EP1688198A1 - Stranggussform und verfahren zum stranggiessen für kupferlegierung - Google Patents

Stranggussform und verfahren zum stranggiessen für kupferlegierung Download PDF

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Publication number
EP1688198A1
EP1688198A1 EP04787939A EP04787939A EP1688198A1 EP 1688198 A1 EP1688198 A1 EP 1688198A1 EP 04787939 A EP04787939 A EP 04787939A EP 04787939 A EP04787939 A EP 04787939A EP 1688198 A1 EP1688198 A1 EP 1688198A1
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Prior art keywords
alloy
mold
continuous casting
metal
pulling out
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EP04787939A
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English (en)
French (fr)
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EP1688198A4 (de
Inventor
Yasuhiro Sumitomo Metal Industries Ltd. Maehara
M. Sumitomo Metal Industries Ltd. YONEMURA
Keiji Sumitomo Metal Industries Ltd. Nakajima
Naotsugu Sumitomo Metal Industries Ltd. YOSHIDA
Masahiro Sumitomo Metals AOKI (Naoetsu), Ltd.
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Materials Solution Inc
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Sumitomo Metal Industries Ltd
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Publication of EP1688198A1 publication Critical patent/EP1688198A1/de
Publication of EP1688198A4 publication Critical patent/EP1688198A4/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/14—Plants for continuous casting
    • B22D11/143—Plants for continuous casting for horizontal casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/004—Copper alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/059—Mould materials or platings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/10—Alloys based on copper with silicon as the next major constituent

Definitions

  • the present invention relates to a continuous casting mold and a continuous casting method of a Cu alloy, particularly, a casting mold used for a direct-connection type of continuous casting machine, in which a mold is directly connected to a holding furnace, and a continuous casting method of a Cu alloy using this mold.
  • the typical first necessary characteristic is higher strength for a reduction in weight
  • the second is higher electric conductivity for suppressing a rise of electric resistance caused by reduction in the sectional area due to the reduction in weight.
  • the improvement in workability such as bending workability due to the downsizing of parts, the improvement in heat resistance in order to ensure usability even in relatively severe environments, and the improvement in fatigue strength are also important problems.
  • Such a highly strong and highly electric-conductive material can also be applied to safety tool materials used in an environment such as an ammunition chamber or a coal mine which needs excellent spark generation resistance, in addition to the wear resistance needed for conventional tools.
  • a material is exemplified the Cu alloy disclosed in the Patent Document 1 below.
  • the first method is a direct-connection type of continuous casting including horizontal type and vertical type casting, using a graphite-made mold directly connected to a holding furnace. Since a supply of a lubricant is extremely difficult in the direct-connection type of continuous casting, graphite with a bulk density of 1.7 to 1.9, which has a self-lubricating property and high heat conductivity, has widely been used for the mold material. This method is suitable for obtaining a slab or a bloom with relatively small sectional area. In such type of continuous casting process, the cooling rate after solidification is relatively high, leading to a high performance of a final product even without a subsequent hot process such as a solution treatment or a hot working.
  • the second method is a non-direct-connection type of continuous casting including vertical type, curved type and vertical-curved type casting, described in the Patent Document 1, in which melt is poured into a mold made of a metal such as Cu or an alloy such as a Cu alloy through a nozzle immersed into a melt pool.
  • the slabs to be cast are limited to a relatively large size with a thickness of about 100 mm or more, since the nozzle can be immersed into the melt pool within the mold.
  • This method essentially requires a hot process such as a solution treatment or a hot working in the later production process because of a low cooling rate in the cooling process after solidification.
  • a proper method is selected from these two kinds of continuous casting methods according to the required alloy composition, slab sectional shape, cooling rate, or the like.
  • the former direct connection type is adapted when a high cooling rate is needed or when the Cu alloy is free from highly reactive elements with C in the graphite.
  • the latter non-direct connection type is adapted when a slab of a large sectional size is needed or when the Cu alloy contains highly reactive elements with C in the graphite.
  • Patent Document Japanese Patent Unexamined Publication No. S61-250134.
  • the primary objective of the present invention is to provide a continuous casting mold suitable for a direct-connection type of continuous casting of the Cu alloy containing elements such as Zr, Ti, and Cr that are reactive with C.
