CA2140337C - Nickel alloy for hydrogen battery electrodes - Google Patents
Nickel alloy for hydrogen battery electrodesInfo
- Publication number
- CA2140337C CA2140337C CA002140337A CA2140337A CA2140337C CA 2140337 C CA2140337 C CA 2140337C CA 002140337 A CA002140337 A CA 002140337A CA 2140337 A CA2140337 A CA 2140337A CA 2140337 C CA2140337 C CA 2140337C
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- metal
- master alloy
- alloy
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- intermetallic compound
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Master alloys and process of producing them are disclosed. In one such process is a process for preparing a master alloy for use in hydrogen storage battery electrodes.
This process includes the step of preparing a first mixture of at least one metal and at least one metal oxide, both in powdered form, and A1 in powdered or granular form, wherein the at least one metal and the metal of the at least one metal oxide are each independently one of the following metals, Ni, V, Cr, Co, or Fe. The at least one metal and at least one metal oxide are alloyed to produce an intermetallic compound in an aluminothermic reaction. The intermetallic compound is sized reduced into powdered form. A second mixture of the powdered intermetallic compound and at least one additional metal or alloy in powdered form is prepared, wherein the metal of the at least one additional metal or the metal of the alloy is one of the following metals, Ni, Ti, Mn, Zr, Cr, Co, V or Fe. The second mixture in powdered form is pressed to produce a compact. The compact is heat fused to produce a master alloy for use in hydrogen storage battery electrodes, the electrodes being produced from one of the following metals, Ni, V, Cr, Co, Fe, Ti, Mn, or Zr.
This process includes the step of preparing a first mixture of at least one metal and at least one metal oxide, both in powdered form, and A1 in powdered or granular form, wherein the at least one metal and the metal of the at least one metal oxide are each independently one of the following metals, Ni, V, Cr, Co, or Fe. The at least one metal and at least one metal oxide are alloyed to produce an intermetallic compound in an aluminothermic reaction. The intermetallic compound is sized reduced into powdered form. A second mixture of the powdered intermetallic compound and at least one additional metal or alloy in powdered form is prepared, wherein the metal of the at least one additional metal or the metal of the alloy is one of the following metals, Ni, Ti, Mn, Zr, Cr, Co, V or Fe. The second mixture in powdered form is pressed to produce a compact. The compact is heat fused to produce a master alloy for use in hydrogen storage battery electrodes, the electrodes being produced from one of the following metals, Ni, V, Cr, Co, Fe, Ti, Mn, or Zr.
Description
(a) TITLE OF THE INVENTION
NICKEL ALLOY FOR HYDROGEN BATTERY ELECTRODES
(b) TECHNICAL FIELD TO WHICH THE INVENTION RELATES
The present invention relates to master alloys, and more particularly to alloys for use in hydrogen storage batteries, and to processes of making of such master alloys.
(c) BACKGROUND ART
Titanium-containing alloys find a broad range of applications in areas where low weight and strength are required, e.g., aerospace and military uses, as well as corrosion resistance and heat applications, including use in turbine blade jet engine parts, high speed cutting tools, and so on. Molybdenum is known to be difficult to diffuse uniformly in titanium, because of its higher melting point and higher density, which causes molybdenum particles to drop to the bottom of a molten titanium pool where they sinter into agglomerates and form inclusions in the ingot produced. (See, e.
g. , U . S .
Patent No . 3 , 508, 910) . The same problems of getting molybdenum to homogenize with titanium are also experienced with columbium, which, like molybdenum, is also high refractory.
Matters are further complicated by the fact that titanium alloys require relatively tight chemistries, and often the chemistry of the desired master alloy is poorly compatible with the homogeneous alloying of the various components, due to differences in component solubility, melting point, density, etc. Furthermore, the chemistry of the alloy is frequently dictated by the alloying process used.
Other methods of melting master alloys have drawbacks as well. For example, induction melting of the components in graphite crucibles causes the resulting alloy to pick up carbon, an impurity which in some applications cannot be tolerated.
Such methods are used, for example, in the alloying of metals for preparing electrodes for hydrogen storage batteries. (See, e.g., U.S. Patent No. 4,551,400).
NICKEL ALLOY FOR HYDROGEN BATTERY ELECTRODES
(b) TECHNICAL FIELD TO WHICH THE INVENTION RELATES
The present invention relates to master alloys, and more particularly to alloys for use in hydrogen storage batteries, and to processes of making of such master alloys.
(c) BACKGROUND ART
Titanium-containing alloys find a broad range of applications in areas where low weight and strength are required, e.g., aerospace and military uses, as well as corrosion resistance and heat applications, including use in turbine blade jet engine parts, high speed cutting tools, and so on. Molybdenum is known to be difficult to diffuse uniformly in titanium, because of its higher melting point and higher density, which causes molybdenum particles to drop to the bottom of a molten titanium pool where they sinter into agglomerates and form inclusions in the ingot produced. (See, e.
g. , U . S .
Patent No . 3 , 508, 910) . The same problems of getting molybdenum to homogenize with titanium are also experienced with columbium, which, like molybdenum, is also high refractory.
