Improvements in the Manufacture of Alloys of Nickel and Copper, and of Alloys of Nickel and Iron, and of Alloys of Nickel, Copper, and Iron.
Year: 1891

page_text: Date of Application, 6th Nov., 1891
Complete Specification Left, 13th July, 1892-Accepted, 13th Aug., 1892
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Alloys of Nickel and Copper,
and of Alloys of Nickel and Iron, and of Alloys of Nickel,
Copper, and Iron.
I FREDERICK WILLIAM MARTINO of No. 199 Arundel Street, Sheffield in the
County of York, German Silver Manufacturer do hereby declare the nature of
this invention to be as follows:-
Alloys of nickel and copper are used for making ammunition and for various
other purposes and alloys of nickel and iron and of copper, nickel and iron are used
in the manufacture of steel and in the manufacture of iron and steel castings.
Both these alloys are ordinarily made by melting the metals together. This method
of manufacture is costly and the results are uncertain.
The object of my invention is to manufacture the said alloys more economically
and with great certainty of composition and consists in making the said alloys
directly from ores containing them in the manner hereinafter described instead of
first reducing the metals separately from ores containing them and afterwards
melting together the metals so obtained.
I will first describe my invention in connection with the manufacture of an alloy
of copper and nickel.
I take the sulphides of the nickel matte or stein of commerce.
The said matte
has an average composition of 30 parts by weight of copper 30 parts by weight of
nickel 15 parts by weight of iron and 25 parts by weight of sulphur.
I mix the powdered sulphides with finely ground quartz-sand and sulphate of
baryta preferably in the following proportions:
100 parts by weight of powdered matte
60 parts by weight of powdered quartz-sand
134 parts by weight of powdered sulphate of baryta.
These proportions are suitable for matte of an average composition but the
amount of quartz-sand and sulphate of baryta are increased if the matte is richer in
iron and sulphur than in the average composition hereinbefore given.
I melt the mixture described in a reverberatory furnace, the iron is thereby
oxidized and forms a slag of silicated oxide of iron. This slag being of less specific
gravity than the sulphides of nickel and copper rises to the surface of the molten
mass and when the separation is completed can be drawn off. The remaining
sulphides of copper and nickel can be tapped and run into receptacles in which
they are allowed to solidify. The solidified sulphides of nickel and copper are
powdered and are roasted in a reverberatory furnace until the whole has been
converted into oxide of nickel and copper. These oxides are heated with charcoal
so as to further reduce them and are then submitted to an analysis and the exact
percentage of each constituent ascertained.
In order to obtain an alloy having the definite composition required I proceed
as follows. I melt in a Siemens-Martin converter or in a reverberatory furnace
such an amount of copper as will together with the copper in the oxide of nickel
and copper obtained from the matte in the manner hereinbefore described bring
the proportion of copper to nickel up to the proportion required in the alloy to
be produced, allowance being made for probable loss of copper in melting. To
prevent the copper during this melting process from absorbing oxygen I add
thereto powdered anthracite or powdered charcoal and when the copper is in a
liquid state I add gradually the oxide of nickel and copper. I rake or rabble

page_text: the molten mass in the furnace from time to time, adding occasionally more
powdered anthracite or charcoal until the whole is thoroughly reduced and after-
wards add sufficient flux, consisting of a mixture of finely ground fluorspar and
horax to clean the metallic bath. The slag may now be drawn off and the alloy
which consists of nickel and copper in the definite proportions desired, run off into
ingot moulds.
If thought desirable samples of the alloy may be taken from the furnace as the
process last described proceeds and submitted to analysis and if the alloy is found
not to consist of the metals in the desired proportion more copper or more of the
oxides of nickel and copper may be added so as to rectify any error before the
charge is tapped.
I will now describe that part of my invention which has for its object the
manufacture of an alloy of iron and nickel which alloy of iron and nickel I shall
hereinafter refer to as ferro-nickel.
I prefer to employ in the manufacture of ferro-nickel the nickel ore known in
commerce as New Caledonian ore which consists essentially of oxides of nickel
and iron in varying proportions.
When however ores consisting essentially of sulphides of nickel, copper and iron
are used in the manufacture of the said ferro-nickel the copper has to be separated
from the other constituents of the ore by the well known process of precipitation
or cementation. For this purpose the sulphides of copper and nickel and iron are
roasted first to transform them into oxides and then roasted again with common
salt leaving the oxides of nickel and iron as a residue.
The oxides of nickel and iron. whether natural or artificially produced are
operated on in the following manner.
I heat the said oxides with charcoal so as to reduce the iron to its lowest state
of oxidation. An analysis is made of the oxide obtained and the exact pro-
portions of the two metals present ascertained.
In order to obtain an alloy of ferro-nickel having a certain definite proportion
of nickel and iron I melt such an amount of pig iron as will together with the iron
in the oxide obtained in the manner last described bring the proportion of iron
to nickel up to that desired. When the said pig iron is melted I gradually
add the oxide of nickel and iron until the whole is reduced to a molten
condition, flux being added to separate oxidized metallic and earthy matters
from the alloy. The charge is tapped and run into ingot moulds. The ferro-
nickel obtained in the manner described will be of the desired composition.
If an alloy of nickel, copper and iron in definite proportions be required the
matte containing these three metals is roasted to remove the sulphur and to trans-
form them into oxides. They are then mixed with charcoal and again roasted
whereby all excess of oxygen is removed. They are then melted in a Siemens
converter or a reverberatory furnace by adding them to a bath of molten copper
and pig iron and an alloy of the required standard thereby produced.
By my invention alloys of nickel and copper or nickel and iron or of nickel,
copper and iron of any required composition can be readily and with certainty
obtained.
Dated the 6th day of November 1891.
W. T. WHITEMAN,
Agent for the Applicant.

