US3528803A - Method for manufacturing oxygen-free copper by casting - Google Patents

Method for manufacturing oxygen-free copper by casting Download PDF

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US3528803A
US3528803A US683285A US3528803DA US3528803A US 3528803 A US3528803 A US 3528803A US 683285 A US683285 A US 683285A US 3528803D A US3528803D A US 3528803DA US 3528803 A US3528803 A US 3528803A
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copper
molten
oxygen
hydrogen
molten copper
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Hiroshi Ichikawa
Rokuro Kawanishi
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Hitachi Cable Ltd
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Hitachi Cable Ltd
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    • 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

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  • a method of manufacturing oxygen-free copper comprises the steps of adding a very small amount of dehydrogenating agent to a molten electrolytic copper to react said dehydrogenating agent with hydrogen contained in said copper and then subjecting said dehydrogenating agent to a reaction with the oxy gen contained in the resultant molten copper and thereafter contacting dehydrogenating agent With a reducing as to effect deoxydation of the molten copper.
  • the present invention pertains to the industries for manufacturing copper articles such as wires, rod, bars and other electric articles.
  • Oxygen-free copper in general, refers to deoxidized copper having no residual deoxidizing agent and is characterized by not becoming brittle when it absorbs hydrogen, and by the superior electric conductivity which is at least 100%, and further by the absence of exfoliation of the oxide film.
  • ASTMB 170-59 describes a method for testing the increased brittleness of copper due to contact with hydrogen.
  • the relationship between the oxygen content of the copper and the increased brittleness due to the absorption of hydrogen by the copper, the permissible oxygen content of oxygen-free copper should be 0.0015% (15 ppm.) or less. It has been elucidated that in case the oxygen content is in the range between 0.0016% and 0.0019% (16-19 p.p.m.), the copper may or may not become brittle, and also that when the oxygen content is in the level of 0.02% (200 ppm), all of the test pieces invariably become brittle.
  • the aforesaid toughpitch copper is relatively superior in both electric conductivity and resistance to developing exfoliation of oxide film, it has a disadvantage that it easily becomes brittle when brought into contact with hydrogen. This poor resistance to brittleness when exposed to hydrogen is attributed to the fact that this tough-pitch copper contains a large amount of oxygen, for example, as much as 0.032% (320 p.p.m.).
  • this tough-pitch copper contains a large amount of oxygen, for example, as much as 0.032% (320 p.p.m.).
  • Another object of the present invention is to provide oxygen-free copper which is superior in the property of not becoming brittle when in contact with hydrogen, which is superior in electric conductivity and which does not develop exfoliation of oxide film.
  • Still another object of the present invention is to provide a novel method for manufacturing oxygen-free copper, said method being such that it is capable of extremely minimizing the oxygen and hydrogen contents of the molten copper.
  • Yet another object of the present invention is to provide a novel method for manufacturing oxygen-free copper, which is easy and which can be put into practice on an industrial basis and which is suitable for quantity production.
  • a further object of the present invention is to provide a novel method for manufacturing oxygen-free copper, said method being such that is suitable for the re-casting of copper ingots such as electrolytic copper.
  • a still further object of the present invention is to provide a novel method for manufacturing oxygen-free copper, said method being such that is suitable for being applied to the semi-continuous casting system and also to the fully-continuous casting system of copper.
  • a yet further object of the present invention is to provide a novel method for manufacturing oxygen-free copper, said method being such that can be applied to the production of either one of the products such as wirebars, ingots, cakes, billets and moldings, irrespective of their size.
  • Another object of the present invention is to provide a novel method for manufacturing oxygen-free copper, said method being such that is extremely economical in the aspect of cost of re-casting relative to the quantity of molten metal.
  • Still another object of the present-invention is to provide a method for manufacturing oxygen-free copper whose oxygen content is 0.0015% ppm.) or less and whose electric conductivity is 100% or more, by the use of a reducing gas.