Matters are further complicated by the fact that titanium alloys require relatively tight chemistries, and often the chemistry of the desired master alloy is poorly compatible with the homogeneous alloying of the various components, due to differences in component solubility, melting point, density, etc. Furthermore, the chemistry of the alloy is frequently dictated by the alloying process used.
Other methods of melting master alloys have drawbacks as well. For example, induction melting of the components in graphite crucibles causes the resulting alloy to pick up carbon, an impurity which in some applications cannot be tolerated.
Such methods are used, for example, in the alloying of metals for preparing electrodes for hydrogen storage batteries. (See, e.g., U.S. Patent No. 4,551,400).
(d) DESCRIPTION OF THE INVENTION
Accordingly, an object of one aspect of this invention is to produce an alloy having low residual aluminum.
An object of another aspect of this invention is to provide an alloy which is useful in the manufacture of electrodes for hydrogen storage batteries, the electrodes having low carbon content.
The present invention in one aspect provide a process of making alloys, wherein an intermetallic compound or compounds are first produced via thermite processing, then size reduced and mixed with powdered alloying components to form a mixture which is then compacted and fusion heated to prepare the desired end product. Thus, one broad aspect of the present invention provides a process for preparing a master alloy for use in hydrogen storage battery electrodes, comprising the steps of preparing a first mixture of at least one metal and at least one metal oxide, both in powdered form, and A1 in powdered or granular form, wherein the at least one metal and the at least one metal 1 S oxide are each independently selected from a metal or from an oxide of a metal which is selected from the group consisting of Ni, V, Cr, Co, and Fe, alloying the at least one metal and the at least one metal oxide to produce an intermetallic compound in an aluminothermic reaction, size reducing the intermetallic compound into powdered form, preparing a second mixture of the powdered intermetallic compound and at least one additional metal or alloy in powdered form, wherein the metal of the at least one additional metal or the metal of the alloy is a metal which is selected from the group consisting of Ni, Ti, Mn, Zr, Cr, Co, V and Fe, pressing the second mixture in powdered form to produce a compact, and fusion heating the compact to produce a master alloy for use in hydrogen storage battery electrodes, the electrodes being formed from a metal which is selected from the group consisting of Ni, V, Cr, Co, Fe, Ti, Mn, and Zr.
By one variant of this process aspect of the invention, the intermetallic compound of the alloying step is produced from a first mixture of A1 fines with Ni powder, Co powder, Fe powder, V205 powder or Cr203 powder.
Accordingly, an object of one aspect of this invention is to produce an alloy having low residual aluminum.
An object of another aspect of this invention is to provide an alloy which is useful in the manufacture of electrodes for hydrogen storage batteries, the electrodes having low carbon content.
The present invention in one aspect provide a process of making alloys, wherein an intermetallic compound or compounds are first produced via thermite processing, then size reduced and mixed with powdered alloying components to form a mixture which is then compacted and fusion heated to prepare the desired end product. Thus, one broad aspect of the present invention provides a process for preparing a master alloy for use in hydrogen storage battery electrodes, comprising the steps of preparing a first mixture of at least one metal and at least one metal oxide, both in powdered form, and A1 in powdered or granular form, wherein the at least one metal and the at least one metal 1 S oxide are each independently selected from a metal or from an oxide of a metal which is selected from the group consisting of Ni, V, Cr, Co, and Fe, alloying the at least one metal and the at least one metal oxide to produce an intermetallic compound in an aluminothermic reaction, size reducing the intermetallic compound into powdered form, preparing a second mixture of the powdered intermetallic compound and at least one additional metal or alloy in powdered form, wherein the metal of the at least one additional metal or the metal of the alloy is a metal which is selected from the group consisting of Ni, Ti, Mn, Zr, Cr, Co, V and Fe, pressing the second mixture in powdered form to produce a compact, and fusion heating the compact to produce a master alloy for use in hydrogen storage battery electrodes, the electrodes being formed from a metal which is selected from the group consisting of Ni, V, Cr, Co, Fe, Ti, Mn, and Zr.
By one variant of this process aspect of the invention, the intermetallic compound of the alloying step is produced from a first mixture of A1 fines with Ni powder, Co powder, Fe powder, V205 powder or Cr203 powder.
By another variant of that process aspect of the invention, or a variant thereof, the alloying step occurs in an inert atmosphere.
By another variant of that process aspect of the invention, or variants thereof, the alloying step occurs at a reduced pressure of 0.3 mm Hg or less.
By another variant of that process aspect of the invention, or variants thereof, the alloying step is performed in a water-cooled, copper, below-ground furnace.
By another variant of that process aspect of the invention, or variants thereof, the size reducing step is performed by cooling the intermetallic compound and then size reducing said intermetallic compound by crushers, ball mills, pug mills, grinders or hydriding.
By another variant of that process aspect of the invention, or variants thereof, the compact of the pressing-step is formed using an isostatic press at a pressure in excess of 7,000 psi.
By another variant of that process aspect of the invention, or variants thereof, the compacts are formed in ten pound discs and stacked intervals for the fusion heating step.
By another variant of that process aspect of the invention, or variants thereof, the fusion heating step is by induction heating in an induction furnace.
