US2850381A - Process and alloy for adding rare earth elements and boron to molten metal baths - Google Patents
Process and alloy for adding rare earth elements and boron to molten metal baths Download PDFInfo
- Publication number
- US2850381A US2850381A US302244A US30224452A US2850381A US 2850381 A US2850381 A US 2850381A US 302244 A US302244 A US 302244A US 30224452 A US30224452 A US 30224452A US 2850381 A US2850381 A US 2850381A
- Authority
- US
- United States
- Prior art keywords
- boron
- rare earth
- alloy
- earth elements
- earth metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims description 35
- 229910052796 boron Inorganic materials 0.000 title claims description 35
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 34
- 229910052751 metal Inorganic materials 0.000 title claims description 22
- 239000002184 metal Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 7
- 229910045601 alloy Inorganic materials 0.000 title description 30
- 239000000956 alloy Substances 0.000 title description 30
- 150000002910 rare earth metals Chemical class 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 13
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 238000007792 addition Methods 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- -1 rare earth metal salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys 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 imparting toughness and hardenability tometa-ls. Itis frequently desirable to add one or more of the rare earth metals and boron to a metal in order to increase its toughness and hardenability. In order to accomplish this it has been the general practice to add boron as ferroboron, boron silicon alloys and other boron combinations and the rare earth metals either in the form of the pure metals or in the form of rare earth metal salts to the molten metal to be treated either in the ladle or in the ingot.
- the alloy of our invention in general, has the following broad range of compositions:
- the single preferred alloy composition is:
- the action of the boron in our alloy is greatly intensified over the same amount of boron in the ordinary alloy used for boron additions. This may be the result of a greater affinity for nitrogen inherent in the rare earth metals which thereby protect the boron against the nitrogen.
- the rare earth recovery in the molten metal is extremely good and is much higher percentagewise than the recovers resulting from the addition of the pure rare earth metals or the salts to the molten metal.
- the use of our alloy substantially eliminates What is commonly termed fading in the steel industry, i. e., the decrease in the boron from the first poured to the last poured ingot.
- the alloy of our invention is particularly useful in electric furnace practice where, because of the presence of large amounts of nitrogen, the usual boron additions must be doubled or trebled in order to get a given boron residual as compared With the open hearth furnace.
- An addition alloy for imparting toughness and hardenability comprising about 10% to 95 manganese, up to about 75 nickel, about 5% to 60% of rare earth metals, about 1% to 10% boron, the balance iron with residual impurities in ordinary amounts.
- An addition alloy for imparting toughness and hardenability comprising about 25% to manganese, about 5% to 65% nickel, about 10% to 30% rare earth metals, about 1% to 10% boron, the balance iron with residual impurities in ordinary amounts.
- An addition alloy for imparting toughness and hardenability comprising about 10% to 95 manganese, up to about nickel, about 5% to 60% rare earth metals, about 1% to 10% boron, up to 20% iron, and the balance usual impurities in ordinary amounts.
- An addition alloy comprising about 40% manganese, about 25% nickel, about 25% rare earth metals, about 5% boron, and the balance iron with residual impurities in ordinary amounts.
- the method of simultaneously adding rare earth elements and boron to metals comprising forming a molten bath of the metal to which the rare earth element is to be added, adding to said molten bath an alloy comprising about 10% to manganese, up to about 75% nickel, about 5% to 60% of rare earth metals, about 1% to 10% boron, the balance being usual impurities in ordinary amounts, permitting the alloy to melt in said molten bath and solidifying the resulting molten mass.
- the method of simultaneously adding rare earth elements and boron to metals comprising forming a molten bath of the metal to which the rare earth element is to be added, adding to said molten bath an alloy comprising about 25% to 65% manganese, about 5% to 65 nickel, about 10% to 30% rare earth metals, about 1% to 10% boron, the balance iron with residual im- 3 purities in ordinary amounts, permitting the alloy to melt in said molten bath and solidifying the resulting molten mass.
- the method of simultaneously adding rare earth elements and boron to metals comprising forming a molten bath of the metal to which the rare earth element is to be added, adding to said molten bath an alloy comprising about 10% to 95% manganese, up to about 75% nickel, about 5% to 60% rare earth metals, about 1% to boron, up to about iron and the balance usual impurities in ordinary amounts, permitting the alloy to melt in said molten bath and solidifying the resulting molten mass.
