WO2011136284A1 - Cu-Ag合金線及びCu-Ag合金線の製造方法 - Google Patents
Cu-Ag合金線及びCu-Ag合金線の製造方法 Download PDFInfo
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- WO2011136284A1 WO2011136284A1 PCT/JP2011/060291 JP2011060291W WO2011136284A1 WO 2011136284 A1 WO2011136284 A1 WO 2011136284A1 JP 2011060291 W JP2011060291 W JP 2011060291W WO 2011136284 A1 WO2011136284 A1 WO 2011136284A1
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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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
Definitions
- the present invention relates to a Cu-Ag alloy wire, a coaxial cable having a central conductor made of the Cu-Ag alloy wire, a coaxial cable bundle in which a plurality of the coaxial cables are bundled, and a method for producing a Cu-Ag alloy wire.
- the present invention relates to a Cu-Ag alloy wire having higher electrical conductivity and higher strength.
- the conductor material of the electric wire is required to have excellent breaking strength.
- a copper wire is used as the conductor of the electric wire, but the copper wire has a low breaking strength. When added, it is easy to break.
- Patent Document 1 discloses a Cu—Ag alloy wire containing Ag.
- copper alloys can be increased in strength, such as breaking strength, due to an increase in additive elements, but the electrical conductivity decreases. Since electric wires used in electronic devices and medical devices are desired to have a low electric resistance, if a low-conductivity wire is used as a conductor, it is necessary to increase the conductor cross-sectional area and reduce the electric resistance. is there. In this case, it is difficult to reduce the diameter. Therefore, it is desired to develop a wire having high conductivity and higher strength even when the diameter is reduced.
- one of the objects of the present invention is to provide a Cu-Ag alloy wire having higher strength while having high conductivity. Another object of the present invention is to provide a method for producing the Cu-Ag alloy wire. Furthermore, another object of the present invention is to provide a coaxial cable having a central conductor made of the Cu-Ag alloy wire and a coaxial cable bundle in which a plurality of the coaxial cables are bundled.
- [Cu-Ag alloy wire] The inventors of the present invention select Ag as an additive element that has a relatively low electrical conductivity and is effective in improving strength, and is equivalent to a conventional Cu-Ag alloy wire for Cu-Ag alloy wires, or Various investigations were made on Cu-Ag alloy wires with higher strength while having equivalent or higher electrical conductivity. As a result, the present inventors have found that the presence of Ag in a very fine granular form makes it possible to obtain a Cu—Ag alloy wire having high conductivity and further improved strength. The present invention is based on the above findings.
- the Cu-Ag alloy wire of the present invention relates to a wire made of a copper alloy containing Ag.
- This Cu-Ag alloy wire contains 0.1 mass% or more and 15 mass% or less of Ag, and the remainder consists of Cu and impurities.
- crystal precipitation when taking an arbitrary observation visual field within 1000 nm ⁇ 1000 nm in the cross section of the Cu-Ag alloy wire, among the crystal precipitates of Ag existing in this observation visual field, crystal precipitation
- the area ratio of crystal precipitates in which the maximum length of a straight line for cutting a product is 100 nm or less is 40% or more.
- the Cu-Ag alloy wire of the present invention has a very fine granular Ag uniformly dispersed therein, so that dispersion strengthening can be achieved, strength can be further improved, and high conductivity can be achieved. Can have.
- the Ag crystal precipitate includes a fibrous precipitate.
- the fiber crystal reinforcement can be achieved by the presence of the Ag crystal precipitate as a fibrous precipitate.
- the Cu—Ag alloy wire of the above form can further improve the strength by precipitation strengthening of Ag by a mixed structure of fiber reinforcement and dispersion reinforcement described above.
- the Cu-Ag alloy wire of the present invention can be used as a central conductor of a coaxial cable.
- the coaxial cable of the present invention is a coaxial cable comprising a center conductor having one or more strands, an insulator covering the periphery of the center conductor, and an outer conductor disposed around the insulator. It is concerned.
- the strand is the Cu—Ag alloy wire of the present invention.
- the coaxial cable bundle of the present invention can be obtained by bundling a plurality of the coaxial cables of the present invention.
- the present coaxial cable and the present coaxial cable bundle can improve the strength (fatigue property) by precipitation strengthening by using the Cu-Ag alloy wire of the present invention for the central conductor.
