IMPROVEMENTS IN THE MANUFACTURE OF IRON, STEEL, COPPER, LEAD, TIN, ZINC, AND THEIR ALLOYS, AND IN THE MANUFACTURE OF COKE
Year: 1860

page_text: LETTERS PATENT to Arthur Warner, of Threadneedle Street, in the City
of London, for the Invention of "IMPROVEMENTS IN THE MANUFACTURE OF
IRON, STEEL, COPPER, LEAD, TIN, ZINC, AND THEIR ALLOYS, AND IN THE
MANUFACTURE OF COKE,"
Sealed the 18th December 1860, and dated the 29th September 1860.
PROVISIONAL SPECIFICATION left by the said Arthur Warner at the
Office of the Commissioners of Patents, with his Petition, on the 29th
September 1860.
I, ARTHUR WARNER, of Threadneedle Street, in the City of London, do
hereby declare the nature of the Invention for "IMPROVEMENTS IN THE MANU-
FACTURE OF IRON, STEEL, COPPER, LEAD, TIN, ZINC, AND THEIR ALLOYS, AND IN THE
MANUFACTURE OF COKE," to be as follows:-
-
This Invention has for its object improvements in the manufacture of iron
steel, copper, lead, tin, zinc, and their alloys, and in the manufacture of coke
and consists in certain means of introducing liquid and solid matters, metals
and their oxides into fluid iron, copper, lead, tin, zinc, and alloys.
The liquid matters used are, sulphuric acid, water, tar, oils, blood, urine, and
others, according to the state of impurity. The solid matters are fluor spar,
manganese, muriate of ammonia, prussiate of potash, as well as other alkaline
and other matters, according to the action desired to be produced. To the
application of none of which matters do I make any claim separately, my
Invention being confined to the manner in which they are introduced into and
are brought to act on the melted metals. For these purposes, the liquid matter
to be used is placed in a metal, glass, or other suitable vessel capable of being
closed, in such manner that the liquid shall not escape till the desired time;
and where a liquid matter is to be used with a solid matter or matters, the
vessel: or vessels containing the required quantity is introduced into a case

page_text: capable of containing the same, together with the solid matter or matters to
be used therewith. This case may be of metal covered with wood, which is
preferred, or of wood such as will, notwithstanding the heat and pressure of
the melted metal for a time, retain the matters together whilst immersed in
the melted metal. The case or cases containing the proper quantity of the
fluid and solid matters (kept separate from each other, as above explained) is
or are introduced in the furnace, vessel, or receiver, in which the molten metal
is, or into which it has to be run, the case or cases in the vessel or receiver
being kept down by a metal rod, or otherwise. The melted metal will destroy
the case containing the solid matter and also the vessel containing the fluid
matter, and then the action of the fluid on the solid matter will take place, and
the products will act on the melted metal. When applying solid matters
without fluid matters, such solid matters are placed in metal vessels, and, by
preference, closed in wood, or in metal or wood cases only.
In the manufacture of coke, the solid and fluid matters are similarly placed
in vessels and cases, or vessels only, and they are introduced in coke ovens, and
the charge is placed in such ovens, and such cases and vessels remain intact
for a time and are then destroyed.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Arthur Warner in the Great Scal Patent Office on the 28th
March 1861.
TO ALL TO WHOM THESE PRESENTS SHALL COME, 1, ARTHUR
WARNER, of Threadneedle Street, in the City of London, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twenty-ninth day of September, in the year of our
Lord One thousand eight hundred and sixty, in the twenty-fourth year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said Arthur Warner, Her special licence that I, the said Arthur Warner, my exe-
cutors, administrators, and assigns, or such others as I, the said Arthur Warner,
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 THE MANUFACTURE OF IRON
STEEL, COPPER, LEAD, TIN, ZINC, AND THEIR ALLOYS, AND IN THE MANUFACTURE
OF COкr," upon the condition (amongst others) that I, the said Arthur Warner,
my executors, or administrators, by an instrument in writing under my, or

