US2479311A - Production of oxygen-free copper - Google Patents

Production of oxygen-free copper Download PDF

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Publication number
US2479311A
US2479311A US604500A US60450045A US2479311A US 2479311 A US2479311 A US 2479311A US 604500 A US604500 A US 604500A US 60450045 A US60450045 A US 60450045A US 2479311 A US2479311 A US 2479311A
Authority
US
United States
Prior art keywords
copper
boron
graphite
crucible
oxygen
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
Application number
US604500A
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English (en)
Inventor
Arthur L Christensen
Horace F Silliman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Smelting and Refining Co
Original Assignee
Int Smelting & Refining Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE464343D priority Critical patent/BE464343A/xx
Application filed by Int Smelting & Refining Co filed Critical Int Smelting & Refining Co
Priority to US604500A priority patent/US2479311A/en
Priority to GB7557/46A priority patent/GB596214A/en
Priority to FR924662D priority patent/FR924662A/fr
Application granted granted Critical
Publication of US2479311A publication Critical patent/US2479311A/en
Anticipated expiration legal-status Critical
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
    • C22B15/0028—Smelting or converting
    • C22B15/0052—Reduction smelting or converting
    • 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

Definitions

  • This invention relates to the production of must be avoided and the residual excess of the oxygen-free copper and has for its object the prodegassing or deoxidizing element must be very vision of an improved method of producing subcarefully controlled.
  • boron has less ef-' stantially oxygen-free copper of high electrical feet on reducing the conductivity of copper than conductivity. 7 most other elements, it has'nevertheless sufiicient
  • the present invention is a variant of the invenefi'ect so that it must be maintained in the copper tion disclosed in the copending application of at less than 0.02%, if the A. S. T. M. specification Christensen, McKean' and Silliman Ser. No.
  • the molten copper e flects a removal these reducing gaseous imis effectively deoxidized by the action thereon of p jtje
  • the oxygen is th removed w t the hot carbon graphite-
  • the resulting cined charcoal, carbon monoxide free of water oxidized moltencopper (preferably at a tempera- Vapor and y g n or by the use of some ture of about 2200 F.) is then treated with boron xidizing l nt su h as phosphorus, lithium, to remove any dlssolved reducmg gasesboron, etc.
  • Elecirolyglcany g coppel contains 1 3 M the deoxidizingelement lowers the electrical con- 1 3 i iggs ig gfi i gg a g it; ductivity of the copper, and hence it is diflicult to 0 002% with arsenic and antimony present in the econommany produce hlghconductmty lesser amounts.
  • this copper has an electrical conductivity thls helietoior? generally zicqepted practlce the ranging from 100.5% to 101.5% I. A. c. s.
  • Cathode copper is a particuiarly desirable form of copper for the production of oxygen-free high conductivity copper, and customarily contains traces oi organic matter and traces of occluded electrolyte and: moisture.
  • the. course oi the: melt down. and deoxidation of the. copper by contact with hot; carbon or graphite, the impurities are. largely converted to, reducing gases such as. hydrogen, hydrogen sulphide and probably some hydrocarbons which may not crack at the prevailing; temperature.
  • reducing gases such as. hydrogen, hydrogen sulphide and probably some hydrocarbons which may not crack at the prevailing; temperature.
  • These re.- ducing gases are dissolved in the oxygen-tree molten copper and are effectively removed b the boron treatment. Since the copper contains. no oxygen, the boron is not a. deoXi-dizing agent, and only a relatively small amount is. required to remove the dissolved reducing gases. From 0.005 to 0.02% oi boron based on.
  • the weight of the molten copper treated is sufiicient for the purpose, and ordinarily about 0.01 boron by weight. gives entirely satisfactory results.
  • The. boron is pref erably introduced into the molten copper in the form of a master alloy of boron and copper con.- taining from 0.5 to boron and the balance copper with less than 1% impurities.
  • a boron-copper alloy admirably adapted for the practice of the invention is made in accordance with Silliman Patent. No. 2,195,433,. and contains 3 to 5% boron, around 95% copper and less than 1% impurities (mostly iron, silicon and magnesium).
  • the. copper is. preferably melted in a graphite crucible of a coreless induction furnace.
  • a graphite crucible With a graphite crucible, the furnace operates under a very steady power load because the crucible absorbs all the eddy currents. The crucible becomes the hottest part of the furnace and the copper is melted entirely by conduction of heat from the crucible.