- [Cu-Ag alloy wire manufacturing method] The inventors of the present invention select Ag as an additive element that has a relatively low electrical conductivity and is effective in improving strength, and is equivalent to a conventional Cu-Ag alloy wire for Cu-Ag alloy wires, or Various methods for improving the strength while having the same or higher high conductivity were studied. As a result, the inventors have obtained the knowledge that a Cu—Ag alloy wire with higher electrical conductivity and higher strength can be obtained by devising the production method while keeping the Ag content in a specific range. More specifically, before performing the wire drawing process, it includes a step of forming a state in which Ag is sufficiently dissolved in Cu, and a specific heat treatment is applied to the wire that has been subjected to the wire drawing process.
- the Cu-Ag alloy wire of the present invention described above can be manufactured by the method for manufacturing the Cu-Ag alloy wire of the present invention described later.
- the conductivity decreases as Ag dissolves in Cu, and the conductivity increases as Ag precipitates. Therefore, the above-mentioned “form a state in which Ag is sufficiently dissolved in Cu” means that in a Cu-Ag alloy containing a certain amount of Ag, Ag is precipitated and the conductivity is higher. Will form a state with low electrical conductivity.
- the method for producing a Cu-Ag alloy wire relates to a method for producing a wire by drawing a cast material made of a copper alloy containing Ag.
- the conductivity C % IACS
- the wire that has been subjected to the wire drawing is subjected to at least one heat treatment at a heating temperature of 300 ° C. or more and a holding time of 0.5 hours or more.
- a calculation method of the conditional expression regarding the conductivity C: C ⁇ ( ⁇ 0.1786) ⁇ x + 97 will be described later.
- a material in which Ag is sufficiently dissolved is formed, this material is subjected to wire drawing, and the wire material that has been further drawn is subjected to the specific heat treatment, Fine Ag particles can be deposited on the surface to form a structure in which these Ag particles are uniformly dispersed.
- the strength of the Cu-Ag alloy wire can be improved by dispersion strengthening of the fine particles with Ag.
- Ag precipitated before the wire drawing process is drawn into a fiber shape by the wire drawing process, and the strength can be improved by fiber reinforcement.
- the ultra-fine Ag described above is present in a uniformly dispersed state, fibrous Ag is present, or both coexist, a Cu-Ag alloy wire with high conductivity and strength can be produced. Conceivable.
- Examples of the Cu-Ag alloy wire obtained by the production method of the present invention include those containing 0.1 to 15% by mass of Ag, the balance being Cu and impurities, and a wire diameter of 1000 ⁇ m or less. .
- the Cu-Ag alloy wire of the present invention has high electrical conductivity and high strength.
- the method for producing a Cu-Ag alloy wire of the present invention can produce a Cu-Ag alloy wire having high conductivity and high strength.
- FIG. 1 is a graph showing the relationship between the Ag content and electrical conductivity in various Cu—Ag alloy materials produced under different manufacturing conditions.
- Fig. 2 is a photomicrograph (500 times) of the wire ( ⁇ 2.6mm) after heat treatment (precipitation heat treatment) on the drawn wire, and Fig. 2 (I) shows sample No. 2-3-2 and Fig. 2. (II) shows Sample No. 2-4-2.
- Fig. 3 is a transmission electron micrograph (magnification 150,000 times) of the wire ( ⁇ 0.9mm) after heat treatment (precipitation heat treatment) on the drawn wire, and Fig. 3 (I) shows sample No. 2-3, 3 (II) shows Sample No. 2-4, and FIG. 3 (III) shows Sample No. 2-110.
- FIG. 2 is a photomicrograph (500 times) of the wire ( ⁇ 2.6mm) after heat treatment (precipitation heat treatment) on the drawn wire
- Fig. 2 (I) shows sample No. 2-3-2 and Fig. 2.
- II shows Sample No.
- FIG. 4 is a schematic diagram for explaining Ag crystal precipitates present in the micrograph of FIG.
- FIG. 5 is a schematic view for explaining the structure constituting the Cu—Ag alloy wire of the present invention.
- FIG. 6 is a perspective view of the coaxial cable of the present invention.
- the Cu-Ag alloy constituting the Cu-Ag alloy wire of the present invention is a binary alloy having an Ag content of 0.1 mass% or more and 15 mass% or less (remainder Cu and impurities).
- the Ag content is 0.1% by mass or more, an effect of improving the strength by precipitation strengthening of Ag is easily obtained, and when it is 15% by mass or less, a decrease in conductivity due to excessive precipitation of Ag is easily suppressed.
- the Ag content is 1% by mass or more and 10% by mass or less because high strength and high electrical conductivity can be provided in a balanced manner.
- a raw material is prepared so that it may become a predetermined composition.
- the raw material Cu and Ag are high in purity, for example, those with Four Nine class (purity 99.99%) or higher have few impurities, especially when manufacturing thin wire rods, reducing foreign matter that may be involved in disconnection. can do.