- the method of simultaneously adding rare earth elements and boron to metals comprising forming a molten bath of the metal to which the rare earth element is to be added, adding to said molten bath an alloy comprising about manganese, about 25% nickel, about 25% rare earth metals, about 5% boron and the balance iron with residual impurities in ordinary amounts, permitting the alloy to melt in said molten bath and solidifying the resulting molten mass.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Description
United States Patent PROCESS AND ALLOY FOR ADDING RARE EARTH ELEMENTS AND BORON T0 M0 TEN METAL BATHS- Wilbur T. Bolkcom, Allison Park, and William E. Knapp,
Pittsburgh, Pa., assignors to American Metallurgicai Products Company, Pittsburgh, Pa-., a partnership N0 Drawing. Application August 1, 1952 SerialNo. 302,244
8 Claims. (Cl. 7'5-129) This invention relates to alloys and particularly to an addition alloy' for imparting toughness and hardenability tometa-ls. Itis frequently desirable to add one or more of the rare earth metals and boron to a metal in order to increase its toughness and hardenability. In order to accomplish this it has been the general practice to add boron as ferroboron, boron silicon alloys and other boron combinations and the rare earth metals either in the form of the pure metals or in the form of rare earth metal salts to the molten metal to be treated either in the ladle or in the ingot. In the case of the rare earth metals this has resulted in a substantial loss of metal through vaporization and failure of the metal to sink into the molten mass of metal being treated. In the case of boron, a large percentage of the boron reacts with nitrogen to form nitrides and the alloying efiect of the boron itself is substantially lost.
We have discovered an alloy by means of which the rare earth metals and boron may be incorporated into molten metals without the substantial loss of rare earth metals by vaporization common to the materials heretofore used and without the substantial loss of boron by the formation of nitrides. Our alloy, moreover, has the advantage of being much more dense than the forms of rare earth metals heretofore used as additions and as a result sinks into the molten metal being treated. At the same time, the melting point of our alloy is lower than the melting point of the usual addition alloys ordinarily added to iron and steel so that danger of segregation of undissolved or partially dissolved additions is avoided.
The alloy of our invention, in general, has the following broad range of compositions:
About 10% to 95% manganese About 0% to 75% nickel About to 60% rare earth metals About 1% to boron Preferably, however, we limit the range within the following composition:
About to 65% manganese About 5% to 65% nickel About 10% to rare earth metals About 1% to 10% boron The single preferred alloy composition is:
About manganese About 25% nickel About 25% rare earth metals About 5% boron 1 Balance iron with residual impurities in ordinary amounts 2,850,381 Patented Sept. 2, 1958 and the iron content of the alloy should for that reason be kept as low as possible. However, iron up to about 20% is generally not objectionable. In addition, our alloy ordinarily contains small amounts of impurities which result from the manufacturing process and are carried in with the raw materials. For example, a certain amount of carbon, silicon, sulphur, and phosphorus are found in the ordinarily raw materials used in the production of our alloy and these, as well as small amounts of other impurities, remain as residual impurities in our alloy. These usual residual impurities in ordinary amounts are not objectonable.
The action of the boron in our alloy is greatly intensified over the same amount of boron in the ordinary alloy used for boron additions. This may be the result of a greater affinity for nitrogen inherent in the rare earth metals which thereby protect the boron against the nitrogen. At the same time, the rare earth recovery in the molten metal is extremely good and is much higher percentagewise than the recovers resulting from the addition of the pure rare earth metals or the salts to the molten metal. The use of our alloy substantially eliminates What is commonly termed fading in the steel industry, i. e., the decrease in the boron from the first poured to the last poured ingot. The alloy of our invention is particularly useful in electric furnace practice where, because of the presence of large amounts of nitrogen, the usual boron additions must be doubled or trebled in order to get a given boron residual as compared With the open hearth furnace.
While we have described a particular embodiment of our invention it will be understood that it may be otherwise embodied within the scope of the following claims.
We claim:
1. An addition alloy for imparting toughness and hardenability comprising about 10% to 95 manganese, up to about 75 nickel, about 5% to 60% of rare earth metals, about 1% to 10% boron, the balance iron with residual impurities in ordinary amounts.
