Classifications

• • 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
  • 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

Definitions

• the present disclosure relates to copper alloy wires.
• wire diameter tends to be thinner than before due to product miniaturization, space saving of wires, and increase in signal lines.
• wire rods of copper alloys such as Cu--Sn, Cu--Cr, and Cu--Ag have been used in place of pure copper wires, which lack strength.
• copper alloys Cu—Ag alloys have an excellent balance between high strength and high electrical conductivity.
• Patent Document 1 an ingot having a copper alloy composition containing 1 to 10% by weight of Ag and the balance being Cu and unavoidable impurities is cold worked, and during the cold working, in a vacuum atmosphere or Heat treatment is performed in an inert gas atmosphere at a temperature of 570 to 680° C. for 0.5 to 5 hours, followed by cold working. C. for 0.5 to 40 hours, a method for producing copper alloys is described.
• Patent Document 2 a Cu—Ag alloy fine wire having an Ag content of 1 to 10 wt%, the balance being Cu and unavoidable impurities, and the entire structure made of a solid solution of Cu is formed from the recrystallized texture.
• a Cu—Ag alloy fine wire is described.
• Patent Documents 1 and 2 above the eutectic phase of Cu and Ag is extended into a filament to improve strength and conductivity. Further, in Patent Document 2, in a method for producing a Cu—Ag alloy fine wire, the strength is improved by heat treatment for developing a recrystallized texture and high working after the heat treatment.
• Patent Document 1 the strength characteristics are insufficient because the control of the precipitation distribution of the eutectic phase, which particularly contributes to the strength after wire drawing, is inappropriate.
• Patent Document 2 appropriate wire drawing conditions are not set before the heat treatment, so embrittlement of the material progresses during the heat treatment, making it difficult to thin the wire. Therefore, due to poor productivity, the product cannot be cost-competitive.
• Patent Documents 1 and 2 it is difficult to simultaneously achieve improvements in wire drawability, which is manufacturability, in addition to improvements in strength and electrical conductivity.
• An object of the present disclosure is to provide a copper alloy wire rod with an excellent balance of strength, electrical conductivity and wire drawability.
• the alloy composition contains 1.0% by mass or more and 6.0% by mass or less of Ag, and the balance is Cu and inevitable impurities, and the peak intensity of 111 diffraction obtained by X-ray diffraction analysis of the surface I ( 111), the peak intensity I (200) at 200 diffraction, the peak intensity I (220) at 220 diffraction and the peak intensity I (311) at 311 diffraction, the peak intensity I (111) with respect to the peak intensity I (220) and Peak intensity ratio of the total intensity of the peak intensity I (200) and the peak intensity I (311) ((the peak intensity I (111) + the peak intensity I (200) + the peak intensity I (311))/ The copper alloy wire, wherein the peak intensity I(220)) is 1.20 or more and 3.00 or less.
• the alloy composition further includes one or more elements selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr in a total of 0.05% by mass or more and 0.30% by mass. % or less, the copper alloy wire according to the above [1].
• the tensile strength satisfies 1000 MPa or more and the electrical conductivity is 60% IACS or more, and the Ag content X (% by mass), the tensile strength Y (MPa) and the electrical conductivity Z (% IACS) are obtained by the following formula (1 ), formula (2), and formula (3), the copper alloy wire according to the above [1] or [2].
• the present inventor focused on the peak intensity of a predetermined surface obtained by X-ray diffraction analysis of the surface of a copper alloy wire, and controlled the ratio of the peak intensity of a predetermined surface within a predetermined range. , found to be excellent in balance of strength, electrical conductivity and wire drawability, and have completed the present disclosure based on such knowledge.