- the size of the fine Ag particles means that “the maximum length of the straight line that cuts the crystal precipitate is 100 nm or less”.
- the Ag crystal precipitates may contain coarse Ag, and the size thereof means “the maximum length of the straight line that cuts the crystal precipitates exceeds 100 nm”.
- fibrous Ag is precipitated as Ag crystal precipitates. This fibrous Ag is obtained by stretching a relatively large Ag out of the precipitated Ag. In particular, when the Ag content is 2% by mass or more, this fibrous Ag is easily confirmed using a microscope. Most of the crystal precipitates are precipitates, and in particular, fine Ag and fibrous Ag are considered to be substantially precipitates. And it is thought that coarse-grained Ag is partially contained as a crystallized product.
- the Cu-Ag alloy wire of the present invention takes an arbitrary observation visual field within 1000 nm ⁇ 1000 nm in the cross section of the Cu-Ag alloy wire, among the Ag crystal precipitates present in the observation visual field,
- the area ratio of Ag is 40% or more.
- coarse Ag may exist in addition to fine Ag. Since fibrous Ag is sufficiently larger than the size of the observation field, it is not included in the “Ag crystal precipitates present in the observation field”. The method for collecting the observation field will be described later.
- the strength can be improved by dispersion strengthening.
- Coarse-grained Ag does not adversely affect the properties of the Cu-Ag alloy wire, but is considered not to contribute to improving the properties.
- the presence of fibrous Ag in addition to fine Ag makes it possible to improve the strength due to fiber reinforcement. It is considered that the Cu-Ag alloy wire has high conductivity and strength due to the presence of uniformly dispersed Ag, the presence of fibrous Ag, and the coexistence of both.
- the following method can be considered as a method of contributing coarse grain Ag to the improvement of the characteristics of the Cu-Ag alloy wire.
- Particularly large Ag among the coarse-grained Ag is stretched into a fiber shape at the time of wire drawing, so that the strength can be improved by fiber reinforcement.
- the coarse-grained Ag Ag that did not become fibrous is dissolved in Cu by heat treatment, and the solid solution is precipitated as fine-grained Ag as much as possible, thereby improving the strength by dispersion strengthening. be able to.
- the coarse Ag can be improved in strength depending on whether the coarse Ag is made fine or fibrous.
- the above-mentioned Cu-Ag alloy wire is typically a round wire with a circular cross section, and examples thereof include various wire diameters.
- the Cu-Ag alloy wire of the present invention has high conductivity and high strength, it is expected that not only a stranded wire obtained by twisting ultrafine wires but also a single wire can be sufficiently used as a conductor of an electric wire. .
- By appropriately changing the degree of processing at the time of wire drawing it is possible to obtain an ultrafine Cu-Ag alloy wire having a wire diameter of 0.01 mm (10 ⁇ m) to 0.08 mm (80 ⁇ m).
- the Cu-Ag alloy wire of the present invention has high conductivity, high strength, and depending on the wire diameter and Ag content, for example, an ultrafine Cu-Ag wire having a wire diameter of ⁇ 0.05 mm (50 ⁇ m) or less. Alloy wire with conductivity of 70% IACS or higher and tensile strength of 1200MPa or higher, or, for example, Cu-Ag alloy wire with wire diameter of ⁇ 1mm to ⁇ 3mm and conductivity of 95% IACS As mentioned above, the form with which the tensile strength satisfies 300 MPa or more is mentioned.
- the Cu—Ag alloy wire of the present invention may have a form in which a plating layer made of Ag, Ag alloy, Sn, Sn alloy or the like is provided on the surface thereof.
- a plating layer made of Ag, Ag alloy, Sn, Sn alloy or the like is provided on the surface thereof.
- the plating layer By providing the plating layer, wettability with solder and corrosion resistance can be improved.
- the plated layer may be formed during the drawing process or after the final drawing.
- the coaxial cable 1 of the present invention includes a center conductor 11, an insulator 12 covering the periphery of the center conductor 11, and an external conductor 13 disposed around the insulator 12.
- the coaxial cable 1 includes an exterior 14 that covers the outer periphery of the outer conductor 13.
- the center conductor 11 has one or more strands, and the strands are the Cu—Ag alloy wires of the present invention.
- the coaxial cable bundle of the present invention can be obtained by bundling a plurality of the coaxial cables of the present invention.
- the method for producing a Cu—Ag alloy wire of the present invention typically includes the following casting step, wire drawing step, and heat treatment step.
- Casting process A process for producing a cast material using a molten metal in which Ag and Cu as raw materials are dissolved.