By another variant of that process aspect of the invention, or variants thereof, the process further comprises the step of: size reducing the master alloy to produce an end product in size reduced form. By a variation thereof, the master alloy is size reduced by hydriding to -200 mesh.
By other variants of that process aspect of the invention, or variants thereof, the intermetallic compound comprises 8-18 % Ni, 38-48 % V, 8-18 % Cr, 10-20 % Co, 20 % Fe, and 0 to 0. 5 % of Al, C, N2, 02, P, Si, S and other impurities, all percentages being percentage by weight; or the master alloy, for use in hydrogen storage battery electrodes, comprises 8-18 % Ti, 17-27 % Zr, 13-23 % V, 24-34 % Ni, 1-11 % Cr, Co, 1-11 % Fe, all percentages being percentage by weight and 0 to 0.025 % C.
By another aspect of the present invention, a master alloy is provided for use in hydrogen storage battery electrodes, the master alloy comprising: 8-18 % Ti, 17-27 % Zr, 13-23 % V, 24-34 % Ni, 1-11 % Cr, 1-11 % Co, 1-11 % Fe, all percentages being percentage by weight and 0 to 0.025 % C.
By one variant of this aspect of the invention, the master alloy is 12. 5 %
Ti, 22 Zr, 17.5 % V, 29.2 % Ni, 5.3 % Cr, 6.2 % Co, 6 % Fe, and 0.025 % C. , all percentages being percentage by weight.
By yet another aspect of the present invention, an intermetallic alloy is provided which is used to produce a master alloy for use in hydrogen storage battery electrodes, the intermetallic alloy comprising: 8-18 % Ni, 38-48 % V, 8-18 % Cr, 10-20 %
Co, 10-20 % Fe, all percentages being percentage by weight and 0 to 0.5 % by weight of Al, C, N2 02 P, Si, S and other impurities.
By still another aspect of this invention, a hydrogen storage battery electrode is provided, the electrode comprising a master alloy as described fully hereinabove.
(e) AT LEAST ONE MODE FOR CARRYING OUT THE INVENTION
A master alloy is an alloy of selected elements that can be added to a charge of metal to provide a desired composition or to deoxidize one or more components of the mixture.
According to one aspect of the present invention, an intermetallic compound is first prepared using thermite processing. Thermite processing involves an exothermic reaction which occurs when finely divided aluminum mixed with metal oxides is ignited, causing reduction of the oxide and reaching temperatures of 2200°C, which is sufficient to propagate heat through the charge to homogenize the components comprising the resulting intermetallic compounds.
Often, a simple thermite process uses a mixture of powdered iron (III) oxide, Fe203 and powdered or granular aluminum. However, oxides of metals other than iron may be used, as discussed herein, and mixtures of these oxides may likewise be used.
In practising aspects of this invention, the thermite components are charged to a furnace, typically a water-cooled, copper, below-ground reaction vessel, e. g.
, that described in "Metallothermic Reduction of Oxides in Water-Cooled Copper Furnaces" , by F.H. Perfect, Transactions of the Metallurgical Society of AIME, Volume 239, August 1967, pp. 1282-1286.
The mixture is thoroughly and intimately mixed prior to being charged to the furnace so that the thermite reaction will occur rapidly and uniformly throughout the 5 charge on ignition.
The reaction vessel is preferably covered after the mixture is charged and the pressure within the vessel may be reduced, for example, to 0.3 mm Hg or less, followed by flooding the vessel with a high purity inert gas, e. g. , argon. Such evacuation and purging results in termites of higher purity, and lower nitrogen content. The thermite reaction is initiated with an igniter and is allowed to proceed to completion.
After the thermite is prepared using thermite processing, it is cooled and size reduced to powdered form using known methods, e. g. , crushers, ball mills, pug mills, grinders, hydriding, etc.
After size reduction, the intermetallic compound which is produced by the thermite process, is then mixed with at least one additional metal in powdered form, for example, Ti, to form a substantially-uniform mixture. The resulting mixture is then pressed into a compact or briquetted with application of pressures of over 7,000 psi and preferably of 15,000-30,000 psi. Typically, such compacts are formed using an isostatic press.
It is preferable, especially when forming large compacts, to place spacers at intervals within the compact in order to insure uniform compaction and produce more manageable compact sizes. Ten pound discs of compact are typically produced.
The discs are then stacked in the furnace and, when the reaction starts, it ends to be semi-continuous and controlled rather than violent. The smaller compacts, when stacked, also help prevent melting of the compact, which is in some cases an undesirable result.
The compacts of briquets are then fused, preferably with induction heat, to form the desired master alloy. No special pressure conditions are required for the fusion, which is generally carried out at atmospheric or a milli for pressure and temperatures of 600-1, 700 ° C, depending on the optimal fusion temperature of the compact.
By another variant of that process aspect of the invention, or variants thereof, the alloying step occurs at a reduced pressure of 0.3 mm Hg or less.
By another variant of that process aspect of the invention, or variants thereof, the alloying step is performed in a water-cooled, copper, below-ground furnace.
By another variant of that process aspect of the invention, or variants thereof, the size reducing step is performed by cooling the intermetallic compound and then size reducing said intermetallic compound by crushers, ball mills, pug mills, grinders or hydriding.