  • Graphite is the preferred form of carbon because it is more dense and burns away less rapidly than other available forms of carbon.
  • the graphite or other form of carbon should be of high purity such for example as high quality Acheson graphite.
  • the graphite or carbon crucible may be locally heated 1 graphite paste bonded joints.
  • the crucible or the like may be made of or lined with carbon or graphite in various Ways.
  • the crucible may be lined with a plastic graphite mix containing a. carbonaceous binder, such, for example, as pitch orsugarsolution.
  • a. carbonaceous binder such as pitch orsugarsolution.
  • prefio-rmed: circle block linings may be used, with It is our present preferred practice to turn out the crucible from high. quality Acheson graphite electrodes.
  • Such electrodes are now available with diameters up to 24- inches.
  • a suitable crucible wall thickness is 3 inches and it is thus possible to develop inside dimensions of 1.8. inches. in diameter by about 3.0" inches: high which is a shape that allows a satisfactory'furnacedesign.
  • Such a crucible can produce about 2000:- pounds of oxygen-free. high conductivity copper per heat in a period or to. 9.0, minutes;
  • the carbon orgraphite crucible is of special advantage with respect to. the. boron treatment, .of' the molten copper.
  • Boron is an extremely energetic reducingagent, and reacts with the metal oxides. and silicates commonly present in many furnace refractories, thereby forming free metals (e. g. silicon and iron). which very deleteriously affect. the electricat conductivity of the copper.
  • free metals e. g. silicon and iron
  • Carbon and graphite are not only resistant to this action of boron, but are available in such pure state as not to contaminate the boron-treated copper.
  • verized graphite was placed on any exposed surface of the bath. The temperature was then taken with an optical pyrometer sighting into a closed end target tube submerged in the bath. If the temperature was 2200 F. treatment with the master alloy was made. If less than 2200" F. some additional heating was done.
  • the boron-copper alloy was used in three different amounts so as to treat the copper with 0.01%, 0.015% and 0.02% by weight of boron.
  • the degree of control obtained by the induction furnace heating was so precise that the electrical conductivities of castings resulting from an 0.02% boron treatment were 0.65% lower than castings resulting from an 0.01% boron treatment.
  • the average results of nine castings from each of the three boron treatments were as follows:
  • Oxygen-free copper with a residual boron content of 0.001 to 0.01% (and usually about 0.005%) can be consistently and economically produced by the invention.
  • the method of producing substantially OX- ygenfree copper which comprises melting copper in contact with carbon heated to a temperature above the melting temperature of copper and protecting the exposed surface of the resulting molten copper with a cover of finely divided carbon for a'suflicient period of time for the molten copper to become substantially completely deoxidized by contact with the hot carbon and to absorb reducing gases, and then removing the reducing gases from the resulting substantially completely deoxidized molten copper by treatment thereof with a boron-containing agent of the group consisting of boron and boron-copper.
  • the method of producing substantially oxygen-free copper which comprises melting copper in a carbon crucible heated to a temperature above the melting temperature of copper and protecting the exposed surface of the resulting molten copper with a cover of finely divided carbon and substantially completely deoxidizing the molten copper by the action thereon of the hot carbon of the crucible and with the absorption therein of reducing gases, and then removing the reducing gases from the resulting substantially completely deoxidized molten copper by treatment thereof with a boron-containing agent of the group consisting of boron and boron-copper in such amount as to introduce into the treated copper less than 0.02% of residual boron.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US604500A 1945-07-11 1945-07-11 Production of oxygen-free copper Expired - Lifetime US2479311A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE464343D BE464343A (en)van) 1945-07-11
US604500A US2479311A (en) 1945-07-11 1945-07-11 Production of oxygen-free copper
GB7557/46A GB596214A (en) 1945-07-11 1946-03-11 Improvements in production of oxygen-free copper
FR924662D FR924662A (fr) 1945-07-11 1946-04-01 Obtention de cuivre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US604500A US2479311A (en) 1945-07-11 1945-07-11 Production of oxygen-free copper