- Wire drawing process A process of producing a wire having a final wire diameter by drawing a material that has undergone the above casting process.
- Heat treatment step a step of subjecting the wire drawing material (including the wire drawing material having the final wire diameter) subjected to the above wire drawing processing to a specific heat treatment described later at least once.
- a solid solution material in which Ag is sufficiently dissolved in Cu is prepared as the material used for wire drawing.
- continuous casting For the production of the cast material, continuous casting can be suitably used.
- continuous casting for example, a form in which a long cast material is continuously produced by holding and pulling the solidified shell with a pinch roll (packing) can be mentioned.
- the casting atmosphere may be an air atmosphere, but if an atmosphere of an inert gas such as Ar is used, oxidation of the molten metal can be prevented.
- the cooling rate of the molten metal in this casting process shall be 8.5 degrees C / sec or more.
- the cooling rate at the time of casting By setting the cooling rate at the time of casting to 8.5 ° C./sec or more, that is, rapidly cooling, it is possible to suppress the precipitation of Ag and form a state in which Ag is sufficiently dissolved.
- a faster cooling rate can suppress the precipitation of Ag, and is preferably 10 ° C./sec or more.
- the cooling rate is preferably as high as possible within the range in which the cast material is continuously produced.
- the cooling rate at the time of casting is the temperature immediately before pouring the mixed molten metal into the mold (for example, the temperature in the tundish) Tm (° C.), the temperature at the solidification start point is Tc (° C. ),
- Tm the temperature in the tundish
- Tc the temperature at the solidification start point
- t mc (sec) is the time for the mixed molten metal to move from the measurement point of temperature Tm to the measurement point of temperature Tc
- a water-cooled copper mold is used as the mold, or the solidified shell drawn out is surrounded so that the solidified shell drawn out from the mold can be sufficiently cooled.
- forced cooling means may be arranged.
- the forced cooling means include air blast means such as a water-cooled copper block and a fan.
- Solid solution treatment Alternatively, as one form for forming the solid solution material, a solution treatment is performed on the cast material obtained by the casting process (which may be the above-described rapidly cooled material or the above-described rapidly cooled material). Is mentioned.
- the heating temperature is preferably 600 ° C. or higher
- the holding time is 0.5 hours or longer
- the cooling rate is 1.5 ° C./sec or higher.
- the heating temperature is 600 ° C. or more and the holding time is 0.5 hours or more, Ag can be sufficiently dissolved in Cu even if Ag is precipitated on the cast material. As the heating temperature is higher, Ag tends to be sufficiently dissolved in Cu. However, if the heating temperature is too high, the Cu—Ag alloy starts to dissolve, and therefore the heating temperature is preferably 850 ° C. or less. Further, as the holding time is longer, Ag tends to be sufficiently dissolved in Cu, and there is no particular upper limit, but it is preferable to select appropriately within a range that does not cause a decrease in productivity.
- the cooling rate at the time of the above solution By setting the cooling rate at the time of the above solution to 1.5 ° C./sec or more, that is, rapidly cooling, it is possible to suppress the precipitation of the solid solution Ag, and it is possible to form a state in which the Ag is sufficiently solid solution.
- the cooling rate during the solution treatment is higher, the precipitation of Ag can be suppressed, more preferably 3 ° C./sec or more, and no particular upper limit is provided.
- the cooling rate during the solution treatment was determined by measuring the temperature of the sample one minute after the start of cooling, the temperature at this time was T 1 (° C.), and the solution treatment temperature was Tr ( ° C), the temperature difference: (Tr-T 1 ) divided by the time: 60 seconds.
- a forced cooling means can be suitably used.
- direct cooling using a fluid refrigerant such as water, oil, sand, blast using a fan, etc.
- a fluid refrigerant such as water, oil, sand, blast using a fan, etc.
- Cooling by the water-cooled copper block can be performed by, for example, arranging the water-cooled copper block so as to surround the wire drawn from the heat treatment furnace and cooling the atmosphere around the wire.
- the cooling rate can be adjusted by appropriately adjusting the refrigerant temperature, the arrangement state of the forced cooling means, the refrigerant quantity, the air quantity, and the like.
- the wire drawing (typically cold) is performed over a plurality of passes until the final wire diameter is reached.
- the degree of processing of each pass may be appropriately adjusted in consideration of the composition (Ag content), the final wire diameter, and the like.
- a wire that has been subjected to wire drawing specifically, a wire that is in the middle of wire drawing, or a wire that has been drawn to the final wire diameter is heat-treated under specific conditions, and Ag is in a sufficiently solid solution state. From this, Ag is precipitated.
