EP2868758B1 - Fil en alliage de cuivre, et procédé de fabrication de celui-ci - Google Patents

Fil en alliage de cuivre, et procédé de fabrication de celui-ci Download PDF

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EP2868758B1
EP2868758B1 EP13813342.6A EP13813342A EP2868758B1 EP 2868758 B1 EP2868758 B1 EP 2868758B1 EP 13813342 A EP13813342 A EP 13813342A EP 2868758 B1 EP2868758 B1 EP 2868758B1
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Prior art keywords
wire
working
copper alloy
cold
heating
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German (de)
English (en)
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EP2868758A1 (fr
EP2868758A4 (fr
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Tsukasa Takazawa
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

Definitions

  • the present invention relates to a copper alloy wire and a method of producing the same, and more specifically the present invention relates to an extra-fine copper alloy wire for magnet wires and a method of producing the same.
  • a coil for micro speakers that is used in mobile phones, smart phones, and the like, is produced by working an extra-fine wire (a magnet wire) having a wire diameter of 0.1 mm or less by winding into a coil shape.
  • Patent Literature 1 proposes a technique of using a high-concentration Cu-Ag alloy containing 2 to 15 mass% of Ag that can enhance the tensile strength almost without lowering the electrical conductivity.
  • Patent Literature 1 proposes a technique of using a high-concentration Cu-Ag alloy containing 2 to 15 mass% of Ag that can enhance the tensile strength almost without lowering the electrical conductivity.
  • Patent Literature 1 proposes a technique of using a high-concentration Cu-Ag alloy containing 2 to 15 mass% of Ag that can enhance the tensile strength almost without lowering the electrical conductivity.
  • Patent Literature 1 proposes a technique of using a high-concentration Cu-Ag alloy containing 2 to 15 mass% of Ag that can enhance the tensile strength almost without lowering the electrical conductivity.
  • Patent Literature 2 there is a proposal of a technique of achieving a balance between physical strength and elongation even in a low-concentration alloy, by carrying out the heating at a temperature lower than or equal to the softening temperature (Patent Literature 2). Furthermore, there is a proposal of a technology of enhancing resistance to bending fatigue, by applying compressive stress by subjecting a soft copper alloy wire with diameter ⁇ 2.6 mm and with electrical conductivity 98%IACS or more, to surface working (Patent Literature 3).
  • US 2002/0066503 A1 discloses an ultrafine copper alloy wire with a diameter of not more than 0.08 mm, consisting of Cu, Ag and, optionally, Mg, In or Sn.
  • US 2004/0238086 A1 discloses a copper-magnesium alloy wire having high strength and high conductivity and a process for producing the same.
  • JP 2001 234309 A discloses an extra-fine copper alloy wire with an outer diameter of 0.01 to 0.08, which wire is produced from a copper alloy that consists of copper and a specified amount of a specified metal.
  • Patent Literature 3 when it is intended to perform surface working so that the technology of Patent Literature 3 can be applied to a soft copper wire or copper alloy wire having a diameter of ⁇ 0.1 mm or less, since the soft copper wire or copper alloy wire having a diameter of ⁇ 0.1 mm or less has a markedly smaller wire diameter than the copper alloy wire described in Patent Literature 3, the strength of the copper alloy wire itself is low, and wire breakage occurs due to the load at the time of working, so that working itself is difficult to conduct.
  • the shape of magnet wires is not limited to round wires, and investigations have also been conducted on the employment of square wires and rectangular wires. Even in the cases of these square wires and rectangular wires, it is requested to employ a wire with a thickness that is thin to the extent of that corresponding to the wire diameter of the round wire.
  • the present invention was achieved in view of the problems in those conventional art, and it is an object of the present invention to provide, at low cost, a copper alloy wire that is excellent in elongation, and resistance to bending fatigue, and that can be suitable for the use in, for example, magnet wires.
  • the inventors of the present invention conducted thorough investigations on various copper alloys, and heating and working conditions therefor, in order to develop a copper alloy wire that is superior in elongation, and resistance to bending fatigue, and that is suitably used in magnet wires, and the like.
  • the inventors have found that when a copper alloy wire having a predetermined alloy composition is subjected to a semi-softening treatment, then the wire surface section is subjected to cold-working at a certain light working ratio, and thereby the hardness is increased to a predetermined level in a certain shallow range from the surface of the wire, a copper alloy wire having excellent elongation and resistance to bending fatigue can be obtained.
  • the present invention was completed based on those findings.
  • the present invention provides the following means:
  • a semi-softened state means a state in which elongation of the copper alloy wire satisfies 10% or more, preferably 10% to 30%.
  • a semi-softening treatment means a heating that brings about the semi-softened state.
  • a softened state means a recovered state in which elongation of a copper alloy wire is more than 30%.
  • a softening treatment means a heating at a high temperature that brings about the softened state.
  • a wire means to include a square wire or a rectangular wire, in addition to a round wire.
  • the wire of the present invention collectively means a round wire, a square wire, and a rectangular wire.
