WO2015152166A1 - 銅合金線材及びその製造方法 - Google Patents
銅合金線材及びその製造方法 Download PDFInfo
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- WO2015152166A1 WO2015152166A1 PCT/JP2015/059965 JP2015059965W WO2015152166A1 WO 2015152166 A1 WO2015152166 A1 WO 2015152166A1 JP 2015059965 W JP2015059965 W JP 2015059965W WO 2015152166 A1 WO2015152166 A1 WO 2015152166A1
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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
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
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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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
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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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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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
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/42—Wire connectors; Manufacturing methods related thereto
- H01L24/43—Manufacturing methods
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/42—Wire connectors; Manufacturing methods related thereto
- H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/43—Manufacturing methods
- H01L2224/438—Post-treatment of the connector
- H01L2224/43848—Thermal treatments, e.g. annealing, controlled cooling
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45147—Copper (Cu) as principal constituent
Definitions
- the present invention relates to a copper alloy wire and a method for producing the same, and more particularly to an ultrafine copper alloy wire for a magnet wire and a method for producing the same.
- a coil for a microspeaker used in a mobile phone, a smartphone, or the like is manufactured by winding an extra fine wire (magnet wire) having a wire diameter of 0.1 mm or less into a coil shape.
- Patent Document 1 a high-concentration Cu-Ag alloy containing 2 to 15% by mass of Ag that can increase the tensile strength with almost no decrease in conductivity is used to adjust the workability of the final processing. It has been proposed to achieve both elongation and strength (Patent Document 1). In general, a processed metal or alloy has an increased tensile strength and a reduced elongation. However, when a heat treatment at a certain temperature or higher is applied thereto, the elongation is restored and the strength is decreased. Thus, it has been proposed that both the strength and elongation be achieved even in a low-concentration alloy by performing the heat treatment temperature below the softening temperature (Patent Document 2).
- Patent Document 3 A technique for performing the above has been proposed (Patent Document 3).
- JP 2009-280860 A Japanese Patent No. 3944304 Japanese Examined Patent Publication No. 4-77060
- Patent Document 1 The method described in Patent Document 1 is for high-cost alloys containing Ag at a high concentration of 2 to 15%. For this reason, there is a need for a technique that can exhibit sufficient strength and elongation even with a lower concentration of Cu—Ag alloy or a copper alloy containing no Ag. Moreover, as described in Patent Document 1, when the Ag content is increased in order to increase the strength, on the other hand, the conductivity is lowered. Furthermore, Ag is an element that improves heat resistance, and heat treatment becomes difficult. In addition, when processing up to an ultrathin line, it may not be possible to obtain sufficient characteristics just by adjusting the final processing degree.
- a general solid solution type highly conductive copper alloy as described in Patent Document 2 has a narrow temperature range for realizing a semi-softening heat treatment. For this reason, it is difficult to realize stable performance. Further, it is difficult to further increase the strength and improve the bending fatigue resistance while securing the conductivity and elongation with the copper alloy described in Patent Document 2.
- the elongation of the wire obtained by the semi-softening heat treatment is lower than the elongation of the wire obtained by the softening treatment, the formability of the wire obtained by the semi-softening heat treatment is suitable for coil winding processing under more severe conditions. It is insufficient for this.
- the method of semi-softening by adding a small amount of Zr to a low concentration Cu—Ag alloy can easily achieve both elongation and strength. In terms of elongation, it was insufficient.
- the shape of the magnet wire is not limited to a round wire, and the use of a square wire or a flat wire is also being studied. Also in the case of these square wires and flat wires, it is required that the wire be thin enough to correspond to the diameter of the round wire.
- the present invention has been made in view of the problems in the prior art, and has high elongation and excellent workability, that is, coil formability.
- the characteristics of the coil obtained using the copper alloy wire An object is to provide a copper alloy wire excellent in (coil life), for example, used for a magnet wire or the like at low cost.
- the present inventors In order to develop a copper alloy wire having high elongation, excellent workability, and excellent coil characteristics (coil life) obtained by using the copper alloy wire, the present inventors have developed various copper alloys. The inventors studied diligently about the alloy and its manufacturing method. As a result, it was found that by properly controlling the recrystallized texture of the copper alloy wire, a copper alloy wire having high elongation, excellent coil formability, and excellent coil characteristics (coil life) can be obtained. . The present invention has been completed based on this finding.
- a copper alloy wire containing 0.1 to 4.0% by mass of Ag with the balance being Cu and inevitable impurities A copper alloy wire in which the area ratio of crystal grains having a ⁇ 101> orientation is 10% or more of the total measurement area when a cross section perpendicular to the longitudinal direction of the wire is observed by an EBSD method from the normal direction of the cross section.
- a copper alloy wire made of mechanical impurities A copper alloy wire in which the area ratio of crystal grains having a ⁇ 101> orientation is 10% or more of the total measurement area when a cross section perpendicular to the longitudinal direction of the wire is observed by an EBSD method from the normal direction of the cross section.
- (6) a step of obtaining a rough drawn wire by melting and casting a copper alloy material containing 0.1 to 4.0% by mass of Ag and the balance being an alloy composition of Cu and inevitable impurities;
- the wire has a process of performing a final cold working and a final annealing in this order with a working degree ⁇ of 0.5 or more and 4 or less,
- the intermediate annealing and the final annealing are both performed at 400 to 800 ° C.
- a method for producing a copper alloy wire which is a heat treatment for 0.1 to 5 seconds at 500 to 850 ° C. (but not less than the recrystallization temperature of the copper alloy material) in an inert gas atmosphere when carried out by the formula.