  • the second objective of the present invention is to provide a continuous casting method of the Cu alloy using the above-described mold.
  • the continuous casting mold of the present invention is highly effective for continuous casting not only of Cu alloys but also of such materials as non-ferrous metals other than Cu alloys.
  • new Cu alloys intended for higher strength and higher electric conductivity contain elements such as Zr, Ti and Cr, which easily react with C. They also need a high cooling rate in the cooling process after solidification in order to attain satisfactory characteristics of the final products.
  • these alloys are found to have the following problems, which results from the reaction of above-mentioned elements with C in the graphite mold.
  • the present invention relates to a continuous casting mold, capable of providing a sufficiently high cooling rate in the cooling process after solidification, while suppressing the sticking of the initially formed solidification shell to the mold, and a continuous casting method using the mold, and involves the following inventions of continuous casting molds (1) to (5) and inventions of continuous casting methods (6) to (14). These inventions are hereinafter referred to as the present inventions (1) to (14), respectively, or often are referred to collectively as the present invention.
  • a continuous casting mold for a Cu alloy using any one member selected from a glassy carbon, a metal-based self-lubricating composite or a graphite with a bulk density exceeding 1.92, at least for the mold member including the solidification starting position of the Cu alloy melt.
  • a continuous casting mold for a Cu alloy composed of any one member selected from a graphite, a ceramic and a metal member or of a combination of two or more parts of members thereof, in which at least the inner wall in the solidification starting position of the Cu alloy melt is coated with a self-lubricant or a metal-based self-lubricating composite material.
  • a continuous casting mold for a Cu alloy composed of a combination of two or more parts of members selected from a self-lubricant, a metal-based self-lubricating composite, a graphite, a ceramic and a metal member, in which the self lubricant or the metal-based self-lubricating composite member is used at least for the inner wall in the solidification starting position of the Cu alloy melt.
  • a continuous casting mold for a Cu alloy composed of a combination of two or more parts of members selected from a self-lubricant, a metal-based self-lubricating composite, a graphite, a ceramic and a metal member, in which at least the inner wall in the solidification starting position of the Cu alloy melt is coated with a self-lubricant or a metal-based self-lubricating composite material.
  • a continuous casting method of a Cu alloy according to (6) above comprised of giving, at the time of continuously casting the Cu alloy by an intermittent pulling out method, a vibration that has a frequency larger than the intermittent pulling out frequency by two orders or more and that has a component vertical to the pulling out direction of the slab.
  • a continuous casting mold capable of continuously and stably producing a sound slab.
  • a continuous casting method of a Cu alloy capable of ensuring excellent characteristics such as strength, electric conductivity, bending workability and fatigue strength of the final product after working and heat treatment, can be provided.
  • a Cu alloy containing Zr, Ti, Cr, Ta, V and so on which are elements that easily form into carbides, a profound effect can be obtained.
  • the present invention is highly effective not only for Cu alloys but also for such materials as non-ferrous metals other than Cu alloys.
  • a mold for a direct-connection type of horizontal continuous casting is shown in Figs. 1 to 7.
  • the mold is directly connected to a refractory constructing the holding furnace wall 2 that stores a Cu alloy melt 1.
  • a connecting refractory such as a feeding nozzle, may be provided between the holding furnace wall and the mold.
  • a cooling jacket 5, adapted to carry cooling water or the like into the mold, is arranged closely to the outside of a mold member 3 and/or another part of mold member 3', in which heat extraction is performed by primarily cooling the Cu alloy melt, and the solidification proceeds to form into a slab 4.
  • the slab 4 leaving the mold is subjected to secondary cooling 6 by water spray, air spray, air-water mixed spray or the like.
  • the slab 4 is pulled out in an arrowed direction 7.
  • the mold according to the present invention may include a coating 8 applied to the inner wall of the mold in the solidification starting position 10 of the Cu alloy melt. It may include a coating 9 applied to the inner wall in the position of the mold , which is located at an upper stream part than the solidification starting position.
  • the mold may be composed of a plurality of parts of mold members, for example, a part of mold member 3 and another part of mold member 3'.
  • the mold inner wall might be deteriorated by oxidation at the time of preheating before casting.