  • the size of the wire means, in the case of a round wire (the cross-section in the transverse direction (TD) is circular), the wire diameter ⁇ (the diameter of the circle of the cross-section) of the round wire; in the case of a square wire (the cross-section in the transverse direction is square), the thickness t and the width w (each being the length of one side of the square of the cross-section and being identical to each other) of the square wire; and in the case of a rectangular wire (the cross-section in the transverse direction is rectangular), the thickness t (the length of a shorter side of the rectangle of the cross-section) and the width w (the length of a longer side of the rectangle of the cross-section) of the rectangular wire.
  • the wire of the present invention is excellent in resistance to bending fatigue, while having elongation necessary in coil-formation, the wire is preferably suitable as, for example, a copper alloy wire for magnet wires. Also, the method of producing the copper alloy wire of the present invention is preferably suitable as the producing method of the copper alloy wire, which is excellent in the performance.
  • Fig. 1 is a front view schematically showing the apparatus used in the test for measuring the number of repeating times at breakage in bending fatigue (the number of repeating times at breakage), which was conducted in the Examples.
  • the nanoindentation hardness in the wire surface section is 1.45 GPa or more as measured by nanoindenter ENT-2100 (manufactured by Elionix, Inc.).
  • the wire surface section starts at the outermost surface of the wire and ranges at maximum to a distance from the outermost surface of the wire that corresponds to 20% of the wire diameter in the case of a round wire or the wire thickness in the case of a square wire or a rectangular wire.
  • the nanoindentation hardness in the wire surface section corresponding to 15% of the wire diameter or the wire thickness is adjusted to 1.45 GPa or more.
  • the region having the particular nanoindentation hardness is formed to acquire the hardness, by work hardening with a final (finish) working that is provided after the final heating resulting in a semi-softened state.
  • the wire surface section is also referred to as "surface worked layer” or "depth region extending from the outermost surface of the wire toward the inner side of the wire diameter or the wire thickness".
  • the center of the wire has a nanoindentation hardness of less than 1.45 GPa as measured by nanoindenter ENT-2100 (manufactured by Elionix, Inc.), and the wire as a whole is not hardened like the wire surface section.
  • the reason why the region having a nanoindentation hardness of 1.45 GPa or more is set to extend from the outermost surface of the wire toward 20% inner side at the maximum of the wire diameter or the wire thickness, is that if the wire is hardened to a deeper region beyond this range (toward the center side of the wire), elongation cannot be sufficiently secured.
  • the wire is in the semi-softened state as a result of the final heating and is not hardened.
  • the nanoindentation hardness on the inner side than the surface worked layer (representatively, the central section of the wire) is usually less than 1.45 GPa, and in order to sufficiently secure elongation, the nanoindentation hardness is preferably 1.3 GPa or less.
  • the nanoindentation hardness means the hardness that can be determined by a method for measuring the hardness of a microscopic region, which is called a nanoindentation method, by pressing a triangular pyramid diamond indenter against the surface of a (wire) sample, and determining the hardness from the load exerted at that time and the contact projection area between the indenter and the sample.
  • a nanoindentation method a method for measuring the hardness of a microscopic region
  • Non-Patent Literature 1 Kinzoku (Metal), Vol. 78 (2008) No. 9, p. 47
  • the wire surface section is formed as a work-hardened surface worked layer, and the resistance to bending fatigue of the wire can be further enhanced by adjusting the nanoindentation hardness at this wire surface section preferably to 1.5 GPa or more.
  • the thickness of the surface worked layer in which this predetermined nanoindentation hardness is 1.5 GPa or more is a depth region extending from the outermost surface of the wire toward at least 5% inner side of the wire diameter or the wire thickness (a depth region extending toward 20% inner side at the maximum, and preferably a depth region extending toward 15% inner side), satisfactory characteristics, such as an elongation of 10% or more, for the copper alloy wire as a whole can be exhibited. Therefore, an excellent magnet wire can be obtained.
  • the nanoindentation hardness at the wire surface section is set to 1.45 GPa or more; however, it is more preferable to set the nanoindentation hardness to 1.6 GPa or more.
  • the upper limit is not particularly limited, but is usually set to 1.7 GPa or less.
  • the copper alloy wire of the present invention contains (i) Ag at a content of 0.5 to 4 mass%, and/or (ii) at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr each at a content of 0.05 to 0.3 mass%, with the balance being Cu and unavoidable impurities.
  • content of an alloy additive element is simply expressed in “percent (%)", this means “mass%”.
  • the total content of at least one alloy component selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr is preferably 0.5 mass% or less.
  • the copper alloy wire of the present invention may contain (i) Ag alone, or may contain (ii) at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr alone, or may contain both (i) Ag and (ii) at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr.
  • These elements each are a solid solution strengthening-type or precipitation strengthening-type element, and when any of these elements is/are added to Cu, physical strength can be enhanced without lowering the electrical conductivity to a large extent.