- the above heat treatment (hereinafter referred to as precipitation heat treatment) may be performed at least once on the wire that has been drawn, or may be performed a plurality of times. If the precipitation heat treatment is performed once, the number of manufacturing processes is small and the productivity is excellent. If the precipitation heat treatment is performed multiple times, the precipitation of Ag, especially the precipitation of fine Ag, is increased to increase the strength and conductivity, or the wire drawing process. It is possible to improve the electrical conductivity by removing the processing strain introduced by, and to facilitate the subsequent wire drawing.
- the above precipitation heat treatment conditions are heating temperature: 300 ° C. or higher and holding time: 0.5 hour or longer.
- the heating temperature is less than 300 ° C. and the holding time is less than 0.5 hour, Ag cannot be sufficiently precipitated or the processing strain cannot be sufficiently removed.
- the higher the heating temperature and the longer the holding time the easier it is to precipitate Ag.
- the heating temperature is preferably 600 ° C. or less, particularly 350 ° C. or more and 550 ° C. or less, more preferably 400 ° C. or more and 450 ° C. or less
- the holding time is preferably 0.5 hours or more and 10 hours or less.
- the cooling at the time of precipitation heat treatment includes, for example, furnace cooling in which it is left in a heat treatment furnace and cooled by natural cooling.
- Cu-Ag alloy material was produced as follows. Prepare copper as the raw material Cu with a purity of 99.99% or more, and silver grains (Ag) with a purity of 99.99% or more as the raw material Ag, put them in a high-purity carbon crucible, and vacuum-melt them in a continuous casting machine. Cu and Ag A mixed molten metal was dissolved. As shown in FIG. 1 and Table 1, the amount of silver grains added was adjusted so that the Ag content (concentration) with respect to the molten mixture was 0.1 mass% to 15 mass%.
- a cast material having a circular cross section with a wire diameter of ⁇ 8.0 mm was manufactured by continuous casting using the obtained mixed molten metal and a high purity carbon mold.
- the sample indicated by ⁇ (casting (slow cooling)) is a sample in which the cooling rate at the time of casting is 1.5 ° C / sec (less than 8.5 ° C / sec) by natural cooling
- the sample indicated by ⁇ (casting (casting)) (Rapid cooling)) is a sample in which forced cooling means such as water-cooled copper is disposed so as to surround the solidified shell drawn out from the mold, and the cooling rate is 10 ° C./sec (8.5 ° C./sec or more)
- the sample (solution treated material) indicated by ⁇ is cast material indicated by ⁇ (cooling rate at casting: 2.5 ° C / sec), 760 ° C x 2 hours, cooling rate: 9 ° C / sec (1.5 ° C / sec or more) This is a sample subjected to the solution treatment.
- the above-mentioned “state in which Ag is solid-dissolved in Cu” means a state having a conductivity equal to or lower than the conductivity when the cooling rate during casting is low, that is, the conductivity C It can be said that (% IACS) satisfies C ⁇ ( ⁇ 0.1786) ⁇ x + 97.
- Test Example 2 Manufacture a material made of Cu-Ag alloy under various conditions, and wire-process this material and heat-treat appropriately to produce a Cu-Ag alloy wire, conductivity (% IACS), tensile strength (MPa) I investigated.
- Each sample was prepared as follows. Prepare the same raw materials as in Test Example 1, prepare a mixed molten Cu and Ag so that the Ag content (concentration) is the amount shown in Table 2, and perform continuous casting as in Test Example 1 A casting with a circular diameter of 8.0 mm was manufactured. Each casting material was changed in cooling conditions during casting so that the cooling rates shown in Table 2 were obtained. A sample having a cooling rate of less than 8.5 ° C./sec is a sample by natural cooling.
- Sample No.2-100 was subjected to heat treatment (solution treatment) on the obtained cast material (wire diameter ⁇ 8.0 mm) under the conditions shown in Table 2, followed by wire drawing, and the wire diameters shown in Table 2 In this case, a final wire diameter (Cu-Ag alloy wire) having a final wire diameter of ⁇ 0.04 mm obtained by performing an intermediate heat treatment under the conditions shown in Table 2 and further performing wire drawing.
- Sample No. 2-110 was subjected to wire drawing on the obtained cast material (wire diameter ⁇ 8.0 mm), and when subjected to intermediate heat treatment under the conditions shown in Table 2 when the wire diameter shown in Table 2, It is a wire (Cu-Ag alloy wire) having a final wire diameter of ⁇ 0.04 mm obtained by drawing.
- the cooling rate during casting is set to 8.5 ° C / sec or more, or the cast material is subjected to a solution treatment under specific conditions, so that the conductivity C (% IACS) satisfies C ⁇ (-0.1786) ⁇ x + 97.