  • an oxidation resisting coating such as metal plating, is preferably applied at least to the inner wall of the mold in the solidification starting position of the inner wall surface of the mold.
  • the oxidation resisting coating material is not particularly limited, but one easily soluble to the melt at the time of casting without deteriorating the characteristics or the like of the final product, is preferably used.
  • Cu is preferably used as the coating material, with a thickness of about several micrometers.
  • the solidification starting position in the present invention is defined as follows. In the mold, molten Cu alloy is fed from the holding furnace, and forms into a solidification shell in a certain position in the mold. This solidification shell forming position is called the solidification starting position.
  • the solidification starting position is slightly varied depending on the casting conditions such as the temperature of the melt in the holding furnace, the cooling condition in both primary and secondary stages, and the pulling out velocity and so on. Thus, the solidification starting position has a certain fluctuation in the pulling out direction.
  • Figures 1 to 7 show examples of the mold for a direct-connection type of horizontal continuous casting according to the present invention, while the mold for a direct connection type of vertical continuous casting can be shown by rotating these figures clockwise by 90°.
  • a continuous casting mold for a Cu alloy according to the present invention will be further described in detail in terms of types (A) to (E). Further, a method for continuously casting a Cu alloy by use of these molds will also be described.
  • a continuous casting mold for a Cu alloy using any one member selected from a glassy carbon, a metal-based self-lubricating composite or a graphite, at least for the mold member including the solidification starting position of the Cu alloy melt:
  • Figure 1 is a schematic view of a continuous casting mold for a Cu alloy as one example of the continuous casting mold, according to the present invention, using a glassy carbon, a metal-based self-lubricating composite or a graphite material for the mold member 3 including the solidification starting position 10 of the Cu alloy melt.
  • the metal-based self-lubricating composite or the graphite material at least for the mold member including the solidification starting position of the Cu alloy melt, a sound slab can be produced continuously, efficiently, and stably.
  • the graphite member preferably has a bulk density exceeding 1.92.
  • a continuous casting method of a Cu alloy capable of ensuring excellent characteristics such as strength, electric conductivity and fatigue strength of a final product after working and heat treatment, can be provided. Particularly, in application to casting of the Cu alloy containing elements such as Zr, Ti, Cr, Ta and V, which easily form into carbides, a profound effect can be obtained.
  • the present inventors found that, when the direct-connection type of continuous casting is executed using a mold member which is made of a conventional graphite material with a bulk density of 1.7 to 1.9, the Cu alloy melt penetrates into a number of open pores which are on the graphite surface, whereby the initially formed solidification shell is stuck to the mold, resulting in mold damage with increase of the pulling out resistance or sometimes into an interruption of process. It was also found that, when the melt contains elements such as Zr, Ti and Cr which are reactive with C, the formation of the carbides in the boundary between the melt and the mold further causes sticking of the initially formed solidification shell to the mold, resulting in mold damage due to mold biting or into an interruption of the slab pulling out process.
  • a glassy carbon or a metal-based self-lubricating composite material is effective from the viewpoint of the reaction between the mold material and the melt.
  • the glassy carbon material has characteristics of being, rarely oxidized, compared with the graphite, and also being rarely reactive with Zr, Ti, and Cr, and therefore, it was found that the purpose can be sufficiently attained.
  • the metal-based self-lubricating composite material means a cermet obtained by dispersing and mixing a self-lubricant such as M O S 2 , WS 2 , BN or mica that rarely reacts with Ti, Cr or Zr into a metal matrix.
  • This composite material can also sufficiently attain the purpose.
  • the method for producing the composite material is not particularly limited. For example, mixing a metal powder with a self-lubricant particle, followed by pressing and sintering, can produce the composite material.
  • the content of the self-lubricant in the composite material is not particularly limited, but is, by volume %, preferably 10% or more, more preferably 30% or more, and further preferably 80% or more.
  • the content is, by volume %, preferably controlled to 85 % or less.
  • the metal constituting the composite material with the self-lubricant is not particularly limited, and any metal or alloy can be used. Use of a metal and/or an alloy having a high melting point and high thermal conductivity is preferred since the mold material makes contact with a Cu alloy melt.
  • the specific examples of the metal of the alloy are a Cu alloy, a stainless steel, a Ni alloy, a Co alloy, and a W alloy.