  • the physical strength of the copper alloy wire itself is enhanced, and the resistance to bending fatigue is enhanced.
  • the wire is worked into an extra-fine wire having a wire diameter or a wire thickness of 0.1 mm or less, followed by subjecting to a heating (semi-softening treatment), since the wire surface section is hardened after the semi-softening treatment, the wire can withstand the final (finish) cold-working.
  • the resistance to bending fatigue is generally proportional to tensile strength
  • elongation is lowered, and the wire cannot be formed into an extra-fine copper alloy wire, such as a magnet wire.
  • the bending strain exerted on the copper alloy wire at the time of bending fatigue increases toward the outer circumference of the wire, and the amount of bending strain decreases as the center is approached.
  • the resistance to bending fatigue can be enhanced, by work hardening the copper alloy wire by finish cold-working such that only a predetermined depth region (the wire surface section) of the wire surface has a predetermined hardness.
  • the entirety of the remaining portion of the wire other than the wire surface section maintains a semi-softened state.
  • elongation of the wire as a whole can be sufficiently secured, forming into an extra-fine copper alloy wire, such as a magnet wire, is enabled.
  • Ag is an element that can particularly enhance physical strength without lowering electrical conductivity, and is an exemplary essential additive element for the copper alloy related to the present invention used in, for example, magnet wires.
  • the Ag content is set to 0.5 to 4.0 mass%, and preferably 0.5 to 2.0 mass%. If the content of Ag is too small, sufficient physical strength cannot be obtained. Also, if the Ag content is too large, electrical conductivity is lowered, and also it becomes excessively high cost.
  • the at least one element selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr is an another example of an essential alloying element in the copper alloy according to the present invention.
  • the contents of those elements are, respectively, 0.05 to 0.3%, and preferably 0.05 % to 0.2%. If this content is too small as the respective content, the effect of strength enhancement owing to the addition of any of these elements cannot be expected in most cases. Also, if this content is too large, since the lowering of the electrical conductivity is too large, the resultant copper alloy is inappropriate as a copper alloy wire, such as a magnet wire.
  • the shape of the copper alloy wire of the present invention is not limited to a round wire, and may also be a square wire or a rectangular wire. Then, these will be described below.
  • the method of producing a copper alloy round wire of the present invention is carried out by performing the steps, for example, of: casting; intermediate cold-working; intermediate heating (intermediate annealing); final-heating (final-annealing); and finish cold-rolling, in this order.
  • the intermediate annealing may be omitted.
  • Ag and/or at least one additive element selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr is/are added, and cast in a casting machine having the interior (internal walls) preferably made of carbon, for example, in a graphite crucible.
  • the atmosphere inside the casting machine at the time of melting is preferably selected to be a vacuum or an inert gas atmosphere, such as nitrogen or argon, in order to prevent occurrence of oxides.
  • the casting method There are no particular limitations on the casting method, and use may be made, for example, of a transverse continuous casting machine or an upcast method. By means of such a continuous casting wire-drawing method, steps can be carried out continuously from casting to wire-drawing, and a roughly-drawn rod is cast with a diameter of generally about ⁇ 8 to 23 mm.
  • a roughly-drawn rod having a diameter of generally about ⁇ 8 to 23 mm is similarly obtained, by subjecting the billet (casting ingot) obtained by casting, to wire-drawing.
  • the roughly-drawn rod When this roughly-drawn rod is subjected to cold-working, the roughly-drawn rod is worked into a fine diameter wire having a diameter of ⁇ 0.1 mm or less. Regarding this cold-working, it is preferable to perform cold wire-drawing.
  • the working ratio in this cold-working may vary depending on the target wire diameter, the copper alloy composition, and the heating or cold-working conditions thereafter, and there are no particular limitations.
  • the working ratio is generally set to 70.0 to 99.9%.
  • this cold-working includes a plurality of cold-working steps, such as first cold-working (wire-drawing) and second cold-working (wire-drawing), intermediate annealing (intermediate heating) may be carried out in the mid course of the first cold-working and the second cold-working.
  • first cold-working wire-drawing
  • second cold-working wire-drawing
  • intermediate annealing intermediate heating
  • the heating method of performing the intermediate annealing may be roughly classified into a batch-type method and a continuous method. Since the batch-type heating requires a longer treatment time period and a larger cost, this method is rather poor in productivity. However, since it is easy to perform the control of temperature or retention time period, it is easy to perform the control of characteristics. On the contrary, since the continuous-type heating can carry out heating and the wire-drawing continuously, this is excellent in productivity. However, since it is necessary to perform this heating in a very short time period, it is necessary to precisely control the heating temperature and time period, to realize characteristics stably. Those heating methods have advantages and disadvantages as described above, and therefore, it is desirable to select the heating method according to the purpose.
  • the batch-type heating for example, it is preferable to perform heating in a heating furnace in an inert atmosphere, such as nitrogen or argon, at 300°C to 600°C for 30 minutes to 2 hours.
  • an inert atmosphere such as nitrogen or argon
  • Examples of the continuous-type heating include an electrically heating-type heating and an in-atmosphere running-type heating.
