WO2023085306A1 - Ｃｕ－Ａｇ系合金線 - Google Patents

Ｃｕ－Ａｇ系合金線 Download PDF

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Publication number
WO2023085306A1
WO2023085306A1 PCT/JP2022/041681 JP2022041681W WO2023085306A1 WO 2023085306 A1 WO2023085306 A1 WO 2023085306A1 JP 2022041681 W JP2022041681 W JP 2022041681W WO 2023085306 A1 WO2023085306 A1 WO 2023085306A1
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Prior art keywords
alloy wire
mass
phase
phases
wire
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PCT/JP2022/041681
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English (en)
French (fr)
Japanese (ja)
Inventor
亮佑 松尾
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Priority to CN202280008536.0A priority Critical patent/CN116710588A/zh
Priority to KR1020237022256A priority patent/KR102915759B1/ko
Priority to JP2023559664A priority patent/JPWO2023085306A1/ja
Priority to EP22892804.0A priority patent/EP4455322A4/en
Publication of WO2023085306A1 publication Critical patent/WO2023085306A1/ja
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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
    • 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
    • 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

Definitions

  • the present invention relates to a Cu-Ag alloy wire.
  • wire diameters of electric wires used for connection cables for electrical and electronic devices are becoming thinner.
  • electric wires there is a tendency to use Cu alloy wires such as Cu--Sn, Cu--Cr, and Cu--Ag-based wires instead of pure Cu wires, which lack strength.
  • Cu alloy wires such as Cu--Sn, Cu--Cr, and Cu--Ag-based wires instead of pure Cu wires, which lack strength.
  • the wire diameter of electric wires tends to become smaller than before.
  • a Cu—Ag alloy wire can be mentioned as a copper alloy wire having a relatively high tensile strength and a relatively high electrical conductivity.
  • Patent Literature 1 discloses a method for producing a copper alloy having high strength and high electrical conductivity by stretching a eutectic phase of Cu and Ag into filaments.
  • Patent Document 2 discloses a Cu—Ag alloy fine wire that develops a recrystallized texture by heat treatment in the middle of the process and is made to have high strength by subsequent high working.
  • Patent Document 2 since appropriate wire drawing process conditions are not adopted before the heat treatment, embrittlement of the material progresses during the heat treatment, making it difficult to thin the wire. There is a problem that it does not become a certain product.
  • Patent Document 3 a part of the Ag crystal precipitates contains very fine granular Ag that is uniformly dispersed, so that Cu-Ag can have high tensile strength and high electrical conductivity.
  • a series alloy wire is disclosed.
  • Patent Document 3 specifies a predetermined distribution of Ag crystal precipitates, even if the desired structure is obtained by tracing the proposed manufacturing method, it is not always possible to obtain high tensile strength and high conductivity in a well-balanced manner. I have a problem that I can't.
  • an object of the present invention is to provide a Cu--Ag alloy wire which is excellent in bending fatigue resistance while having high strength and high electrical conductivity.
  • the gist and configuration of the present invention are as follows.
  • the phase has a plurality of Ag phases distributed linearly in series in the substantially longitudinal direction of the Cu—Ag alloy wire, and the Ag atomic concentration of the Ag phase is 0.5 to 50.0%. range, and the Ag phase having an average diameter of 0.5 to 20.0 nm when measured in a cross section perpendicular to the longitudinal direction of the Cu—Ag alloy wire is the Cu—Ag alloy wire.
  • the average value of the narrowest and shortest distances among the distances between the adjacent Ag phases measured in the cross section is in the range of 3 to 30 nm.
  • the Cu—Ag alloy wire contains at least one component selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr, each having a chemical composition of 0.05 to 0.
  • the Cu—Ag alloy wire is a ribbon wire having a width of 0.02 to 0.32 mm and a thickness of 0.002 to 0.040 mm, and having a substantially rectangular cross section.
  • the present invention it is possible to provide a Cu-Ag alloy wire that has high tensile strength and high electrical conductivity, and also has excellent resistance to bending fatigue. As a result, it has become possible to miniaturize electric and electronic equipment, save space in electric wire installation areas, and increase the number of signal wiring lines, which has not been possible until now. can contribute.
  • FIG. 1 shows an approximately conical sample prepared from a Cu—Ag alloy wire, which is one embodiment of the present invention, and a 140 nm distance from a first position (0 nm position) corresponding to the tip of the prepared sample.
  • FIG. 3 is a diagram of the isoconcentration surface of an Ag phase with an Ag atomic concentration of 2.0 atomic %, as measured from the side;
  • FIG. 2 shows data obtained in the same manner as in FIG.
  • FIG. 1 is a diagram of an isoconcentration surface of an Ag phase having an Ag atomic concentration of 3.5 atomic % when the lower portion of the tip portion up to 1 is measured from the upper surface side.