- Sample Nos. 2-1 to 2-15 in which the material was formed, the solid solution material was subjected to wire drawing, and further subjected to a specific heat treatment (precipitation heat treatment), Slow ones (see casting (slow cooling) in Table 1). And it can be seen that Sample Nos. 2-1 to 2-15 have high strength even in the final wire diameter.
- Sample No. 2-100 which has a slow cooling rate during casting, a low heating temperature during the solution treatment, and a slow cooling rate
- Sample No. 2- which has a slow cooling rate during casting and is not subjected to a solution treatment
- 110 has a higher conductivity even after high solution treatment. It can be seen that both the strength immediately after the heat treatment in the middle of the wire and the strength at the final wire diameter are low.
- Sample No.2-120 which does not use a specific solid solution material before wire drawing, has a lower strength than Sample No.2-4,2-3-2,2-4-2. I understand.
- the cross section was observed with a microscope (500 times), and the observed image was processed by image processing.
- the long and slender string-like shape is obtained by stretching the precipitated Ag. It can be seen that the size of the fibrous Ag is on the micro order and the length is about several tens of ⁇ m.
- the Ag crystal precipitate is observed. If fibrous Ag can be confirmed in the micrograph, a sample for observing an Ag crystal precipitate is collected at a location where the fibrous Ag does not exist. In order to exclude fibrous Ag, the observation sample is preferably observed in a longitudinal section (cut surface along the drawing direction of the Cu-Ag alloy wire). By taking an arbitrary observation field within 1000 nm ⁇ 1000 nm from this observation sample and observing it with a transmission electron microscope, Ag crystal precipitates can be confirmed. *
- FIG. 3 shows a cross-sectional transmission electron micrograph (magnified 150,000) for Samples Nos. 2-3, 2-4, and 2-110.
- the observation visual field is a region of 440 nm ⁇ 326 nm.
- the number of precipitates having a maximum length of a straight line cutting the crystal precipitates of 100 nm or less (fine particles) was counted, and the total area of the fine particles was measured.
- the entire grains included in the observation visual field were measured, and the grains partially located at the outline of the observation visual field were excluded from the measurement.
- FIG. 4 shows a schematic diagram for explaining Ag counted as fine particles among the Ag crystal precipitates present in the micrograph of FIG.
- Table 3 shows the total area of the crystal precipitates, the total area of the fine particles, the area ratio of the crystal precipitates in the observation field, and the area ratio of the fine particles in the crystal precipitates for each sample.
- Table 3 also shows sample Nos. 2-1 and 2-2. *
- FIG. 5 shows a schematic diagram for explaining the structure constituting the Cu—Ag alloy wire of the present invention.
- an ellipsoid and a black circle in a rectangular frame represent precipitated Ag, and a white circle represents solid solution Ag.
- One of the factors that led to the electrical conductivity and tensile strength shown in Table 2 was due to fiber reinforcement due to the presence of Ag stretched as shown in FIG. 2 and nano-order as shown in FIG. It is conceivable to be due to dispersion strengthening due to the presence of very fine Ag particles dispersed uniformly or to have a mixed structure of both. For example, as shown in FIG.
- the mixed structure is a solution in which the cast material is subjected to a solution treatment, and the precipitated Ag is dissolved, and the amount of the Ag solution is increased.
- the formed Ag is formed in a fine granular form and precipitated in a large amount.
- the cooling rate during casting is slow, a relatively large amount of Ag is precipitated.
- this Ag is drawn by wire drawing, the above precipitation heat treatment is further performed.
- granular Ag is not precipitated so much, and only fibrous Ag is present. It is considered that the difference in strength occurs as described above due to the difference in the presence state of Ag.
- the sample with the solution treatment on the casting material under specific conditions tends to have higher strength than the sample with the cooling rate during casting of 8.5 ° C / min or more. It can be said that there is.
- the specific heat treatment precipitation heat treatment
- the higher the cooling rate at the time of forming the solid solution material the higher the strength after both the heat treatment and the final wire diameter. It can be said that there is.
- the present invention is not limited to the above-described embodiment, and can be modified as appropriate without departing from the gist of the present invention.
- Ag content, cooling rate during casting, solution treatment conditions (temperature, holding time, cooling rate), wire diameter for solution treatment or precipitation heat treatment, precipitation heat treatment conditions (heating temperature, holding time) Etc. can be appropriately changed.
- the Cu-Ag alloy wire of the present invention is an electric wire of various electric / electronic devices such as portable electronic devices such as mobile phones, electronic parts mounted on automobiles, medical devices, industrial robots, typically coaxial cables. It can be suitably used for other conductors (center conductor and shield conductor).