  • the electrically heating-type heating is a method of: providing electrode rings in the mid course of the wire-drawing step; passing an electric current to the copper alloy wire that passes among the electrode rings; and performing heating by the Joule heat generated by the copper alloy wire itself.
  • the in-atmosphere running-type heating is a method of: providing a vessel for heating in the mid course of wire-drawing; and performing heating by passing a copper alloy wire in the atmosphere of the vessel for heating that has been heated to a predetermined temperature (for example, 300°C to 700°C).
  • the intermediate annealing By performing the intermediate annealing in the mod course of a plurality of cold-working steps, elongation of the wire thus obtainable can be recovered, and thereby workability can be enhanced. Also, Ag precipitation is accelerated by the intermediate annealing, and thus the physical strength and electrical conductivity of the wire thus obtainable can be further enhanced. For example, it is preferable to carry out the intermediate annealing under the conditions that satisfy the characteristics of a tensile strength of 330 MPa or more and an elongation of 10% or more of the copper alloy wire after this intermediate heating.
  • the copper alloy wire that has been worked to a desired size (wire diameter) by the steps described above, is subjected to finish-annealing as the final-heating.
  • the heating as the finish-annealing is carried out under the conditions that satisfy the characteristics of a tensile strength of 330 MPa or more and an elongation of 10% or more of the copper alloy wire after the heating.
  • the finish-annealing is carried out by such a semi-softening treatment, the physical strength of the copper alloy wire itself is enhanced, the resistance to bending fatigue is enhanced, and it can be made easier to perform finish cold-working on the surface after the heating.
  • Examples of the heating method of conducting finish-annealing include, similarly to the intermediate annealing, a batch-type heating and a continuous-type heating.
  • the tensile strength and elongation in the wire after the final-heating may undergo slight changes, depending on the composition of copper alloy wire or the working ratio.
  • the heating temperature and the heating retention time period for the final heating are appropriately adjusted such that the tensile strength of 330 MPa or more and the elongation would be 10% or more of the copper alloy wire obtainable by this finish-annealing.
  • the heating temperature is higher, the heating is carried out for a shorter time period, and as the heating temperature is lower, the heating is carried out for a longer time period.
  • the heating is carried out at 300°C to 450°C for 30 minutes to 2 hours.
  • the finish-annealing is carried out in a continuous mode, the heating is carried out at 300°C to 700°C for 0.5 to 5 seconds.
  • the finish-working is carried out after this final-annealing.
  • the characteristics of the copper alloy wire before the final-annealing are adjusted, and the final-annealing conditions are determined, as described above, so that the final characteristics of the copper alloy wire obtainable by the finish cold-working after this final-annealing give a tensile strength of 350 MPa or more and an elongation of 7% or more.
  • the copper alloy wire that has been subjected to the final-heating described above is subjected to final (finish) cold-working, and thereby the copper alloy wire is hardened so as to obtain a nanoindentation hardness at the wire surface section of 1.45 GPa or more. Since the copper alloy wire of the present invention has high strength, even an extra-fine wire having a wire diameter ⁇ or a wire thickness t of 0.1 mm or less can be subjected to finish cold-working. In general, the resistance to bending fatigue is proportional to tensile strength; however, when working is further applied in order to enhance the tensile strength, elongation is lowered, and the wire cannot be formed into a magnet wire or the like.
  • the bending strain exerted on the wire at the time of bending fatigue increases toward the outer circumference of the wire, and the amount of bending strain decreases as the center is approached.
  • the resistance to bending fatigue can be enhanced, by hardening only the wire surface section by performing finish cold-working.
  • only the wire surface section of the wire is hardened while the center side of the wire maintains a semi-softened state, elongation of the wire as a whole can be sufficiently secured, and forming into an extra-fine wire, such as a magnet wire, is also enabled.
  • the risk of wire breakage can be effectively decreased, by performing a semi-softening heating that gives characteristics of a strength of 350 MPa or more and an elongation of 7% or more in the copper alloy wire of the final product, before the wire is subjected to finish cold-working.
  • this finish cold-working wire-drawing work is carried out, and the working ratio of this wire-drawing is usually 3 to 15%, preferably 5 to 15%, and more preferably 7 to 12%. If the working ratio of this finish cold-working is too low, the surface working and strength are insufficient, and the effect of enhancing the resistance to bending fatigue may be insufficient. Furthermore, if the working ratio of this finish cold-working is too high, the relevant working affects the entirety of the wire beyond the wire surface section, so that elongation is impaired, and also the risk of wire breakage in working may be increased.
  • the method of producing a copper alloy rectangular wire of the present invention is the same as the method of producing a round wire described above, except for containing rectangular wire-working, and that finish cold-working appropriate for a rectangular shape is carried out.