- a method for producing a copper alloy wire which is a heat treatment for 0.1 to 5 seconds at 500 to 850 ° C. (but not less than the recrystallization temperature of the copper alloy material) in an inert gas atmosphere when carried out by the formula.
- At least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is contained in an amount of 0.05 to 0.30% by mass, and the balance is inevitable with Cu.
- the wire has a process of performing a final cold working and a final annealing in this order with a working degree ⁇ of 0.5 or more and 4 or less,
- the intermediate annealing and the final annealing are both performed at 300 to 800 ° C. or 400 to 800 ° C.
- a method for producing a copper alloy wire which is a heat treatment of 0.1 to 5 seconds at a temperature higher than the recrystallization temperature of the material.
- the wire means a square wire or a flat wire in addition to the round wire.
- the wire of the present invention refers to a round wire, a square wire, and a flat wire unless otherwise specified.
- the size of the wire means that the wire diameter ⁇ (diameter of the circle of the cross section) of the round wire is a square wire (in the wire drawing direction) if the wire is a round wire (a cross section perpendicular to the wire drawing direction is circular). If the cross section perpendicular to the square is square, the thickness t and width w of the square wire (both are the length of one side of the square of the cross section and have the same value) are converted into rectangular wires (drawing direction). Is the thickness t (the length of the short side of the rectangle of the cross section) and the width w (the length of the long side of the rectangle of the cross section).
- the balance between the predetermined strength required for coil forming and good elongation is excellent, and in addition to this, the characteristics of the coil obtained by using the copper alloy wire (specifically, bending fatigue resistance) It is possible to obtain a copper alloy wire excellent in coil life expressed by characteristics and coil formability that can form a long copper alloy wire into a coil with few defects.
- the copper alloy wire of the present invention can be suitably used for, for example, a magnet wire.
- the manufacturing method of the copper alloy wire of this invention the said copper alloy wire can be manufactured stably cheaply.
- FIG. 1 is a schematic diagram showing changes in strength and elongation of a copper alloy wire with respect to changes in heat treatment temperature.
- FIG. 1 the example in the copper alloy composition of Example 52 was shown.
- FIG. 2 is a front view schematically showing an apparatus used in a test for measuring the number of bending fatigue fractures (number of repetitions until fracture) performed in the examples.
- the copper alloy wire of the present invention contains 0.1 to 4% by mass of Ag and / or at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr.
- the content is preferably 0.05 to 0.30% by mass, and the balance consists of Cu and inevitable impurities.
- the content of the alloy additive element is simply “%”, it means “mass%”.
- the total content of at least one alloy component selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr other than Ag is preferably 0.50% by mass or less. More preferably, it is 0.05 to 0.30 mass%.
- [1] Ag may be contained alone, or [2] from Sn, Mg, Zn, In, Ni, Co, Zr and Cr. Or at least one selected from the group consisting of [3] these [1] Ag and [2] group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr You may contain both at least 1 sort (s) chosen from.
- These elements are solid solution strengthening type or precipitation strengthening type elements, respectively, and by adding these elements to Cu, the strength can be increased without significantly reducing the conductivity.
- This addition increases the strength of the copper alloy wire itself and improves the bending fatigue resistance.
- the bending fatigue resistance is proportional to the tensile strength, but if processing is performed in order to increase the tensile strength, the elongation decreases and it becomes impossible to form into an ultrafine copper alloy wire such as a magnet wire.
- the bending strain applied to the copper alloy wire during bending fatigue is larger at the outer peripheral portion of the wire, and the bending strain is smaller as it is closer to the center portion.
- the whole wire is maintaining the softened state. For this reason, since the elongation as a whole wire can be secured sufficiently, it becomes possible to form an ultrafine copper alloy wire such as a magnet wire.
- Ag is an element that can increase the strength without lowering the conductivity
- a Cu—Ag alloy is suitable as the copper alloy according to the present invention used for, for example, a magnet wire.
- Ag is an example of an essential additive element in the copper alloy according to the present invention.
- the Ag content is 0.1 to 4.0%, preferably 0.5 to 2.0%. If the Ag content is too low, sufficient strength cannot be obtained. Moreover, when there is too much Ag content, while electroconductivity will fall, cost will become high too much. In addition, when Ag content is less than 0.1 mass%, it is regarded as an inevitable impurity.
- At least one element selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is another example of the essential additive element in the copper alloy according to the present invention.
- the content of these elements is preferably 0.05 to 0.30% by mass, more preferably 0.05 to 0.20% by mass, as the content of each.
- this content is too small as each content, the effect of the strength increase by addition of these elements is hardly expected.
- the fall of electrical conductivity is too large and it is unsuitable as copper alloy wires, such as a magnet wire.
- at least one element selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is less than 0.05% by mass, it is regarded as an inevitable impurity.
- the copper alloy wire of the present invention is characterized in that the ⁇ 101> texture is 10% or more of the whole.
- the ⁇ 101> texture is preferably 20% or more of the whole.
- ⁇ 101> the texture is 10% or more of the whole
- a cross section perpendicular to the longitudinal direction (drawing direction) of the wire is observed from the normal direction of the cross section by the EBSD method
- ⁇ 101 > The area ratio of crystal grains having an orientation is 10% or more of the total measurement area.
- ⁇ 101> a copper alloy wire satisfying a texture of 10% or more of the entire structure has excellent elongation and excellent coil formability. It has been found that it exhibits its characteristics. In addition, if there are too many ⁇ 101> textures, the strength may be insufficient. Therefore, the ⁇ 101> texture is preferably 40% or less of the total.