• the copper alloy wire of the embodiment has an alloy composition containing 1.0% by mass or more and 6.0% by mass or less of Ag, the balance being Cu and inevitable impurities, and 111 diffraction obtained by surface X-ray diffraction analysis
• the peak intensity I (111) of , the peak intensity I (200) of 200 diffraction, the peak intensity I (220) of 220 diffraction and the peak intensity I (311) of 311 diffraction the peak intensity relative to the peak intensity I (220)
• the peak intensity ratio of the total intensity of I (111), the peak intensity I (200), and the peak intensity I (311) ((the peak intensity I (111) + the peak intensity I (200) + the peak intensity I (311))/the peak intensity I(220)) is 1.20 or more and 3.00 or less.
• the copper alloy wire of the above embodiment has an alloy composition containing 1.0% by mass or more and 6.0% by mass or less of Ag, with the balance being Cu and inevitable impurities.
• Ag is an element necessary for increasing the strength of the copper alloy wire, and contains 1.0% by mass or more and 6.0% by mass or less of Ag.
• the Ag content is 1.0% by mass or more, the strength of the copper alloy wire can be increased by solid solution and precipitation of Ag. Further, when the Ag content is 6.0% by mass or less, a decrease in electrical conductivity of the copper alloy wire can be suppressed, and high electrical conductivity of the copper alloy wire can be maintained. Furthermore, if the Ag content exceeds 6.0% by mass, it is not possible to increase the strength enough to meet the increase in material costs due to the increase in the amount of Ag used, so it will contribute to the added value of the customer's product. becomes difficult.
• the Ag content is 1.0% by mass or more, preferably 1.5% by mass or more, and 6.0% by mass or less, Preferably, it is 4.0% by mass or less.
• the alloy composition of the copper alloy wire further includes one or more elements selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr in a total amount of 0.05% by mass or more and 0.30% by mass. % or less. That is, the copper alloy wire is selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr as an optional subcomponent in addition to Ag, which is an essential basic component. A total of 0.05 mass % or more and 0.30 mass % or less of one or more components can be contained.
• the content of the accessory component is 0.05% by mass or more, the strength characteristics of the copper alloy wire are improved, and some elements have the effect of alleviating the brittleness of the copper alloy wire.
• the content of the subcomponent is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and still more preferably 0.10% by mass or more, while preferably 0.30% by mass. % or less, more preferably 0.25 mass % or less, and still more preferably 0.20 mass % or less.
• the Sn (tin) content is 0.05% by mass or more, it contributes to improving the strength of the copper alloy wire, and when the Sn content is 0.20% by mass or less, the conductivity of the copper alloy wire is improved. It doesn't hurt much. Therefore, the Sn content is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more, On the other hand, it is preferably 0.20% by mass or less, more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
• Mg manganesium
• Mg content is 0.05% by mass or more, it contributes to the strength improvement of the copper alloy wire and has the effect of alleviating the brittleness of the copper alloy wire.
• Mg content is 0.20% by mass or less, the electrical conductivity of the copper alloy wire and the manufacturability during casting are not greatly impaired.
• the content of Mg is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more, On the other hand, it is preferably 0.20% by mass or less, more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
• ⁇ Zn 0.05% by mass or more and 0.30% by mass or less>
• Zn (zinc) When the content of Zn (zinc) is 0.05% by mass or more, it contributes to the strength improvement of the copper alloy wire and has the effect of alleviating the brittleness of the copper alloy wire.
• Zn content When the Zn content is 0.30% by mass or less, the electrical conductivity of the copper alloy wire is not greatly impaired.
• the Zn content is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more, On the other hand, it is preferably 0.30% by mass or less, more preferably 0.25% by mass or less, still more preferably 0.20% by mass or less, and particularly preferably 0.15% by mass or less.
• the In content is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more, On the other hand, it is preferably 0.20% by mass or less, more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
• Ni (nickel) content is 0.05% by mass or more, there is an effect of contributing to improvement in the strength of the copper alloy wire.
• the Ni content is 0.30% by mass or less, the electrical conductivity of the copper alloy wire is not greatly impaired. Therefore, the Ni content is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more, On the other hand, it is preferably 0.30% by mass or less, more preferably 0.25% by mass or less, still more preferably 0.20% by mass or less, and particularly preferably 0.15% by mass or less.