  • the method of producing a rectangular wire of the present invention is carried out by performing steps of, for example, casting; intermediate cold-working (cold-wire-drawing); rectangular wire-working; final-heating (final-annealing); and finish cold-working, in this order. It is also the same as the method of producing a round wire from the viewpoint that if necessary, intermediate annealing (intermediate heating) is included between the intermediate cold-working and the rectangular wire-working.
  • the conditions of the working/heating for the steps, such as casting, cold-working, intermediate annealing, and final-annealing, and preferred conditions thereof are also the same as those for the method of producing a round wire.
  • the production work is the same as that for the round wire, in which an ingot obtained by casting is subjected to cold-working (wire-drawing) to obtain a roughly-drawn rod having a round wire shape, and the roughly-drawn rod is further subjected to intermediate annealing if necessary.
  • the round wire (roughly-drawn rod) thus obtained is subjected to cold rolling using a rolling machine, cold rolling using a cassette roller die, pressing, drawing, and the like.
  • the transverse direction (TD) cross-section shape is worked into a rectangular shape, to obtain the shape of a rectangular wire. This rolling and the like are generally carried out in one to five passes.
  • the reduction ratio in each pass and the total reduction ratio at the time of rolling and the like are not particularly limited, and may be appropriately set to obtain a desired rectangular wire size.
  • the reduction ratio is the ratio of change in the thickness in the rolling direction upon performing the rectangular wire-working, and when the thickness before rolling is designated as t 1 , and the thickness of the wire after rolling is designated as t 2 , the reduction ratio (%) is represented by: ⁇ 1 - (t 2 /t 1 )) ⁇ 100.
  • this total reduction ratio can be adjusted to 10 to 90%, and the reduction ratio in each pass can be adjusted to 10 to 50%.
  • the aspect ratio is generally 1 to 50, preferably 1 to 20, and more preferably 2 to 10.
  • the aspect ratio (represented by w/t as described below) is the ratio of a shorter side to a longer side in the rectangle that forms the transverse direction (TD) cross-section of a rectangular wire.
  • a rectangular wire thickness t is equal to the shorter side of the rectangle that forms the transverse direction (TD) cross-section
  • a rectangular wire width w is equal to the longer side of the rectangle that forms the transverse direction (TD) cross-section.
  • the rectangular wire thickness is generally 0.1 mm or less, preferably 0.08 mm or less, and more preferably 0.06 mm or less.
  • the rectangular wire width is generally 1 mm or less, preferably 0.7 mm or less, and more preferably 0.5 mm or less.
  • Finish cold-working is carried out, in the case of a rectangular wire, in the same manner as in the rectangular wire-working. It is the same as in the case of a round wire that the rectangular wire is hardened by this finish cold-working so as to obtain a nanoindentation hardness of the wire surface section of 1.45 GPa or more.
  • the finish cold-working on the rectangular wire is carried out by cold rolling using a rolling machine, or cold rolling using a cassette roller die.
  • This working ratio is usually 3 to 15%, preferably 5 to 15%, and more preferably 7 to 12%. If the working ratio of this finish cold-working is too low, surface working and strength are insufficient, and the effect of enhancing the resistance to bending fatigue may be insufficient. Furthermore, if the working ratio of this finish cold-working is too high, the relevant working affects the entirety of the wire beyond the wire surface section, elongation is impaired, and the risk of wire breakage in working may be increased.
  • a rectangular wire produced by such working and heating is provided with a hardened layer having a nanoindentation hardness of 1.45 GPa or more as a surface worked layer by finish cold-working, in a region extending from the wire surface toward at least 5% in depth (a region extending from the wire surface toward 20% in depth at the maximum, and preferably a region extending from the wire surface toward 15% in depth) in the upper and lower surface layers in the thickness direction.
  • a difference lies in that in the case of the round wire, the hardened layer is retained at the surface worked layer over the entire surface of the wire in the circumferential direction, while in the case of the rectangular wire, the hardened layer is retained as the surface worked layer respectively on the upper surface and the lower surface in the thickness direction at the surface of the wire.
  • the round wire and the rectangular wire (and the square wire) have a common factor that the hardened layer is retained as the surface worked layer in the wire surface section in a predetermined shallow range.
  • subjecting a rectangular wire to coil working in the thickness direction implies winding a rectangular wire into a coil shape while taking the width w of the rectangular wire as the width of the coil.
  • Another embodiment of the method of producing a copper alloy wire of the present invention may be a whole production process of: first subjecting a roughly-drawn rod obtained by casting to first cold-working (wire-drawing); recovering elongation by intermediate annealing; further performing second cold-working (wire-drawing) to obtain a desired wire diameter or a desired wire thickness; and controlling a predetermined mechanical strength and elongation by final (finish) annealing; and then adjusting the nanoindentation hardness of the wire surface section by final (finish) cold-working, while simultaneously finally adjusting the entire copper alloy wire so as to have predetermined mechanical strength and elongation.
  • the respective working ratios for these first and second cold wire-drawings vary depending on the target wire diameter or wire thickness, the copper alloy composition, and the conditions for the two heating of intermediate annealing and finish-annealing, and there are no particular limitations on the working ratios. However, generally, the working ratio for the first cold-working (wire-drawing) is set to 70.0 to 99.9%, and the working ratio for the second cold-working (wire-drawing) is set to 70.0 to 99.9%.