- EBSD method The EBSD method is used for the observation and analysis of the crystal orientation in the present invention.
- EBSD is an abbreviation for Electron BackScatter Diffraction, and is a crystal orientation analysis technique using reflected electron Kikuchi line diffraction that occurs when a sample is irradiated with an electron beam in a scanning electron microscope (SEM).
- the cross section (transverse section) perpendicular to the longitudinal direction of the wire is scanned in 0.02 ⁇ m steps to analyze the orientation of each crystal grain.
- a surface whose deviation angle from the ⁇ 101> orientation is within ⁇ 10 degrees is defined as a ⁇ 101> surface
- a cross section perpendicular to the longitudinal direction of the wire is observed by the EBSD method from the normal direction of the cross section
- a crystal grain having a plane whose deviation angle from the ⁇ 101> orientation is within ⁇ 10 degrees is defined as a crystal grain having a ⁇ 101> orientation.
- the ratio of the area of the crystal grains having the ⁇ 101> orientation has the ⁇ 101> orientation.
- the area ratio (%) of crystal grains is obtained. What is necessary is just to determine the said scanning step suitably according to the magnitude
- analysis software OIM software (trade name) manufactured by TSL Solution can be used.
- Information obtained in the analysis of crystal grains by EBSD measurement includes information up to a depth of several tens of nanometers in which the electron beam penetrates the sample, but is sufficiently small with respect to the measured width. In the inside, it treats as an area ratio of a crystal grain.
- the area of the crystal grains differs in the longitudinal direction (LD) of the wire, it is preferable to average some points in the longitudinal direction.
- the average crystal grain size of base material of copper alloy wire is preferably 0.2 to 5.0 ⁇ m.
- the average crystal grain size is too small, since the crystal grains are excessively fine, the work hardening ability is lowered, and the elongation may be slightly lowered.
- the average crystal grain size is too large, non-uniform deformation is likely to occur, and elongation may decrease.
- the manufacturing method of the copper alloy wire of the present invention will be described.
- the shape of the copper alloy wire of the present invention is not limited to a round wire, and may be a square wire or a flat wire, which will be described below.
- the copper alloy wire of the present invention is not a processed finish but an annealed finish.
- the copper alloy round wire manufacturing method of the present invention includes, for example, casting, cold working (specifically, cold wire drawing, also called intermediate cold working), intermediate annealing, and final cold working. And each step of final annealing.
- cold working and intermediate annealing may be performed in this order as necessary, and these processes may be repeated twice or more in this order.
- the number of repetitions of cold working and intermediate annealing is not particularly limited, but is usually 1 to 5 times, preferably 2 to 4 times.
- the ingot size is close to the final wire diameter (for example, when the degree of processing from the ingot to the final wire diameter is in the range of 0.5 to 4, that is, when the ingot size is small or the final wire diameter is large) It can be omitted without necessarily requiring intermediate annealing. In this case, cold working as intermediate wire drawing after intermediate annealing is also omitted.
- the additive elements of Cu and Ag, Sn, Mg, Zn, In, Ni, Co, Zr, and Cr are melted and cast.
- the atmosphere of the crucible when melting is preferably an atmosphere of an inert gas such as a vacuum or nitrogen or argon in order to prevent formation of oxides.
- an inert gas such as a vacuum or nitrogen or argon in order to prevent formation of oxides.
- the continuous casting wire drawing methods such as a horizontal type continuous casting machine and an Upcast method, can be used. According to these continuous casting wire drawing methods, rough drawing wire having a diameter of about ⁇ 8 to 23 mm is usually obtained by continuously performing the steps from casting to wire drawing.
- a billet (ingot) obtained by casting is subjected to wire drawing to obtain a rough drawing wire having a diameter of about 8 to 23 mm.
- Cold working, intermediate annealing You may perform cold processing and heat processing (intermediate annealing) with respect to this rough drawing wire at least once in this order as needed. By performing these cold working and heat treatment (intermediate annealing), a thin wire having a diameter of usually about 0.06 to 1 mm is obtained.
- each cold working is performed so as to obtain a wire (thin diameter wire) within a range of a working degree ( ⁇ ) of 0.5 or more and 4 or less.
- the orientation of the ⁇ 101> texture (area ratio of the crystal grains having the ⁇ 101> orientation) is less than 10%, and instead the ⁇ 111> texture is It increases and affects the structure after finish annealing (final annealing), and the elongation becomes low.
- each cold working may be performed by a plurality of cold working passes.
- the number of cold working passes between two consecutive heat treatments (intermediate annealing) is not particularly limited, but is usually 2 to 40 times.
- intermediate annealing is performed as necessary. As described above, intermediate annealing may be omitted when the ingot size is close to the final wire diameter. Although the specific heat treatment temperature differs depending on the alloy composition, the intermediate annealing needs to be performed at a temperature higher than the recrystallization temperature. Copper alloy wires are roughly classified into two types of crystal structure states. One is a processed structure. This is a structure state in which many strains are introduced into the crystal by wire drawing or the like. The other is a recrystallized structure. This is a textured state with little variation in crystal grain size and relatively little distortion.
- the processed structure of the copper alloy wire changes to a recrystallized structure.
- a temperature at which almost all of the metal structure is changed to a recrystallized structure is defined as a “recrystallization temperature”.
- a heat treatment (temperature / time) that changes almost all of the metal structure to a recrystallized structure is called a softening process.
- the temperature and time of the softening process vary depending on the composition, processing degree, thermal history, etc. of the copper alloy wire. In particular, it is known that a copper alloy wire added with Ag or Zr has a high recrystallization temperature. The greater the degree of processing, the softer the treatment becomes even at lower temperatures.