Publications (1)

Publication Number Publication Date
US2479311A true US2479311A (en) 1949-08-16

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ID=24419848

Family Applications (1)

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US604500A Expired - Lifetime US2479311A (en) 1945-07-11 1945-07-11 Production of oxygen-free copper

Country Status (4)

Country Link
US (1) US2479311A (en)van)
BE (1) BE464343A (en)van)
FR (1) FR924662A (en)van)
GB (1) GB596214A (en)van)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2670284A (en) * 1950-06-28 1954-02-23 Olin Ind Inc Production of nonferrous alloys
US2842438A (en) * 1956-08-02 1958-07-08 American Metal Climax Inc Copper-zirconium alloys
US2847303A (en) * 1957-01-04 1958-08-12 Georges Rene Jean Lafeuille Copper-base alloys
US2891860A (en) * 1957-08-13 1959-06-23 Thomas L Woolard Copper base brazing alloy
US3031568A (en) * 1956-08-02 1962-04-24 Ici Ltd Process of arc welding copper
US3352667A (en) * 1964-09-29 1967-11-14 Raytheon Co Prevention of hydrogen-embrittlement in oxygen-bearing copper
US3525605A (en) * 1966-05-04 1970-08-25 Outokumpu Oy Method for decreasing the softening temperature and improving the electrical conductivity of high conductivity oxygen-free copper
US3528803A (en) * 1966-12-28 1970-09-15 Hitachi Cable Method for manufacturing oxygen-free copper by casting
US3805000A (en) * 1970-03-23 1974-04-16 Itt Vacuum interrupter and methods of making contacts therefor
US4118256A (en) * 1976-05-11 1978-10-03 Electroschmelzwerk Kempten Gmbh Process for the production of oxygen-free copper casting and moldings
WO1983002681A1 (en) * 1982-02-02 1983-08-04 Scm Corp Incandescent lamp leads
US4400351A (en) * 1980-06-13 1983-08-23 Mitsubishi Kinzoku Kabushiki Kaisha High thermal resistance, high electric conductivity copper base alloy
US4749548A (en) * 1985-09-13 1988-06-07 Mitsubishi Kinzoku Kabushiki Kaisha Copper alloy lead material for use in semiconductor device
US4814235A (en) * 1984-07-21 1989-03-21 Kabel- Und Metallwerke Gutehoffnungshutte Ag Use of oxygen-free copper deoxidized by boron or lithium as material for hollow sections
US5306465A (en) * 1992-11-04 1994-04-26 Olin Corporation Copper alloy having high strength and high electrical conductivity
US5370840A (en) * 1992-11-04 1994-12-06 Olin Corporation Copper alloy having high strength and high electrical conductivity
US5486244A (en) * 1992-11-04 1996-01-23 Olin Corporation Process for improving the bend formability of copper alloys
CN102436863A (zh) * 2011-09-09 2012-05-02 西安近代化学研究所 塑性测压敏感元件用铜线
EP2476765A4 (en) * 2009-09-07 2015-10-07 Shirogane Co Ltd COPPER ALLOY AND METHOD FOR MANUFACTURING THE SAME
CN116445715A (zh) * 2022-12-22 2023-07-18 广州江铜铜材有限公司 一种铜杆连铸连轧生产线废弃氧化铜颗粒的处理方法
US11753700B2 (en) 2017-05-10 2023-09-12 Haldor Topsøe A/S Process for reducing the content of oxygen in metallic copper

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1023604A (en) * 1911-06-30 1912-04-16 Gen Electric Metal-casting.
US1578044A (en) * 1925-08-04 1926-03-23 Metals Refining Corp Method of purifying molten metals
US1955726A (en) * 1933-07-21 1934-04-24 Smith Corp A O Method of melting copper to produce dense castings low in oxygen
GB423697A (en) * 1932-06-06 1935-02-06 Electro Chimie Metal Process for the deoxidation of copper
US2003889A (en) * 1933-10-20 1935-06-04 American Brass Co Method of making deoxidized copper and copper alloys
US2195433A (en) * 1938-02-03 1940-04-02 American Brass Co Process for producing boron-copper alloys