  • FIG. 3 is a diagram when the extension direction and the number of each Ag phase are plotted and calculated from the result of the isoconcentration surface of the Ag phase shown in FIG.
  • FIG. 4 is a graph showing the interval (and the average diameter) between adjacent Ag phases calculated from the result of the equiconcentration surface of the Ag phase shown in FIG. 2 .
  • FIG. 5 shows, for one Ag phase out of the plurality of Ag phases calculated by FIG. 2 is a graph showing the results of atomic concentration analysis of the elements Cu, Ag, N, and O in the lower portion of the tip portion up to .
  • a Cu—Ag alloy wire according to one embodiment of the present invention is a Cu—Ag alloy wire having a chemical composition containing 1.0 to 6.0% by mass of Ag, with the balance being Cu and unavoidable impurities.
  • a Cu--Ag-based alloy wire has a plurality of Ag phases distributed linearly in a matrix in a matrix along a substantially longitudinal direction of the Cu--Ag-based alloy wire, and Ag atoms in the Ag phase
  • the concentration is in the range of 0.5 to 50.0%, and the average diameter when measured in a cross section perpendicular to the longitudinal direction of the Cu—Ag alloy wire is in the range of 0.5 to 20.0 nm.
  • the number of Ag phases present in a measurement region of 10000 nm 2 in the cross section of the Cu—Ag alloy wire is in the range of 10 to 400 lines.
  • the Cu—Ag alloy wire of the present invention contains 1.0 to 6.0% by mass of Ag. Ag is therefore an essential additive component. Ag exists in a solid solution state in Cu, which is the mother phase (first phase), or in a crystallized state as an Ag phase, which becomes a second phase during casting of a Cu—Ag alloy wire, and is solid. It exerts the action of solution strengthening or dispersion strengthening.
  • the Ag content is set to 1.0 to 6.0% by mass. Furthermore, in a wide range of applications, when more emphasis is placed on the balance of electrical conductivity, the Ag content is more preferably 1.0 to 4.5% by mass.
  • the Cu—Ag alloy wire which is one embodiment of the present invention, contains at least one component selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr as an optional additive component. , respectively in the range of 0.05 to 0.30% by mass. All of these optionally added components are present mainly in the form of a solid solution in Cu, which is the matrix phase, and are elements that exert the effect of solid solution strengthening or dispersion strengthening, as in the case of Ag. In addition, when it is contained together with the Ag phase, it exists as a second phase of a ternary system or higher such as a Cu--Ag--Zr system, and contributes to further solid-solution strengthening or dispersion strengthening.
  • a ternary system or higher such as a Cu--Ag--Zr system
  • the content of each individual component is described below.
  • Sn (tin) content is 0.05% by mass or more, it contributes to the improvement of the strength of the copper alloy wire. do not have. Therefore, the Sn content is 0.05% by mass or more, preferably 0.07% by mass or more, more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more.
  • the Sn content is 0.30% by mass or less, more preferably 0.18% by mass or less, still more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
  • Mg manganesium
  • the content of Mg 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 Mg content is 0.30% by mass or less, the electrical conductivity of the copper alloy wire and the manufacturability during casting are not greatly impaired. Therefore, the content of Mg is 0.05% by mass or more, preferably 0.07% by mass or more, more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more.
  • the Mg content is 0.30% by mass or less, preferably 0.18% by mass or less, more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
  • the Zn (zinc) content is 0.05% by mass or more, it contributes to the improvement of the strength of the copper alloy wire and has the effect of alleviating the brittleness of the copper alloy wire.
  • the Zn content is 0.30% by mass or less, the electrical conductivity of the copper alloy wire is not greatly impaired. Therefore, the Zn content is 0.05% by mass or more, preferably 0.07% by mass or more, more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more.
  • the Zn content is 0.30% by mass or less, more preferably 0.25% by mass or less, even 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, preferably 0.07% by mass or more, more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more.
  • the In content is 0.30% by mass or less, preferably 0.18% by mass or less, 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 the strength improvement 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 0.05% by mass or more, preferably 0.07% by mass or more, more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more.
  • the Ni content is 0.30% by mass or less, preferably 0.25% by mass or less, more preferably 0.20% by mass or less, and particularly preferably 0.15% by mass or less.
  • Co (cobalt) content is 0.05% by mass or more, it contributes to the improvement of the strength of the copper alloy wire. do not have. Therefore, the Co content is 0.05% by mass or more, preferably 0.07% by mass or more, more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more. On the other hand, the Co content is 0.30% by mass or less, preferably 0.18% by mass or less, more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
  • ⁇ Zr 0.05 to 0.30% by mass>
  • the content of Zr zirconium
  • Zr zirconium
  • the Zr content is 0.05% by mass or more, preferably 0.07% by mass or more, more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more.