page_text: .
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Alloys of Nickel and Copper,
and of Alloys of Nickel and Iron, and of Alloys of Nickel,
Copper, and Iron.
I FREDERICK WILLIAM MARTINO, of No. 199 Arundel Street, Sheffield, in
the County of York German Silver Manufacturer, do hereby declare the nature
of my invention and in what manner the same is to be performed to be particularly
described and ascertained in and by the following statement :-
Alloys of nickel and copper are used for making ammunition and for various
other purposes and alloys of nickel and iron and of copper nickel and iron are used
in the manufacture of steel and in the manufacture of iron and steel castings.
These alloys are generally made by melting the metals together. This method
of manufacture is costly and the results are uncertain.
The object of my invention is to manufacture the said alloys economically and
with great certainty of composition, and in a form convenient for use in large
furnaces, such as the Siemens-Martin furnace and consists in making the said
alloys directly from ores containing them or some of them in the manner herein-
after described instead of first reducing the metals separately from ores containing
them and afterwards melting together the metals so obtained.
I will first describe my invention in connection with the manufacture of an alloy
of copper and nickel.
I take the sulphides or matte of commerce which are obtained from the Lake
Superior mines or the ores from New Caledonia. If the latter are used I convert
them into sulphides or matte by smelting them with sulphur or with materials
containing sulphur such for example as soda waste or gas lime.
The matte from Lake Superior contains copper, nickel" and iron in the state of
sulphides. The matte produced from New Caledonian orés contains more
frequently only nickel and iron as sulphides. The Lake Superior matte has an
average composition of 25 parts by weight of copper; 25 parts by weight of
nickel; 15 parts by weight of iron and 30 parts by weight of sulphur. These
proportions may however vary considerably. The matte is reduced to powder by
means of crushers and rollers and passed through fine meshed sieves. It is then
mixed with quartz-sand and sulphate of baryta, if this latter can be obtained
cheap; otherwise with sulphate of soda or Glauber salts which can either be
made or obtained at a very low price preferably in the following proportions.
100 parts by weight of powdered matte
60 parts by weight of quartz-sand
134 parts by weight of sulphate of baryta or sulphate of soda.
These proportions are suitable for matte of an average composition but the
amount of quartz-sand and sulphate of baryta or sulphate of soda must be increased
if the matte is richer in iron and sulphur than matte of the average composition as
hereinbefore given.
I melt the mixture described in a reverberatory furnace.. The sulphur of the
iron is oxydised into sulphurous acid and passes off by the chimney, the iron
becoming ferrous oxide combines with the silica forming silicate of iron which
These proportions are suitable for matte of an average composition but the
amount of quartz-sand and sulphate of baryta or sulphate of soda must be increased
if the matte is richer in iron and sulphur than matte of the average composition as
hereinbefore given.
I melt the mixture described in a reverberatory furnace.. The sulphur of the
iron is oxydised into sulphurous acid and passes off by the chimney, the iron
becoming ferrous oxide combines with the silica forming silicate of iron which
rises to the surface as a slag leaving the sulphides of nickel and copper as a molten
mass which when the separation is complete can be tapped, the slag having been
previously drawn off. The slag may however be drawn off with the sulphides
of nickel and copper and separated from the sulphides when the mass has cooled.
The solidified sulphides of nickel and copper are crushed and powdered and the
fine powder is roasted in a calcining or roasting furnace, or in a set of furnaces of
graduated heat, until the whole has been converted into oxide of nickel and
copper. These oxides are then mixed with charcoal in pieces of about the size of
ཝཱ