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1023604A (en) * 1911-06-30 1912-04-16 Gen Electric Metal-casting.
US1578044A (en) * 1925-08-04 1926-03-23 Metals Refining Corp Method of purifying molten metals
GB423697A (en) * 1932-06-06 1935-02-06 Electro Chimie Metal Process for the deoxidation of copper
US1955726A (en) * 1933-07-21 1934-04-24 Smith Corp A O Method of melting copper to produce dense castings low in oxygen
US2003889A (en) * 1933-10-20 1935-06-04 American Brass Co Method of making deoxidized copper and copper alloys
US2195433A (en) * 1938-02-03 1940-04-02 American Brass Co Process for producing boron-copper alloys

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2670284A (en) * 1950-06-28 1954-02-23 Olin Ind Inc Production of nonferrous alloys
US2842438A (en) * 1956-08-02 1958-07-08 American Metal Climax Inc Copper-zirconium alloys
US3031568A (en) * 1956-08-02 1962-04-24 Ici Ltd Process of arc welding copper
US2847303A (en) * 1957-01-04 1958-08-12 Georges Rene Jean Lafeuille Copper-base alloys
US2891860A (en) * 1957-08-13 1959-06-23 Thomas L Woolard Copper base brazing alloy
US3352667A (en) * 1964-09-29 1967-11-14 Raytheon Co Prevention of hydrogen-embrittlement in oxygen-bearing copper
US3525605A (en) * 1966-05-04 1970-08-25 Outokumpu Oy Method for decreasing the softening temperature and improving the electrical conductivity of high conductivity oxygen-free copper
US3528803A (en) * 1966-12-28 1970-09-15 Hitachi Cable Method for manufacturing oxygen-free copper by casting
US3805000A (en) * 1970-03-23 1974-04-16 Itt Vacuum interrupter and methods of making contacts therefor
US4118256A (en) * 1976-05-11 1978-10-03 Electroschmelzwerk Kempten Gmbh Process for the production of oxygen-free copper casting and moldings
US4400351A (en) * 1980-06-13 1983-08-23 Mitsubishi Kinzoku Kabushiki Kaisha High thermal resistance, high electric conductivity copper base alloy
WO1983002681A1 (en) * 1982-02-02 1983-08-04 Scm Corp Incandescent lamp leads
US4426598A (en) 1982-02-02 1984-01-17 Scm Corporation Incandescent lamp leads of dispersion strengthened copper wires
US4814235A (en) * 1984-07-21 1989-03-21 Kabel- Und Metallwerke Gutehoffnungshutte Ag Use of oxygen-free copper deoxidized by boron or lithium as material for hollow sections
US4749548A (en) * 1985-09-13 1988-06-07 Mitsubishi Kinzoku Kabushiki Kaisha Copper alloy lead material for use in semiconductor device
US5306465A (en) * 1992-11-04 1994-04-26 Olin Corporation Copper alloy having high strength and high electrical conductivity
US5370840A (en) * 1992-11-04 1994-12-06 Olin Corporation Copper alloy having high strength and high electrical conductivity
US5486244A (en) * 1992-11-04 1996-01-23 Olin Corporation Process for improving the bend formability of copper alloys
US5601665A (en) * 1992-11-04 1997-02-11 Olin Corporation Process for improving the bend formability of copper alloys
EP2476765A4 (en) * 2009-09-07 2015-10-07 Shirogane Co Ltd COPPER ALLOY AND METHOD FOR MANUFACTURING THE SAME
CN102436863A (zh) * 2011-09-09 2012-05-02 西安近代化学研究所 塑性测压敏感元件用铜线
US11753700B2 (en) 2017-05-10 2023-09-12 Haldor Topsøe A/S Process for reducing the content of oxygen in metallic copper
CN116445715A (zh) * 2022-12-22 2023-07-18 广州江铜铜材有限公司 一种铜杆连铸连轧生产线废弃氧化铜颗粒的处理方法

Also Published As

Publication number Publication date
GB596214A (en) 1947-12-30
BE464343A (en)van)
FR924662A (fr) 1947-08-12

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