  • the Zr content is 0.30% by mass or less, preferably 0.20% by mass or less, more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
  • the Cr (chromium) content is 0.05% by mass or more, it contributes to improving the strength of the copper alloy wire. do not have. Therefore, the Cr content is 0.05% by mass or more, preferably 0.07% by mass or more, more preferably 0.08% by mass or more, and particularly preferably 0.10% by mass or more. On the other hand, the Cr content is 0.30% by mass or less, preferably 0.18% by mass or less, more preferably 0.15% by mass or less, and particularly preferably 0.12% by mass or less.
  • the optional additive components are preferably contained in a total amount of 0.05 to 1.0% by mass. If the content is less than 0.05% by mass, the decrease in electrical conductivity is small, but it does not contribute to high tensile strength. On the other hand, if the content exceeds 1.0% by mass, the tensile strength is further increased, but the electrical conductivity is significantly lowered and the high electrical conductivity characteristics cannot be maintained. Therefore, it is preferable that the total content of the optional additive components is in the range of 0.05 to 0.7% by mass. More preferably, the content is in the range of 0.05 to 0.5% by mass.
  • the balance other than the above components is Cu and unavoidable impurities.
  • Cu is the mother phase of the Cu—Ag alloy wire of the present invention, and Ag and the like, which are essential additive components, are present in a solid solution state or a precipitated state.
  • the unavoidable impurity is an impurity of a content level that can be unavoidably included in the manufacturing process of the Cu—Ag alloy wire of the present invention. Inevitable impurities may cause a decrease in electrical conductivity depending on the content. Therefore, considering the decrease in electrical conductivity, it is preferable to suppress the content of unavoidable impurities. Examples of unavoidable impurities include Pb, S, P, and the like.
  • the metal structure of the Cu—Ag alloy wire of the present invention is described below.
  • the Cu—Ag alloy wire of the present invention has a plurality of Ag phases linearly distributed in a matrix in a matrix extending in a substantially longitudinal direction of the Cu—Ag alloy wire, and the Ag phase comprises Ag atoms.
  • the concentration is in the range of 0.5 to 50.0%, and the average diameter when measured in a cross section orthogonal to the longitudinal direction of the Cu—Ag alloy wire is in the range of 0.5 to 20.0 nm.
  • the number existing in the measurement area of 10000 nm 2 in the cross section is in the range of 10 to 400 lines.
  • a three-dimensional atom probe (3DAP) method is measured by a three-dimensional atom probe (3DAP) method.
  • 3DAP method is an analysis technique that enables three-dimensional composition analysis of nanoprecipitates and clusters in metals and semiconductors. The principle is as follows. A needle-shaped sample with a diameter of about 100 nm is prepared with the tip formed in a substantially conical shape. Evaporate them one by one.
  • a two-dimensional position detector detects the time-of-flight and position measurement of ions field-evaporated by pulse voltage and laser irradiation, and measures the two-dimensional coordinate position of each ion.
  • Time-of-flight mass spectrometry analysis is also possible by measuring the time from the point of vaporization at the tip of the needle until the ion reaches the detector, so that the arriving ion species can be identified.
  • information on the two-dimensional coordinate position of the ions and information on the depth direction of the sample can be obtained.
  • three-dimensional composition information can be obtained. is possible.
  • FIG. 1 shows a substantially conical sample prepared from a Cu—Ag alloy wire (Ag concentration: 2.0% by mass), which is one embodiment of the present invention, and corresponds to the tip of the prepared sample.
  • FIG. 2 shows data obtained in the same manner as in FIG.
  • FIG. 4 shows an isoconcentration surface of the Ag phase with an Ag atomic concentration of 3.5 atomic % when the lower portion of the tip portion up to 1 is measured from the upper surface side.
  • FIG. 3 shows a graph obtained by figuring out the extending direction and the number of each Ag phase from the result of the isoconcentration surface of the Ag phase shown in FIG. 2 .
  • FIG. 4 shows a graph obtained by figuring out the distance (and average diameter) between adjacent Ag phases from the result of the isoconcentration surface of the Ag phase shown in FIG.
  • an Ag threshold with the same concentration as the Ag concentration is set, and the location where the concentration distribution exceeding this threshold can be confirmed is temporarily Ag phase and As shown in FIG. 1, it is possible to measure the longitudinal plane of the Ag phase having an atomic concentration exceeding a predetermined threshold value. Further, as shown in FIG. 2, it is possible to measure an image diagram of the Ag phase having an atomic concentration exceeding a predetermined threshold as viewed from the cross-sectional direction.
  • the number of phases was counted by assigning Ag confirmed when 3.5 at% of the Ag equiconcentration surface in the cross section of the alloy wire was set as the threshold.