  • a sheet or a strip having a predetermined alloy composition is produced, and the sheet or strip is slit, to obtain a rectangular wire or square wire having a desired wire width.
  • This production process for example, contains: casting, hot-rolling, cold-rolling, finish-annealing, finish cold-working, and slitting.
  • the intermediate annealing may be carried out in the middle of a plurality of cold rollings.
  • Slitting may be carried out before the finish-annealing, or before the finish cold-working.
  • the wire diameter or the wire thickness of the copper alloy wire of the present invention is preferably 0.1 mm or less, more preferably 0.08 mm or less, and even more preferably 0.06 mm or less.
  • the lower limit of the wire diameter or the wire thickness is generally 0.01 mm or more.
  • the use of the copper alloy wire of the present invention is not particularly limited.
  • Examples of the use include an extra-fine magnet wire, for example, of a magnet wire, for use in speaker coils that are used in mobile telephones, smart phones, and the like.
  • the tensile strength of the copper alloy wire of the present invention is set to 350 MPa or more, because, if the tensile strength is less than 350 MPa, the strength is insufficient when the diameter is made finer by wire-drawing, and the wire is poor in resistance to bending fatigue.
  • the elongation of the copper alloy wire of the present invention is set to 7% or more, because, if the elongation is less than 7%, the wire is poor in workability, and the resultant wire is occurred with defects, such as wire breakage, at the time of forming into a coil.
  • the copper alloy wire of the present invention obtained by the above method exhibits high resistance to bending fatigue and exhibits elongation that enables forming into an extra-fine copper alloy wire, such as an extra-fine magnet wire.
  • the copper alloys in Examples according to this invention having the respective alloy composition, as shown in Tables 1 to 3, each containing Ag at a content of 0.5 to 4 mass%, and/or at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr each at a content of 0.05 to 0.3 mass%, with the balance being Cu and unavoidable impurities; and the copper alloys in Comparative examples having the respective alloy composition as shown in Tables 1 to 3, were cast into roughly-drawn rods with diameters ⁇ 10 mm, respectively, by a transverse-type continuous casting method.
  • the heating of intermediate annealing and finish-annealing were carried out by any manner selected from three patterns of batch annealing, electric current annealing, and running annealing, each under a nitrogen atmosphere.
  • the intermediate annealing was carried out only once in the mid course of the first cold-working (wire-drawing) and the second cold-working (wire-drawing).
  • the intermediate annealing was not conducted in Test Examples.
  • the intermediate annealing was conducted in some Test Examples, while not conducted in the other Test Examples.
  • the wire diameter before the intermediate annealing after the first cold-working (wire-drawing) in the Test Examples in which intermediate annealing was carried out is presented in the column "Wire diameter (mm)" of "Intermediate annealing” in Table 3.
  • the working ratio of the first cold-working (wire-drawing) was adjusted to 70.0 to 99.9%
  • the working ratio of the second cold-working (wire-drawing) was adjusted to 70.0 to 99.9%.
  • Rectangular wire samples were produced in the same manner as the above round wires, except that rectangular wire-working was carried out after the roughly-drawn rods were subjected to cold-working (wire-drawing), or after intermediate annealing if performed, then finish-annealing was carried out, and then finish cold-working was carried out. As shown in Table 4, some samples were subjected to intermediate annealing, and the other samples were not subjected to intermediate annealing.
  • TS tensile strength
  • EI elongation
  • the number of repeating times at breakage in bending fatigue was obtained by measuring the number of repeating times until the test specimen of wire broke in a bending fatigue test, using the apparatus illustrated in Fig. 1 .
  • a test specimen of a copper alloy wire sample with a wire diameter ⁇ or wire thickness t of 0.04 mm (40 ⁇ m) was sandwiched between two dies, and a load was applied thereon by hanging a weight (W) of 10 g at the lower end of the specimen in order to suppress deflection (flexure) of the wire.
  • W weight
  • the sample was mounted to be sandwiched between the two dies in the wire thickness direction (ND).
  • the upper end of the specimen was fixed with a connecting jig.
  • the specimen While having the specimen maintained in this state, the specimen was bended 90° on the left side and the right side, respectively, bending was repeatedly carried out at a speed of 100 times per minute, and the number of repeating times at breakage in bending was measured for each specimen, i.e. the respective sample.
  • the number of repeating times in bending one reciprocation of 1 ⁇ 2 ⁇ 3 in Fig. 1 was counted as one time, and the distance between the two dies was set to 1 mm so that the specimen of the copper alloy wire would not be compressed in the test. Determination of breakage was made such that the specimen was judged to be broken when the weight hung at the lower end of the specimen dropped.
  • the radius of bending (R) was set to 2 mm, depending on the curvature of the dies.
