US3295963A - Alloys containing rare earth metals - Google Patents
Alloys containing rare earth metals Download PDFInfo
- Publication number
- US3295963A US3295963A US297695A US29769563A US3295963A US 3295963 A US3295963 A US 3295963A US 297695 A US297695 A US 297695A US 29769563 A US29769563 A US 29769563A US 3295963 A US3295963 A US 3295963A
- Authority
- US
- United States
- Prior art keywords
- weight
- rare earth
- silicon
- calcium
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/10—Making spheroidal graphite cast-iron
- C21C1/105—Nodularising additive agents
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
-
- 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
- Rare earth metals have previously been used as elements of addition in various metal systems to improve the characteristics and the properties thereof, as for example in additions to cast iron for the purpose of improving ductility and also for purposes of producing nodular or spherical graphite cast irons. Additions of rare earth metals have also been made to stainless steels, standard steels and special steels, and particularly steels obtained from scrap iron which are usually contaminated with copper, tin and lead, to improve the properties thereof. Other impurities in steels, such as phosphorus, arsenic, oxygen, nitrogen, and especially sulphur and hydrogen, appear to be effectively fixed by rare earth metals such as are made available for misch metal. For such purposes, use has been made of misch metal containing a mixture of cerium and lanthanum in dominant amounts.
- the rare earth metals such as cerium, lanthanum, neodymium, praseodymium, Samarium, gadolinium and yttrium, and misch metal can be prepared in a substantially pure state by igneous electrolysis or by thermal reaction of the metal in the presence of reducing agents such as calcium, but the preparation of such metals in a purified state involves careful and costly procedures. Because of the relatively low specific gravity of misch metal, cerium, etc. by comparison with iron, the misch metal, cerium, etc.
- rare earth metals appear to gather into pools or puddles at the time when introduced in molten iron, whereby solution or uniform distribution into the molten iron or steel is achieved very slowly and with difiiculty, and considerable misch metal, etc. is lost from the surface by combustion or oxidation.
- the misch metal, cerium, etc. have also been made available for use as alloys but in which relatively large amounts of silicon and/or calcium are also present to render such alloys unsuitable for use in steel making. Large amounts of calcium are particularly undesirable since calcium tends to promote the formation of undesirable inclusions.
- alloys of misch metal and other alloys of the rare earth metals which are capable of being inexpensively produced, easily and rapidly dissolved and uniformly distributed in desired amounts throughout the bath of the molten ferrous based metal or steel or alloy without the introduction of undesirable amounts of such impurities as calcium, silicon, carbon and the like, and
- the misch metal or rare earth metals can be formulated into an alloy system or mixture from which as much as 85-95% of the misch metal or rare earth metal is retained in the final product and wherein such.
- Patented Jan. 3, 1967 misch metal or rare earth metals in high concentrations are adapted for use in the production of nodular cast iron with the introduction of a minimum amount of misch metal or rare earth metal thereby to enhance effective control of the amounts of rare earth metal introduced without simultaneously introducing excessive amounts of impurities.
- the metal alloy produced in accordance with the practice of this invention for addition to ferrous metals and steels is formulated to contain more than 15% by weight of the rare earth metal or metals but not in excess of by weight; at least 12% by weight silicon but less than 45% by weight silicon; up to 6% by weight of calcium; and up to 65% by weight of iron.
- the materials are formulated to be present in the ratios of 1 part by weight silicon to .8-5 parts by weight of the rare earth metals and 1 part by weight of calcium to 5-150 parts by weight of the rare earth metals and the resulting alloy will have a specific gravity of about 4.
- alloy systems of this invention may be sub-divided in accordance to compositions as follows.
- the weight ratio of rare earth metals to silicon is maintained between 1 to 5, or 1 part by weight silicon to 1-5 parts by weight of rare earth metals, and the weight ratio of rare earth metals to calcium is maintained between 5 to 60 or 1 part by weight calcium to 5-60 parts by weight rare earth metals.
- Rare earth metals 40-55 Silicon 25-40 Calcium Up to 1 Iron 5-15 The ratio of components is maintained within the range of 1 part by weight silicon to 1-5 parts by weight rare earth metals and 1 part by weight of calcium to 20-100 parts by weight of rare earth metals.
- Rare earth metals More than 15 Rare earth metals Up to 35 Silicon 12-35 Calcium Up to .5 Iron 30-65 part by yttrium but in which the weight range of the yttrium in the above compositions may be expanded to within the range of .565% by weight while the other components remain substantially the same.
- the resulting alloy is especially well adapted for use in the introduction of rare earth metals into stainless steels which are adapted to contain a nickel and/or chromium or into nickel or chromium alloys or alloys of nickel and chromium, such as an alloy formed of 80% by weight chromium and 20% by Weight nickel.
- the rare earth metal alloys embodying the features of this invention are of sufiicient density and specific gravity to pass through the slag layer into the molten metal bath for admixture therewith or for solution therewith while the covering slag layer protects the introduced rare earth metals against loss by oxidation.