page_text: 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 per-
formed, 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 Arthur Warner, do hereby declare the
nature of the 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 thereof, that is to say:-
This Invention has for its object improvements in the manufacture of iron,
steel, copper, lead, tin, zinc, and their alloys, and in the manufacture of coke,
and consists in certain means of introducing liquid and solid matters, metals
and their oxides into fluid iron, copper, lead, tin, zinc, and alloys.
The liquid matters used are sulphuric acid, water, tar, oils, blood, urine, and
others, according to the state of impurity. The solid matters are fluor spar,
manganese, muriate of ammonia, prussiate of potash, as well as other alkaline
and other matters, according to the action desired to be produced; to the
application of none of which matters do I make any claim separately, my
Invention being confined to the manner in which they are introduced into and
are brought to act on the melted metals. For these purposes, the liquid matter
to be used is placed in a metal, glass, or other suitable vessel capable of being
closed, in such manner that the liquid shall not escape till the desired time,
and where a liquid matter is to be used with a solid matter or matters, the
vessel or vessels containing the required quantity is introduced into a case
capable of containing the same, together with the solid matter or matters to
be used therewith. This case may be of metal covered with wood, which is
preferred, or of wood such as will, notwithstanding the heat and pressure of
the melted metal for a time, retain the matters together whilst immersed in
the melted metal. The case or cases containing the proper quantity of the
fluid and solid matters (kept separate from each other, as above explained) is
or are introduced in the furnace, vessel, or receiver in which the molten metal
is, or into which it has to be run, the case or cases in the vessel or receiver
being kept down by a metal rod, or otherwise. The melted metal will destroy
the case containing the solid matter and also the vessel containing the fluid
matter, and then the action of the fluid on the solid matter will take place, and
the products will act on the melted metal. When applying solid matters
without fluid matters, such solid matters are placed in metal vessels, and, by
preference, closed in wood, or in metal or wood cases only.
In the manufacture of coke, the solid adn fluid matters are similarly placed

page_text: in vessels and cases, or vessels only, and they are introduced in coke ovens, and
the charge is placed in such ovens, and such cases and vessels remain intact
for a time and are then destroyed.
With a view of removing silica and other earthy impurities from iron, of
driving off carbon, sulphur, phosphorus, and other volatile matters, and also of
rendering the metal more malleable and tenaceous, I make use of certain
gases, viz., hydrofluoric acid, nitrogen, oxygen, chlorine, hydrogen, and carbu-
retted hydrogen, which are evolved and applied to the metal in the following
manner Packages or cylinders of strong paper, sheet metal, or other suit-
able material containing the proper proportions of the ingredients for the
formation of the required gases are placed in the ladle or vessel, into which the
molten metal is teemed or run from the blast, cupola, or other furnace, or in
which it is heated, reheated, or remelted. These packages or cylinders are
kept at the bottom of the vessel (by an arrangement hereafter to be described),
and on the liquid metal being run in, they discharge their contents and the
gases are evolved.
The gases thus formed pass through the whole body of metal, causing
violent ebullition, which continues for a considerable time until the whole or
the greater portion of the impurities contained in the iron are either volatilized
or fused and rise to the surface as a scum. The impurities, however, usually
found in iron being of both an earthy and gaseous nature, and varying in their
proportions according to the district from which the ore is obtained, it is of the
highest importance to ascertain the exact nature and proportions before pro-
ceeding to deal with them. For example, north country iron contains a larger
per-centage of phosphorus or silica than Welsh iron, whilst on the other hand
the Welsh iron contains more sulphur than Staffordshire. I therefore take as
a basis the iron of the Cleveland district, which, from analysis, is found to
contain the following average proportions of impurities, viz. :-
Silica
Phosphorus
Sulphur
Carbon
- 3'0 per cent.
- 1'25 "
-0°25
"
3.25
"
In order to effect the complete expulsion of these from the metal, I apply
the chymicals in the manner hornafter