  • An increased vibration frequency is more preferable, and it is preferably set to 5000 cpm (83 Hz) or more, and more preferably to 60000 cpm (1 kHz) or more, which is close to the ultrasonic area.
  • a fine particle of MoS 2 , WS 2 , BN, mica, or carbon is recommended to be supplied between the mold inner wall and the slab.
  • a superfine particle of CaCO 3 which is difficult to agglomerate, is strongly recommended as the anti-sticking material.
  • the continuous supply thereof is performed, for example, by injecting a solution of the fine particle of the lubricant or anti-sticking material suspended in mineral oil, synthetic ester or a mixture thereof through a number of through-holes of about 20 ⁇ m provided in the mold inner wall by the use of a pressure pump. A sufficient effect can be obtained in an injection quantity of about 0.1 cc/cm 2 ⁇ min, which is as little as sweat.
  • a continuous casting mold for a Cu alloy composed of any one member selected from a graphite, a ceramic and a metal member or of a combination of two or more parts of members thereof, in which at least the inner wall in the solidification starting position of the Cu alloy melt is coated with a self-lubricant or a metal-based self-lubricating composite material:
  • Figure 2 is a schematic view of a continuous casting mold for a Cu alloy as an example of the continuous casting mold according to the present invention, in which the mold member 3 is composed of any one member selected from a graphite, a ceramic and a metal, and in which a coating 8 of a self-lubricant or a metal-based self-lubricating composite material is applied to the inner wall in the solidification starting position 10 of the Cu alloy melt.
  • a mold which is composed of any one member selected from the graphite, the ceramic and the metal member, with a coating of the self-lubricant or the metal-based self-lubricating composite material applied to the inner wall of the mold, is used, whereby a sound slab can be continuously, efficiently and stably produced.
  • a continuous casting method of a Cu alloy capable of ensuring excellent characteristics such as strength, electric conductivity and fatigue strength of the final product after working and heat treatment, can be provided. Particularly, in application to casting of a Cu alloy containing elements such as Zr, Ti, Cr, Ta and V, which easily form into carbides, a profound effect can be obtained.
  • a compact coating material composed of C, for example, a glassy carbon, a layered carbon and a diamond-like carbon, which are self-lubricant materials, are preferably selected in order to enhance the adhesion between the mold material and the coating film. Since the surface unevenness of the coating film almost reflects the surface unevenness of the graphite itself, it is desirable to select a graphite with a bulk density as high as possible. Although the bulk density is not particularly limited, it is preferably 1.7 or more, more preferably 1.8 or more, or further preferably more than 1.92.
  • an inorganic material composed of one or more selected from oxides, nitrides, carbides and borides is used.
  • a BN material and a sialon material a compound consisting of Si, Al, O, and N, shown by a phase diagram of Si 3 N 4 ⁇ AlN ⁇ Al 2 O 3 ⁇ SiO 2 are preferable because of the mechanical strength and thermal conductivity to be provided as the mold material.
  • the thinner mold thickness that is, the narrower distance between the slab and a cooling jacket is preferably adapted.
  • a compact coating material composed of a nitride compound, for example, a BN material that is a self-lubricant is preferably selected in order to enhance the adhesion between the mold material and the coating film.
  • the metal is not particularly limited, and any metal or alloy can be used. Use of a metal or an alloy having a high melting point and high thermal conductivity is preferred, for example, a Cu alloy, a stainless steel, a Ni alloy, a Co alloy, a W alloy, since the mold material will make contact with the Cu alloy melt.
  • a metal-based compact coating material such as a metal-based self-lubricant material is preferably selected in order to enhance the adhesion between the mold material and the coating film.
  • the metal-based self-lubricating composite material means a cermet obtained by dispersing and mixing a self-lubricant such as MoS 2 , WS 2 , BN and mica that rarely reacts with Zr, Ti or Cr in a metal matrix. It was found that the purpose can be sufficiently attained by applying this to the metal or alloy used for the mold material by electroless plating, electrolytic plating or spray coating. After the coating , the surface is polished preferably with an emery paper of about No. 1000.