  • the average diameter of the Ag phase was calculated from the area, assuming that the Ag phase is a perfect circle from the cross section perpendicular to the longitudinal direction of the tentative Ag phase.
  • a phase having an average diameter in the range of 0.5 to 20.0 nm was selected as the Ag phase.
  • the Ag atomic concentration was measured by analyzing the profile of the temporary Ag phase along the longitudinal direction, and selecting those having a continuous Ag atomic concentration of 0.5 to 50% in a length of 60 nm.
  • the number of Ag phases counts the number of Ag phases that satisfy both the average diameter of the Ag phase and the selection based on the Ag atomic concentration, and the number of Ag phases is proportional to the area. 2 range equivalent.
  • FIG. 3 shows the result of assigning the Ag phase in the longitudinal direction of the line
  • FIG. 4 shows the result of assigning the Ag phase in the cross section of the line. This is the result shown.
  • FIG. 5 shows, for one Ag phase out of the plurality of Ag phases calculated by FIG. 2 is a graph showing the results of atomic concentration analysis of Cu, Ag, and (N, O) elements in the lower portion of the tip portion up to .
  • the Ag atomic concentration in the Ag phase varies (fluctuates) within the range of 2 to 7 atomic concentration %.
  • the amount of (N, O) elements is very small and is affected by noise in the surrounding environment, and the influence on the Cu--Ag alloy is very small and negligible.
  • the Cu--Ag alloy wire of the present invention has a matrix in which a plurality of Ag phases are linearly distributed in series in the substantially longitudinal direction of the Cu--Ag alloy wire.
  • the Ag phases are not perfectly aligned in the longitudinal direction, but are substantially parallel and extend along the longitudinal direction of the wire.
  • the term “a phase continuous in the longitudinal direction” does not form a uniform phase with a constant Ag atomic concentration in the longitudinal direction. while forming a phase.
  • the atomic concentration indicates the existence ratio of Ag, and it is important that a phase continuous in the longitudinal direction exists in the range of 0.5 to 50.0%.
  • the Ag phase If it is less than 0.5%, it is impossible to distinguish whether Ag is in a precipitated state or in a solid solution state, making it impossible to determine the second phase. On the other hand, if it exceeds 50.0%, the Ag phase becomes sufficiently coarse, and the intervals between the Ag phases tend to become sparse, so high tensile strength cannot be obtained. Therefore, the Ag phase must have an Ag atomic concentration within the range of 0.5 to 50.0 atomic percent. Moreover, if the Ag phases are not continuous in the longitudinal direction, the intervals between the Ag phases become sparse, and the tensile strength and bending fatigue resistance cannot be improved. Therefore, the Ag phase forms a plurality of Ag phases distributed linearly in series in the substantially longitudinal direction of the Cu—Ag alloy wire.
  • the Ag phase has an average diameter in the range of 0.5 to 20 nm when measured in a cross section orthogonal to the longitudinal direction, and 10000 nm 2 in a cross section that is continuously or intermittently connected in the longitudinal direction. There are 10 to 400 lines existing in the measurement area of . If the average diameter of the Ag phase is less than 0.5 nm, the size is almost the same as the atomic diameter, and it is difficult to determine the solid solution or precipitation state of Ag with the resolution of existing analytical equipment. It is set as the lower limit because the relationship with the characteristics can be sufficiently clarified by specifying the .
  • the presence ratio is low and the interval between the Ag phases is wide, so it hardly contributes to densification. From this, since the improvement in tensile strength and bending fatigue resistance is at a negligible level, the presence of 20 nm or more need not be considered.
  • the intervals between the Ag phases become sparse, resulting in tensile strength and bending fatigue resistance. cannot be improved.
  • the upper limit of the number of Ag phases present in the measurement region of 10000 nm 2 in the cross section of the Cu—Ag alloy wire was because there were no Cu—Ag alloy wires with more than 400 Ag phases. , 400.
  • the Cu—Ag alloy wire has the shortest distance between the outer circumferences among the distances between adjacent Ag phases measured in the cross section (see FIGS. 2 and 4).
  • the average value is preferably in the range of 3-30 nm. 2 and 4 indicate the cross section of the Ag phase. When the average value of the shortest spacing of the Ag phase exceeds 30 nm, the strength contribution of the Ag phase becomes small.
  • the lower limit of the average value of the shortest interval of the Ag phase is not set in terms of characteristics, and as in the case of the average diameter of the Ag phase, there is a possibility that there may be an Ag phase that cannot be confirmed in terms of resolution,
  • the lower limit was set because the characteristics can be clarified by specifying the average value of the shortest distances between the Ag phases in the above range.
  • the bending fatigue resistance of metals is a phenomenon in which the durability of metal materials decreases when they are subjected to continuous or repeated bending of mechanical stress. characteristics are determined.