- the softening heat treatment becomes possible even at lower temperatures.
- the temperature of the softening treatment is increased, recrystallization further proceeds, the elongation of the copper alloy wire is recovered, and the strength is lowered.
- the recovery of elongation and the decrease in strength reach an inflection point at the recrystallization temperature.
- heat treatment above this inflection point is called softening treatment.
- the heat treatment at a temperature below the recrystallization temperature up to the vicinity of the recrystallization temperature has a large elongation and change in strength with respect to the change in the heat treatment temperature, but the heat treatment temperature at a temperature higher than the recrystallization temperature. The change in elongation and strength with respect to the change is small.
- a heat treatment at a temperature higher than the recrystallization temperature is performed, the structure is rearranged into the recrystallized structure and the strain is eliminated, so that the strength decreases and the elongation improves (recovers).
- a heat treatment is performed for a predetermined time in a temperature range from a temperature at which the recovery of elongation and a decrease in strength occur (temperature exceeding about 200 ° C. in the example shown in FIG. 1) to below the recrystallization temperature (less than 500 ° C.).
- the semi-softened structure is a structure in which a processed structure and a recrystallized structure are mixed.
- the temperature range of the semi-softening heat treatment also varies depending on the alloy composition, the amount of deformation, the thermal history, etc., as in the softening treatment.
- the relationship between the annealing temperature, strength, and elongation in the copper alloy composition of Example 52 is shown in FIG.
- the recrystallization temperature or softening temperature is 500 ° C.
- softening treatment and semi-softening treatment are distinguished as treatments that give different physical properties to the copper alloy wire.
- the intermediate annealing in the method for producing a copper alloy wire according to the present invention corresponds to “softening treatment”. Therefore, the heat treatment temperature is higher than the recrystallization temperature.
- the heat treatment method for performing the intermediate annealing is roughly classified into a batch type and a continuous type.
- Batch-type heat treatment is inferior in productivity because it takes processing time and cost, but it is easy to control characteristics because temperature and holding time are easy to control.
- continuous heat treatment is excellent in productivity because it can be heat treated continuously with the wire drawing process, but since heat treatment needs to be performed in an extremely short time, the heat treatment temperature and time are accurately controlled to stabilize the characteristics. It is necessary to realize this. Since each heat treatment method has advantages and disadvantages as described above, a heat treatment method according to the purpose is selected. In general, the heat treatment is performed in a shorter time as the heat treatment temperature is higher, and the heat treatment is performed in a longer time as the heat treatment temperature is lower.
- the intermediate annealing is performed in a batch system, for example, heat treatment is performed at 300 to 800 ° C. for 30 minutes to 2 hours in a heat treatment furnace in an inert gas atmosphere such as nitrogen or argon.
- an element for improving heat resistance such as Ag or Zr
- the specific heat treatment temperature varies depending on the alloy composition, but the intermediate annealing temperature is equal to or higher than the recrystallization temperature.
- the intermediate annealing performed in batch mode is also abbreviated as batch annealing.
- examples of the continuous heat treatment include an electric heating method and an in-atmosphere heat treatment method.
- the electric heating method is a method in which an electrode ring is provided in the middle of the wire drawing process, a current is passed through the copper alloy wire passing between the electrode wheels, and heat treatment is performed by Joule heat generated in the copper alloy wire itself.
- the in-atmosphere running heat treatment method is a method in which a heating container is provided in the middle of wire drawing, and a copper alloy wire is passed through the heating container atmosphere heated to a predetermined temperature to perform heat treatment. Any of the heat treatment methods is preferably performed in an inert gas atmosphere in order to prevent oxidation of the copper alloy wire.
- the heat treatment conditions when the intermediate annealing is performed continuously are preferably performed at 400 to 850 ° C. for 0.1 to 5 seconds.
- an element for improving heat resistance such as Ag or Zr
- the specific heat treatment temperature varies depending on the alloy composition, but the intermediate annealing temperature is equal to or higher than the recrystallization temperature.
- the intermediate annealing performed by the two types of continuous heat treatment of the energization heating method and the in-atmosphere running heat treatment method will be abbreviated as current annealing and running annealing, respectively. If the intermediate annealing by any one of these heat treatments is insufficient, sufficient strain removal and recrystallization cannot be performed and the ⁇ 111> processed texture remains, so that the final product has sufficient elongation. It cannot be expressed.
- finish cold working is performed on the wire subjected to the cold working and intermediate annealing to obtain a desired wire diameter.
- This finish cold work is also performed within the range in which the degree of work ( ⁇ ) of the copper alloy wire is 0.5 or more and 4 or less, similar to the intermediate cold work.
- the degree of work is too small, sufficient work cannot be given, so that the work hardening of the copper alloy wire becomes insufficient, and the strength of the copper alloy wire obtained after finish annealing (final annealing) becomes insufficient.
- the degree of work is too large, ⁇ 101> texture cannot be obtained 10% or more after finish annealing, and sufficient elongation cannot be obtained.
- the finish cold working is performed within a range where the degree of work is 0.5 or more and 3 or less, and more preferably, the finish cold work is performed within a range where the degree of work ( ⁇ ) is 0.5 or more and 2 or less. Do. By performing finish cold working at this preferred degree of work, it is possible to obtain a superior copper alloy wire having a ⁇ 101> texture of 10% or more and an elongation of 25% or more.
- finish annealing performed in batch mode is also abbreviated as batch annealing.
- finish annealing performed by the two types of continuous methods is also abbreviated as current annealing and running annealing, respectively.