  • the content of the self-lubricant in the composite material (cermet) to be plated or sprayed is not particularly limited. However, although the reaction resistance and the lubricating property are improved, an increased content of the self-lubricant causes deterioration of the peeling resistance of the film, then the content is preferably set to about 10 to 30 vol.%.
  • the metal in the composite material to be coated by plating is not particularly limited, and any metal or alloy can be used. Particularly, use of a metal or an alloy having a high melting point and high thermal conductivity is preferred, for example, a Cu alloy, stainless steel, a Ni alloy, a Co alloy and a W alloy.
  • the similar effect can be obtained over a longer time.
  • An increased vibration frequency is more preferable, and the frequency is preferably set to 5000 cpm (83 Hz) or more, and more preferably to 60000 cpm (1 kHz) or more, which is close to the ultrasonic area.
  • the lubricant to be supplied between the inner wall of the mold and the slab is the same as described above.
  • a continuous casting mold for a Cu alloy composed of a combination of two or more parts of members selected from a self-lubricant, a metal-based self-lubricating composite, a graphite, a ceramic and a metal member, in which the self-lubricant or the metal-based self-lubricating composite member is used at least for the inner wall in the solidification starting position of the Cu alloy melt:
  • Figure 3 is a schematic view of a continuous casting mold for a Cu alloy as an example of the continuous casting mold according to the present invention.
  • This is an example of the mold that is composed of a combination of plurality of parts, that is, the mold composed of a part of mold member 3 including an inner wall in the solidification starting position 10 of the Cu alloy melt, and another part of mold member 3'.
  • the self-lubricant or the metal-based self-lubricating composite member is used for the part of mold member 3 including the inner wall in the solidification starting position 10 of the Cu alloy melt, and any one member selected from the graphite, the ceramic and the metal member is used for the other part of mold member 3'.
  • the mold composed of a plurality of parts, that is, the mold composed of a combination of a part of mold member including an inner wall in the solidification starting position, using a self-lubricant or a metal-based self-lubricating composite material, and another part of mold member using any one of the selected from a self lubricant, a metal-based self-lubricating composite, a graphite, a ceramic and a metal material, leads to a sound slab which can be continuously, efficiently and stably produced.
  • a continuous casting method of a Cu alloy ensuring excellent characteristics such as strength, electric conductivity, bending workability and fatigue strength of a final product after working and heat treatment can be provided.
  • a Cu alloy containing elements such as Zr, Ti, Cr, Ta and V that easily form into carbides, a profound effect can be obtained.
  • any of a glassy carbon, a layered carbon, a BN (example 22), and a metal-based self-lubricating composite member obtained by dispersing and mixing a self-lubricant such as MoS 2 , WS 2 , BN, or mica that rarely reacts with Zr, Ti or Cr in a metal matrix can be selected.
  • a self-lubricant such as MoS 2 , WS 2 , BN, or mica that rarely reacts with Zr, Ti or Cr in a metal matrix
  • a continuous casting mold for a Cu alloy composed of a combination of two or more parts of members selected from a self-lubricant, a metal-based self-lubricating composite, a graphite, a ceramic and a metal member, in which at least the inner wall in the solidification starting position of the Cu alloy melt is coated with a self-lubricant or a metal-based self-lubricating composite material:
  • Figure 4 is a schematic view of a continuous casting mold for a Cu alloy as one example of the continuous casting mold according to the present invention, which is composed of a plurality of parts of members, and which has a coating 8 of a self-lubricant or a metal-based self-lubricating composite material applied to the inner wall of the mold in the solidification starting position 10 of the Cu alloy melt.
  • the mold is composed of a part of mold member 3 and another part of mold member 3', using two kinds of parts of members selected from a metal-based self-lubricating composite, a graphite, a ceramic and a metal member.
  • the mold which is composed of a part of any one member of mold selected from a graphite, a ceramic and a metal member, and another downstream part of a metal-based self-lubricating composite or a graphite member, has a coating of the self-lubricant or the metal-based self-lubricating composite material applied to the inner wall in the solidification starting position of a Cu alloy melt.
  • the mold leads to a sound slab that can be continuously, efficiently and stably produced.
  • a continuous casting method of the Cu alloy ensuring excellent characteristics such as strength, electric conductivity, bending workability and fatigue strength of the final product after working and heat treatment, can be provided.
