US3738827A - Method for adding solid metal to molten metal - Google Patents

Method for adding solid metal to molten metal Download PDF

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Publication number
US3738827A
US3738827A US00059348A US3738827DA US3738827A US 3738827 A US3738827 A US 3738827A US 00059348 A US00059348 A US 00059348A US 3738827D A US3738827D A US 3738827DA US 3738827 A US3738827 A US 3738827A
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US
United States
Prior art keywords
metal
copper
molten
clad
present
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
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US00059348A
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English (en)
Inventor
J Winter
M Pryor
J Crane
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Olin Corp
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Olin Corp
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Publication date
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Publication of US3738827A publication Critical patent/US3738827A/en
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Assigned to LASALLE NATIONAL BANK reassignment LASALLE NATIONAL BANK LICENSE MORTGAGE Assignors: LAWRENCE BROTHERS, INC.
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
    • 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
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • C22B9/103—Methods of introduction of solid or liquid refining or fluxing agents
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12222—Shaped configuration for melting [e.g., package, etc.]

Definitions

  • the disclosure teaches a method for adding solid metal to molten metal, especially without deleterious reaction with air.
  • the method is characterized by providing the solid metal in rod. or wire form clad with a material compatible with the molten metal and feeding the clad material into the molten metal.
  • the disclosure teaches novel composites to achieve this end. The method is particularly useful in deoxidizing molten metal.
  • the present invention relates to a novel means for adding solid metal to molten metal, preferably continuously, particularly the art of deoxidizing molten metal.
  • Metals of the lanthanide series are added to molten metal for a variety of reasons. These additions are commonly added to the melt in bulk form prior to the initiation of casting. They are known to improve the properties of lead bronzes and tin-lead bronzes. They are known to prevent burn-out in aluminum-magnesium alloys. They are also known to be highly useful in deoxidizing copper and copper base alloys.
  • ETP electrolytic tough pitch copper
  • OFHC oxygen-free, high conductivity
  • ETP copper does not resist hydrogen embrittlement, and in certain severe forming operations, does not perform as well as oxygen-free, high conductivity copper.
  • Metals of the lanthanide series are effective in reducing copper oxide and, therefore, providing an improved deoxidized copper which overcomes the foregoing dis advantages attributed to the performance of ETP copper.
  • the addition of one or more solid metallic elements of the lanthanide series to a molten copper mass added to the melt prior to casting presents particular difficulties arising from the reactivity of these elements with air.
  • the problem manifests itself in the formation of large clinker type oxides which can plug molten metal flow channels and appear as gross segregated impurities in the final ingot.
  • This problem has been circumvented by melting in vacuum or inert gas atmospheres.
  • melting in controlled atmospheres is a poorer solution for 3,738,827 Patented June 12, 1973 commercial preparation because it results in increased manufacturing costs.
  • boron, zirconium, titanium, chromium, magnesium and vanadium may be added for strengthening and other benefits. These may also cause severe problems when added directly to the melt and require special, often expensive, precautions in order to insure retention of the addition in useful form.
  • the addition of boron and zirconium to copper, for example, causes problems in maintaining control for these additions, especially at the low level at which they are normally added.
  • the problem with adding such elements relates both to avoiding oxidation and reaction with certain melt covers because of an undesirable reaction product and also because of distribution and control of level of addition. Similar problems exist in air melted or reactive environments, including reactions with atmospheres, containers (crucible materials), or melt covers, such as fluxes.
  • the present invention provides a method for adding a. solid metal to a molten metal 'mass, especially without deleterious reactions with air.
  • the process comprises:
  • (B) providing a solid metal, preferably in rod or wire Naturally, when the solid metal is not in rod or wire form, said solid metal must be substantially covered by the cladding.
  • the present invention is particularly useful in deoxidizing metal and especially deoxidizing copper base alloys with a metal of the lanthanide series in view of the difiiculties known heretofore in this art.
  • the present invention also provides a novel composite rod or wire which comprises a metal of the lanthanide series clad with a dissimilar metal, preferably clad with copper or a copper base alloy.
  • the present invention is admirably suited for use in any method wherein it is necessary or desirable to add a solid metal to a molten metal mass, especially where it is necessary to exercise particular precautions to avoid deleterious reactions with air.
  • certain covers or fluxes be used to protect the molten base metal alloy or to provide some desired reaction with the molten bath.
  • such materials are incompatible with certain additions.
  • the use of carbon covers although compatible with copper is incompatible with many desirable alloy additions, such as zirconium, titanium and chromium, which all combine with carbon to form undesirable carbides. Often, this provides difiiculties in getting the addition into solution without removing the cover and, therefore, resulting in undesirable exposure of the melt to air. Cladding of the addition prevents this premature side reaction.
  • the present invention circumvents many of these undesirable conditions. It allows, in particular, the addition to be made in a controlled fashion at the point of the melting or casting operation that is most desirable from the standpoint of the addition. Further, the present invention also prevents the interaction problems cited above.
