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US2810640A - Master alloys containing rare earth metals - Google Patents

Master alloys containing rare earth metals Download PDF

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Publication number
US2810640A
US2810640A US504653A US50465355A US2810640A US 2810640 A US2810640 A US 2810640A US 504653 A US504653 A US 504653A US 50465355 A US50465355 A US 50465355A US 2810640 A US2810640 A US 2810640A
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Prior art keywords
rare earth
earth metals
metal
metals
titanium
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US504653A
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Wilbur T Bolkcom
William E Knapp
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American Metallurgical Products Co
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American Metallurgical Products Co
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006Adding metallic additives
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C28/00Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00

Definitions

  • This invention relates to alloys and particularly to an addition alloy for steel and the like metals whereby rare earth metal may be more elfectively incorporated into the matrix metal.
  • the use of rare earth metals as an additive to metals matrices has long been known.
  • the use of the rare earth metals has, however, been somewhat limited by reason of the relatively low efiicienoy upon addition to the base or matrix material.
  • Rare earth metals have generally been added to metal matrices in the form of individual pure rare earth metals or in the form of mixtures such as Misch Metal which is a mixture of rare earth metals in the proportions in which they normally occur in ore bodies.
  • the effectiveness of the rare earth metals can be markedly increased by combining them with one or more metals of the group zirconium, titanium and hafnium in the form of an addition alloy.
  • zirconium, titanium and hafnium may be admixed with the rare earth metals in the following proportions:
  • the rare earth metals and one or more members of the group zirconium, titanium and hafnium in the above proportions may be and preferably is admixed with a diluent to form an addition alloy which has a high density and other desirable properties set out hereinafter.
  • the diluent is a mixture of metals having a high density and a relatively low melting point.
  • manganese and nickel in the proportion of about 1 /2 parts of manganese to 1 part nickel has a high density and a low melting point of about 1750 F.
  • the diluent may be iron, manganese, nickel, copper or similar metals either alone or in combination, to which are added a rare earth metal or rare earth metal mixture and one or more of the group zirconium, titanium and hafnium.
  • the addition alloy of our invention may have the following general composition:
  • preferred alloy has the following composition:
  • Rare earth metal 10 to 30 Diluent (preferably 1 /2 parts of manganese to 1 part nickel) Balance ited States Patent Patented Oct. 22, 1957
  • the alloy of our invention gives a much greater efficiency than the ordinary miseh metal of commerce, for example, in low alloy steel where the rare earth metals are added for improved impact properties, approximately 1 lb. per ton of ordinary miseh metal was required in order to achieve a minimum of 20 lbs. impact level on a V notch charpy test at minus 40 F. with a Brinell hardness of 500.
  • Our new alloy of this invention consisting of 45% manganese, 30% nickel, 20% miseh metal and 5% zirconium, required a total alloy addition of 1 lb. per ton or only 0.2 lb. per ton of rare earth metal. In short, we are able to obtain an identical result with the use of only /5 as much rare earth metal as has been required in the past.
  • the titanium, zirconium or hafnium appears to flux out residual dirt which sometimes occurs when rare earth metals are used in steel under unfavorable conditions and which has been a deterrent to the use of rare earth metals.
  • Misch metal is the term comm-only used in the industry for a mixture of rare earth metals produced by reduction from naturally occurring rare earth ores and contains an admixture of various rare earth metals in the approximate proportions in which they occur in the ore.
  • the most common rare earth metals are cerium, lanthanum, neodymium and praseodymium and these metals are the principal constituents of misch metal.
  • An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of a mixture of about 25% to 93% rare earth metals and about 7% to 75% of one or more metals selected from the group zirconium, titanium and hafnium all incorporated in a suflicient amount of metal diluent of high density compatible with the metal bath to form a mixture whose density is greater than the bath.
  • An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of a mix- .ture of about 45% to 93% rare earth metals and about 7% to 55% of one or more metals selected from 'the group zirconium, titanium and hafnium allincorporated in a sufiicient amount of metal diluent of high density compatible with the metal bath to form a mixture whose density is greater than the bath.
  • An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to of one or more metals selected from the group zirconium, titanium and hafnium and the balance a metal diluent of high density compatible with the metal bath.
  • An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 10% of one or more metals selected from the group zirconium, titanium and hafnium and the balance a metal diluent selected from the group manganese, nickel, copper and iron and mixtures thereof.
  • An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 25% of one or more metals selected from the group zirconium, titanium and hafnium and the balance made up of manganese and nickel in the proportions of 1 /2 parts of manganese to 1 part of nickel.
  • An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 12% of one or more metals selected from the group zirconium, titanium and hafnium and the balance made up of manganese and nickel in the proportions of about 1 /2 parts of manganese to 1 part of nickel.
  • An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 20% misch metal, 5% zirconium, 30% nickel and 45% manganese.
  • An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 20% misch metal, 5% titanium, 30% nickel and 45% manganese.
  • the method of adding rare earth metals to a metal bath comprising the steps of forming a molten bath of the metal to be treated, adding to the bath an alloy consisting essentially of about 25% to 93% rare earth metals and about 7% to of one or more metals selected from the group zirconium, titanium and hafnium.
  • the method of adding rare earth metals to a metal bath comprising the steps of forming a molten bath of thev metal to be treated, adding to the bath an admixture consisting essentially of about 10% to 30% rare earth metals, about 2% to 25% of one or more metals selected from the group zirconium, titanium and hafnium and the balance metal diluent of high density compatible with the metal bath.
  • An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 25 of one or more metals seletced from the group zirconium, titanium and hafnium and the balance iron.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)