  • molten copper points to such copper as electrolytic copper or other mass of copper which requires re-casting and which is in the state of being molten by being melted in a melting furnace or in an electric furnace.
  • casting herein used implies the casting processes which are generally used in the semi-continuous casting system, as well as in the fully-continuous casting system and also in other types of casting process of copper.
  • mold used in such casting is understood to mean such mold as is used in any one of these proc esses.
  • The'terms cast product of copper not only include Wirebars, ingots, cakes, billets and mold-castings, but also other cast masses obtained from casting and further includes all kinds of copper products obtained by further processing these cast masses into rods, wires, pipes or the like, regardless of their shape and size.
  • the dehydrogenating agent which is used in a very small amount in the present invention includes P, Li, Na, Pd and V. Besides these, Cr and Mn are also usable.
  • the amount of such a dehydrogenating agent which is used is very small.
  • the dehydrogenating agent consists of, for example, Li, Pd or V
  • the amount is 0.003% or less by weight.
  • the amount is in the range between 0.003% and 0.001% or less by weight.
  • the amount may be 0.0003%0.0004% by weight, or in some other cases, it may be 0.0006 %-0.0008% by weight.
  • dehydrogenating agent With some other kind of dehydrogenating agent, it is uniformly introduced into 16-18 tons of molten copper contained in a melting furnace in an amount of 0.0003 0.0004% by weight so that the dehydrogenating agent is uniformly contained in the cast product in an amount 0.0003% or less by weight.
  • dehydrogenating agents may be introduced into the molten copper either independently or in appropriate combination or in the form of an appropriate alloy of copper, and in appropriate shape such as ingot, plate, rod, chip, grain and powder.
  • Such a dehydrogenating agent may be charged into the melting furnace simultaneously with the copper stock which is to be re-cast.
  • the dehydrogenating agent may be added to the molten copper at a desired arbitrary site or sites such as in the molten metal transport vessel, the casting holding furnace and the casting vessel.
  • grains of Cu-base alloy consisting of 15% by weight of P, and Cu for the remaining part are introduced into the melting furnace continuously.
  • 0.01% by weight of P and 500 to 1000 kg. of copper billet after being deoxidized with phosphorus are charged jointly at predetermined intervals of time.
  • copper tubes having a diameter of 15 mm. and having, therein enclosed, powder of Cubase alloy containing 15% by weight of P are charged into a melting furnace at predetermined intervals of time.
  • a 30 kg. of a Cu-base alloy containing 0.15% by weight of P is charged into the melting furnace at each calculated casting time.
  • the agent is contained in the copper in the stage where the latter is melted in the melting furnace, because by doing so, the dehydrogenating agent is uniformly blended in the molten copper and also because the dehydrogenating agent can be made to conveniently contact a reducing atmosphere, in the later stage, which is produced by the use of a reducing agent.
  • dehydrogenating functions of the aforesaid dehydrogenating agents which are displayed by their reaction with hydrogen, are shown, as an example, as follows:
  • FIG. 1 shows the oxygenhydrogen equilibrium of the molten copper.
  • electrolytic copper is melted in a melting furnace while being covered by a layer of charcoal and then the molten copper is reduced with CO in the molten copper transport vessel, the molten copper is rendered to a condition that the latter quite easily absorbs hydrogen (H and as a result, the molten copper is allowed to absorb a large amount of H till an equilibrium value is attained in accordance with the amount of the water vapor (moisture) or the partial pressure of H in the atmosphere to which tre molten copper is exposed.
  • H hydrogen
  • the oxygen content of the molten copper may be arranged so as to assume an ideal value such as 0.001%0.0004% (1.0-4 p.p.m.).
  • an ideal value such as 0.001%0.0004% (1.0-4 p.p.m.).