page_text: hazel nuts together with charcoal in fine powder and moistened with coal tar and
water with which a little burnt lime and clay have been mixed, so as to form a
paste. This paste is pressed in forms of desirable size into briquettes. This
briquetting is done by briquetting machines of the ordinary kind. The briquettes
are afterwards slowly dried and are when quite dry placed in converters and
exposed to a bright red heat. They are then ready for the smelting operation
which I will now describe.
The composition of the briquettes is ascertained by melting a weighed sample
and by analysis of the metallic product obtained whereby the ratio of nickel and
copper is ascertained.
In order to obtain an alloy having the definite composition required I proceed
as follows: I melt in a Siemens-Martin converter or in a reverberatory furnace
such an amount of copper as will, together with the copper in the oxide of nickel
and copper obtained in the manner hereinbefore described from the matte, bring
the proportion of copper to nickel up to the proportion required in the alloy to be
produced, allowance being made for loss of copper in melting. To prevent the
copper during the melting process from absorbing oxygen I add thereto anthracite
or charcoal in small pieces and when the copper is in a liquid state I add gradually
the briquettes of nickel and copper. I rake or rabble the molten mass in the
furnace from time to time adding occasionally more anthracite or charcoal until
the whole is thoroughly reduced and afterwards add sufficient flux consisting of a
mixture of finely ground fluor-spar and borax to clean the metallic bath. The slag
may now be drawn off and the alloy which consists of nickel and copper in the
definite proportions desired run off into ingot moulds.
If thought desirable samples of the alloy may be taken from the furnace as the
process last described proceeds and submitted to analysis and if the alloy is found
not to consist of the metals in the desired proportion more copper or more briquettes
of the prepared oxides of nickel and copper may be added so as to rectify any error
in the composition of the alloy before the charge is tapped.
I will now describe that part of my invention which has for its object the manu-
facture of an alloy of iron and nickel which alloy of iron and nickel I shall herein-
after refer to as ferro-nickel.
I prefer to employ in the manufacture of ferro-nickel the nickel ore known in
commerce as New Caledonian ore which consists essentially of oxides of nickel and
iron in varying proportions.
When, however, ores consisting essentially of sulphides of nickel, copper and
iron such as the Lake Superior ores, are used in the manufacture of the said ferro-
nickel, the copper has to be separated from the other constituents of the ore by the
well known process of precipitation or cementation which I do not consider it
necessary to describe.
The oxides of nickel and iron. whether natural or artificially produced, are
operated on in the following manner. I mix the said oxides with charcoal in small
pieces together with charcoal in powder with coal tar and water containing lime
and clay and press the whole into briquettes as herein before described in treating
the oxides of copper and nickel. The briquettes are slowly dried and then exposed
to a bright red heat in a converter. An analysis is made of the reduced briquettes
and the exact proportions of the two metals present ascertained.
In order to obtain an alloy of ferro-nickel having a certain definite proportion
of nickel and iron I melt such an amount of pig iron as will, together with the iron
in the oxide obtained in the manner last described, bring the proportion of iron to
nickel up to that desired. When the said pig iron is melted I gradually add the
oxide of nickel and iron in the form of briquettes until the whole is reduced to a
molten condition, flux of the kind hereinbefore described being added to separate
oxidized metallic and earthy matters from the alloy. The charge is tapped and
run into ingot moulds. The ferro-nickel obtained in the manner described will be
of the desired composition.
If an alloy of nickel, copper and iron in definite proportions be required, the

page_text: matte containing these three metals, is roasted to remove the sulphur and to convert
them into oxides. They are then mixed with charcoal in small pieces together
with powdered charcoal and formed into a pasty mass with coal tar and water
containing lime and clay. The pasty mass is pressed into briquettes and is dried
and heated in a converter as already described. The briquettes are then added
to the molten iron and copper in the requisite proportion, in a Siemens-Martin
converter or in a reverberatory furnace and an alloy of the required standard is
thereby produced.
In making alloys of nickel and copper, and of nickel and iron and of nickel,
copper and iron, the processes I have described may be modified as follows.
Instead of adding the prepared briquettes to melted copper or melted pig iron
or to melted copper and pig iron to obtain the required standards I proceed as
follows:-
In the manufacture of ferro-nickel after having ascertained by analysis the
exact percentage of the two oxides obtained from the roasted matte, I add more
oxide of nickel or more oxide of iron, till the required standard is reached. The
whole is well mixed in a rotatory mixing pan, and is then briquetted as herein-
before described, dried and calcined at a red heat. This process yields the ferro-
nickel in the form of carbides with a metallic lustre and this compound when
broken up may in some cases be preferable to the molten product, as for instance,
for Siemens' furnaces of large calibre where it would assist in the converting process
of pig iron into steel by rendering unnecessary a certain amount of "spiegel" or
ferro-silicon-manganese now in use.
The same method of adding oxides of copper for making cupro-nickel or cupro-
ferro-nickel may be employed.
By my invention alloys of nickel and copper or of nickel and iron, or of
nickel, copper and iron of any required composition can be readily and with
certainty obtained.
Having now particularly described and ascertained the nature of my invention
and in what manner the same is to be performed I declare that I claim as my
invention of "Improvements in the manufacture of alloys of nickel and copper
and of alloys of nickel and iron and of allɔys of nickel copper and iron."
Manufacturing the said alloys directly from ores containing the metals of the
said alloys or some of the said metals instead of obtaining the metals separately
and afterwards melting them together or alloying them the said manufacture being
conducted in the ways hereinbefore described whereby the said alloys are obtained
economically and with the exact composition required.
Dated the 11th day of July 1892.
FREDERICK WILLIAM MARTINO.