IMPROVEMENTS IN VULCANISING INDIA-RUBBER
Year: 1864

page_text: LETTERS PATENT to Charles Humfrey, of Suffolk Grove, Southwark, in
the County of Surrey, for the Invention of "IMPROVEMENTS IN VULCANISING
INDIA-RUBBER."
Sealed the 30th August 1864, and dated the 5th March 1864.
PROVISIONAL SPECIFICATION left by the said Charles Humfrey at the
Office of the Commissioners of Patents, with his Petition, on the 5th
March 1864.
I, CHARLES HUMFREY, of Suffolk Grove, Southwark, in the County of
Surrey, do hereby declare the nature of the said Invention for "IMPROVE-
MENTS IN VULCANISING INDIA-RUBBER," to be as follows :-
These improvements consist in the substitution of petroleum spirit and
petroleum products treated as hereafter described as a solvent for chloride of
sulphur in the place of bi-sulphuret of carbon, spirit of turpentine, and
camphine, which are ordinarily used for that purpose. It is well known that
chloride of sulphur is immediately decomposed by contact with water, or with
any compound containing water, and if mixed or dissolved in petroleum spirit

page_text: or other petroleum product in their ordinary hydrated state it is immediately
resolved into hydrochloric and hyposulphurous acids, and rendered unfit for
use; but if the petroleum spirit or other petroleum products be rendered
anhydrous such decomposition does not take place, and they can then be used
as solvents for chloride of sulphur, and applied in the ordinary way to vulcanise
india-rubber by the cold process. It is essential therefore so to treat these
petroleum products that they shall be rendered perfectly anhydrous, and this I
effect by the following process:-I take ordinary petroleum spirit or other
petroleum product of usual commercial quality, and in a convenient vessel
provided with an agitator I add to them about ten per cent. of concentrated
sulphuric acid, and bring the two into intimate contact by continued and
violent agitation. The acid is then allowed to settle, and the petroleum
product run into a still, taking care to keep the whole apparatus perfectly dry,
and about four or five pounds to every one hundred gallons of petroleum
products of dry caustic lime in fine powder is then added, together with a
small quantity of peroxide of manganese, and distilled over in the usual way.
The resulting petroleum spirit or other petroleum product will thus be rendered
perfectly anhydrous, and can be used as a solvent for chloride of sulphur for
vulcanising india-rubber. The object of the addition of the peroxide of
manganese is to get rid of any sulphurous acid which is likely to be formed
by the action of the concentrated sulphuric acid on the petroleum products.
An excellent test of the fitness of petroleum spirit or other petroleum products
for dissolving chloride of sulphur is the following:-If a small portion of
potassium with a freshly cut surface be immersed in ordinary petroleum spirit
or other petroleum product, the cut surface is rather rapidly tarnished, no
doubt from the presence of water, but if a like piece of potassium be immersed
in petroleum spirit or other petroleum product rendered anhydrous by the
process above described, the cut surface remains untarnished, and the
potassium can be preserved unchanged for any length of time.
In the above Provisional Specification I have used the expression "petroleum
products," meaning thereby the spirit and oil obtained from Pennsylvanian and
Wallachian earth oils, and I consider these the best for the purpose, but all
petroleum products, including the products from the distillation of coal shale
and peat can be used for the same purpose when prepared in the same
manner.

page_text: by the said Charles Humfrey in the Great Seal Patent Office on the
5th September 1864.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, CHARLES
HUMFREY, of Suffolk Groove, Southwark, in the County of Surrey, send
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Fifth day of March, in the year of our Lord One
thousand eight hundred and sixty-four, in the twenty-seventh year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto me, the said
Charles Humfrey, Her special licence that I, the said Charles Humfrey, my
executors, administrators, and assigns, or such others as I, the said Charles
Humfrey, my executors, administrators, and assigns, should at any time 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 "IMPROVEMENTS IN VULCANISING
INDIA-RUBBER," upon the condition (amongst others) that I, the said Charles
Humfrey, my executors or administrators, by an instrument in writing
under my, or their, or one of their hands and seals, 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 Charles Humfrey, do hereby declare
the nature of my said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement:-
These improvements consist in the substitution of petroleum spirit and
petroleum products, treated as hereafter described, as a solvent for chloride of
sulphur in the place of bi-sulphuret of carbon, spirit of turpentine, and
camphine, which are ordinarily used for that purpose. It is well known that
chloride of sulphur is immediately decomposed by contact with water, or with
any compound containing water, and if mixed or dissolved in petroleum spirit.
or other petroleum product in their ordinary hydrated state it is immediately
resolved into hydrochloric and hyposulphurous acids, and rendered unfit for

page_text: use; but if the petroleum spirit or other petroleum products be rendered
anhydrous such decomposition does not take place, and they can then be used
as solvents for chloride of sulphur, and applied in the ordinary way to
vulcanise india-rubber by the cold process. It is essential therefore so to
treat these petroleum products that they shall be rendered perfectly anhydrous,
and this I effect by the following process:-I take ordinary petroleum spirit
or other petróleum product of usual commercial quality, and in a convenient
vessel provided with an agitator I add to them about ten per cent. of con-
centrated sulphuric acid, and bring the two into intimate contact by continued
and violent agitation. The acid is then allowed to settle, and the petroleum
.product run into a still, taking care to keep the whole apparatus perfectly dry,
and about four or five pounds to every one hundred gallons of petroleum
products of dry caustic lime in fine powder is then added, together with a
small quantity of peroxide of manganese, and distilled over in the usual way.
The resulting petroleum spirit or other petroleum product will thus be
rendered perfectly anhydrous, and can be used as a solvent for chloride of
sulphur for vulcanising india-rubber. The object of the addition of the
peroxide of manganese is to get rid of any sulphurous acid which is likely to
be formed by the action of the concentrated sulphuric acid on the petroleum
products. An excellent test of the fitness of petroleum spirit or other
petroleum products for dissolving chloride of sulphur is the following:-If a
small portion of potassium with a freshly cut surface be immersed in ordinary
petroleum spirit or other petroleum product, the cut surface is rather rapidly
tarnished, no doubt from the presence of water, but if a like piece of potassium
be immersed in petroleum spirit or other petroleum product rendered
anhydrous by the process above described, the cut surface remains unchanged
for any length of time.
:
In the above Specification I have used the expression "petroleum pro-
ducts," meaning thereby the spirit and oil obtained from Pennsylvanian and
Wallachian earth oils, and I consider these the best for the purpose, but all
petroleum products, including the products from the distillation of coal shale
and peat can be used for the same purpose when prepared in the same
manner.
Having now described the nature of my said Invention, and the manner
in which the same is to be performed, I would remark, in conclusion, that I
do not limit myself to the precise details and proportions described, as the
same may be varied or modified without departing from the principle of the
Invention; but what I claim, and desire to be secured to me by the herein in

page_text: part recited Letters Patent, are, the "Improvements in Vulcanising India-
rubber," substantially as herein specified.
In witness whereof, I, the said Charles Humfrey, have hereunto set my
hand and seal, this Third day of September, in the year of our Lord
One thousand eight hundred and sixty-four.
Witness,
ALEX. PRINCE,
Office for Patents,
4, Trafalgar Square,
Charing Cross.
CHARLES HUMFREY. (L.S.)