  • the service life of a coil was evaluated as follows, based on the number of repeating times at breakage in bending fatigue measured by the test method described above. From the results of the bending fatigue test, a sample which had the number of times at breakage of 7,000 or more times was rated as " ⁇ (excellent)", a sample which had the number of times at breakage of 5,000 times or more but less than 7,000 times was rated as " ⁇ (good)", a sample which had the number of times at breakage of 3,000 times or more but less than 5,000 times was rated as " ⁇ (slightly poor)", and a sample which had the number of times at breakage of less than 3,000 times was rated as " ⁇ (poor)”.
  • the wire-drawing property was evaluated by the presence or absence of wire breakage in wire-drawing.
  • the hardness of the wire surface section and the wire center section was measured, using a nanoindenter (ENT-2100, manufactured by Elionix, Inc.).
  • the thickness ( ⁇ m) of the worked layer on the surface side of the wire was determined from microstructure observation of a wire transverse cross-section (TD cross-section) and the change in hardness in the nanoindenter test, and the thickness was designated as the "surface worked layer thickness ( ⁇ m)". Furthermore, from this thickness ( ⁇ m) of the worked layer thus determined, the ratio (%) of the thickness from the outermost surface of the wire to the innermost core side of the worked layer, with respect to the wire diameter ⁇ of wire or the wire thickness t was calculated, and the ratio was designated as the "surface worked layer thickness (%)".
  • Table 1 shows the results of measuring and evaluating the characteristics of samples of round wires of Examples (Examples 1 to 6) and samples of round wires of Comparative examples (Comparative examples 1 to 7) obtained by working and heating Cu-2% Ag alloy wires to have a final wire diameter of 0.04 mm ( ⁇ 40 ⁇ m).
  • the conditions for the final-heating (finish-annealing) were changed as indicated in Table 1, and the strength and elongation before the finish cold-working were changed to various values.
  • Examples 1 to 6 it is understood that when a copper alloy wire that had been subjected to a final-heating (finish-annealing) so as to have a tensile strength of 330 MPa or more and an elongation of 10% or more, was subjected to finish cold-working at a working ratio of 3 to 15%, a worked layer having a nanoindentation hardness of 1.45 GPa or more was formed in the wire surface section, and the resistance to bending fatigue could be enhanced. Furthermore, as shown in Examples 3 to 5, when the working ratio of the finish cold-working was 7 to 12%, the effect of enhancing the resistance to bending fatigue is superior, and thus it is preferable.
  • the elongation of the copper alloy wire after finish cold-working is less than 7%, and insufficient coil formability is obtained. Furthermore, if softening is carried out excessively as the final-heating before the finish cold-working as illustrated in Comparative example 7, and the tensile strength of the copper alloy wire is less than 330 MPa, the hardness of the wire surface section is insufficient, and the strength after the finish-annealing is also insufficient. Furthermore, wire breakage at the time of finish cold-working is brought about.
  • Example 7 to 12 and Comparative examples 8 and 9 the results for evaluating the wire-drawing property when Cu-1% Ag alloy round wires having various diameters obtained by changing the conditions for the final-heating (finish-annealing) as indicated in Table 2, and varying the strength before the finish cold-working to various values, were subjected to finish cold-working at a working ratio of 10%.
  • Comparative examples 10 and 11 the test was carried out in the same manner as described above, except that Cu-0.3% Ag alloy round wires were used instead of the Cu-1% Ag alloy wires.
  • wire-drawing in the case of performing wire-drawing on a relatively thick wire with wire diameter ⁇ 0.5 mm or more, wire-drawing can be achieved without any wire breakage; however, in the case of subjecting a wire with diameter ⁇ 0.1 mm or less to wire-drawing, the tensile strength of the copper alloy wire after the finish-annealing before the wire-drawing working is preferably 330 MPa or more.
  • the resistance to bending fatigue can be enhanced, by performing surface working on a fine wire having a diameter of ⁇ 0.1 mm or less, under the production conditions defined in the production method of the present invention.
  • Table 3 shows Examples according to the present invention and Comparative examples of round wires produced from copper alloys of various other alloy compositions. It is understood that when copper alloy wires having a tensile strength of 330 MPa or more and an elongation of 10% or more are produced by a final-heating (finish-annealing) before the finish cold-working, finish cold-working can be performed to obtain a diameter of ⁇ 0.1 mm or less, at a working ratio of 3 to 15%, preferably 5 to 15%, and more preferably 7 to 12%.
  • Table 4 shows Examples according to the present invention and Comparative examples of rectangular wires produced from copper alloys of various alloy compositions. From the results shown in Table 4, also in the case of rectangular wires, the same results as in the case of the round wires can be obtained.