2. An addition alloy for imparting toughness and hardenability comprising about 25% to manganese, about 5% to 65% nickel, about 10% to 30% rare earth metals, about 1% to 10% boron, the balance iron with residual impurities in ordinary amounts.
3. An addition alloy for imparting toughness and hardenability comprising about 10% to 95 manganese, up to about nickel, about 5% to 60% rare earth metals, about 1% to 10% boron, up to 20% iron, and the balance usual impurities in ordinary amounts.
4. An addition alloy comprising about 40% manganese, about 25% nickel, about 25% rare earth metals, about 5% boron, and the balance iron with residual impurities in ordinary amounts.
5. The method of simultaneously adding rare earth elements and boron to metals comprising forming a molten bath of the metal to which the rare earth element is to be added, adding to said molten bath an alloy comprising about 10% to manganese, up to about 75% nickel, about 5% to 60% of rare earth metals, about 1% to 10% boron, the balance being usual impurities in ordinary amounts, permitting the alloy to melt in said molten bath and solidifying the resulting molten mass.
'6. The method of simultaneously adding rare earth elements and boron to metals comprising forming a molten bath of the metal to which the rare earth element is to be added, adding to said molten bath an alloy comprising about 25% to 65% manganese, about 5% to 65 nickel, about 10% to 30% rare earth metals, about 1% to 10% boron, the balance iron with residual im- 3 purities in ordinary amounts, permitting the alloy to melt in said molten bath and solidifying the resulting molten mass.
7. The method of simultaneously adding rare earth elements and boron to metals comprising forming a molten bath of the metal to which the rare earth element is to be added, adding to said molten bath an alloy comprising about 10% to 95% manganese, up to about 75% nickel, about 5% to 60% rare earth metals, about 1% to boron, up to about iron and the balance usual impurities in ordinary amounts, permitting the alloy to melt in said molten bath and solidifying the resulting molten mass.
8. The method of simultaneously adding rare earth elements and boron to metals comprising forming a molten bath of the metal to which the rare earth element is to be added, adding to said molten bath an alloy comprising about manganese, about 25% nickel, about 25% rare earth metals, about 5% boron and the balance iron with residual impurities in ordinary amounts, permitting the alloy to melt in said molten bath and solidifying the resulting molten mass.
References Cited in the file of this patent UNITED STATES PATENTS 1,869,497 Osborg Aug. 2, 1932 1,986,585 Kroll Jan. 1, 1935 2,144,200 Rohn et a1 Jan. 17, 1939 2,339,252 Dean Jan. 18, 1944 2,360,717 Phelps Oct. 17, 1944 2,622,022 Crome Dec. 16, 1952 2,642,358 Kent June 16, 1953 2,683,661 Tisdale et a1. July 13, 1954 FOREIGN PATENTS 375,792 Great Britain June 20, 1932 OTHER REFERENCES Udy: Boron in Steel, Metal Progress, August 1947, pages 257-264. (Copy in Div. 3, -B.) Pages 258 and 259 particularly pertinent.
Corbett et al.: Effects of Boron in Steel, Bureau of 20 Mines Report of Investigations 3816, June 1945, 21
pages. (Copy in Sci. Li-br.) Pages 5 and 12 particularly pertinent.