- the method for producing a Cu-Ag alloy wire of the present invention can be suitably used for producing the above-described Cu-Ag alloy wire of the present invention having high electrical conductivity and high strength.
- the coaxial cable of the present invention and the coaxial cable bundle of the present invention can be suitably used for the power supply wiring of the various electric / electronic devices.
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Abstract
Description
本発明者らは、導電率が比較的低下し難く、強度の向上に効果がある添加元素としてAgを選択し、Cu-Ag合金線を対象として、従来のCu-Ag合金線と同等、或いは同等以上の高い導電率を有しながら、強度が更に高いCu-Ag合金線を種々検討した。その結果、Agが非常に微細な粒状で存在することによって、導電率が高く、かつ強度がより向上したCu-Ag合金線とすることができる、との知見を得た。本発明は、上記知見に基づくものである。
本発明者らは、導電率が比較的低下し難く、強度の向上に効果がある添加元素としてAgを選択し、Cu-Ag合金線を対象として、従来のCu-Ag合金線と同等、或いは同等以上の高い導電率を有しながら、強度をより向上させるための手法を種々検討した。その結果、Agの含有量を特定の範囲とすると共に、製造方法を工夫することで、導電率が高く、かつ強度がより向上したCu-Ag合金線が得られる、との知見を得た。より具体的には、伸線加工を施す前において、AgをCu中に十分に固溶させた状態を形成する工程を具え、伸線加工が施されている線材に特定の熱処理を施してAgを析出することで、上述のAgを固溶させる工程が無い場合と比較して、同等な導電率を有していながら、強度が更に高い線材が得られる、との知見を得た。上述した本発明のCu-Ag合金線は、後述する本発明のCu-Ag合金線の製造方法により製造することができる。
[Cu-Ag合金線]
本発明のCu-Ag合金線を構成するCu-Ag合金は、Agの含有量が0.1質量%以上15質量%以下である二元合金である(残部Cu及び不純物)。Agの含有量が0.1質量%以上の場合、Agの析出強化による強度の向上効果が得られ易く、15質量%以下の場合、Agの過剰析出に伴う導電率の低下を抑制し易い。特に、Agの含有量が1質量%以上10質量%以下であると、高強度と高導電率とをバランスよく具えることができてより好ましい。所定の組成となるように、原料を用意する。原料Cuや原料Agは純度の高いもの、例えば、フォーナインクラス(純度99.99%)以上のものを利用すると不純物が少なく、特に、細径の線材を製造するにあたり、断線に関与し得る異物を低減することができる。
本発明の同軸ケーブル1は、図6に示すように、中心導体11と、当該中心導体11の周囲を覆っている絶縁体12と、当該絶縁体12の周囲に配置される外部導体13とを具える。更に、同軸ケーブル1は、外部導体13の外周を覆う外装14を具える。上記中心導体11は、1本以上の素線を有しており、この素線が本発明のCu-Ag合金線であることを特徴とする。そして、上記の本発明の同軸ケーブルを複数束ねて、本発明の同軸ケーブルバンドルを得ることができる。同軸ケーブル1の中心導体11に本発明のCu-Ag合金線を用いることによって、析出強化による強度(疲労特性)の向上を図ることができる。
本発明のCu-Ag合金線の製造方法は、代表的には、以下の鋳造工程、伸線工程、及び熱処理工程を具える。
鋳造工程:原料のAg及びCuを溶解した混合溶湯を用いて、鋳造材を作製する工程。
伸線工程:上記鋳造工程を経た素材に伸線加工を施して、最終線径の線材を作製する工程。
熱処理工程:上記伸線加工が施されている伸線材(最終線径の伸線材も含む)に後述する特定の熱処理を少なくとも1回施す工程。
特に、伸線加工に供する上記素材として、AgがCu中に十分に固溶された状態の固溶素材を用意する。