Description

MASTER ALLOYS CONTAINING RARE EARTH METALS Wilbur T. Bolkcorn, Allison Park, and William E. Knapp, Pittsburgh, Pa., assignors to American Metallurgical Products (30., Pittsburgh, Pa., a partnership No Drawing. Application April 28, 1955, Serial No. 504,653
13 Claims. (Cl. 75-134) This invention relates to alloys and particularly to an addition alloy for steel and the like metals whereby rare earth metal may be more elfectively incorporated into the matrix metal. The use of rare earth metals as an additive to metals matrices has long been known. The use of the rare earth metals has, however, been somewhat limited by reason of the relatively low efiicienoy upon addition to the base or matrix material. Rare earth metals have generally been added to metal matrices in the form of individual pure rare earth metals or in the form of mixtures such as Misch Metal which is a mixture of rare earth metals in the proportions in which they normally occur in ore bodies.
We have found that the effectiveness of the rare earth metals can be markedly increased by combining them with one or more metals of the group zirconium, titanium and hafnium in the form of an addition alloy. We have found that zirconium, titanium and hafnium may be admixed with the rare earth metals in the following proportions:
Percent Rare earth metals 25 to 93 One or more of the group zirconium, titanium and hafnium 7 to 75 We have found that the rare earth metals and one or more members of the group zirconium, titanium and hafnium in the above proportions may be and preferably is admixed with a diluent to form an addition alloy which has a high density and other desirable properties set out hereinafter. Preferably the diluent is a mixture of metals having a high density and a relatively low melting point. We have found, for example, that manganese and nickel in the proportion of about 1 /2 parts of manganese to 1 part nickel has a high density and a low melting point of about 1750 F. The diluent, however, may be iron, manganese, nickel, copper or similar metals either alone or in combination, to which are added a rare earth metal or rare earth metal mixture and one or more of the group zirconium, titanium and hafnium. Broadly, the addition alloy of our invention may have the following general composition:
Percent One or more of the group zirconium, titanium and hafnium 2 to 25 Rare earth metal to 30 Diluent (preferably 1 /2 parts of manganese to 1 part nickel) Balance Preferably, however, we limited the composition of our addition alloy to a somewhat narrower range. The
preferred alloy has the following composition:
Percent One or more of the group zirconium, titanium and hafnium 2 to 12.
Rare earth metal 10 to 30 Diluent (preferably 1 /2 parts of manganese to 1 part nickel) Balance ited States Patent Patented Oct. 22, 1957 We have found that the alloy of our invention gives a much greater efficiency than the ordinary miseh metal of commerce, for example, in low alloy steel where the rare earth metals are added for improved impact properties, approximately 1 lb. per ton of ordinary miseh metal was required in order to achieve a minimum of 20 lbs. impact level on a V notch charpy test at minus 40 F. with a Brinell hardness of 500. Our new alloy of this invention consisting of 45% manganese, 30% nickel, 20% miseh metal and 5% zirconium, required a total alloy addition of 1 lb. per ton or only 0.2 lb. per ton of rare earth metal. In short, we are able to obtain an identical result with the use of only /5 as much rare earth metal as has been required in the past.
In stainless steel ordinary unprotected miseh metal gives a recovery of only approximately 50% of the rare earth elements, whereas the use of the present alloy permits recovery between to Several stainless steel heats using miseh metal in one series and the alloy of this invention (consisting of 45% manganese, 30% nickel, 20% miseh metal and 5% zirconium) in the other were prepared and the recovery or rare earth metals determined. The results of this study are set out in Table 1 herein below:
the titanium, zirconium or hafnium, as the case may be, appears to flux out residual dirt which sometimes occurs when rare earth metals are used in steel under unfavorable conditions and which has been a deterrent to the use of rare earth metals.