- the recovery of the rare earth metals introduced as an additive into the steel or other molten metal is maximized to provide yields in excess of 85% and up to 95% or better.
- An important feature of this invention resides in the utilization of the alloys described in the fabrication of nodular cast iron of regular or special steels wherein the reliability of the process depends upon the accuracy with respect to the quantity of the rare earth metals retained by the suitably de-oxidized ferrous metal bath. Such accurate control was not heretofore possible because of the large and uncontrolled losses of rare earth metal components by reason of oxidation at the surface.
- the rare earth metal alloys embodying the features of this invention are relatively free of loss by oxidation thereby to enable more accurate control in the amount of rare earth metal retained by the molten metal bath and thereby to enhance the procedures for addition and uniform distribution of the rare earth metal component.
- Another feature of this invention resides in the use of the rare earth metals alloyed in accordance with the practice of this invention for the manufacture of ordinary and special steels wherein the carbon, silicon and calcium content must be maintained at a minimum.
- Such usage was not available with rare earth metal systems of the type heretofore produced since it was previously unknown to provide a rare earth metal alloy having at most .06 carbon and moderate amounts, such as between 12-40% by weight silicon, and a low concentration, such as at most 1% by weight calcium, and particularly because of the rapid carburization of the alloy having a relatively low silicon content and containing rare earth metals.
- the invention also contemplates the use of the aforesaid alloys as mother alloys in the preparation of a number of variations of metal alloys of the type desired within the limits of specific gravity and for use in welding electrodes.
- a concept of this invention resides also in rare earth metal alloys containing silicon, carbon and iron within the limits described but in which part or all of the rare earth metal component comprises yttrium with the amount of yttrium being within the range of .5-15 by weight and within the ratio of yttrium to silicon and calcium of 1 part by weight silicon to .54 parts by weight yttrium and 1 part by weight of calcium to 2-100 parts by weight yttrium.
- the important feature of this invention resides in the use of this alloy in the preparation of nodular cast iron and improved steels.
- the yield of misch metal into the final product corresponds to a value of between 92-94% of the misch metal introduced. This indicates accurate control in the amount of rare earth metals introduced into the final product.
- the alloy which has a density of 4.2 and a melting point of 1260 C., is adapted for use in the introduction of yttrium in special steels.
- a rare earth metal alloy having the composition consisting essentially of 40-55% !by weight of rare earth metals, 25-40% by Weight of silicon, up to 1% by weight of calcium, and 5-15 by weight of iron and in which the silicon and calcium are present in the ratio of one part by weight of silicon to 1-5 parts by weight of the rare earth metal component and one part by weight of calcium to 20-100 parts by weight of the rare earth metal component said alloy having a specific gravity of at least 4.
- a rare earth metal alloy having the composition consisting essentially of 15-35% by weight of earth metals, 12-35% by weight of silicon, up to 0.5% by Weight of calcium and 30-65% by weight of iron and in which the silicon and calcium are present in the ratio of one part by weight of silicon to 0.8-4 parts by weight of the rare earth metal component and one part by weight of calcium to -150 parts by .weight of the rare earth metal component said alloy having a specific gravity of at least 4.
- a rare earth metal alloy as claimed in claim 1 in which the rare earth metal component is composed at least in part of yttrium present in an amount within the range of 05-15% by weight and in which the ratio of silicon and calcium to yttrium is within the range of 1 part :by weight silicon to 0.4-4 parts by weight yttrium and 1 part by weight calcium to 2-100 parts by weight yttrium.
- a rare earth metal alloy as claimed in claim 2 in which the rane earth metal component is composed at least in part of yttrium present in anamount within the range of 05-15% by weight and in which the ratio of silicon and calcium to yttrium is within the range of 1 part by weight silicon to 0.4-4 parts by weight yttrium and 1 part by weight calcium to 2-100 parts by weight yttrium.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR905267A FR1336858A (fr) | 1962-07-27 | 1962-07-27 | Alliages contenant des métaux des terres rares |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3295963A true US3295963A (en) | 1967-01-03 |
Family
ID=8784049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US297695A Expired - Lifetime US3295963A (en) | 1962-07-27 | 1963-07-25 | Alloys containing rare earth metals |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3295963A (de) |