- the heat treatment for the finish annealing is preferably at or above the recrystallization temperature (recrystallization temperature + 200 ° C.) or less, more preferably at or above the recrystallization temperature (recrystallization temperature + 100 ° C.) or less, more preferably at or above the recrystallization temperature (recrystallization temperature). (Crystal temperature + 50 ° C.) or less. If the temperature of the final heat treatment (final annealing) is too high, the strength decreases. Furthermore, if the heat treatment is performed at a temperature higher than (recrystallization temperature + 200 ° C.), the crystal grains become coarse and elongation decreases.
- the manufacturing method of the copper alloy rectangular wire of the present invention is the same as the manufacturing method of the round wire, except that it has a rectangular wire processing step.
- the method for producing a copper alloy flat wire of the present invention includes, for example, casting, cold working (cold drawing), flat wire working, and final heat treatment (final annealing) in this order. .
- intermediate annealing intermediate heat treatment
- the conditions of processing and heat treatment in each step of casting, cold working, intermediate annealing, and final annealing, and preferable conditions thereof, and the number of repetitions of cold working and intermediate annealing are the same as in the method of manufacturing the round wire.
- the rolling reduction and the total rolling reduction in each pass during rolling or the like are not particularly limited, and may be set as appropriate so that a desired rectangular wire size can be obtained.
- the rolling reduction is the rate of change in thickness in the rolling direction when rectangular wire processing is performed.
- the rolling reduction ( %) Is represented by ⁇ 1- (t 2 / t 1 ) ⁇ ⁇ 100.
- the total rolling reduction can be 10 to 90%, and the rolling reduction in each pass can be 10 to 50%.
- the cross-sectional shape of the rectangular wire is not particularly limited, but the aspect ratio is usually 1 to 50, preferably 1 to 20, and more preferably 2 to 10.
- the aspect ratio (expressed as w / t below) is the ratio of the long side to the short side of the rectangle that forms the width direction (TD) cross section (ie, the cross section perpendicular to the longitudinal direction) of the flat wire.
- the thickness t of the flat wire is equal to the short side of the rectangle forming the width direction (TD) cross section
- the width w of the flat wire is the length of the rectangle forming the cross section of the width direction (TD). Equal to edge.
- the thickness t of the flat wire is usually 0.1 mm or less, preferably 0.07 mm or less, more preferably 0.05 mm or less.
- the width w of the flat wire is usually 1 mm or less, preferably 0.7 mm or less, more preferably 0.5 mm or less.
- winding a flat wire in the thickness direction means winding the flat wire in a coil shape with the width w of the flat wire being the width of the coil.
- a plate material or strip material having a predetermined alloy composition can be manufactured, and these plates or strips can be slit to obtain a rectangular wire material or a rectangular wire material having a desired line width.
- this manufacturing process for example, there is a method comprising casting, hot rolling, cold rolling, finish annealing, and slit processing. If necessary, intermediate annealing may be performed during the cold rolling. In some cases, the slit processing may be performed before the finish annealing.
- a copper alloy wire having a ⁇ 101> structure area ratio of 10% or more, preferably 20% or more (usually 40% or less) can be obtained.
- the copper alloy wire of the present invention preferably has a tensile strength of 260 MPa or more, more preferably 300 MPa or more. If the tensile strength is too small, the strength when the diameter is reduced is insufficient, and the bending fatigue resistance may be inferior. Although there is no restriction
- the copper alloy wire of the present invention preferably has an elongation (tensile elongation at break) of 20% or more, more preferably 30% or more. If the elongation is too small, problems such as breakage may occur when the coil is formed. Although there is no restriction
- the copper alloy wire of the present invention preferably has a conductivity of 70% IACS or more, more preferably 80% IACS or more, and still more preferably 90% IACS or more. Higher conductivity is preferable as a magnet wire, for example, because energy loss is lower.
- the conductivity of the magnet wire is required to be 70% IACS or more, preferably 80% IACS or more, and more preferably 90% IACS or more. Although there is no restriction
- the copper alloy wire of the present invention preferably exhibits high bending fatigue resistance while having high elongation that can be formed as an ultrafine wire magnet wire. Moreover, the copper alloy wire of the present invention is preferably excellent in coil characteristics (coil life, coil formability). Furthermore, the copper alloy wire of the present invention preferably has a high electrical conductivity.
- wire diameter or wire thickness is 0.1 mm or less, More preferably, it is 0.07 mm or less, More preferably, it is 0.05 mm or less.
- the lower limit of the wire diameter or the wire thickness is not particularly limited, but is usually 0.01 mm or more in the current technology.
- the use of the copper alloy wire of the present invention is not particularly limited, and examples thereof include a magnet wire that is an extra fine wire used for a speaker coil used in a mobile phone, a smartphone, and the like.
- the cast material is made of 0.1 to 4% by mass of Ag and / or 0.05 to 0.3% by mass of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr as each content.
- a book having various alloy compositions shown in Tables 1-1, 2-1, 2-6, 2-11, 4-1, which contains at least one selected from the group, and the balance being Cu and inevitable impurities The copper alloy material of the invention example (Example) and the copper alloy material of the comparative example having various alloy compositions shown in Tables 1-1, 2-1, 2-6, 2-11, 4-1 Each was cast into an ingot (rough drawing wire) having a diameter of 8 to 22 mm by a horizontal continuous casting method.
- the rough drawing wire is subjected to cold working (intermediate cold drawing), intermediate annealing (intermediate heat treatment), final cold working (finish cold drawing) and final annealing (finish heat treatment) in this order,
- Each round wire sample (test material) of the various wire diameters shown was created.