By another variant of that process aspect of the invention, or variants thereof, the compact of the pressing-step is formed using an isostatic press at a pressure in excess of 7,000 psi.
By another variant of that process aspect of the invention, or variants thereof, the compacts are formed in ten pound discs and stacked intervals for the fusion heating step.
By another variant of that process aspect of the invention, or variants thereof, the fusion heating step is by induction heating in an induction furnace.
By another variant of that process aspect of the invention, or variants thereof, the process further comprises the step of: size reducing the master alloy to produce an end product in size reduced form. By a variation thereof, the master alloy is size reduced by hydriding to -200 mesh.
By other variants of that process aspect of the invention, or variants thereof, the intermetallic compound comprises 8-18 % Ni, 38-48 % V, 8-18 % Cr, 10-20 % Co, 20 % Fe, and 0 to 0. 5 % of Al, C, N2, 02, P, Si, S and other impurities, all percentages being percentage by weight; or the master alloy, for use in hydrogen storage battery electrodes, comprises 8-18 % Ti, 17-27 % Zr, 13-23 % V, 24-34 % Ni, 1-11 % Cr, Co, 1-11 % Fe, all percentages being percentage by weight and 0 to 0.025 % C.
By another aspect of the present invention, a master alloy is provided for use in hydrogen storage battery electrodes, the master alloy comprising: 8-18 % Ti, 17-27 % Zr, 13-23 % V, 24-34 % Ni, 1-11 % Cr, 1-11 % Co, 1-11 % Fe, all percentages being percentage by weight and 0 to 0.025 % C.
By one variant of this aspect of the invention, the master alloy is 12. 5 %
Ti, 22 Zr, 17.5 % V, 29.2 % Ni, 5.3 % Cr, 6.2 % Co, 6 % Fe, and 0.025 % C. , all percentages being percentage by weight.
By yet another aspect of the present invention, an intermetallic alloy is provided which is used to produce a master alloy for use in hydrogen storage battery electrodes, the intermetallic alloy comprising: 8-18 % Ni, 38-48 % V, 8-18 % Cr, 10-20 %
Co, 10-20 % Fe, all percentages being percentage by weight and 0 to 0.5 % by weight of Al, C, N2 02 P, Si, S and other impurities.
By still another aspect of this invention, a hydrogen storage battery electrode is provided, the electrode comprising a master alloy as described fully hereinabove.
(e) AT LEAST ONE MODE FOR CARRYING OUT THE INVENTION
A master alloy is an alloy of selected elements that can be added to a charge of metal to provide a desired composition or to deoxidize one or more components of the mixture.
According to one aspect of the present invention, an intermetallic compound is first prepared using thermite processing. Thermite processing involves an exothermic reaction which occurs when finely divided aluminum mixed with metal oxides is ignited, causing reduction of the oxide and reaching temperatures of 2200°C, which is sufficient to propagate heat through the charge to homogenize the components comprising the resulting intermetallic compounds.
Often, a simple thermite process uses a mixture of powdered iron (III) oxide, Fe203 and powdered or granular aluminum. However, oxides of metals other than iron may be used, as discussed herein, and mixtures of these oxides may likewise be used.
In practising aspects of this invention, the thermite components are charged to a furnace, typically a water-cooled, copper, below-ground reaction vessel, e. g.
, that described in "Metallothermic Reduction of Oxides in Water-Cooled Copper Furnaces" , by F.H. Perfect, Transactions of the Metallurgical Society of AIME, Volume 239, August 1967, pp. 1282-1286.
The mixture is thoroughly and intimately mixed prior to being charged to the furnace so that the thermite reaction will occur rapidly and uniformly throughout the 5 charge on ignition.
The reaction vessel is preferably covered after the mixture is charged and the pressure within the vessel may be reduced, for example, to 0.3 mm Hg or less, followed by flooding the vessel with a high purity inert gas, e. g. , argon. Such evacuation and purging results in termites of higher purity, and lower nitrogen content. The thermite reaction is initiated with an igniter and is allowed to proceed to completion.
After the thermite is prepared using thermite processing, it is cooled and size reduced to powdered form using known methods, e. g. , crushers, ball mills, pug mills, grinders, hydriding, etc.
After size reduction, the intermetallic compound which is produced by the thermite process, is then mixed with at least one additional metal in powdered form, for example, Ti, to form a substantially-uniform mixture. The resulting mixture is then pressed into a compact or briquetted with application of pressures of over 7,000 psi and preferably of 15,000-30,000 psi. Typically, such compacts are formed using an isostatic press.
It is preferable, especially when forming large compacts, to place spacers at intervals within the compact in order to insure uniform compaction and produce more manageable compact sizes. Ten pound discs of compact are typically produced.
The discs are then stacked in the furnace and, when the reaction starts, it ends to be semi-continuous and controlled rather than violent. The smaller compacts, when stacked, also help prevent melting of the compact, which is in some cases an undesirable result.
The compacts of briquets are then fused, preferably with induction heat, to form the desired master alloy. No special pressure conditions are required for the fusion, which is generally carried out at atmospheric or a milli for pressure and temperatures of 600-1, 700 ° C, depending on the optimal fusion temperature of the compact.