上記鋳造材の製造には、連続鋳造を好適に利用することができる。連続鋳造は、例えば、ピンチロール(パッキン)により凝固シェルを挟持して引っ張ることで、長尺な鋳造材を連続的に製造する形態が挙げられる。鋳造の雰囲気は、大気雰囲気としてもよいが、Arなどの不活性ガスによる雰囲気とすると、溶湯の酸化を防止することができる。そして、上記固溶素材を形成するための一形態として、この鋳造工程における溶湯の冷却速度を8.5℃/sec以上とすることが挙げられる。鋳造時の冷却速度を8.5℃/sec以上にする、即ち急冷することで、Agの析出を抑制して、Agが十分に固溶した状態を形成することができる。冷却速度が速いほどAgの析出を抑制でき、10℃/sec以上がより好ましい。なお、上述のように凝固シェルを引っ張る形態では、冷却速度を速めるために凝固シェルを引っ張る速度を速めると、凝固シェルが十分に追従できなくなる恐れがある。従って、上記冷却速度は、鋳造材が連続的に製造される範囲でできるだけ大きくすることが好ましい。
或いは、上記固溶素材を形成するための一形態として、上記鋳造工程により得られた鋳造材(上述した急冷したものでも、上述した急冷したものでなくてもよい)に溶体化処理を施すことが挙げられる。この溶体化処理は、加熱温度を600℃以上、保持時間を0.5時間以上、冷却速度を1.5℃/sec以上とすることが好ましい。
上記伸線加工(代表的には冷間)は、最終線径となるまで複数パスに亘って行う。各パスの加工度は、組成(Agの含有量)、最終線径などを考慮して適宜調整するとよい。
伸線加工が施された線材、具体的には伸線加工途中にある伸線材、或いは最終線径まで伸線された伸線材に特定の条件の熱処理を施し、Agが十分に固溶した状態からAgを析出させる。この熱処理により、ナノオーダーといった非常に微粒のAgが析出されると考えられる。この超微粒のAgが均一的に分散して存在することにより、Agの析出量が同じであり、かつ主として繊維状のAgが存在する組織の線材と比較して、導電率が同程度であっても、強度が更に高いCu-Ag合金線を製造できると考えられる。
種々の条件でCu-Ag合金材を製造し、Agの含有量と導電率との関係を調べた。その結果を図1及び表1に示す。
種々の条件でCu-Ag合金からなる素材を製造し、この素材に伸線加工、及び適宜熱処理を行ってCu-Ag合金線を製造し、導電率(%IACS)、引張強さ(MPa)を調べた。
11 中心導体 12 絶縁体 13 外部導体 14 外装
Claims (8)
- Agを含有する銅合金からなるCu-Ag合金線であって、
Agを0.1質量%以上15質量%以下含有し、残部がCu及び不純物からなり、
当該Cu-Ag合金線の断面において1000nm×1000nm以内で任意の観察視野をとったとき、この観察視野中に存在するAgの晶析出物のうち、晶析出物を切断する直線の最大長さが100nm以下である晶析出物の面積率が40%以上であることを特徴とするCu-Ag合金線。 - さらに、前記Agの晶析出物には、繊維状の析出物が含まれることを特徴とする請求項1に記載のCu-Ag合金線。
- 1本以上の素線を有する中心導体と、当該中心導体の周囲を覆っている絶縁体と、当該絶縁体の周囲に配置される外部導体とを具える同軸ケーブルであって、
前記素線が請求項1又は2に記載のCu-Ag合金線であることを特徴とする同軸ケーブル。 - 請求項3に記載の同軸ケーブルを複数本束ねたことを特徴とする同軸ケーブルバンドル。
- Agを含有する銅合金からなる鋳造材に伸線加工を施して線材を製造するCu-Ag合金線の製造方法であって、
Agの含有量をx(質量%)とするとき(但し、0.1質量%≦x≦15質量%)、前記伸線加工を施す前の素材として、当該素材の導電率C(%IACS)がC≦(-0.1786)×x+97を満たす固溶素材を形成し、
前記伸線加工が施されている線材に、加熱温度が300℃以上、保持時間が0.5時間以上の熱処理を少なくとも1回施すことを特徴とするCu-Ag合金線の製造方法。 - 前記固溶素材は、前記鋳造材に溶体化処理を施すことで形成し、
前記溶体化処理は、加熱温度を600℃以上、保持時間を0.5時間以上、冷却速度を1.5℃/sec以上とすることを特徴とする請求項5に記載のCu-Ag合金線の製造方法。 - 前記鋳造材は、その鋳造工程における溶湯の冷却速度を8.5℃/sec以上とすることで形成することを特徴とする請求項5又は6に記載のCu-Ag合金線の製造方法。
- 請求項5~7のいずれか1項に記載のCu-Ag合金線の製造方法により得られ、
Agを0.1質量%以上15質量%以下含有し、残部がCu及び不純物からなり、
線径が1000μm以下であることを特徴とするCu-Ag合金線。
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WO2023085305A1 (ja) * | 2021-11-12 | 2023-05-19 | 古河電気工業株式会社 | Cu-Ag系合金線 |
WO2023085306A1 (ja) * | 2021-11-12 | 2023-05-19 | 古河電気工業株式会社 | Cu-Ag系合金線 |
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