  • the Cu—Ag alloy wire of the present invention has a unique metal structure, for example, one of which is the outer circumference of the adjacent Ag phase, which is analyzed and measured from the cross section perpendicular to the longitudinal direction and the side surface. By setting the average value of the shortest distances between 3 and 30 nm, the structural change can be suppressed, and high tensile strength and improved bending fatigue resistance can be achieved at the same time.
  • the Cu—Ag alloy wire of the present invention has these unique metal structures, so that high tensile strength and excellent bending fatigue resistance can be obtained without lowering high electrical conductivity.
  • the Cu—Ag alloy wire preferably has an electrical conductivity of 65% IACS or higher, more preferably 75% IACS or higher.
  • Cu-Ag alloy wires tend to be used more and more as ultra-thin wires, which are thinner than conventional wire diameters. Even such ultrafine wires are required to have high tensile strength and high electrical conductivity.
  • a Cu alloy with high tensile strength is desired, and the Cu—Ag alloy wire of the present invention preferably has a tensile strength of at least 900 MPa or more, more preferably 1000 MPa or more. As a result, even if the wire diameter of the Cu--Ag alloy wire of the present invention is reduced, a Cu--Ag alloy wire with high tensile resistance can be obtained.
  • the Cu—Ag alloy wire of the present invention is preferably a round wire having a wire diameter of 0.01 mm to 0.08 mm.
  • high tensile strength and high conductivity materials with a diameter of 0.01 mm to 0.08 mm are required as conductors used in parts.
  • the lower limit of the wire diameter of 0.01 mm ⁇ reflects the needs of the market, and if there is a demand for further reduction in diameter in the future, the Cu—Ag alloy wire of the present invention will be applied. Is possible. If the wire diameter exceeds 0.08 mm ⁇ , the dimensions are too large and the wire cannot function as an extra fine wire.
  • the Cu—Ag alloy wire of the present invention is preferably a ribbon wire having a width of 0.02 to 0.32 mm and a thickness of 0.002 to 0.040 mm and having a substantially rectangular cross section. .
  • a manufacturing method for example, there is a method of rolling the drawn round wire into a desired shape.
  • the dimensions of the ribbon are preferably 0.02 to 0.32 mm in width and 0.002 to 0.040 mm in thickness for the same reason as the upper and lower limits of the wire diameter.
  • the strip width corresponds to the width direction of the rolling rolls, and the strip thickness corresponds to the direction between the rolls. At the ends in the strip width direction, the non-contacting roll roll portions are deformed while maintaining the shape of an arc.
  • the longer value in the cross section of the ribbon wire is the width, and the shorter value is the thickness.
  • a method for producing a Cu—Ag alloy wire according to the present invention will be described. However, the described manufacturing method is an example of manufacturing the present invention, and the manufacturing method of the present invention is not limited to this method.
  • a method for producing a Cu—Ag alloy wire according to the present invention includes a casting step of melting and casting a Cu—Ag alloy material having a predetermined chemical composition and cooling to obtain an ingot, and A first wire drawing step in which the Cu—Ag alloy material is subjected to wire drawing treatment, a first heat treatment step in which the wire drawn Cu—Ag alloy material is subjected to heat treatment, and a second wire drawing step in which wire drawing is performed.
  • It has a wire process, a second heat treatment process for further heat treatment, and a third wire drawing process for obtaining a Cu--Ag alloy wire by performing a final wire drawing process.
  • the wire drawing process the precipitate size becomes smaller and the interval narrows, so the production distribution is controlled in each heat treatment so that the precipitate system and phase interval at the stage when the final wire drawing is completed are within the scope of the invention. ing.
  • the cooling rate is set to 10° C./second or more in order to suppress excessive appearance of Ag crystal precipitates in the Cu matrix during cooling during casting. If the crystal precipitates during casting become large, the subsequent wire drawing in the wire drawing process will not produce an Ag phase with an appropriate average diameter, or the spacing between Ag phases will increase, so the final Cu It causes the tensile strength of the -Ag alloy wire to decrease.
  • the working rate is preferably about 50 to 90% in order to promote sufficient precipitation of Ag during heat treatment. If the work ratio is less than 50%, sufficient precipitation is not generated and the Ag phase spacing after wire drawing is not sufficiently narrowed, so that the increase in strength with respect to the work ratio in the second and subsequent wire drawing steps becomes small. This makes it difficult to obtain high tensile strength when the wire diameter of the Cu—Ag alloy wire is relatively large. On the other hand, although precipitation is promoted in a wire drawing process with a working ratio of 90% or more, it is difficult to obtain a high tensile strength because the working ratio in the wire drawing process after the heat treatment cannot be high. , preferably set an upper limit of 90%.