In yet another preferred embodiment of the invention, a master alloy for use in hydrogen storage battery electrodes is prepared via thermite processing. A
charge of 32-42 % V205, 6-16 % C203, 7-17 % Co powder, 5-15 % Ni powder, 7-17 % Fe powder and 20-40 % A1 fines is mixed and ignited using thermite processing as previously discussed.
As is known, calcium oxide, fluorspar and NaC103 may be added to the charge.
The resulting intermetallic compound preferably comprises 8-18 % Cr, 10-20 % Fe, 8-Bum 38-48 % Va and trace amounts (less than 1 % ) of Al, C, N2, OZm P, Si, S
and other impurities. Most preferably, the resulting intermetallic compound comprises 12.9 % Cr, 15.3 % Co, 15 % Fe, 12.9 % Ni, 43.3 % Va and less than 5 % Al, C, N2, O2, P, Si, S and Ta.
The resulting intermetallic compound is size reduced as previously discussed and is then mixed with an appropriate amount of powdered metal to form a second mix which is compacted and fused by induction heating. This powdered metal preferably is Ni, Ti, Mn or Zr or mixtures thereof. Preferably, the powdered metals comprise a mixture of 20-30 % Ni, 7-17 % Ti and 18-28 % Zr, O-5 % Mn. Most preferably, the mixture of powdered metals added to the size reduced thermite comprises 25 units Ni, 12 units Ti and 23 units Zr. The powdered metals and size reduced thermite are .intimately mixed, compacted and fusion heated to yield an alloy of the general Formula TiX ZrY
VaZ Nim Cr", where the variables x, y, z, m and n may be as set forth in U.S. Patent Nos.
4,728,586 and 4,551,400. As disclosed in such prior art patents, particularly in U.S.
Patent No. 4,728,586 (col. 8, lines 17-21 and col. 11, lines 19-25), n is less than 0.20;
m is between 0.6*(1-n) and 3.5*(1-n); y is between 0 and 1.5*(1-n); z is (4-m)*(1-n) and x is (2-y)*(1-n).
In a highly preferred embodiment of the invention, the resulting alloy comprises 8-18 % Ti, 17-27 % Zr, 13-23 % V, 24-34 % Ni, 1-11 % Cr, 1-11 % Fe. A most preferred embodiment of the invention comprises 12. 5 % Ti, 22 % Zr, 17.5 % V , 29.2 %
Ni, 5 . 3 Cr, 6.2 % Co, and 6 % Fe. When prepared using the combined thermite and fusion heating steps as described, it has been found that such an alloy contains very low carbon, as low as 0.025 % , as little as one tenth that which had been produced using prior art graphite crucible melting furnace techniques.
charge of 32-42 % V205, 6-16 % C203, 7-17 % Co powder, 5-15 % Ni powder, 7-17 % Fe powder and 20-40 % A1 fines is mixed and ignited using thermite processing as previously discussed.
As is known, calcium oxide, fluorspar and NaC103 may be added to the charge.
The resulting intermetallic compound preferably comprises 8-18 % Cr, 10-20 % Fe, 8-Bum 38-48 % Va and trace amounts (less than 1 % ) of Al, C, N2, OZm P, Si, S
and other impurities. Most preferably, the resulting intermetallic compound comprises 12.9 % Cr, 15.3 % Co, 15 % Fe, 12.9 % Ni, 43.3 % Va and less than 5 % Al, C, N2, O2, P, Si, S and Ta.
The resulting intermetallic compound is size reduced as previously discussed and is then mixed with an appropriate amount of powdered metal to form a second mix which is compacted and fused by induction heating. This powdered metal preferably is Ni, Ti, Mn or Zr or mixtures thereof. Preferably, the powdered metals comprise a mixture of 20-30 % Ni, 7-17 % Ti and 18-28 % Zr, O-5 % Mn. Most preferably, the mixture of powdered metals added to the size reduced thermite comprises 25 units Ni, 12 units Ti and 23 units Zr. The powdered metals and size reduced thermite are .intimately mixed, compacted and fusion heated to yield an alloy of the general Formula TiX ZrY
VaZ Nim Cr", where the variables x, y, z, m and n may be as set forth in U.S. Patent Nos.
4,728,586 and 4,551,400. As disclosed in such prior art patents, particularly in U.S.
Patent No. 4,728,586 (col. 8, lines 17-21 and col. 11, lines 19-25), n is less than 0.20;
m is between 0.6*(1-n) and 3.5*(1-n); y is between 0 and 1.5*(1-n); z is (4-m)*(1-n) and x is (2-y)*(1-n).
In a highly preferred embodiment of the invention, the resulting alloy comprises 8-18 % Ti, 17-27 % Zr, 13-23 % V, 24-34 % Ni, 1-11 % Cr, 1-11 % Fe. A most preferred embodiment of the invention comprises 12. 5 % Ti, 22 % Zr, 17.5 % V , 29.2 %
Ni, 5 . 3 Cr, 6.2 % Co, and 6 % Fe. When prepared using the combined thermite and fusion heating steps as described, it has been found that such an alloy contains very low carbon, as low as 0.025 % , as little as one tenth that which had been produced using prior art graphite crucible melting furnace techniques.