  • a Cu alloy containing elements such as Zr, Ti, Cr, Ta and V that easily form into carbides, a profound effect can be obtained.
  • the graphite member, the ceramic member, the metal member, and the metal-based self-lubricating composite member to be used for the mold member are the same as described above.
  • any of the glassy carbon, the layered carbon, and the BN which are self-lubricants and the metal-based self-lubricating composite member obtained by dispersing and mixing self-lubricants such as MOS 2 , WS 2 , BN and mica, that rarely react with Zr, Ti or Cr in a metal matrix, can be selected.
  • the mold member 3 including a mold portion in the solidification starting position 10 of the Cu alloy melt, is composed of a metal-based self-lubricating composite, and a coating 9 of a ceramic material is applied to the inner wall in the position that contacts with the Cu alloy melt in order to suppress the reaction with the melt.
  • the coating method of the ceramic can be applied by spraying, CVD, etc.
  • This continuous casting mold for a Cu alloy is composed of a metal member for the mold member 3. in which a coating 8 of the metal-based self-lubricating composite material is applied to the inner wall in the solidification starting position 10 of the Cu alloy melt, and a coating 9 of the ceramic is applied to the inner wall in the position of the mold that contacts with the Cu alloy melt in order to suppress the reaction with the melt.
  • the coating method of the ceramic is the same as described above.
  • This continuous casting mold for a Cu alloy is composed of an upstream part of mold of a metal member and another downstream part of mold of a graphite member.
  • the part of mold of a metal member has a coating 8 of a metal-based self-lubricating composite material applied to the inner wall in the solidification starting position 10 of the Cu alloy melt, and has a coating 9 of a ceramic material applied to the inner wall in the position of the mold that contacts with the Cu alloy melt in order to suppress the reaction with the melt.
  • the coating method of the ceramic is the same as described above.
  • the part of mold when the part of mold is composed of the metal or metal-based self-lubricating composite member, it is further effective to apply the coating of the ceramic to the inner wall in the position of the mold that contacts with the Cu alloy melt in order to avoid the reaction of the member with Zr, Ti, Cr and so on in the melt.
  • the coating method of ceramics it is recommended as the coating method of ceramics to apply a coating of a cushioning material about 50 ⁇ m thick (e.g., Ni plating, frame-coating of WC-27 wt% NiCr, and so on), and then apply a ceramic coating about 200 ⁇ m thick thereon by frame coating.
  • a ceramic composed of a further stable oxide, at a casting temperature of the Cu alloy of 1250°C is preferred.
  • ZrO 2 -8 wt%Y 2 O 3 , ZrO 2 -25 wt% MgO, ZrO 2 -5 wt% CaO and so on are recommended since no adhesion of the Cu alloy is caused.
  • the inner wall in the position of the upstream part of mold to be coated is preliminarily ground so as not to form a difference in level after ceramic coating.
  • Cu alloys including Cu-Ti-X alloys (X: Cr, Fe, Co, Ta, Nb, Mo, V, Mn, Be, Si, Ni, Sn, Ag, etc.), Cu-Zr-X alloys (X: Cr, Fe, Co, Ta, Nb, Mo, V, Mn, Be, Si, Ni, Sn, Ag, etc.), and Cu-Ti-Zr alloys..
  • Some compounds such as Ti-Cr and Zr-Cr and some metals such as Ti, Zr and Cr precipitates in a certain high-temperature region in the cooling process after solidification, which is apparent from the phase diagrams of Ti-Cr, Zr-Cr and Ti-Zr binary alloy systems shown in Figs. 8, 9 and 10. These precipitates formed in a certain high-temperature region in the cooling process after solidification tend to be coarsened or aggregated, and it is quite difficult to dissolve them by the subsequent solution treatment, which is apparent from the phase diagrams.
  • a slab or bloom, according to the present invention has a profound effect through the process of working such as rolling at 600°C or lower and an aging treatment in the temperature region of 150 to 750°C, without a hot process such as hot rolling and solution treatment described in the above-mentioned Patent Document 1.
  • the alloy is strengthened by a fine precipitation of an intermetallic compound between Cu and an alloy element such as Cu 4 Ti and Zr 9 Cu 2 or between the alloy elements, or a fine metal precipitate of Ti, Zr, Cr and so on. Then, it is enhanced in electric conductivity by the resulting reduction of the dissolved elements such as Ti, Zr, and Cr that are harmful to electric conductivity.