  • the inside of the preserving vessel through which the molten metal is passed is kept under a reducing atmosphere by having the surface of the molten metal covered with a thick layer of charcoal, the molten metal will be cast, with H being retained in the metal.
  • gas-exhausting means 1n the equipment there is provided. However, such gas-exhausting means does not evenly exhaust gas from the molten metal. If the gas-exhausting function is such that is effective, for example, up to the depth of mm.
  • the gas expulsion function of such means is not carried out with a suflicient eifectiveness, with the result that the retention of H in the molten metal will not be avoided. If the hydrogen content of the molten meal exceeds a certain level, pinholes will develop in the ingot, and further, will result in the occurrence of a secondary crack formation in the ingot, leading to a reduction in the specific gravity of the ingot.
  • the technological problems in the present invention is focused on how to effectively control the presence of hydrogen which is easily absorbed into the molten metal during the manufacture of oxygen-free copper ingot.
  • the aim of the present invention lies in how to deviate the oxygen-hydrogen equilibrium from its relation diagram shown in FIG. 1 and eliminate oxygen and hydrogen from the molten copper.
  • the experiments consisted of daily draining 2 tons of molten copper which was stabilized in an induction furnace after setting the melting furnace and the preserving vessel into operation, and the corresponding quantity of copper was supplemented accordingly.
  • P, Li, Pd and V are used as the dehydrogenating agents for the expulsion of hydrogen from the molten copper and also for the prevention of intrusion of hydrogen into the molten copper.
  • the amount of the dehydrogenating agent used in the present invention is quite small, and in case the dehydrogenating agent consists of P, the amount used is 0.001% or less by weight,
  • the amount is 0.003% or less by weight.
  • a dehydrogenating agent for example, P
  • P is introduced into a melting furnace which contains H the charged P begins to react with this H (in accordance with the reaction formula already described), and the reacted P and H is discharged outside the molten copper in the form of gas which is insoluble in the molten copper.
  • the P which is located in the interface between the molten copper and the space thereabove then reacts with the H contained in the atmosphere located in the space above the face of the molten copper so that the P prevents the intrusion of hydrogen into the molten copper.
  • the intrusion of hydrogen into the molten copper contained in the furnaces of the casting equipment is inhibited.
  • the oxygen-hydrogen equilibrium in the molten copper, shown in FIG. 1 is broken. This is a very important element of the present invention.
  • the hydrogen-free molten copper can then be easily deoxidized by a reducing agent, for example, CO, which will be described later, without being restrained by the oxygen-hydrogen equilibrium of the molten copper.
  • a reducing agent for example, CO, which will be described later
  • substantially pure copper containing hardly any hydrogen or oxygen can Ibe manufactured.
  • the amount of the dehydrogenating agent which is used in the present invention can be determined, within a range of a trifle amount, appropriately, in accordance with the hydrogen content of the molten copper.
  • reducing agent used in the present invention point to carbon monoxide (CO), carbonic acid gas (CO carbon (C), and hydrocarbons (both saturated and unsaturated hydrocarbons), which may be used either independently or in appropriate combination.
  • Carbon includes charcoal.
  • the principal object of bringing molten copper into contact with a reducing agent in the present invention resides in the expulsion of oxygen contained in the molten copper. Therefore, the means of doing so as well as the sites where such contact is effected can vary.
  • a melting furnace is provided with an opening through which the materials are charged.
  • a reducing agent such as CO is not suitable for use in a melt ing furnace, but charcoal will satisfy the purpose.
  • the molten copper transport vessels are connected to a melting furnace sideways or verticalwise in case the molten copper is drained from the melting furnace into the trans port vessels, this means that the atmosphere in the melting furnace will be completely dissociated from the transport vessels and also from the subsequent stages.
  • Both the preserving furnace and the transport vessel are, on the other hand, generally substantially closed and, therefore, they share the same atmosphere.
  • the oxygen content of the copper ingot and molded product can be reduced to 0.0008%0.0004% (84 p.p.m.).