  • the first heat treatment step is a step of performing a heat treatment for precipitating Ag in the Cu matrix to form an Ag phase.
  • heat treatment is performed in the temperature range of 350 to 500° C. for 2 to 10 hours.
  • the second wire drawing step is a step of performing a wire drawing treatment with a reduction ratio of 5 to 40% in order to precipitate Ag and promote the formation of the Ag phase in the subsequent second heat treatment step.
  • heat treatment is performed in the temperature range of 350 to 500° C. for 10 to 20 hours.
  • the treatment temperature or treatment time in the first and second heat treatment steps is below the lower limit of the above range, the amount of precipitation of Ag phase decreases, and a metal structure having a precipitation density of Ag phase within the scope of the present invention is obtained. cannot be obtained, and finally high tensile strength cannot be obtained.
  • the treatment temperature exceeds the upper limit the solid solubility limit decreases and the amount of Ag phase precipitates decreases.
  • the average value of the shortest distance exceeds the upper limit due to the decrease in the number of precipitates within the range of the invention, so sufficient tensile strength and bending fatigue resistance cannot be obtained.
  • the number density is not sufficient with the desired precipitate size, and similarly the average value of the shortest distance exceeds the upper limit, resulting in insufficient strength characteristics and bending fatigue resistance. Therefore, in order to further improve strength characteristics and bending fatigue resistance, it is necessary to increase the number density of Ag phases, and (second wire drawing step) ⁇ (second heat treatment step) may be inserted.
  • the driving force for precipitation of the Ag phase changes greatly depending on the amount of plastic working before heat treatment, and the optimum heat treatment conditions also change. It is not necessary to adhere to this condition.
  • the working rate of the third wire drawing step is desirably about 90% to 99.9999% in order to sufficiently develop the strength characteristics of the present alloy.
  • a low processing rate does not result in a sufficient increase in strength.
  • the upper limit of the processing rate comes from a practical limit and has nothing to do with the characteristics.
  • a ribbon-shaped wire was produced by rolling a round wire produced in a circular shape to a specified thickness.
  • the final Cu--Ag alloy wire can be obtained by the finishing heat treatment step in which heat treatment is performed at the end of the manufacturing process (product after heat treatment).
  • the conditions of this final heat treatment are not particularly limited, but it is preferable that the temperature is 450 to 600° C. and the time is 10 seconds to 30 minutes.
  • this ingot was drawn to a wire diameter of 1.0 to 9.5 mm ⁇ so that the processing rate was 35 to 95% (first wire drawing step).
  • an aging heat treatment for both precipitation and recrystallization was performed at 350 to 550° C. for 1 to 15 hours (first heat treatment step).
  • second wire drawing step 3 to 99.9% wire drawing was performed (second wire drawing step).
  • the temperature was maintained at 350 to 550° C. for 5 to 50 hours, and aging heat treatment was performed at 350 to 550° C. for 1 to 15 hours (second heat treatment step).
  • cold wire drawing was performed to a wire diameter of 65 to 99.998% and 0.02 to 0.08 mm ⁇ (third wire drawing step).
  • Bending fatigue resistance was measured by a repeated bending test according to JIS H 0500 No. 4100. Since the fatigue properties depend on the wire diameter, 0.03 mm ⁇ was used as the test target, and for this test, samples with a smaller diameter, rolled material, or large diameter material were used in the process of processing, and the wire was drawn again. Unify the wire diameter.
  • Conductivity was measured using a four-probe method based on JIS H 0505-1975 in a constant temperature bath controlled at 20 ° C. ( ⁇ 1 ° C.), and the conductivity was measured for two of each test piece and averaged. The value (%IACS) was taken as the measured value. At this time, the distance between terminals was set to 100 mm.
  • FIB For the FIB, SIINT-3050TB and Helios G4 (manufactured by FEI) were used.
  • a Ga ion beam with an acceleration voltage of 30 kV is used to fabricate a conical sample with a circular bottom surface with a diameter of about 80 nm and a length of about 140 nm.
  • the longitudinal direction of the Cu—Ag alloy wire was taken as the length direction of the sample, but the diameter direction of the cross section perpendicular to the longitudinal direction of the Cu—Ag alloy wire may be taken as the length direction.
  • the final finish used a 5 kV ion beam to reduce the damaged layer as much as possible.
  • LEAP4000XSi manufactured by AMETEK was used as the 3DAP analysis device.
  • the irradiated pulsed laser was vaporized using ultraviolet light with a wavelength of 355 nm. Also, the voltage applied to the sample was set to 1 to 5 kV.
  • Analysis software such as IVAS 3.8.8 (manufactured by CAMECA) or IVAS LT was used to analyze the atomic concentration of the Ag phase and the shortest interval.