  • the average cooling rate from the temperature of the start of solidification to 600°C is preferably 1°C/s or more, and further preferably 10°C/s or more.
  • a Cu alloys according to the present invention include the Cu alloy containing, by mass%, one or more components selected from Cr: 0.01 to 5%, Ti: 0.01 to 5%, Zr: 0.01 to 5%, Nb: 0.01 to 5%, Ta: 0.01 to 5%, Al: 0.01 to 5%, Mo: 0.01 to 5%, V: 0.01 to 5%, Co: 0.01 to 5%, Mn: 0.01 to 5%, Si: 0.01 to 5%, Be: 0.01 to 5%, and Hf: 0.01 to 5%.
  • a Cu alloy containing, in addition to the above components, by mass%, 0.001 to 5 mass% in total of one or more of the alloy components selected from at least one group of the following three groups is given:
  • a Cu alloy further containing 0.001 to 2 mass% in total of one or more alloy components selected from Li, Ca, Mg and rare earth elements is also given.
  • the rare earth elements include Sc, Y and lanthanoide, and each element may be added alone as raw material or in a form of mish metal.
  • a Cu alloy with given chemical composition Prior to continuous casting using the mold according to the present invention, a Cu alloy with given chemical composition is prepared by a melting furnace.
  • the melting is desirably performed under a non-oxidizing atmosphere. While the melting is inevitably performed in the air, it is effective to suppress the oxidation by shrouding the melt by a flux (e.g., cryolite, fluorite, etc.) or charcoal particles.
  • the melt is poured into a holding furnace.
  • the melting is desirably conducted using the holding furnace in order to suppress the oxidation during the pouring.
  • any of horizontal type, vertical type and so on can be adapted to this continuous casting if it is the direct-connection type of continuous casting using the mold directly connected to a holding furnace.
  • the mold according to the present invention has minimized operational problems in the production of the Cu alloy according to the present invention because of the low reactivity with the melt and a satisfactory lubricating property.
  • the inner wall in the vicinity of the solidification starting position in the mold is gradually thinned by the reaction with the melt or abrasion, the slab might be caught thereby and not easily pulled out. In such a case, it is effective to uniformly thin the inner wall by adjusting the cooling condition of the mold, the pulling out rate, or the like and moving the solidification position. In general, the slab is intermittently pulled out.
  • the final product is obtained by a combination of working such as rolling at 600°C or lower and the aging treatment at 150 to 750°C. This working may be performed, of course, in the cooling process after continuous casting.
  • Cu alloys containing 2.0 ⁇ 0.1 wt% of Ti, 1.0 ⁇ 0.1 wt% of Cr, 0.4 ⁇ 0.02 wt% of Sn, and 0.1 ⁇ 0.01 wt% of Zn were melted in a high frequency vacuum melting furnace, and a continuous casting test was carried out in 37 kinds of various production methods shown in Tables 1 and 2.
  • Each Cu alloy melt was transferred to a holding furnace, and a slab of 20 mmx200mm section was intermittently pulled out in a predetermined condition while holding the temperature of the furnace at 1250°C.
  • graphite was used as a refractory of the melting furnace and the holding furnace.
  • the oxidation of the melt was suppressed by an Ar gas flow during pouring in addition to charcoal covering.
  • a water-cooled jacket composed of the Cu alloy was located adjacent to the mold in order to perform primary cooling, and the slab leaving the mold was cooled again by an air-water mixed spray.
  • the temperature measurement was performed basically after leaving the mold by use of a thermocouple or radiation thermometer. In some cases, the mold temperature was measured by boring a through-hole from the mold outer wall to a position 5 mm inside and inserting the thermocouple. Using both the measured data and the physical properties of each mold material, whereby the solidification starting position was estimated, performed a heat transfer analysis. The average cooling rate from the solidification start point to 600°C was calculated based on the above data. In the tests shown in Tables 1 and 2, the cooling rate was controlled to the range of 5 ⁇ 2°C.