As is known, it is preferred to use alcohol to keep the mix from separating prior to compaction. As previously discussed, the resulting alloy may be hydrided to produce an end product in size-reduced form, as is known.
Example It was desired to produce a master alloy for use in hydrogen storage battery electrode applications, the master alloy having 29 % Ni, 12 % Ti, 17 % V , 22 % Zr, 5 Cr, 6 % Co, and 6 % Fe. A thermite was first prepared by mixing 17 units of calcium oxide, 24 units of fluorspar, 7 units of NaC103, 42 units of aluminum fines, 12 units of iron powder, 10 units of nickel powder, 12 units of cobalt powder, 16 units of Cr203, and 67 units of VZOS. The mixture is reacted using thermite processing as described previously, and the resulting thermite was size reduced. 3,742 grams of this size-reduced thermite were mixed with 2268 grams of powdered nickel, 1089 grams of powdered titanium, 2077 grams of powdered zirconium and 75 ml of alcohol, and the mixture was mixed, compacted and fusion treated as described in Example 1 to produce a product which was hydrided as descried herein for size reduction to -200 mesh, yielding an alloy having the following analysis:
RAI McCreath A1 - 0.07 C - 0.025 Cr - 5. 32 Co - 6.23 Fe - 6.04%
H - 0.659 % (from hydriding step) Ni - 29.17 N - 0.008 O - 0.271 P - 0.01 Si - 0.100%
S - 0.001 Ti - 12.53 Va - 17.53 Zr - 22.00
Example It was desired to produce a master alloy for use in hydrogen storage battery electrode applications, the master alloy having 29 % Ni, 12 % Ti, 17 % V , 22 % Zr, 5 Cr, 6 % Co, and 6 % Fe. A thermite was first prepared by mixing 17 units of calcium oxide, 24 units of fluorspar, 7 units of NaC103, 42 units of aluminum fines, 12 units of iron powder, 10 units of nickel powder, 12 units of cobalt powder, 16 units of Cr203, and 67 units of VZOS. The mixture is reacted using thermite processing as described previously, and the resulting thermite was size reduced. 3,742 grams of this size-reduced thermite were mixed with 2268 grams of powdered nickel, 1089 grams of powdered titanium, 2077 grams of powdered zirconium and 75 ml of alcohol, and the mixture was mixed, compacted and fusion treated as described in Example 1 to produce a product which was hydrided as descried herein for size reduction to -200 mesh, yielding an alloy having the following analysis:
RAI McCreath A1 - 0.07 C - 0.025 Cr - 5. 32 Co - 6.23 Fe - 6.04%
H - 0.659 % (from hydriding step) Ni - 29.17 N - 0.008 O - 0.271 P - 0.01 Si - 0.100%
S - 0.001 Ti - 12.53 Va - 17.53 Zr - 22.00
Claims (18)
1. A process for preparing a master alloy for use in hydrogen storage battery electrodes, comprising the steps of:
(a) preparing a first mixture of at least one metal and at least one metal oxide, both in powdered form, and A1 in powdered or granular form, wherein said at least one metal and said at least one metal oxide are each independently a metal or an oxide of a metal which is selected from the group consisting of Ni, V, Cr, Co, and Fe;
(b) alloying said at least one metal and said at least one metal oxide to produce an intermetallic compound in an aluminothermic reaction;
(c) size reducing said intermetallic compound into powdered form;
(d) preparing a second mixture of said powdered intermetallic compound and at least one additional metal or alloy in powdered form, wherein said at least one additional metal or alloy is a metal or an alloy of a metal which is selected from the group consisting of Ni, Ti, Mn, Zr, Cr, Co, V and Fe;
(e) pressing said second mixture in powdered form to produce a compact; and (f) fusion heating said compact to produce a master alloy for use in hydrogen storage battery electrodes, said electrodes being formed of a metal which is selected from the group consisting of Ni, V, Cr, Co, Fe, Ti, Mn, and Zr.
(a) preparing a first mixture of at least one metal and at least one metal oxide, both in powdered form, and A1 in powdered or granular form, wherein said at least one metal and said at least one metal oxide are each independently a metal or an oxide of a metal which is selected from the group consisting of Ni, V, Cr, Co, and Fe;
(b) alloying said at least one metal and said at least one metal oxide to produce an intermetallic compound in an aluminothermic reaction;
(c) size reducing said intermetallic compound into powdered form;
(d) preparing a second mixture of said powdered intermetallic compound and at least one additional metal or alloy in powdered form, wherein said at least one additional metal or alloy is a metal or an alloy of a metal which is selected from the group consisting of Ni, Ti, Mn, Zr, Cr, Co, V and Fe;
(e) pressing said second mixture in powdered form to produce a compact; and (f) fusion heating said compact to produce a master alloy for use in hydrogen storage battery electrodes, said electrodes being formed of a metal which is selected from the group consisting of Ni, V, Cr, Co, Fe, Ti, Mn, and Zr.
2. The process according to claim 1, wherein said intermetallic compound of said alloying step (b) is produced from a first mixture of A1 fines with Ni powder, Co powder, Fe powder, V2O5 powder or Cr2O3 powder.