Claims (1)
- 5. THE METHOD OF SIMULTANEOUSLY ADDING RARE EARTH ELEMENTS AND BORON TO METALS COMPRISING FORMING A MOLTEN BATH OF THE METAL TO WHICH THE RARE EARTH ELEMENT IS TO BE ADDED, ADDING TO SAID MOLTEN BATH AN ALLOY COMPRISING ABOUT 10% TO 95% MANGANESE, UP TO ABOUT 75% NICKEL, AND 5% TO 60% OF RARE EARTH METALS, ABOUT 1% TO 10% BORON, THE BALANCE BEING USUAL IMPURITIES IN ORDINARY AMOUNTS, PERMITTING THE ALLOY TO MELT IN SAID MOLTEN BATH AND SOLIDIFYING THE RESULTING MOLTEN MASS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US302244A US2850381A (en) | 1952-08-01 | 1952-08-01 | Process and alloy for adding rare earth elements and boron to molten metal baths |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US302244A US2850381A (en) | 1952-08-01 | 1952-08-01 | Process and alloy for adding rare earth elements and boron to molten metal baths |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2850381A true US2850381A (en) | 1958-09-02 |
Family
ID=23166915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US302244A Expired - Lifetime US2850381A (en) | 1952-08-01 | 1952-08-01 | Process and alloy for adding rare earth elements and boron to molten metal baths |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2850381A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3124451A (en) * | 1964-03-10 | Manganese-base brazing alloys | ||
| US3189056A (en) * | 1961-10-18 | 1965-06-15 | Steel Heddle Mfg Co | Textile reed |
| DE1242986B (en) * | 1960-12-26 | 1967-06-22 | Kazuji Kusaka | Additional alloy for use in welding and steel manufacture |
| US4121924A (en) * | 1976-09-16 | 1978-10-24 | The International Nickel Company, Inc. | Alloy for rare earth treatment of molten metals and method |
| US4130447A (en) * | 1977-04-27 | 1978-12-19 | Centro Sperimentale Metallurgico S.P.A. | Annealing separator and steel sheet coated with same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB375792A (en) * | 1930-06-26 | 1932-06-20 | Krupp Ag | Improvements relating to processes for improving iron-boron alloys |
| US1869497A (en) * | 1931-06-26 | 1932-08-02 | Osborg Hans | Process of treating molten ferrous metals and alloys with compositions containing "lithium-alkali" alloys and products resulting from such treatments |
| US1986585A (en) * | 1930-03-08 | 1935-01-01 | Siemens Ag | Nickel alloy |
| US2144200A (en) * | 1936-06-27 | 1939-01-17 | Heraeus Vacuumschmelze Ag | Method of manufacturing siliconiron alloys |
| US2339252A (en) * | 1939-11-06 | 1944-01-18 | Chicago Dev Co | Manganese nickel alloy |
| US2360717A (en) * | 1942-11-27 | 1944-10-17 | Cerium Corp | Method of eliminating aluminate and silicate inclusions |
| US2622022A (en) * | 1948-07-31 | 1952-12-16 | Dayton Malleable Iron Co | Method for producing cast iron |
| US2642358A (en) * | 1949-09-20 | 1953-06-16 | Kent Paula | Cerium base alloy |
| US2683661A (en) * | 1951-10-31 | 1954-07-13 | Molybdenum Corp | Fine grain iron and method of production |
-
1952
- 1952-08-01 US US302244A patent/US2850381A/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1986585A (en) * | 1930-03-08 | 1935-01-01 | Siemens Ag | Nickel alloy |
| GB375792A (en) * | 1930-06-26 | 1932-06-20 | Krupp Ag | Improvements relating to processes for improving iron-boron alloys |
| US1869497A (en) * | 1931-06-26 | 1932-08-02 | Osborg Hans | Process of treating molten ferrous metals and alloys with compositions containing "lithium-alkali" alloys and products resulting from such treatments |
| US2144200A (en) * | 1936-06-27 | 1939-01-17 | Heraeus Vacuumschmelze Ag | Method of manufacturing siliconiron alloys |
| US2339252A (en) * | 1939-11-06 | 1944-01-18 | Chicago Dev Co | Manganese nickel alloy |
| US2360717A (en) * | 1942-11-27 | 1944-10-17 | Cerium Corp | Method of eliminating aluminate and silicate inclusions |
| US2622022A (en) * | 1948-07-31 | 1952-12-16 | Dayton Malleable Iron Co | Method for producing cast iron |
| US2642358A (en) * | 1949-09-20 | 1953-06-16 | Kent Paula | Cerium base alloy |
| US2683661A (en) * | 1951-10-31 | 1954-07-13 | Molybdenum Corp | Fine grain iron and method of production |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3124451A (en) * | 1964-03-10 | Manganese-base brazing alloys | ||
| DE1242986B (en) * | 1960-12-26 | 1967-06-22 | Kazuji Kusaka | Additional alloy for use in welding and steel manufacture |
| US3189056A (en) * | 1961-10-18 | 1965-06-15 | Steel Heddle Mfg Co | Textile reed |
| US4121924A (en) * | 1976-09-16 | 1978-10-24 | The International Nickel Company, Inc. | Alloy for rare earth treatment of molten metals and method |
| US4130447A (en) * | 1977-04-27 | 1978-12-19 | Centro Sperimentale Metallurgico S.P.A. | Annealing separator and steel sheet coated with same |
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