The effectiveness of rare earth metal additions to a base steel is perhaps most strikingly illustrated by a comparison of V notch charpy tests. A series of samples of a steel having 1.48% manganese, 28% carbon, 35% silicon, .0l5% sulphur, .Oll% phosphorus, .63% chromium, 58% molybdenum, .11% nickel and 002% boron were tested both with the addition of our new alloy, standard rare earth miseh metal, and without the addition of any We have found that the addition alloy of the present invention can be made most successfully by incorporating the titanium, zirconium or hafnium in the form of relatively pure metal such as sponge metal or scrap rather than in the form of their ferro alloys. We have found that the usual ferro titanium, ferro zirconium or nickelsilicon-titanium or nickel-silicon-zirconium form high melting intermetallic components when added to the rare earth metals, so that the recovery is relatively low and is extremely variable. For this reason and other reasons which are apparent from the foregoing disclosure the separate addition of rare earth metals and alloys of zirconium,'titanium or hafnium to the molten bath will not produce the unusual advantages characteristic of the addition alloy of our invention.
When we speak of rare earth metals in this application we have reference to that group of metals having atomic members between 58 and 71 of the periodic table. Misch metal is the term comm-only used in the industry for a mixture of rare earth metals produced by reduction from naturally occurring rare earth ores and contains an admixture of various rare earth metals in the approximate proportions in which they occur in the ore. The most common rare earth metals are cerium, lanthanum, neodymium and praseodymium and these metals are the principal constituents of misch metal.
We have set out certain preferred compositions of our alloy and have described a preferred method of making the same. It will be understood, however, that the alloy of this invention may be otherwise made and embodied within the scope of the following claims.
We claim:
1. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of a mixture of about 25% to 93% rare earth metals and about 7% to 75% of one or more metals selected from the group zirconium, titanium and hafnium all incorporated in a suflicient amount of metal diluent of high density compatible with the metal bath to form a mixture whose density is greater than the bath. 2. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of a mix- .ture of about 45% to 93% rare earth metals and about 7% to 55% of one or more metals selected from 'the group zirconium, titanium and hafnium allincorporated in a sufiicient amount of metal diluent of high density compatible with the metal bath to form a mixture whose density is greater than the bath.
3. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to of one or more metals selected from the group zirconium, titanium and hafnium and the balance a metal diluent of high density compatible with the metal bath.
4. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 10% of one or w into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 25 of one or more metals selected from the group zirconium, titanium and hafnium and the balance a metal diluent selected from the group manganese, nickel, copper and iron and mixtures thereof.
6. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 10% of one or more metals selected from the group zirconium, titanium and hafnium and the balance a metal diluent selected from the group manganese, nickel, copper and iron and mixtures thereof.
7. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 25% of one or more metals selected from the group zirconium, titanium and hafnium and the balance made up of manganese and nickel in the proportions of 1 /2 parts of manganese to 1 part of nickel.
8. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 12% of one or more metals selected from the group zirconium, titanium and hafnium and the balance made up of manganese and nickel in the proportions of about 1 /2 parts of manganese to 1 part of nickel.
9. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 20% misch metal, 5% zirconium, 30% nickel and 45% manganese.
10. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 20% misch metal, 5% titanium, 30% nickel and 45% manganese.
11. The method of adding rare earth metals to a metal bath comprising the steps of forming a molten bath of the metal to be treated, adding to the bath an alloy consisting essentially of about 25% to 93% rare earth metals and about 7% to of one or more metals selected from the group zirconium, titanium and hafnium.
12. The method of adding rare earth metals to a metal bath comprising the steps of forming a molten bath of thev metal to be treated, adding to the bath an admixture consisting essentially of about 10% to 30% rare earth metals, about 2% to 25% of one or more metals selected from the group zirconium, titanium and hafnium and the balance metal diluent of high density compatible with the metal bath.
13. An addition alloy for incorporating rare earth metals into a metal bath consisting essentially of about 10% to 30% rare earth metals, about 2% to 25 of one or more metals seletced from the group zirconium, titanium and hafnium and the balance iron.
References Cited in the file of this patent UNITED STATES PATENTS 1,023,208 Lesmuller Apr. 16, 1912 2,642,358 Kent June 16, 1953 FOREIGN PATENTS 488,322 Great Britain July 5, 1938 498,599 Belgium Feb. 1, 1951