3. The process according to claim 1 or claim 2, wherein said alloying step (b) occurs in an inert atmosphere.
4. The process according to claim 1 or claim 2, wherein said alloying step (b) occurs at a reduced pressure of 0.3 mm Hg or less.
5. The process according to claims 1 to 4, wherein said alloying step (b) is performed in a water-cooled, copper, below-ground furnace.
6. The process according to claims 1 to 5, wherein said size reducing step (c) is performed by cooling said intermetallic compound and then size reducing said intermetallic compound by crushers, ball mills, pug mills, grinders or hydriding.
7. The process according to claims 1 to 6, wherein said compact of said pressing-step (e) is formed using an isostatic press at a pressure in excess of 7,000 psi.
8. The process according to claim 7, wherein said compacts are formed in ten pound discs and stacked intervals for the fusion heating step (f).
9. The process according to claims 1 to 8, wherein said fusion heating step (e) is by induction heating in an induction furnace.
10. The process according to claims 1 to 9, further comprising the step of:
(g) size reducing said master alloy to produce an end product in size reduced form.
(g) size reducing said master alloy to produce an end product in size reduced form.
11. The process according to claim 10, wherein said master alloy is size reduced by hydriding to -200 mesh.
12. The process according to claims 1 to 11, wherein said intermetallic compound comprises 8-18 % Ni, 38-48 % V, 8-18 % Cr, 10-20 % Co, 10-20 % Fe, and 0 to 0.5 % of Al, C, N2, O2, P, Si, S and other impurities, all percentages being percentage by weight.
13 . The process according to claims 1 to 11, wherein said master alloy, for use in hydrogen storage battery electrodes, said master alloy comprising 8-18 % Ti, 17-27 % Zr, 13-23 % V, 24-34 % Ni, 1-11 % Cr, 1-11 % Co, 1-11 % Fe, all percentages being percentage by weight and 0 to 0.025 % C.
14. A master alloy for use in hydrogen storage battery electrodes, said master alloy comprising: 8-18 % Ti, 17-27 % Zr, 13-23 % V, 24-34 % Ni, 1-11 % Cr, 1-11 % Co, 1-11 % Fe, all percentages being percentage by weight and 0 to 0.025 % C.
15. A master alloy according to claim 14, wherein said master alloy is 12.5 Ti, 22 % Zr, 17. 5 % V , 29.2 % Ni, 5.3 % Cr, 6.2 % Co, 6 % Fe, and 0. 025 %
C., all percentages being percentage by weight.
C., all percentages being percentage by weight.
16. An intermetallic alloy used to produce a master alloy for use in hydrogen storage battery electrodes, said intermetallic alloy comprising: 8-18 % Ni, 38-48 % V, 8-18 % Cr, 10-20 % Co, 10-20 % Fe, all percentages being percentage by weight and 0 to 0.5 % by weight of Al, C, N2 O2 P, Si, S and other impurities.
17. A hydrogen storage battery electrode, said electrode being formed from a master alloy which has been prepared by the process of claims 1 to 11.
18. A hydrogen storage battery electrode, said electrode being formed from a master alloy according to claim 14 or claim 15.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US919,171 | 1992-07-23 | ||
| US07/919,171 US5364587A (en) | 1992-07-23 | 1992-07-23 | Nickel alloy for hydrogen battery electrodes |
| PCT/US1993/006898 WO1994002274A1 (en) | 1992-07-23 | 1993-07-23 | Nickel alloy for hydrogen battery electrodes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2140337A1 CA2140337A1 (en) | 1994-02-03 |
| CA2140337C true CA2140337C (en) | 1999-09-28 |
Family
ID=25441635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002140337A Expired - Fee Related CA2140337C (en) | 1992-07-23 | 1993-07-23 | Nickel alloy for hydrogen battery electrodes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5364587A (en) |
| EP (2) | EP0950454A1 (en) |
| JP (1) | JP2787617B2 (en) |
| CA (1) | CA2140337C (en) |
| WO (1) | WO1994002274A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040099350A1 (en) * | 2002-11-21 | 2004-05-27 | Mantione John V. | Titanium alloys, methods of forming the same, and articles formed therefrom |
| KR100533329B1 (en) * | 2003-09-08 | 2005-12-05 | 한국과학기술연구원 | Preparation method of Ni-Al alloy anode for fuel cells using nickel powder |
| DE102008000433A1 (en) * | 2008-02-28 | 2009-09-03 | Chemetall Gmbh | Process for the production of alloy powders based on titanium, zirconium and hafnium alloyed with the elements Ni, Cu, Ta, W, Re, Os and Ir |
| CN102154566B (en) * | 2011-03-25 | 2012-07-25 | 重庆大学 | Method for preparing high-manganese-content manganese-aluminum masteralloy by taking pyrolusite as raw material |