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Claims (3)

  1. Fil en alliage de cuivre ayant une composition d'alliage se composant de (i) 0,5 à 4 % en poids de Ag et/ou (ii) d'au moins un élément sélectionné dans le groupe consistant en Sn, Mg, Zn, In, Ni, Co, Zr et Cr chacun à une teneur de 0,05 à 0,3 % en poids, avec le reste constitué par Cu et les impuretés inévitables,
    dans lequel le fil en alliage de cuivre a un diamètre de fil ou une épaisseur de fil de 0,1 mm ou moins, et
    dans lequel la dureté de nanoindentation dans la section de surface de fil est de 1,45 GPa ou plus, telle que mesurée par le nanopénétrateur ENT-2100 (fabriqué par Elionix, Inc.), la section de surface de fil commençant au niveau de la surface située le plus à l'extérieur du fil et s'étendant au maximum à une distance de la surface qui correspond à 20 % du diamètre de fil ou de l'épaisseur de fil ; la dureté de nanoindentation, au centre du fil, est inférieure à 1,45 GPa, telle que mesurée par le nanopénétrateur ENT-2100 (fabriqué par Elionix, Inc.), la résistance à la traction du fil est de 350 MPa ou plus, et l'allongement du fil est de 7 % ou plus.
  2. Procédé pour produire le fil en alliage de cuivre selon la revendication 1, comprenant les étapes suivantes :
    travailler le fil en soumettant un fil grossièrement tréfilé d'un alliage de cuivre ayant une composition d'alliage se composant de (i) de 0,5 à 4 % en poids de Ag et/ou (ii) au moins un élément sélectionné dans le groupe se composant de Sn, Mg, Zn, In, Ni, Co, Zr et Cr chacun à une teneur de 0,05 à 0,3 % en poids, avec le reste constitué par Cu et les impuretés inévitables, au travail à froid, pour former un fil ayant un diamètre de fil ou une épaisseur de fil de 0,1 mm ou moins ;
    le chauffage final, qui est réalisé dans un mode différé de 300 °C à 450 °C pendant 30 minutes à 2 heures, ou dans un mode continu de 300 °C à 700 °C pendant 0,5 à 5 secondes ; et
    travailler à froid le fil qui a été soumis au chauffage, à un rapport d'usinage de 3 à 15 %.
  3. Procédé pour produire un fil en alliage de cuivre selon la revendication 2, dans lequel à l'étape du travail du fil, le chauffage intermédiaire est réalisé au cours d'une pluralité d'étapes de travail à froid de sorte que le fil, après ce chauffage intermédiaire, a une résistance à la traction de 330 MPa ou plus et un allongement de 10 % ou plus.
EP13813342.6A 2012-07-02 2013-07-02 Fil en alliage de cuivre, et procédé de fabrication de celui-ci Active EP2868758B1 (fr)

Applications Claiming Priority (2)

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JP2012148920 2012-07-02
PCT/JP2013/068160 WO2014007259A1 (fr) 2012-07-02 2013-07-02 Fil en alliage de cuivre, et procédé de fabrication de celui-ci

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JP6201815B2 (ja) * 2014-02-28 2017-09-27 株式会社オートネットワーク技術研究所 銅合金撚線の製造方法
CN106164306B (zh) * 2014-03-31 2020-03-17 古河电气工业株式会社 铜合金线材及其制造方法
CN105420534A (zh) * 2015-11-06 2016-03-23 广西南宁智翠科技咨询有限公司 一种超高导电率的合金导线
CN105274389A (zh) * 2015-11-06 2016-01-27 广西南宁智翠科技咨询有限公司 一种低电阻的铜合金导线
SG10201509913XA (en) * 2015-12-02 2017-07-28 Heraeus Materials Singapore Pte Ltd Silver alloyed copper wire
CN105624460B (zh) * 2015-12-29 2017-10-31 陕西通达电缆制造有限公司 一种高导电率高韧性的铜合金电缆导线及其制备方法
WO2017199906A1 (fr) 2016-05-16 2017-11-23 古河電気工業株式会社 Matériau de fil en alliage de cuivre
CN108359837B (zh) * 2018-03-16 2019-08-02 重庆鸽牌电工材料有限公司 一种高纯无氧高含银铜杆的制备方法
JPWO2019181320A1 (ja) * 2018-03-20 2021-02-04 古河電気工業株式会社 銅合金線材及び銅合金線材の製造方法
CN108777180A (zh) * 2018-05-10 2018-11-09 保定维特瑞光电能源科技有限公司 一种基于动态交通流量监测的地磁感应线圈及其制备方法
CN113299421B (zh) 2020-02-06 2023-10-31 株式会社博迈立铖 铜合金线、镀敷线、电线和电缆
CN114406228A (zh) * 2022-01-10 2022-04-29 营口理工学院 一种凝固过程中形成纳米铬相的铜合金铸件及铸造方法

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JPWO2014007259A1 (ja) 2016-06-02
EP2868758A1 (fr) 2015-05-06
KR20150034678A (ko) 2015-04-03
CN104169447B (zh) 2017-03-01
CN104169447A (zh) 2014-11-26
KR101719889B1 (ko) 2017-03-24
JP5840235B2 (ja) 2016-01-06
EP2868758A4 (fr) 2016-05-25
WO2014007259A1 (fr) 2014-01-09

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