  • the analysis software IVAS is used to set the Ag threshold of the same concentration as the Ag concentration in the cross section perpendicular to the longitudinal direction of the Cu—Ag alloy wire, and the concentration exceeding this threshold
  • the portion where the distribution could be confirmed was tentatively defined as the Ag phase.
  • the average diameter of the Ag phase was calculated from the area by assuming that the Ag phase is a perfect circle from a cross section perpendicular to the longitudinal direction of the provisional Ag phase.
  • phases having an average diameter in the range of 0.5 to 20.0 nm were selected as Ag phases.
  • the Ag atomic concentration was measured by analyzing the profile of the temporary Ag phase along the longitudinal direction, and selecting those having a continuous Ag atomic concentration of 0.5 to 50% in a length of 60 nm.
  • the number of Ag phases the number of Ag phases satisfying both the average diameter of the Ag phases and the selection based on the Ag atomic concentration was counted.
  • the area range of the target sample was approximately 5000 nm 2 , which was converted to an area of 10000 nm 2 and used as the provisional phase number.
  • the shortest distance between the Ag phases is defined as the shortest distance between the outer circumferences of the Ag phases that are closest to each other, and the average value (n ⁇ 10) of the shortest distances between the Ag phases in the cross section of the bottom surface of the same sample. Calculated.
  • Examples 1-1 to 1-12, Comparative Examples 1-1 to 1-10) use a Cu—Ag alloy wire having a chemical composition of Cu—1.5 mass % Ag, and change the manufacturing conditions. , the Ag atomic concentration of the Ag phase, the average diameter, the number of Ag phases, and the average value of the shortest distance between the Ag phases.
  • Table 1 shows the manufacturing conditions of Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-10.
  • Example 1-10 a circular shape with a final diameter of 0.03 mm was processed and formed into a ribbon shape with a thickness of 0.008 mm and a width of 0.08 mm.
  • the underlines shown in the table indicate that they are outside the scope of the present invention.
  • Table 2 shows evaluation results of metal structures and properties of Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-10.
  • the evaluation items are the minimum and maximum Ag atomic concentration % of the Ag phase as the metal structure, the average diameter of the Ag phase, the number of Ag phases, the average value of the shortest interval of the Ag phase, and the tensile strength and bending fatigue resistance as mechanical properties. It is a characteristic.
  • the average value of the final diameter, the Ag atomic concentration of the Ag phase, the average diameter of the Ag phase, the number of Ag phases, and the shortest interval of the Ag phase It is within the scope of the present invention. All of them have a high tensile strength of 1000 MPa or more. Further, in Examples 1-7 to 1-12, the bending fatigue resistance is "O".
  • Examples 1-1 to 1-6 the average value of the shortest distance between the Ag phases was in the range of 3 to 30 nm, so the bending fatigue resistance was "excellent.”
  • the final diameter, the Ag atomic concentration of the Ag phase, and the average diameter of the Ag phase are within the scope of the present invention, but the number of Ag phases is small and the number of Ag phases is small. Since the average value of the shortest distance is 30 nm or more, the tensile strength is low and the bending fatigue resistance is also "x".
  • the number of Ag phases is within the scope of the present invention by making the third processing rate very low, but the average value of the shortest intervals of Ag phases is 30 nm or more. , the tensile strength is low, and the bending fatigue resistance is also "x".
  • Example 2-1 to 2-12 Comparative Examples 2-1 to 2-10
  • samples were prepared using a Cu—Ag alloy wire having a chemical composition of Cu-2.0 mass % Ag. .
  • Table 3 shows the manufacturing conditions of Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-10.
  • Table 4 shows evaluation results of metal structures and properties of Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-10.
  • Examples 2-1 to 2-12 have metal structures within the scope of the present invention.
  • the tensile strength is as high as 1100 MPa or more.
  • the bending fatigue resistance is "O".
  • the average value of the shortest distance between Ag phases is in the range of 3 to 30 nm, the bending fatigue resistance is "excellent”.
  • the final diameter, the Ag atomic concentration of the Ag phase, and the average diameter of the Ag phase are within the scope of the present invention, but the number of Ag phases is small and the number of Ag phases is small.
  • the number of Ag phases is within the scope of the present invention by making the third processing rate very low, but the average value of the shortest intervals of Ag phases is 30 nm or more. , the tensile strength is low, and the bending fatigue resistance is also "x".
  • Examples 3-1 to 3-12, Comparative Examples 3-1 to 3-10) In Examples 3-1 to 3-12 and Comparative Examples 3-1 to 3-10, samples were prepared using a Cu—Ag alloy wire having a chemical composition of Cu-4.0 mass % Ag. .
  • Table 5 shows the manufacturing conditions of Examples 3-1 to 3-12 and Comparative Examples 3-1 to 3-10.