page_text: gas thus disengaged immediately attacks the silica and dissolves it; it also
dissolves any oxide of titanium or titanic acid, which may exist in the metal,
causing it to become alloyed or incorporated with the iron and greatly improving
its quality, a result not accomplished by other means (except perhaps to a
small extent in the refining furnace).
Second. Nitrogen gas obtained from guano.-This I use for the purpose of
combining with a portion of the carbon contained in the iron so as to form
cyanogen. As, however, too large a proportion of this gas renders the metal
brittle and steely, it is necessary to exercise caution in the use of it, and
I therefore employ a larger or smaller quantity according to the quality of iron
required.
Third. Oxygen gas.-This I use for the purpose of decarbonizing and
cleansing the metal, and I procure it from the peroxide of manganese in powder
by means of sulphuric acid.
Fourth. Chlorine gas.-This has the effect of driving off sulphur and
phosphorus. I procure it in the ordinary way from a mixture of chloride of
sodium and peroxide of manganese acted on by sulphuric acid.
Fifth. Hydrogen and carburetted hydrogen gases. In all cases where it is
desirable to deoxidize the iron, I use one of these gases. The hydrogen I
procure from water, either alone or in combination with sulphuric acid and
iron filings or scraps of zinc. The carburetted hydrogen I procure
from coal tar, powdered resin, pitch, powdered coal, bituminous shale, or
other substances.
This Invention is also applicable to a great variety of other substances which
may be used in the purification of iron.
Having thus described the nature and objects of my Invention, I now pro-
ceed to explain the method by which the gases are introduced into the metal
and their action upon it.
First, for the generation of hydrofluoric acid gas, I place a bottle or vessel
containing sulphuric acid in a cylinder or hollow case of paper or sheet metal
of the required size. The case or cylinder is then filled up with fluoride of
calcium (ground to powder) and the whole hermetically sealed.
Second, for the production of nitrogen, I introduce into the case containing
the fluor spar, Peruvian guano in the proportions to be hereafter stated, or
in case of being unable to obtain guano, I substitute for it another cylinder
containing liquid blood or the urine of animals.
Third, for producing oxygen, I use a similar bottle or vessel of sulphuric
acid, placing it as before in the case of paper or sheet metal, and filling up the
case with peroxide of manganese in powder,

page_text: Fourth, for evolving chlorine a similar bottle of sulphuric acid is placed in
the case or cylinder, which is then filled with a mixture of chloride of sodium
and peroxide of manganese.
Fifth, for hydrogen, I place in the case or cylinder a bottle containing water
and sulphuric acid surrounding it with iron filings or scraps of zinc.
Sixth, for carburetted hydrogen, the cylinder is filled with powdered resin,
pitch, coal tar, powdered coal, or other suitable substance or composition.
The required number of these cases or cylinders is then packed in a wooden
box, which is placed at the bottom of the receiver into which the molten metal
is run, the said box being retained in its position by a perpendicular iron rod
running through a bar placed across the top of the receiver, or by a wooden
wedge, which is a more simple plan and found to be fully as effective. The
metal is violently agitated by the passage of the gases through it, and is kept
in a state of ebullition for a period of 30 to 50 minutes according to the
quantity acted on. With a view, however, to the more perfect mixing of the
metal, and keeping the fluxes below the surface, I use a plunger of wrought
iron, which is worked over a wheel or pulley. This produces, to a certain
extent, a similar result to that of puddling, and consequently metal made by
this process is puddled in much less time and with a considerable saving of fuel.
As regards the proportions of the various chymicals employed these must, as
before stated, be adjusted to the nature of the impurities in the iron and the
quality of metal required.
For cable iron, which to be really good must be neither cold-short nor red-
short, easily welded and possessing great toughness, I find the following pro-
portions produce the best result, viz., for 1 ton of Cleveland iron, such as
before stated, I take,
Hydrofluoric acid
Hydrofluoric acid
and nitrogen
Oxygen
5lbs. ground fluor spar,
5lbs. sulphuric acid,
5lbs. ground fluor spar,
5lbs. sulphuric acid,
1lb. Peruvian guano,
contained in 2 cases and
marked No. 0.
in 2 cases marked No. 1.
{2}lbs. peroxide of manganese,
1lb. sulphuric acid,
}
in 2 cases marked No. 2.
Chlorine
2 lbs. chloride of sodium,
14lb. peroxide of manganese,
1lb. sulphuric acid,
in 2 cases marked No. 3.
Carburetted hydrogen,
gallon coal tar or animal oil.
I have referred to Cleveland iron, as an example, but in cases where the
proportions of impurities differ from what are given above then the proportions