- the heat treatment of intermediate annealing and final annealing was performed by any one method selected from three patterns of batch annealing, current annealing, and running annealing, and all were performed in a nitrogen atmosphere. In each table, the method of heat treatment performed is indicated as “batch”, “current”, and “running”. The heat treatment temperature and heat treatment time of the heat treatment are shown in each column.
- the intermediate annealing and the final annealing are shown in the order of heat treatment 1 ⁇ heat treatment 2 ⁇ heat treatment 3 ⁇ .
- “X” shown as “heat treatment X” indicates the order (number) of the number of times (Xth) annealing. Of these, the last heat treatment is final annealing.
- the value shown in the “wire diameter” column in the “heat treatment X” section is the value of the wire after the cold working (intermediate cold working or final cold working) immediately before the X-th heat treatment. The wire diameter.
- the degree of work in this cold work is shown in the “work degree” column.
- the degree of working in the final cold working is shown in the “Degree of working in final working” column. .
- Examples of rectangular wires, comparative examples Using the copper alloys of the examples of the present invention (Examples) having various alloy compositions shown in Table 3-1 and the copper alloy of the comparative example in the same manner as the round wire, except that the ingot was cold worked. After subjecting the rough drawn wire obtained by (drawing) to intermediate annealing (heat treatment 1 in the table), at least one cold working (drawing) and intermediate annealing (heat treatment 2 ⁇ heat treatment 3 in the table ⁇ After being subjected to the heat treatment 4), a rectangular wire was processed, and then finish annealing (any one of heat treatment 3, heat treatment 4, and heat treatment 5 in the table) was performed to produce a rectangular wire sample.
- the flat wire processing is performed by converting a round wire having a diameter ⁇ (mm) before each flat wire processing into thickness t (mm) ⁇ width w (mm). Were processed by cold rolling into a rectangular wire of the size.
- Table 3-4 shows the degree of working in the final cold working (finish cold drawing) in the column of “Degree of working in final working”.
- Tables 1-1 to 1-3, 2-1 to 2-15, 3-1 to 3-5, and 4-1 to 4-3 show the manufacturing conditions of the copper alloy wire according to the present invention and the copper alloy wire of the comparative example. And the average crystal grain size of the base material and the area ratio of particles having ⁇ 101> orientation are shown together with the properties of the obtained copper alloy wire. In addition, the area ratio of particles having ⁇ 100> orientation or ⁇ 111> orientation is shown.
- Tensile strength (TS) and elongation (El) were measured according to JIS Z2201 and Z2241, respectively, for the copper alloy wires after the final annealing. In the table, “tensile strength after heat treatment” and “elongation after heat treatment” are shown, respectively. A tensile strength of 260 MPa or more was judged acceptable. The elongation was judged to be 10% or more.
- the electrical conductivity (EC) was measured according to JIS H0505.
- the electrical conductivity was evaluated as 70% IACS or higher, 80% IACS or higher as good, 90% IACS or higher as excellent, and less than 70% IACS as unacceptable.
- the average crystal grain size (GS) was measured by a cutting method (JIS G0551) from microstructural observation of a cross section (cross section) perpendicular to the longitudinal direction of each sample wire. In each table, it was simply indicated as “crystal grain size”.
- the crystal orientation of the recrystallized texture was measured and evaluated as follows using an EBSD (Electron Backscatter Diffraction) method.
- the cross section perpendicular to the longitudinal direction of each copper alloy wire sample wire was scanned in steps of 0.02 ⁇ m, and the orientation of each crystal grain was observed and analyzed.
- analysis software OIM software (trade name) manufactured by TSL Solutions was used.
- a plane whose deviation angle from the ⁇ 101> orientation is within ⁇ 10 degrees is defined as a ⁇ 101> plane, and a cross section perpendicular to the longitudinal direction of each copper alloy wire sample is taken from the normal direction of the cross section.
- a crystal grain having a plane whose deviation angle from the ⁇ 101> orientation is within ⁇ 10 degrees when observed by the EBSD method is defined as a crystal grain having a ⁇ 101> orientation.
- the area ratio (%) of the crystal grain which has ⁇ 101> orientation was calculated
- ⁇ 101> area ratio is indicated.
- the area ratio of particles having ⁇ 100> orientation or ⁇ 111> orientation was also determined in the same manner.
- the coil life was evaluated by performing the bending fatigue test using the apparatus shown in FIG. 2, measuring the number of bending fatigue fractures until the test piece of the copper alloy wire broke, and evaluating the number of fractures.
- a sample of a copper alloy wire having a wire diameter ⁇ or a wire thickness t is sandwiched between dies as a sample, and a 20 g weight (W) is hung on the lower end to apply a load in order to suppress the deflection of the wire. It was.
- W 20 g weight
- the sample was set so as to be sandwiched between dies in the wire thickness direction (ND). The upper end of the sample was fixed with a connector.
- the sample was bent 90 degrees to the left and right, repeatedly bent at a rate of 100 times per minute, and the number of bending until breaking was measured for each sample.
- the number of times of bending was counted as one round trip of 1 ⁇ 2 ⁇ 3 in the figure, and the interval between the two dies was set to 1 mm so as not to press the copper alloy wire sample during the test.
- the determination of breakage was made when the weight suspended at the lower end of the sample dropped.
- the bending radius (R) was set to 1 mm depending on the curvature of the die.