  • the gas produced from imperfect combustion of charcoal is composed roughly of 6% of CO, 12.5% of CO and 3% of H
  • the oxygen content of the copper ingot and cast product obtained from the use of said gas can be reduced to 0.001% (10 ppm.) or less.
  • the oxygen content can be decreased to 0.0006% (6 ppm).
  • the dioxidizing action of CO will decrease where the amount of CO decreases to 4% or less.
  • Electrolytic copper plates were continuously charged into the melting furnace through the inlet, while copperbase alloy ingots containing 0.15% by weight of phosphorus were introduced at each calculated casting time to insure that blending be made so that the 16 to 18 tons of molten copper in the melting furnace uniformly contained 0.0003% to 0.0004% by weight of phosphorus.
  • a thick layer of charcoal was laid on the surface of molten copper contained in both the melting furnace and the preserving furnace so as to cover the surface of the molten copper.
  • a gas having the composition of 30% of CO and 70% of N and serving as the reducing agent was fed to three sites, namely, a central portion of the molten copper transport vessel, a side portion of the preserving furnace and an upper portion of the preserving furnace, through pipes, respectively.
  • the molten copper contained in the melting furnace was passed from the outlet thereof into the molten copper transport vessel, and therefrom to the preserving furnace, and therefrom into the casting vessel, successively, and then finally into the mold, and thus a desired cast product was obtained.
  • the dehydrogenating agent reacted with the hydrogen which was present in the molten copper as well as in the space above the face of the molten copper, in the following manner, namely,
  • the hydrogen contained in the molten copper reacted with phosphorus and was discharged outside the molten copper in the form of a gas insoluble in the molten copper.
  • the hydrogen contained in the molten copper was expelled therefrom, while the hydrogen located in the space above the molten copper also selectively reacted with the phosphorus which was located in the interface between the molten copper and the space so as to prevent the hydrogen from intruding into the molten copper.
  • the resulting hydrogen-free molten copper was then brought into contact, in both the molten copper transport vessel and the preserving furnace, with the CO which was fed from the protective gas generator and was positively deoxidized thereby, and thus, it was possible to obtain a cast product of pure copper which hardly contains any oxygen or hydrogen.
  • the phosphorus content of the cast product thus obtained was 0.0005 (5' p.p.m.) or less by weight, while the oxygen content was in the range between 0.0008% and 0.0004% (between 8 and 4 ppm.) by weight.
  • composition of the oxygen-free copper which was produced by casting the molten copper according to the present invention was compared with the compositions of the already reported cast copper products, and the result is shown in the following Table 1.
  • the cast products obtained according to the present invention are of an extremely high purity and are perfectly homogeneous in contrast to the tough-pitch copper which is heterogeneous and contains a eutectic of CD20.
  • the oxygen-free copper of the present invention completely eliminates the shortcomings of both the tough-pitch copper and the copper deoxidized by phosphorus of the prior art, but bears all the strong points of these copper products of the prior art.
  • the ingot or the cast product of the present invention is sound in itself and does not tend to develop flaws during the subsequent processing steps. Moreover, it has a high electric conductivity, does not discharge any gas, can be easily processed, and can be easily drawn deeply and has a superior arc-resisting property.
  • the ingot and the cast product of the present invention is manufactured in such manner that its hydrogen and oxygen contents are minimized to an extreme degree by a novel manufacturing method designed so as to break the oxygen-hydrogen equilibrium of the molten copper.
  • the product is given a superior property not to develop exfoliation of oxide film and not to develop pinholes or blowholes in the cast mass, and thus, the cast product of the present invention is characterized by its being sound in quality as a cast mass and also by high density of the cast mass.
  • the density of the cast mass of the product of the present invention is compared with that of the toughpitch copper in the following Table 2.
  • the superior quality of the cast product of the present invention will be appreciated by reviewing this table.