page_text: of the matters above given should be varied according to the actual quantities
of impurities present.
For foundry iron, I find that the same proportions of fluorine, chlorine, and
carburetted hydrogen (omitting the oxygen and nitrogen) greatly improve the
quality, but they must be varied according to the quantity of carbon already
existing in the metal.
In the manufacture of malleable iron and steel, I take the metal which has
been refined by this process, (either fluid or in pigs) and reheat the same in
combination with an equal weight of wrought iron. According, however, to
the nature of the iron or steel required, and the purity of the metal used, I
vary these proportions down to one-fifth of wrought and four-fifths of cast iron.
The crucible or vessel used in this operation should be of clay, plumbago, or
such other material as will resist the intense heat, and of such a form as will
answer the purpose of a mould (the metal being left therein to cool) by which
means it is prevented from becoming honeycombed. As a means of heating
the crucibles, I prefer using the gas from the blast furnace (first passing it
through lime to free it from carbonic oxide and other impurities) and by
adapting Griffin's Patent gas burners I obtain sufficient heat to fuse wrought
iron. The iron thus made can be reheated and hammered out into any form
required.
This Invention is also applicable to the purification of coke from sulphur.
I desulphurize the coke by means of chlorine, which is introduced into it in
the following manner: A wooden box containing 12lbs of common salt, 6lbs.
of peroxide of manganese, and 6lbs. of sulphuric acid (either in a glass or lead
bottle) is placed inside the coke oven and covered with the charge of coal
which is then lighted at the top. The heat gradually penetrating through
the mass at length reaches the box, which is consumed, and the contents being
discharged a large evolution of chlorine takes place. This quantity is suffi-
cient for a charge of 1 ton of coal.
Copper and its alloys. In the manufacture or refining of copper and its
alloys of tin and zinc, my Invention applies to the removal of impurities, but
more especially the volatile impurities, sulphur, arsenic, &c., with a view of
imparting softness and malleability.. I run the copper or its alloys from the
furnace into a receiver or vessel, at the bottom of which I place and fix the
cylinders or cases containing the proper proportions of chymicals, in the manner
before described for iron, having previously ascertained the nature and pro-
portions of the impurities in the metal which I have to deal with. I find
that some of the harder and commoner descriptions of copper imported into this
country from South America and other places are rendered soft, malleable,

page_text: and tough by remelting and treating with muriate of ammonia and prussiate
of potash.
The most satisfactory result is produced from a mixture of 8lbs. of muriate
of ammonia and Ilb. of prussiate of potash to the ton. The use of chlorine
as a cleansing agent in the proportion before described for iron is also
beneficial.
Tin. In dealing with tin, I run the metal from the furnace into a receiver
or vessel, and there treat it with hydrofluoric acid and chlorine administered in
the proportions and manner before described for iron. This has the effect of
removing silica and arsenic, and also of fusing the tungsten and forming a
perfect alloy with it. For the reduction of oxide of tin or other oxides, I
employ powdered coal, charcoal, or other suitable substance.
Lead. This Invention is also applicable to lead, some of the harder kinds
of which may be rendered tough and tenacious by the use of nitrate of potash
administered as before described in the proportion of 8lbs. to the ton of metal.
A similar result is produced by the use of various other salts or substances, I
do not, however, claim the use of any of these, but only the mode of applying
or introducing them to the metal.
Zinc. When a hard quality of zinc is required for casting, I administer to
the metal hydrofluoric acid in the proportions and mode before described for
iron.
I would remark that although I have confined my description to the use of
particular chemicals or matters for removing certain impurities from iron and
other metals, I would state that it is well known that other chemicals or
matters have before been used for removing like and other impurities from
iron and other metals, I therefore do not confine my Invention to the use of
the particular chemicals or matters above named, nor do I make any claim
thereto. my Invention consisting in the manner herein-before described of
applying the chemicals and matters above mentioned and others, whether fluid
or solid.
In witness whereof, I, the said Arthur Warner, have hereunto set my
hand and seal, this Twenty-second day of March, in the year of our Lord
One thousand eight hundred and sixty-one.
ARTHUR WARNER. (L.S.)