| US9771634B2 (en) | 2014-11-05 | 2017-09-26 | Companhia Brasileira De Metalurgia E Mineração | Processes for producing low nitrogen essentially nitride-free chromium and chromium plus niobium-containing nickel-based alloys and the resulting chromium and nickel-based alloys |
| US10041146B2 (en) | 2014-11-05 | 2018-08-07 | Companhia Brasileira de Metalurgia e Mineraçäo | Processes for producing low nitrogen metallic chromium and chromium-containing alloys and the resulting products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2678272A (en) * | 1951-10-06 | 1954-05-11 | Climax Molybdenum Co | Molybdenum-columbium alloys |
| US2678269A (en) * | 1951-10-06 | 1954-05-11 | Climax Molybdenum Co | Molybdenum-titanium alloys |
| US2850385A (en) * | 1955-08-29 | 1958-09-02 | Universal Cyclops Steel Corp | Molybdenum-base alloy |
| US2819960A (en) * | 1956-11-15 | 1958-01-14 | Rem Cru Titanium Inc | Formable acid resistant titanium alloys |
| US2821475A (en) * | 1957-01-24 | 1958-01-28 | Rem Cru Titanium Inc | Titanium base alloys |
| US2938789A (en) * | 1959-05-18 | 1960-05-31 | Kennecott Copper Corp | Titanium-molybdenum alloys with compound formers |
| US3110589A (en) * | 1961-07-31 | 1963-11-12 | Du Pont | Molybdenum-titanium-silicon-nitrogen products and process for making same |
| US3370946A (en) * | 1965-09-21 | 1968-02-27 | Reactive Metals Inc | Titanium alloy |
| US3508910A (en) * | 1966-02-01 | 1970-04-28 | Crucible Inc | Master alloy |
| US3645727A (en) * | 1969-10-28 | 1972-02-29 | Crucible Inc | Method for melting titanium alloys |
| US3982924A (en) * | 1971-05-26 | 1976-09-28 | Reading Alloys, Inc. | Process for producing carbide addition agents |
| US4104059A (en) * | 1977-05-27 | 1978-08-01 | Reading Alloys, Inc. | Molybdenum-titanium-zirconium-aluminum master alloys |
| US4119457A (en) * | 1977-05-27 | 1978-10-10 | Reading Alloys, Inc. | Molybdenum-titanium-zirconium-aluminum master alloys |
| US4292077A (en) * | 1979-07-25 | 1981-09-29 | United Technologies Corporation | Titanium alloys of the Ti3 Al type |
| US4331475A (en) * | 1980-07-28 | 1982-05-25 | Reading Alloys, Inc. | Process for aluminothermic production of chromium and chromium alloys low in nitrogen |
| US4374667A (en) * | 1981-10-14 | 1983-02-22 | Reading Alloys, Inc. | Ferrovanadium carbide addition agents and process for their production |
| US4623597A (en) * | 1982-04-28 | 1986-11-18 | Energy Conversion Devices, Inc. | Rechargeable battery and electrode used therein |
| DE3409614A1 (en) * | 1984-03-16 | 1985-09-19 | GfE Gesellschaft für Elektrometallurgie mbH, 4000 Düsseldorf | ALLOY FOR THE PRODUCTION OF A TITANIUM ALLOY |
| US4551400A (en) * | 1984-04-18 | 1985-11-05 | Energy Conversion Devices, Inc. | Hydrogen storage materials and methods of sizing and preparing the same for electrochemical applications |
| JPS6148548A (en) * | 1984-08-13 | 1986-03-10 | Kobe Steel Ltd | Ti alloy having high pitting corrosion resistance in environment containing bromine ion |
| US4738822A (en) * | 1986-10-31 | 1988-04-19 | Titanium Metals Corporation Of America (Timet) | Titanium alloy for elevated temperature applications |
| US4728586A (en) * | 1986-12-29 | 1988-03-01 | Energy Conversion Devices, Inc. | Enhanced charge retention electrochemical hydrogen storage alloys and an enhanced charge retention electrochemical cell |
| US5002730A (en) * | 1989-07-24 | 1991-03-26 | Energy Conversion Devices | Preparation of vanadium rich hydrogen storage alloy materials |
| US5196048A (en) * | 1992-01-30 | 1993-03-23 | Teledyne Industries, Inc. | Process for preparing a vanadium-nickel-chromium master alloy |
-
1992
- 1992-07-23 US US07/919,171 patent/US5364587A/en not_active Expired - Lifetime
-
1993
- 1993-07-23 CA CA002140337A patent/CA2140337C/en not_active Expired - Fee Related
- 1993-07-23 EP EP99202002A patent/EP0950454A1/en not_active Withdrawn
- 1993-07-23 EP EP93918315A patent/EP0651682A4/en not_active Withdrawn
- 1993-07-23 JP JP6504689A patent/JP2787617B2/en not_active Expired - Lifetime
- 1993-07-23 WO PCT/US1993/006898 patent/WO1994002274A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0651682A4 (en) | 1997-01-02 |
| CA2140337A1 (en) | 1994-02-03 |
| JPH07506627A (en) | 1995-07-20 |
| JP2787617B2 (en) | 1998-08-20 |
| EP0950454A1 (en) | 1999-10-20 |
| EP0651682A1 (en) | 1995-05-10 |
| WO1994002274A1 (en) | 1994-02-03 |
| US5364587A (en) | 1994-11-15 |
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| EEER | Examination request | ||
| MKLA | Lapsed |