- AA (excellent) means that the number of times of repeated bending until bending (number of bending fatigue ruptures) is more than 2001, “A (excellent)” means that it is more than 1001 to 2000 times, “501” Those that were 1000 times were evaluated as “B (good)”, and those that were 500 times or less were evaluated as “D (poor)”.
- the coil formability was evaluated by the frequency of disconnection per 100 km by testing the frequency of occurrence of disconnection when a specimen of 100 km of copper alloy wire was wound into a coil having a diameter of 3 mm ( ⁇ 3 mm). “A (excellent)” when the occurrence frequency of the disconnection was 0 times or more and less than 0.3 times, “B (good)” when the occurrence frequency was 0.3 times or more and less than 0.6 times, Those that were not less than 1.0 and less than 1.0 were evaluated as “C (possible)”, and those that were not less than 1.0 were evaluated as “D (poor)”.
- A excellent as a copper alloy wire for ultrafine wire coils at a low cost, judging from the tensile strength, elongation, electrical conductivity, and coil characteristics (coil life, coil formability). Then, “B (good)”, “C (good)”, and “D (poor)” were evaluated.
- Tables 1-1 to 1-3 show round wire samples (Examples 1 to 10) of the present invention in which Cu-2% Ag alloy wires were processed and heat-treated so as to have a final wire diameter of 0.1 mm ( ⁇ 0.1 mm). The results of measuring and evaluating the characteristics of the comparative round wire sample (Comparative Examples 1 to 10) are shown.
- Example 10 where the final annealing temperature was as high as 850 ° C., the elongation was not so high as compared with the other examples. For this reason, in these Examples 8, 9, and 10, compared with other Examples, the coil formability was not so high.
- Comparative Examples 1 to 6 since the final cold work degree was too large, the area ratio of the ⁇ 101> texture was small, and the elongation and the coil formability were inferior.
- Comparative Example 7 since the temperature of the final heat treatment was low in the semi-softening temperature range, the area ratio of the ⁇ 101> texture was small, the strength was high and the coil life was excellent, but the elongation and the coil formability were inferior.
- Comparative Example 8 since the degree of work ( ⁇ ) before intermediate annealing was too large exceeding 4, the texture of ⁇ 111> orientation remained much, the area ratio of the texture of ⁇ 101> orientation was small, and the elongation was Coil formability was inferior.
- Comparative Example 9 since the intermediate heat treatment was insufficient, the processing strain could not be sufficiently removed and it was carried over to the next process. Therefore, the area ratio of ⁇ 101> texture was small, and the elongation and coil formability were low. inferior.
- Comparative Example 10 the degree of work before heat treatment was too high, and the temperature of intermediate annealing was high, so the crystal grains were coarsened, and the elongation and coil formability were inferior.
- These Comparative Examples 1 to 10 were all inferior in elongation and coil formability.
- the ⁇ 101> texture can be controlled by appropriately controlling the heat treatment temperature and the degree of processing, and it has a higher level of strength and elongation, as well as coil characteristics. An excellent copper alloy wire can be obtained.
- Tables 2-1 to 2-15 show examples and comparative examples of copper alloy round wires having various alloy compositions other than Cu-2% Ag alloy.
- a copper alloy round wire in which at least one element selected from the group consisting of (1) Ag and / or (2) Sn, Mg, Zn, In, Ni, Co, Zr and Cr is added to Cu.
- the Ag alloy by controlling the ⁇ 101> texture amount to obtain the area ratio of crystal grains having a predetermined ⁇ 101> orientation, the elongation, strength and conductivity are high, and the coil characteristics ( Coil life and coil formability were also excellent.
- Cu—Ag alloy round wire has higher strength than other copper alloy round wires. For example, comparing Examples 11 to 25 and Examples 26 to 43, which were subjected to substantially the same processing and heat treatment, Examples 11 to 25 were superior in characteristics, and the Cu—Ag alloy round wire was particularly suitable for a magnet wire. It turns out that it is.
- Tables 3-1 to 3-5 show examples of flat wire rods and comparative examples.
- the size after flat wire processing is indicated by thickness t (mm) ⁇ width w (mm).
- heat treatment 2 heat treatment 3 or heat treatment 4
- Heat treatment 4 or heat treatment 5 The last heat treatment shown in the column of “Heat Treatment 3, Heat Treatment 4 or Heat Treatment 5” is the final heat treatment (final annealing).
- Tables 4-1 to 4-3 show examples of the present invention and comparative examples of round wires in which the final wire diameter is swung from ⁇ 0.05 mm to 0.2 mm with a Cu-2% Ag alloy.
- the bending radius R was fixed to 1 mm so that the bending strain was constant at any wire diameter.
- the copper alloy round wire of any wire diameter showed excellent characteristics in the example of the present invention and excellent coil characteristics.
- the performance difference between the example of the present invention and the comparative example becomes more prominent, and it can be seen that the present invention is very effective with an extra fine wire.
- the same result as in the case of the round wire is obtained.