  • the presence of phosphorus in the cast product of copper is effected in such pattern that the phosphorus is present in the form of solid solution, and this phosphorus reduces the electric conductivity of the product. Therefore, phosphorus is used in the present invention only in a very minute amount and strictly as a dehydrogenating agent.
  • the content of such phosphorus in the copper is in the order of from 0.0002% to 0.0005 (2 to 5 p.p.m.). As such, the cast product of the present invention is of an excellent electric conductivity.
  • the manufacturing method of the present invention is suitable for use in the re-casting of, for example, electrolytic copper into a cast product.
  • this method is employed in the semi-continuous casting system and fullycontinuous casting system, it will provide a good efficiency of the operation, and therefore, the method of the present invention is suitable for quantity production and satisfies the industrial requirements.
  • One advantage of the manufacturing method of the present invention in the aspect of operation is that the performance and control of this method can be quite easily effected.
  • electrolytic copper where electrolytic copper is re-casted, for example, there are detected not only the elements which constitute the electrolytic copper, i.e. 99.997% by weight of Cu, 6.1 gr./ton of Ag, 0.068 gr./ton of Au, 0.0001% by weight of Ni, 0.0001% by weight each of Sb, As, Fe and Zn and further 0.0006% by weight of S and 0.0003% by weight of Pb, but also P, Li, Na or Pd which is used as a dehydrogenating agent. It is, therefore, easily inferred when these substances are detected by the analysis of the product, that the manufacturing method of the present invention is employed in the manufacture of such product.
  • a method of manufacturing oxygen-free copper comprising:
  • dehydrogenating agent is selected from the group consisting of P, Li, Pd, Na, Cr, Mn and V.
  • a method of manufacturing cast oxygen-free copper ingots comprising the steps of:
  • dehydrogenating agent is selected from the group consisting of P, Li, Pd, Na, Cr, Mn, and V.
  • a method of manufacturing cast oxygen-free copper ingots comprising:
  • molten copper admixing molten copper with an effective amount up to about 0.003% by weight of a dehydrogenating agent so as to cause reactions between the dehydrogenating agent and hydrogen contained in the molten copper and between the dehydrogenating agent at the top surface of the said molten copper and the hydrogen present in the atmosphere in the space above the surface while the copper is still in the molten state, thereby effecting dehydrogenation of the molten cop P contacting said dehydrogenaetd molten copper with a reducing agent to deoxidize: the molten copper;
  • dehydrogenating agent is selected from the group consisting of P, Li, Pd, Na, Cr, Mn and V.
  • a method of manufacturing cast oxygen-free copper ingots comprising the steps of:
  • the reducing agent is a reducing gas such as carbon monoxide (CO).
  • a method of manufacturing oxygen-free copper which comprises:

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3987224A (en) * 1975-06-02 1976-10-19 General Electric Company Oxygen control in continuous metal casting system
US4055415A (en) * 1975-04-16 1977-10-25 Csepeli Femmu Process for the removal of alloying impurities in a slag-covered copper refining bath
US5306329A (en) * 1993-04-09 1994-04-26 Goodman Jr Warren B Phosphorous deoxidation of metal
US20030194893A1 (en) * 2002-04-15 2003-10-16 Sumitomo Wiring Systems, Ltd. Arc-resistant terminal, arc-resistant terminal couple and connector or the like for automobile
EP1385363A4 (en) * 2001-04-06 2005-06-29 Mitsui Mining & Smelting Co PRINTED CIRCUIT BOARD AND METHOD FOR CARRYING OUT THE SAME, AND LAMINATED PRINTED CIRCUIT BOARD