  • the method of the present invention is particularly suitable in deoxidizing copper or copper base alloys with a metal of the lanthanide series. Accordingly, the present invention will be discused with particular reference to this art. It should be understood, however, that the present invention is more broadly relevant, as stated hereinabove.
  • ETP copper may be readily deoxidized using a metal of the lanthanide series and that this can be achieved commercially using air melting.
  • any copper base alloy may be conveniently utilized as the molten mass of metal.
  • the present invention readily provides a simple and convenient method for deoxidizing these copper base alloys.
  • a key feature of the present invention is the provision of a composite rod or wire which comprises a metal of the lanthanide series clad with a dissimilar metal.
  • the dissimilar metal should be compatible with the molten mass of metal to which the composite is added.
  • the clad rod or wire can be provided in various lengths and at various diameters.
  • the relationship of cladding to core dimensions can be chosen on the basis of the required addition. It is a principal intention of the present invention to provide a means for readily and conveniently incorporating alloying additions into the melt, generally in minor amounts up to 10% Therefore, the rod diameter must be proportionately related to casting rate.
  • ETP copper was deoxidized with misch metal clad copper rod according to the present invention. When casting at a rate of 800 lbs. per minute, 0.450" rod (misch metal clad with 0.030" copper) was fed at a rate of 25" per minute. This was sufiicient to give at 0.10% alloying addition to the melt.
  • the clad rod will vary from 0.125 to 1.0 inch in diameter, with the cladding preferably comprising from 5 to 25% thereof.
  • the present invention enables the introduction of the deoxidizing metal without the necessity of taking these unusual precautions.
  • the cladding be copper since it does not contain any impurities at levels that will elfect the product deleteriously. Furthermore, since its melting temperature is significantly higher than that of the lanthanide, the lanthanide will be protected until it is submerged beneath the level of the molten stream of copper. This reduces the lanthanide losses but more importantly prevents the formation of gross lanthanide oxide-coppercarbon clinkers which form the slag subsequent to deoxidation of copper when the lanthanide is added to a melting furnace of copper.
  • Misch metal is a mixture of rare earth metals containing a major amount of cerium, a minor amount of lanthanum and various other rare earth metals in smaller amounts.
  • the preferred material is misch metal or cerium.
  • the clad material may be readily prepared commercially.
  • misch metal may be inserted in commercial copper tubing and the assembly drawn through a drawing die which readily clads the misch metal to the copper tubing.
  • other methods may be utilized, if desired.
  • the control of the misch metal addition to the melt is maintained by selection of rod or wire diameter and rate of feeding into the melt.
  • the present invention is highly advantageous in other systems, several of which have been referred to hereinabove.
  • steel clad misch metal for boiler plates may be fed into the poor stream.
  • Copper covered magnesium or magnesium alloys are highly useful for adding magnesium to copper alloys.
  • the cladding should be the base metal itself or a metal compatible therewith and the core either the elemental addition or a master alloy thereof.
  • Several other systems include adding magnesium, manganese, boron and/ or titanium into copper, nickel or ferrous alloys.
  • lithium, gallium, sodium and/or calcium may be readily added to nickel and copper systems in accordance with the present invention as a means of broadening alloying availability.
  • EXAMPLE I An 8000 pound charge of ETP copper was induction melted using a charcoal-graphite cover in a commercial sized melting furnace. The residual oxide level was brought down to below 0.02% as determined by metallographic analysis. An 0.15% charge representing 12 pounds of misch metal was introduced and stirred both mechanically and electrically through the use of the inductive motor action to provide homogeneity. Of the 8000 pound charge, 6000 pounds were cast into a 5 /2" thick x 28 /2" wide rolling ingot. A glassy slag was found to be entrained in the solid material which, upon subsequent analysis, was revealed to be a complex formation consisting of graphite, misch metal, copper and other impurities. The material was not useable.
  • EXAMPLE II A clean furnace was charged with an 8000 pound charge of ETP copper and deoxidized with a charcoalgraphite cover to the 0.02% oxygen level in a manner similar to Example I. Instead of charging the misch metal to the furnace and stirring to achieve homogeneity. 4 diameter misch metal rods which had been encased (clad) in a copper tube were continuously fed into the stream of molten copper as it entered the 5% x 28 /2" mold. An amount equivalent to 0.10% which was equal to 8 pounds was carefully and uniformly introduced. The resulting ingot had discrete fine particles of misch metal oxide, but no gross glass-like slag inclusions were obvious as in Example I. The material was useable.
  • EXAMPLE III An experiment was conducted to determine whether bare misch metal could be used instead of the copper clad product. A section of A" extruded rod, 2-feet long was clamped in a vise and torch heated at the opposite end to bring the misch metal to its melting point of 1600 F. Long before approaching this elevated temperature, the misch metal ignited and was consumed in a violent combustion reaction.
  • a method for deoxidizing a molten metal mass selected from the group consisting of copper and copper base alloys which comprises:
  • a method for deoxidizing a molten metal mass selected from the group consisting of copper and copper base alloys which comprises:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Metal Extraction Processes (AREA)
US00059348A 1970-07-29 1970-07-29 Method for adding solid metal to molten metal Expired - Lifetime US3738827A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US5934870A 1970-07-29 1970-07-29