• the Co content is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more, On the other hand, it is preferably 0.20% by mass or less, more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
• ⁇ Zr 0.05% by mass or more and 0.20% by mass or less>
• Zr zirconium
• the content of Zr (zirconium) is 0.05% by mass or more, it contributes to improving the strength of the copper alloy wire and has the effect of alleviating the brittleness of the copper alloy wire.
• the Zr content is 0.20% by mass or less, the electrical conductivity of the copper alloy wire and the manufacturability during casting are not greatly impaired.
• the Zr content is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more, On the other hand, it is preferably 0.20% by mass or less, more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
• the Cr content is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more, On the other hand, it is preferably 0.20% by mass or less, more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
• the balance other than the components mentioned above is Cu (copper) and unavoidable impurities.
• Unavoidable impurities are inevitably mixed in during the manufacturing process, and depending on the content, they may cause a reduction in one or more of the strength, electrical conductivity, and wire drawability of the copper alloy wire, and have an impact on the environment. or cause material embrittlement. Therefore, the content of unavoidable impurities is preferably as small as possible. Examples of unavoidable impurities include elements such as S, Pb, Sb, and Bi.
• the upper limit of the content of the inevitable impurities is preferably less than 0.0001% by mass for each element, and preferably less than 0.0005% by mass in total for the above elements.
• peak intensities of 111, 200, 220, and 311 diffraction obtained by X-ray diffraction analysis of the surface of the copper alloy wire are respectively set as I (111), I (200), I (220), and I (311)
• the peak Peak intensity ratio of total intensity of peak intensity I (111), peak intensity I (200) and peak intensity I (311) to intensity I (220) ((peak intensity I (111) + peak intensity I (200) + Peak intensity I(311))/Peak intensity I(220)) (hereinafter also simply referred to as peak intensity ratio) is 1.20 or more and 3.00 or less.
• the peak intensity ratio is 1.20 or more
• the drawability of the copper alloy wire can be improved.
• strength of a copper alloy wire can be increased as a peak intensity ratio is 3.00 or less.
• the peak intensity ratio is 1.20 or more, preferably 1.30 or more, more preferably 1.50 or more, in order to achieve both strength improvement and wire drawability improvement of the copper alloy wire and balance with conductivity, On the other hand, it is 3.00 or less, preferably 2.80 or less, more preferably 2.50 or less.
• the correlated ⁇ 111 ⁇ plane tends to reduce the drawability of the copper alloy wire while contributing to the strength improvement of the copper alloy wire.
• heat treatment is not performed in the manufacturing process of the copper alloy wire described later, even if the peak strength I(111) is high, the copper alloy wire may show a decrease in drawability without an increase in strength.
• the correlated ⁇ 100 ⁇ plane tends to contribute to the improvement of the drawability of the copper alloy wire, but its contribution to the improvement of the strength is relatively low.
• the ratio of the ⁇ 111 ⁇ planes and the ⁇ 100 ⁇ planes is relatively reduced, and the effect is relatively decreased.
• the degree of contribution is relatively low, it contributes to improving the strength and drawability of the copper alloy wire.
• the ratio of ⁇ 111 ⁇ planes and ⁇ 100 ⁇ planes will be relatively reduced, and the effect will be relatively reduced.
• the degree of contribution is relatively low, it contributes to improving the strength and drawability of the copper alloy wire.
• the X-ray diffraction analysis of the surface of the copper alloy wire is measured as follows. Using an X-ray diffractometer, the side surface, which is the surface of the copper alloy wire, is measured by the ⁇ -2 ⁇ method, and the X-ray diffraction intensity between 40 ° and 100 ° is measured, and the noise is calculated from the confirmed peak intensity. Subtract the background value, which is , to obtain the peak intensity for each plane. In X-ray diffraction analysis, a plurality of copper alloy wires are placed in parallel in the same direction on a sample holder in contact with each other.