| AT (1) | AT252292B (de) |
| ES (1) | ES290323A1 (de) |
| FR (1) | FR1336858A (de) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3440041A (en) * | 1966-05-06 | 1969-04-22 | Goldschmidt Ag Th | Method of producing rare earth metals and silicon alloys |
| US3440040A (en) * | 1966-05-06 | 1969-04-22 | Goldschmidt Ag Th | Process of making rare earth metals and silicon alloys |
| US3537844A (en) * | 1967-10-02 | 1970-11-03 | Ronson Corp | Process for preparing rare earth metal and silicon alloys |
| US3623862A (en) * | 1968-06-24 | 1971-11-30 | Int Harvester Co | Use of rare earth elements for reducing nozzle deposits in the continuous casting of steel process |
| US3977917A (en) * | 1974-06-17 | 1976-08-31 | Tohoku Metal Industries Limited | Permanent magnet materials |
| US3980468A (en) * | 1973-11-01 | 1976-09-14 | Cabot Corporation | Method of producing a ductile rare-earth containing superalloy |
| US3997338A (en) * | 1974-03-22 | 1976-12-14 | Centre De Recherches Scientifiques Et Techniques De L'industrie Des Fabrications Metalliques, En Abrege C.R.I.F. | Gray cast iron |
| US4018597A (en) * | 1975-08-05 | 1977-04-19 | Foote Mineral Company | Rare earth metal silicide alloys |
| US4636353A (en) * | 1983-07-05 | 1987-01-13 | Rhone-Poulenc Specialites Chimiques | Novel neodymium/iron alloys |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT260557B (de) * | 1965-05-06 | 1968-03-11 | Treibacher Chemische Werke Ag | Legierung zum Einbringen von SE-Metallen und/oder von Thorium in Metalle |
| FR2421948A1 (fr) * | 1978-04-06 | 1979-11-02 | Pro Chi Met Produits Chim Meta | Procede de preparation d'alliages ferreux sensiblement exempts de cerium, permettant d'ameliorer notamment leurs proprietes mecaniques grace a l'emploi de lanthane, et alliages ferreux obtenus par ce procede |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2221781A (en) * | 1938-04-14 | 1940-11-19 | Electro Metallurg Co | Addition agent and its use in the treatment of iron and steel |
| US2280284A (en) * | 1940-10-02 | 1942-04-21 | Electro Metallurg Co | Method and agent for treating iron and steel |
| US3055756A (en) * | 1958-12-15 | 1962-09-25 | Crane Co | Yttrium containing ferrous products and methods for preparing same |
| US3211549A (en) * | 1960-12-26 | 1965-10-12 | Yawata Iron & Steel Co | Additional alloys for welding and steel making |
-
1962
- 1962-07-27 FR FR905267A patent/FR1336858A/fr not_active Expired
-
1963
- 1963-07-24 AT AT591863A patent/AT252292B/de active
- 1963-07-25 US US297695A patent/US3295963A/en not_active Expired - Lifetime
- 1963-07-26 ES ES290323A patent/ES290323A1/es not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2221781A (en) * | 1938-04-14 | 1940-11-19 | Electro Metallurg Co | Addition agent and its use in the treatment of iron and steel |
| US2280284A (en) * | 1940-10-02 | 1942-04-21 | Electro Metallurg Co | Method and agent for treating iron and steel |
| US3055756A (en) * | 1958-12-15 | 1962-09-25 | Crane Co | Yttrium containing ferrous products and methods for preparing same |
| US3211549A (en) * | 1960-12-26 | 1965-10-12 | Yawata Iron & Steel Co | Additional alloys for welding and steel making |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3440041A (en) * | 1966-05-06 | 1969-04-22 | Goldschmidt Ag Th | Method of producing rare earth metals and silicon alloys |
| US3440040A (en) * | 1966-05-06 | 1969-04-22 | Goldschmidt Ag Th | Process of making rare earth metals and silicon alloys |
| US3537844A (en) * | 1967-10-02 | 1970-11-03 | Ronson Corp | Process for preparing rare earth metal and silicon alloys |
| US3623862A (en) * | 1968-06-24 | 1971-11-30 | Int Harvester Co | Use of rare earth elements for reducing nozzle deposits in the continuous casting of steel process |
| DE1931694B2 (de) * | 1968-06-24 | 1975-01-09 | International Harvester Co., Chicago, Ill. (V.St.A.) | Mischung zum Verhindern eines Verstopfens der Tauchausgußdüsen beim StahlstranggieBen |
| DE1931694C3 (de) * | 1968-06-24 | 1975-09-11 | International Harvester Co., Chicago, Ill. (V.St.A.) | Mischung zum Verhindern eines Verstopfens der Tauchausgußdüsen beim Stahlstranggießen |
| US3980468A (en) * | 1973-11-01 | 1976-09-14 | Cabot Corporation | Method of producing a ductile rare-earth containing superalloy |
| US3997338A (en) * | 1974-03-22 | 1976-12-14 | Centre De Recherches Scientifiques Et Techniques De L'industrie Des Fabrications Metalliques, En Abrege C.R.I.F. | Gray cast iron |
| US3977917A (en) * | 1974-06-17 | 1976-08-31 | Tohoku Metal Industries Limited | Permanent magnet materials |
| US4018597A (en) * | 1975-08-05 | 1977-04-19 | Foote Mineral Company | Rare earth metal silicide alloys |
| US4636353A (en) * | 1983-07-05 | 1987-01-13 | Rhone-Poulenc Specialites Chimiques | Novel neodymium/iron alloys |
| EP0272250A1 (de) * | 1983-07-05 | 1988-06-22 | Rhone-Poulenc Chimie | Verfahren zur Herstellung von Neodymlegierungen |
Also Published As
| Publication number | Publication date |
|---|---|
| AT252292B (de) | 1967-02-10 |
| ES290323A1 (es) | 1964-02-16 |
| FR1336858A (fr) | 1963-09-06 |
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