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US3738827A true US3738827A (en) 1973-06-12

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Country Status (5)

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US (1) US3738827A (cs)
CA (1) CA949756A (cs)
DE (1) DE2137996A1 (cs)
FR (1) FR2099656B1 (cs)
GB (2) GB1346438A (cs)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955967A (en) * 1973-05-02 1976-05-11 The Algoma Steel Corporation, Limited Treatment of steel
US3976477A (en) * 1974-12-23 1976-08-24 Olin Corporation High conductivity high temperature copper alloy
US4094666A (en) * 1977-05-24 1978-06-13 Metal Research Corporation Method for refining molten iron and steels
US4108637A (en) * 1976-10-06 1978-08-22 Ford Motor Company Sheathed wire feeding of alloy and inoculant materials
US4143211A (en) * 1974-05-01 1979-03-06 Nippon Steel Corporation Continuous casting addition material
US4154604A (en) * 1976-07-28 1979-05-15 Mannesmann Aktiengesellschaft Feeding additives into the interior of molten metal
FR2435598A1 (fr) * 1978-08-25 1980-04-04 Dresser Ind Outil de battage a resistance hydraulique variable, pour repechage d'objets dans un puits fore
US4224085A (en) * 1978-07-21 1980-09-23 The International Nickel Co., Inc. Wire forming process
US4308056A (en) * 1979-04-27 1981-12-29 Italsider S.P.A. Method and apparatus for introducing solid substances into liquid metals
US4330328A (en) * 1980-10-24 1982-05-18 Olin Corporation Process and apparatus for making a metal alloy
US4330327A (en) * 1980-10-24 1982-05-18 Olin Corporation Disposable bed filter process and apparatus
US4413813A (en) * 1980-10-24 1983-11-08 Olin Corporation Disposable bed filter apparatus
US6811589B2 (en) 2002-12-09 2004-11-02 Specialty Minerals Michigan Inc. Method for adding solid zinc-aluminum to galvanizing baths

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2269581A1 (en) * 1974-05-01 1975-11-28 Nippon Steel Corp Continuous casting and alloying of steel - by introducing the additions in the form of a shielded wire
US3921700A (en) * 1974-07-15 1975-11-25 Caterpillar Tractor Co Composite metal article containing additive agents and method of adding same to molten metal
CN117684013B (zh) * 2024-01-31 2024-06-07 赤峰金通铜业有限公司 降低铜冶炼锢铍发生率的装置及方法

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955967A (en) * 1973-05-02 1976-05-11 The Algoma Steel Corporation, Limited Treatment of steel
US4143211A (en) * 1974-05-01 1979-03-06 Nippon Steel Corporation Continuous casting addition material
US3976477A (en) * 1974-12-23 1976-08-24 Olin Corporation High conductivity high temperature copper alloy
US4154604A (en) * 1976-07-28 1979-05-15 Mannesmann Aktiengesellschaft Feeding additives into the interior of molten metal
US4108637A (en) * 1976-10-06 1978-08-22 Ford Motor Company Sheathed wire feeding of alloy and inoculant materials
US4094666A (en) * 1977-05-24 1978-06-13 Metal Research Corporation Method for refining molten iron and steels
US4224085A (en) * 1978-07-21 1980-09-23 The International Nickel Co., Inc. Wire forming process
FR2435598A1 (fr) * 1978-08-25 1980-04-04 Dresser Ind Outil de battage a resistance hydraulique variable, pour repechage d'objets dans un puits fore
US4308056A (en) * 1979-04-27 1981-12-29 Italsider S.P.A. Method and apparatus for introducing solid substances into liquid metals
US4330328A (en) * 1980-10-24 1982-05-18 Olin Corporation Process and apparatus for making a metal alloy
US4330327A (en) * 1980-10-24 1982-05-18 Olin Corporation Disposable bed filter process and apparatus
US4413813A (en) * 1980-10-24 1983-11-08 Olin Corporation Disposable bed filter apparatus
US6811589B2 (en) 2002-12-09 2004-11-02 Specialty Minerals Michigan Inc. Method for adding solid zinc-aluminum to galvanizing baths

Also Published As

Publication number Publication date
CA949756A (en) 1974-06-25
GB1346439A (en) 1974-02-13
GB1346438A (en) 1974-02-13
DE2137996A1 (de) 1972-02-10
FR2099656B1 (cs) 1975-02-07
FR2099656A1 (cs) 1972-03-17

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Owner name: LASALLE NATIONAL BANK, ILLINOIS

Free format text: LICENSE MORTGAGE;ASSIGNOR:LAWRENCE BROTHERS, INC.;REEL/FRAME:007613/0037

Effective date: 19950725