  • Table 6 shows evaluation results of metal structures and properties of Examples 3-1 to 3-12 and Comparative Examples 3-1 to 3-10.
  • Examples 3-1 to 3-12 have metal structures within the scope of the present invention.
  • the tensile strength is as high as 1300 MPa or more.
  • the bending fatigue resistance is "O".
  • the average value of the shortest distance between the Ag phases is in the range of 3 to 30 nm, so the bending fatigue resistance is "excellent”.
  • the final diameter, the Ag atomic concentration of the Ag phase, and the average diameter of the Ag phase are within the scope of the present invention, but the number of Ag phases is small and the number of Ag phases is small.
  • the number of Ag phases is within the scope of the present invention by making the third processing rate very low, but the average value of the shortest intervals of Ag phases is 30 nm or more. , the tensile strength is low, and the bending fatigue resistance is also "x".
  • Example 4-1 to 4-12 Comparative Examples 4-1 to 4-10
  • samples were prepared using a Cu—Ag alloy wire having a chemical composition of Cu-6.0 mass % Ag. .
  • Table 7 shows the manufacturing conditions of Examples 4-1 to 4-12 and Comparative Examples 4-1 to 4-10.
  • Table 8 shows evaluation results of metal structures and properties of Examples 4-1 to 4-12 and Comparative Examples 4-1 to 4-10.
  • Examples 4-1 to 4-12 have metal structures within the scope of the present invention.
  • the tensile strength is as high as 1400 MPa or more.
  • the bending fatigue resistance is "O".
  • the average value of the shortest distance between the Ag phases was in the range of 3 to 30 nm, so the bending fatigue resistance was "excellent”.
  • the final diameter, the Ag atomic concentration of the Ag phase, the number of Ag phases, and the average value of the shortest interval are within the scope of the present invention, but the average diameter of the Ag phase is 30 nm. From the above, the tensile strength is low and the bending fatigue resistance is "x".
  • Comparative Example 4-10 it is difficult to make the number of Ag phases within the range of the present invention by making the third processing rate very low, and the number is 20 nm or more, so the tensile strength is low and , and the bending fatigue resistance is also "x".
  • Comparative Examples 5-1 to 5-4 are Cu—Ag alloy wires containing 1.0 to 6.0% by mass of Ag outside the range of the present invention, and Cu-0.5% by mass of Ag , Cu-0.8 mass % Ag, Cu-6.5 mass % Ag, and Cu-8.0 mass % Ag.
  • Table 9 shows the manufacturing conditions of Comparative Examples 5-1 to 5-4.
  • Table 10 shows evaluation results of metal structures and properties of Comparative Examples 5-1 to 5-4.
  • Comparative Example 5-4 the tensile strength was greater than 900 MPa because the Ag addition amount was greater than the upper limit of 6.0% by mass.
  • the atomic concentration and the like of the Ag phase are within the range of the present invention, the bending fatigue resistance is "A".
  • Comparative Example 5-3 and Example 4-3, and Comparative Example 5-4 and Example 4-4 are compared, there is no difference in the effects of tensile strength and bending fatigue resistance, and the amount of Ag added is Even if it is increased, there is a problem that the cost becomes high.
  • Examples 6-1 to 6-8, Comparative Examples 6-1 to 6-3 are selected from Cu-2.0 mass% Ag and Sn, Mg, Zn, In, Ni, Co, Zr and Cr A sample is prepared using a Cu—Ag alloy wire having a chemical composition containing one.
  • Table 11 shows the manufacturing conditions of Examples 6-1 to 6-8 and Comparative Examples 6-1 to 6-3.
  • Table 12 shows evaluation results of metal structures and properties of Examples 6-1 to 6-8 and Comparative Examples 6-1 to 6-3.
  • Examples 6-1 to 6-8 have metal structures within the scope of the present invention. As a result, the tensile strength is as high as 1100 MPa or more. Further, in Examples 6-1 to 6-8, the average value of the shortest distance between the Ag phases was in the range of 3 to 30 nm, so that the bending fatigue resistance was "excellent". In addition, Comparative Example 6-1 contains 0.5% by mass of Sn, and Comparative Example 6-2 contains 0.5% by mass of Mg, so that the conductivity is 60% IACS or less. The rate is low and there is a problem in practical use. In Comparative Example 6-3, the 0.5% by mass Zr content causes ingot cracks during production, making it difficult to produce round wires and the like, which is problematic in terms of production.

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WO2025094259A1 (ja) * 2023-10-31 2025-05-08 Ｓｗｃｃ株式会社 Ｃｕ－Ａｇ合金線の製造方法

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WO2025094259A1 (ja) * 2023-10-31 2025-05-08 Ｓｗｃｃ株式会社 Ｃｕ－Ａｇ合金線の製造方法

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