US6944930B2 (en) * 2000-02-24 2005-09-20 Mitsubishi Materials Corporation Method for manufacturing low-oxygen copper
US10236272B2 (en) 2015-05-26 2019-03-19 Nippon Micrometal Corporation Cu alloy core bonding wire with Pd coating for semiconductor device
CN115493402A (zh) * 2022-08-29 2022-12-20 金川集团股份有限公司 一种工频感应炉熔沟凝固和二次起熔的方法
US11753700B2 (en) 2017-05-10 2023-09-12 Haldor Topsøe A/S Process for reducing the content of oxygen in metallic copper

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1869498A (en) * 1931-06-26 1932-08-02 Osborg Hans Process of treating molten copper and copper alloys with compositions containing "lithium-alkali" alloys and products resulting from such treatments
US2031518A (en) * 1934-06-27 1936-02-18 American Lurgi Corp Method of producing copper having high electrical conductivity and being free from oxygen
US2102742A (en) * 1935-03-26 1937-12-21 American Smelting Refining High conductivity, phosphorus-deoxidized copper and process for making the same
US2452996A (en) * 1946-06-15 1948-11-02 Linde Air Prod Co Process for refining copper and its alloys
US2479311A (en) * 1945-07-11 1949-08-16 Int Smelting & Refining Co Production of oxygen-free copper

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1869498A (en) * 1931-06-26 1932-08-02 Osborg Hans Process of treating molten copper and copper alloys with compositions containing "lithium-alkali" alloys and products resulting from such treatments
US2031518A (en) * 1934-06-27 1936-02-18 American Lurgi Corp Method of producing copper having high electrical conductivity and being free from oxygen
US2102742A (en) * 1935-03-26 1937-12-21 American Smelting Refining High conductivity, phosphorus-deoxidized copper and process for making the same
US2479311A (en) * 1945-07-11 1949-08-16 Int Smelting & Refining Co Production of oxygen-free copper
US2452996A (en) * 1946-06-15 1948-11-02 Linde Air Prod Co Process for refining copper and its alloys

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4055415A (en) * 1975-04-16 1977-10-25 Csepeli Femmu Process for the removal of alloying impurities in a slag-covered copper refining bath
US3987224A (en) * 1975-06-02 1976-10-19 General Electric Company Oxygen control in continuous metal casting system
US5306329A (en) * 1993-04-09 1994-04-26 Goodman Jr Warren B Phosphorous deoxidation of metal
US7524356B2 (en) 2000-02-24 2009-04-28 Mitsubishi Materials Corporation Method for manufacturing low-oxygen copper
US6944930B2 (en) * 2000-02-24 2005-09-20 Mitsubishi Materials Corporation Method for manufacturing low-oxygen copper
EP1385363A4 (en) * 2001-04-06 2005-06-29 Mitsui Mining & Smelting Co PRINTED CIRCUIT BOARD AND METHOD FOR CARRYING OUT THE SAME, AND LAMINATED PRINTED CIRCUIT BOARD
US7163753B2 (en) * 2002-04-15 2007-01-16 Sumitomo Wiring Systems, Ltd. Arc-resistant terminal, arc-resistant terminal couple and connector or the like for automobile
US20030194893A1 (en) * 2002-04-15 2003-10-16 Sumitomo Wiring Systems, Ltd. Arc-resistant terminal, arc-resistant terminal couple and connector or the like for automobile
US10236272B2 (en) 2015-05-26 2019-03-19 Nippon Micrometal Corporation Cu alloy core bonding wire with Pd coating for semiconductor device
US10497663B2 (en) 2015-05-26 2019-12-03 Nippon Micrometal Corporation Cu alloy core bonding wire with Pd coating for semiconductor device
US10672733B2 (en) 2015-05-26 2020-06-02 Nippon Micrometal Corporation Cu alloy core bonding wire with Pd coating for semiconductor device
US11753700B2 (en) 2017-05-10 2023-09-12 Haldor Topsøe A/S Process for reducing the content of oxygen in metallic copper
CN115493402A (zh) * 2022-08-29 2022-12-20 金川集团股份有限公司 一种工频感应炉熔沟凝固和二次起熔的方法

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