  • the casting was intended to ensure a length of about 60 m upon completion. However, due to an abnormal rise of pulling out resistance because of mold biting in the initial solidification shell was observed in some cases in the middle of the pulling out.
  • the quality of the slab surface was evaluated by visually determining flaws thereon. It is apparent from Tables 1 and 2 that the complete casting was successful in the present invention with good quality. However, in the comparative, complete casting could not be performed and the quality was not acceptable to commercial work.
  • test piece 13 B according to the regulation of JIS Z 2201, was collected from each specimen, and the tensile strength [TS (MPa)] at room temperature (25°C) was determined according to the method regulated in JIS Z 2241.
  • a test piece with width of 10mm ⁇ length of 60 mm was prepared from each specimen, current was carried in the longitudinal direction of the test piece in order to measure the potential difference between both ends of the test piece, and the electric resistance was determined by a 4-terminal method. Successively, the electric resistance (resistivity) per unit volume was calculated from the volume of the test piece that was measured by a micrometer, and the electric conductivity [IACS (%)] was determined from its ratio to resistivity 1.72 ⁇ cm of a reference sample obtained by annealing polycrystalline pure copper.
  • the present invention involves a continuous casting mold used mainly for a direct-connection type of continuous casting, with a mold directly connected to a holding furnace, and a continuous casting method of a Cu alloy.
  • the present invention provides a mold capable of continuously and efficiently producing a sound slab or bloom, and also a continuous casting method of a Cu alloy which ensures excellent characteristics, such as strength, electric conductivity, vending workability, impact resistance and fatigue strength of the final product after working and heat treatment.
  • the application of the production of the Cu alloy containing elements such as Zr, Ti, Cr, Ta and V that easily generate carbides provides a profound effect.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Continuous Casting (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
EP04787939A 2003-09-24 2004-09-21 Stranggussform und verfahren zum stranggiessen für kupferlegierung Withdrawn EP1688198A4 (de)

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RU2510420C2 (ru) * 2009-09-07 2014-03-27 Сирогане Ко., Лтд. Медный сплав и способ получения медного сплава
CN102634688A (zh) * 2011-02-10 2012-08-15 湖南特力新材料有限公司 一种无铅易切削铜合金及制备方法
CN102634688B (zh) * 2011-02-10 2014-05-07 湖南特力新材料有限公司 一种无铅易切削铜合金及制备方法
CN103114218A (zh) * 2013-03-11 2013-05-22 武汉大学 一种铜铬合金的制备方法
CN104046831A (zh) * 2014-06-05 2014-09-17 锐展(铜陵)科技有限公司 一种汽车用铜合金电线的制备方法
CN104046832A (zh) * 2014-06-05 2014-09-17 锐展(铜陵)科技有限公司 一种汽车发电机用高导电铜合金线的制备方法
CN104588618A (zh) * 2014-11-28 2015-05-06 太原科技大学 一种镁合金复合板连铸装置及连铸方法
CN104630546A (zh) * 2015-03-05 2015-05-20 苏州市凯业金属制品有限公司 一种高强耐热铜合金金属管
CN104928523A (zh) * 2015-07-10 2015-09-23 苏州科茂电子材料科技有限公司 一种通信电缆用铜合金导线材料及其制备方法
CN110396621A (zh) * 2019-08-27 2019-11-01 天长市华海电子科技有限公司 一种抗晶间腐蚀锻造件及其制备方法
CN111850345A (zh) * 2020-07-23 2020-10-30 唐山中科量子激光科技有限公司 一种耐磨抗高温侵蚀合金材料、结晶器铜板表面处理方法及结晶器铜板
CN111850345B (zh) * 2020-07-23 2021-06-18 唐山中科量子激光科技有限公司 一种耐磨抗高温侵蚀合金材料、结晶器铜板表面处理方法及结晶器铜板
RU2811355C1 (ru) * 2023-06-26 2024-01-11 федеральное государственное автономное образовательное учреждение высшего образования "Пермский национальный исследовательский политехнический университет" Способ получения композиционного материала на основе порошка меди

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JPWO2005028143A1 (ja) 2007-11-15
US20060180293A1 (en) 2006-08-17
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WO2005028143A1 (ja) 2005-03-31
TWI272145B (en) 2007-02-01
EP1688198A4 (de) 2007-03-21

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