• the copper alloy wire satisfies a tensile strength of 1000 MPa or more and an electrical conductivity of 60% IACS or more, and the Ag content is X (% by mass), the tensile strength of the copper alloy wire is Y (MPa), and the copper alloy wire is
• the conductivity of is Z (%IACS)
• the Ag content X, tensile strength Y and conductivity Z preferably satisfy the following formulas (1), (2) and (3).
• a copper alloy wire that satisfies such a configuration has a better balance between strength and electrical conductivity.
• the tensile strength of the copper alloy wire is measured by performing a tensile test in accordance with JIS Z 2241:2011.
• the conductivity of the copper alloy wire is measured according to JISH0505:1975.
• the cross section of the copper alloy wire is preferably circular with a diameter of 0.02 mm or more and 0.08 mm or less.
• the cross section of the copper alloy wire may be ribbon-shaped having a long side of 0.060 mm or more and 0.500 mm or less and a short side of 0.005 mm or more and 0.040 mm or less. Even in the case of a ribbon-like extra-fine wire having a cross section with long sides and short sides within the above range, the copper alloy wire has an excellent balance between high strength and high conductivity.
• the strength and conductivity of the ribbon-shaped copper alloy wire do not differ greatly from the strength and conductivity of the columnar copper alloy wire before being formed into a ribbon, for example, the columnar ultra-fine wire. That is, if the strength and conductivity of the cylindrical copper alloy wire before being formed into a ribbon shape are desired values or more, the strength and conductivity of the ribbon-shaped copper alloy wire are desired values or more.
• the copper alloy wire has high drawability, even if the copper alloy wire is thinned to an ultra-thin wire, it is possible to obtain an ultra-thin wire with an excellent balance between high strength and high conductivity, which has not been possible in the past. .
• This makes it possible to reduce the size of electric products, save circuit space, and increase the number of circuits at a level that has not been realized so far, and can contribute to increasing the added value of products.
• heat treatment is performed at least once while the ingot having the above alloy composition is drawn to the final wire diameter of the copper alloy wire.
• This heat treatment is an aging heat treatment for the purpose of precipitation and recrystallization of Ag.
• the heat treatment temperature is preferably 400° C. or higher and 500° C. or lower.
• the heat treatment time is preferably 10 hours or more and 100 hours or less in order to obtain a sufficient amount of precipitated Ag.
• cold wire drawing is performed on the samples before and after the heat treatment.
• the cold wire drawing process before the heat treatment is called the first wire drawing process
• the cold wire drawing process after the heat treatment is called the second wire drawing process.
• a copper alloy wire can be manufactured by subjecting the sample cooled after the heat treatment to the second wire drawing process.
• the ratio of the degree of processing of the first wire drawing to the degree of processing of the second wire drawing (the degree of processing of the first wire drawing/the degree of processing of the second wire drawing) (hereinafter also simply referred to as the degree of processing ratio) is It is 5.0 or more and 12.0 or less. If the working degree ratio is less than 5.0, the copper alloy wire obtained after the second wire drawing process will have a significantly reduced final drawing rate, making it impossible to obtain the desired strength. When the workability ratio is 5.0 or more, the accumulated strain can be eliminated by early recrystallization in the heating and holding temperature range from the temperature rise during the heat treatment, and the second wire drawing process, which is a post-process, can be performed. can suppress embrittlement that causes poor wire drawing.
• the drawing rate of the first wire drawing before the heat treatment is lowered, so that the sample with a low workability is heat treated.
• the release of strain during heat treatment is delayed, and embrittlement progresses, making it difficult to thin wires in the subsequent process.
• the one-pass area reduction rate in each wire drawing process is 15% or more and 35% or less for wire diameters larger than 0.9 mm, and 10% or more and 25% or less for wire diameters of 0.9 mm or less.
• Other wire drawing conditions apply wire drawing speed, die size and capstan diameter, which are very common conditions used in operations.
• the working degree of each wire drawing can be calculated by the following formula.
• the recrystallization orientation and degree of wire drawing during heat treatment greatly contribute to the peak strength of the copper alloy wire.