Claims (1)

  1. 4. AN ADDITION ALLOY FOR INCORPORATING RARE EARTH METALS INTO A METAL BATH CONSISTING ESSENTIALLY OF ABOUT 10% TO 30% RARE EARTH METALS, ABOUT 2% TO 10% OF ONE OR MORE METALS SELECTED FROM THE GROUP ZIRCONIUM. TITANIUM AND HAFNIUM AND THE BALANCE A METAL DILUENT OF HIGH DENSITY COMPATIBLE WITH THE METAL BATH
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3163744A (en) * 1962-02-23 1964-12-29 United Aircraft Corp Non-consumable arc-melting and arc-welding electrodes
DE1242986B (en) * 1960-12-26 1967-06-22 Kazuji Kusaka Additional alloy for use in welding and steel manufacture
US3446615A (en) * 1967-05-11 1969-05-27 Iit Res Inst Hafnium base alloys
US3505064A (en) * 1965-10-21 1970-04-07 Atomic Energy Commission Hafnium alloy
US3515543A (en) * 1965-12-02 1970-06-02 Imp Metal Ind Kynoch Ltd Hafnium alloys
US3515544A (en) * 1965-12-02 1970-06-02 Imp Metal Ind Kynoch Ltd Hafnium alloys
FR2364972A1 (en) * 1976-09-16 1978-04-14 Inco Europ Ltd ALLOYS FOR THE PROCESSING OF MELTED METAL
US4221613A (en) * 1978-02-03 1980-09-09 Namiki Precision Jewel Co., Ltd. Rare earth-cobalt system permanent magnetic alloys and method of preparing same
US5200004A (en) * 1991-12-16 1993-04-06 Iowa State University Research Foundation, Inc. High strength, light weight Ti-Y composites and method of making same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE498599A (en) *
US1023208A (en) * 1908-12-30 1912-04-16 Ludwig Weiss Process for the production of pyrophorous substances for ignition and illumination.
GB488322A (en) * 1937-04-29 1938-07-05 Leonard Bessemer Pfeil Improvements in the alloying of metals
US2642358A (en) * 1949-09-20 1953-06-16 Kent Paula Cerium base alloy

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE498599A (en) *
US1023208A (en) * 1908-12-30 1912-04-16 Ludwig Weiss Process for the production of pyrophorous substances for ignition and illumination.
GB488322A (en) * 1937-04-29 1938-07-05 Leonard Bessemer Pfeil Improvements in the alloying of metals
US2642358A (en) * 1949-09-20 1953-06-16 Kent Paula Cerium base alloy

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1242986B (en) * 1960-12-26 1967-06-22 Kazuji Kusaka Additional alloy for use in welding and steel manufacture
US3163744A (en) * 1962-02-23 1964-12-29 United Aircraft Corp Non-consumable arc-melting and arc-welding electrodes
US3505064A (en) * 1965-10-21 1970-04-07 Atomic Energy Commission Hafnium alloy
US3515543A (en) * 1965-12-02 1970-06-02 Imp Metal Ind Kynoch Ltd Hafnium alloys
US3515544A (en) * 1965-12-02 1970-06-02 Imp Metal Ind Kynoch Ltd Hafnium alloys
US3446615A (en) * 1967-05-11 1969-05-27 Iit Res Inst Hafnium base alloys
FR2364972A1 (en) * 1976-09-16 1978-04-14 Inco Europ Ltd ALLOYS FOR THE PROCESSING OF MELTED METAL
US4121924A (en) * 1976-09-16 1978-10-24 The International Nickel Company, Inc. Alloy for rare earth treatment of molten metals and method
US4221613A (en) * 1978-02-03 1980-09-09 Namiki Precision Jewel Co., Ltd. Rare earth-cobalt system permanent magnetic alloys and method of preparing same
USRE31317E (en) * 1978-02-03 1983-07-19 Namiki Precision Jewel Co., Ltd. Rare earth-cobalt system permanent magnetic alloys and method of preparing same
US5200004A (en) * 1991-12-16 1993-04-06 Iowa State University Research Foundation, Inc. High strength, light weight Ti-Y composites and method of making same

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