bromine, iodine; or sulphur directly with turpentine, the latter is first
mixed with about one-fourth its weight of sulphuric acid or is boiled
with a small quantity of sulphur. Caoutchouc or other gum is worked
with iodine as before described, or the gum may be incorporated with the
second preparation (above referred to) of bromine and iodine, the
materials being in some cases combined in the proportion of one pound
of gum and one and a half ounces of the preparation; the proportion of
gum may however be increased if a more elastic product is desired. To
produce useful or ornamental articles from this composition it is moulded
or otherwise reduced to the desired shape, and subjected to a dry heat of
such a degree and for such a length of time as may be found desirable.
In practice the subjection of the articles to a heat of from about 200°
to 320° Fahrenheit for from ten minutes to one hour has been found/suit-
able, the toughness of the product increasing with the duration of the
application of heat. Any desired color may be imparted by combining
with the material before hardening suitable coloring matter: A third
composition may be made by combining caoutchouc or other analogous
gum with the third and fourth preparations before described, the two
preparations being first melted together and then added to the gum in
proportions of about three ounces of the mixture, to one pound of gum.
This composition may be moulded or otherwise formed of any desired
shape, and articles thus produced may be hardened by baking them
in an oven, the temperature of which during the first thirty minutes
is raised to about 320° Fahrenheit, and is then maintained at this
temperature for about an hour or until the desired change has been
effected.
Instead of preparing the gum as above described articles of utility
and ornament may be made of unprepared gum (previously reduced to
the desired shape) by immersing the articles in the first preparation,
where it should remain until thoroughly impregnated with the same.
After removal from the preparation and the evaporation of the chloroform
the gum will be found to have become hardened or "changed" and
possessed of properties differing from those of the gum in its natural
state. A solution of the gum in the first preparation may be made, and
this solution may be applied to objects of iron or other material to form
a coating, which is "changed" as the chloroform evaporates, or it may be
deposited on the interior of moulds to form hollow articles. Wherever
iodine and bromine have been referred to a mixture of sulphur and the

page_text: bromine or iodine may be employed, the materials being used in pro-
portions to be varied in accordance with the result desired.
Having now described and particularly ascertained the nature of
the said Invention, and the manner in which the same. is or may be
used or carried into effect, I would observe in conclusion that what I
consider to be novel and original, and therefore claim as the Invention
secured to me by the herein-before in part recited Letters Patent is,-
First. The manufacture and use of a composition consisting of
caoutchouc, gutta percha, or analogous gum combined and treated with
iodine, substantially as described.
Second. The employment of clay or other suitable minerial substance
in connection with the above composition of caoutchouc or other gum
with iodine for the purpose specified.
Third. The employment of wolfram or tungsten oxide in connection
with the said composition for the purpose specified.
Fourth. The application to the said composition of bromine through
the medium of any of the within described preparations for the purpose
specified.
Fifth. The manufacture of vulcanized articles from the above com-
position of caoutchouc or equivalent gum with or without the addition
of bromine or sulphur.
Sixth. The manufacture of articles by first shaping caoutchouc or
cquivalent gum, then subjecting the articles to a solution of bromine in
chloroform, and subsequently evaporating the latter.
Seventh. The manufacture and use of a coating composition consisting
of caoutchouc or other analogous gum dissolved in a solution of bromine
and chloroform for the purpose specified.
In witness whereof, I, the said John Henry Johnson, have to
this my Specification set my hand and seal, this Tenth day of
May One thousand eight hundred and seventy.
TATTOY
J. HENRY JOHNSON. (L.S.)