• the peak strength I (200) is low and the peak strength I (111) is too high, resulting in a copper alloy wire. Wire drawability decreases. Furthermore, normally, when the peak strength I(111) increases, the strength of the copper alloy wire tends to increase, but if heat treatment is not performed, the degree of increase in the strength of the copper alloy wire may decrease.
• the peak intensity I(200) is too high and the peak intensity I(111) is too low, affecting the peak intensity ratio.
• the workability ratio exceeds 12.0, the peak intensity I(200) is low and the peak intensity I(111) is too high, affecting the peak intensity ratio.
• the peak intensity I (220) and the peak intensity I (311) are not actively controlled, the effect of the peak intensity I (200) and the peak intensity I (111) increases when the ratio of these increases. There are relatively declining adverse effects. By satisfying the above manufacturing conditions, it is possible to keep the thickness within a desired range.
• the peak intensity obtained by X-ray diffraction analysis can be controlled by performing the heat treatment, the first wire drawing process, and the second wire drawing process, and by setting the degree of drawing ratio within the above range.
• the heating rate when the heating rate is set to 1°C/min or more in the above heat treatment, the progress of embrittlement during the heating process can be efficiently suppressed.
• the faster the temperature rise rate during heat treatment the more effective it is in suppressing the progress of embrittlement, but in order to simplify the heat treatment apparatus, the upper limit of the temperature rise rate is preferably 15 ° C./min or less. .
• the degree of working of the first wire drawing before the heat treatment is 0.69 or more and 2.31 or less, the progress of embrittlement can be suppressed, and the wire thinning in the second wire drawing, which is a post-processing, can be easily performed. Become.
• a solution heat treatment may be performed to promote precipitation of Ag in the heat treatment.
• the heat treatment temperature is preferably 700° C. or more and 900° C. or less, and the heat treatment time is preferably 10 minutes or more and 5 hours or less.
• the solution heat treatment is for causing Ag to form a solid solution, and is effective in precipitating a large amount of more homogeneous Ag precipitates.
• a ribbon-shaped copper alloy wire can be manufactured by rolling the copper alloy wire obtained by the second wire drawing.
• the copper alloy wire described above is suitably used for device connection cables such as micro speaker lead wires that require an excellent balance of strength, conductivity and drawability.
• the strength, conductivity and elongation can be obtained.
• a copper alloy wire having excellent linearity balance can be obtained.
• Examples 1 to 34 and Comparative Examples 1 to 12, 14 An ingot having an alloy composition shown in Table 1 and cast to an outer diameter of 6 mm or more and 39 mm or less is subjected to the first wire drawing process, which is a cold wire drawing process, to a wire diameter of 4 mm or more and 9 mm or less under the conditions shown in Table 2. Then, heat treatment was performed at a temperature increase rate of 10° C./min, and after cooling, a second wire drawing process, which is a cold wire drawing process, was performed to the final wire diameter to produce a cylindrical copper alloy wire.
• Example 35 A columnar copper alloy wire was obtained in the same manner as in Example 1. Subsequently, the cylindrical copper alloy wire was rolled to produce a ribbon-shaped copper alloy wire having a cross section with a long side of 0.080 mm and a short side of 0.007 mm.
• Examples 36-3-7 A copper alloy wire was produced in the same manner as in Example 1, except that the ingot was subjected to solution heat treatment at 800° C. for 2 hours before the first wire drawing.
• Comparative Example 13 A cylindrical copper alloy wire having the alloy composition shown in Table 1 and having the final wire diameter shown in Table 2 was produced by casting. That is, in Comparative Example 13, the heat treatment, the first wire drawing process, and the second wire drawing process in Example 1 were not performed.
• the copper alloy wire shown in Table 1 contains S, Pb, Sb, and Bi as inevitable impurities. It was less than % by mass.
• the number of wire breakages per wire drawn length is 1 time/100km or less: ⁇
• the wire breakage frequency per wire drawn length is more than 1 time/100km: ⁇

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