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Abstract
Description
(1)Agを0.1~4.0質量%含有し、残部がCuと不可避的不純物からなる銅合金線材であって、
線材の長手方向に垂直な断面を該断面の法線方向からEBSD法で観察した際に、<101>方位を有する結晶粒の面積率が全測定面積の10%以上である銅合金線材。
(2)Agを0.1~4.0質量%含有し、Sn、Mg、Zn、In、Ni、Co、ZrおよびCrからなる群から選ばれる少なくとも1種を各々の含有量として0.05~0.30質量%含有し、残部がCuと不可避的不純物からなる銅合金線材であって、
線材の長手方向に垂直な断面を該断面の法線方向からEBSD法で観察した際に、<101>方位を有する結晶粒の面積率が全測定面積の10%以上である銅合金線材。
(3)Sn、Mg、Zn、In、Ni、Co、ZrおよびCrからなる群から選ばれる少なくとも1種を各々の含有量として0.05~0.30質量%含有し、残部がCuと不可避的不純物からなる銅合金線材であって、
線材の長手方向に垂直な断面を該断面の法線方向からEBSD法で観察した際に、<101>方位を有する結晶粒の面積率が全測定面積の10%以上である銅合金線材。
(4)前記<101>方位を有する結晶粒の面積率が全測定面積の20%以上である(1)~(3)のいずれか1項に記載の銅合金線材。
(5)母材の平均結晶粒径が0.2~5.0μmである(1)~(4)のいずれか1項に記載の銅合金線材。
(6)Agを0.1~4.0質量%含有し、残部がCuと不可避的不純物からなる合金組成を与える銅合金材料を溶解、鋳造して荒引線を得る工程と、
該荒引線に、加工度ηが0.5以上4以下の冷間加工と中間焼鈍を少なくとも1回ずつこの順で繰り返して所定の線径の線材を得る工程と、
その後、該線材に、加工度ηが0.5以上4以下の最終冷間加工と最終焼鈍をこの順で行う工程とを有し、
前記中間焼鈍および前記最終焼鈍は、いずれも、バッチ式で行う場合は不活性ガス雰囲気下において400~800℃(ただし前記銅合金材料の再結晶温度以上)で30分~2時間、または、連続式で行う場合は不活性ガス雰囲気下において500~850℃(ただし前記銅合金材料の再結晶温度以上)で0.1~5秒の熱処理である、銅合金線材の製造方法。
(7)Agを0.1~4.0質量%含有し、Sn、Mg、Zn、In、Ni、Co、ZrおよびCrからなる群から選ばれる少なくとも1種を各々の含有量として0.05~0.30質量%含有し、残部がCuと不可避的不純物からなる合金組成を与える銅合金材料を溶解、鋳造して荒引線を得る工程と、
該荒引線に、加工度ηが0.5以上4以下の冷間加工と中間焼鈍を少なくとも1回ずつこの順で繰り返して所定の線径の線材を得る工程と、
その後、該線材に、加工度ηが0.5以上4以下の最終冷間加工と最終焼鈍をこの順で行う工程とを有し、
前記中間焼鈍および前記最終焼鈍は、いずれも、バッチ式で行う場合は不活性ガス雰囲気下において400~800℃(ただし前記銅合金材料の再結晶温度以上)で30分~2時間、または、連続式で行う場合は不活性ガス雰囲気下において500~850℃(ただし前記銅合金材料の再結晶温度以上)で0.1~5秒の熱処理である、銅合金線材の製造方法。
(8)Sn、Mg、Zn、In、Ni、Co、ZrおよびCrからなる群から選ばれる少なくとも1種を各々の含有量として0.05~0.30質量%含有し、残部がCuと不可避的不純物からなる合金組成を与える銅合金材料を溶解、鋳造して荒引線を得る工程と、
該荒引線に、加工度ηが0.5以上4以下の冷間加工と中間焼鈍を少なくとも1回ずつこの順で繰り返して所定の線径の線材を得る工程と、
その後、該線材に、加工度ηが0.5以上4以下の最終冷間加工と最終焼鈍をこの順で行う工程とを有し、
前記中間焼鈍および前記最終焼鈍は、いずれも、バッチ式で行う場合は不活性ガス雰囲気下において300~800℃若しくはZrを含有する場合は400~800℃(ただしいずれの場合も前記銅合金材料の再結晶温度以上)で30分~2時間、または、連続式で行う場合は不活性ガス雰囲気下において400~850℃若しくはZrを含有する場合は500~850℃(ただしいずれの場合も前記銅合金材料の再結晶温度以上)で0.1~5秒の熱処理である、銅合金線材の製造方法。
本発明の上記及び他の特徴及び利点は、適宜添付の図面を参照して、下記の記載からより明らかになるであろう。
本発明の銅合金線材は、Agを0.1~4質量%含有し、並びに/又はSn、Mg、Zn、In、Ni、Co、Zr及びCrからなる群から選ばれる少なくとも1種を各々の含有量として好ましくは0.05~0.30質量%含有し、残部はCuと不可避的不純物からなる。ここで、合金添加元素の含有量について単に「%」という場合は、「質量%」の意味である。また、Sn、Mg、Zn、In、Ni、Co、Zr及びCrからなる群から選ばれる少なくとも1種の合金成分の合計含有量には特に制限はないが、銅合金線材の導電率の著しい低下を防ぐためには、Ag以外のSn、Mg、Zn、In、Ni、Co、Zr及びCrからなる群から選ばれる少なくとも1種の合金成分の含有量は合計で好ましくは0.50質量%以下、より好ましくは0.05~0.30質量%である。
この添加によって、銅合金線材自体の強度が上がり、耐屈曲疲労特性が向上する。一般に耐屈曲疲労特性は引張強さに比例するが、引張強さを大きくするために加工を加えると伸びが低下しマグネットワイヤ等の極細銅合金線材へ成形することができなくなる。ここで、屈曲疲労時に銅合金線材にかかる曲げ歪は線材の外周部ほど大きく、中心部に近いほど曲げ歪量は小さくなる。本発明によれば、線材全体が軟化状態を維持している。この為、線材全体としての伸びを十分確保することができるので、マグネットワイヤ等の極細銅合金線材への成形が可能となる。
なおAg含有量が0.1質量%よりも少ない場合は不可避不純物と見做す。
なおSn、Mg、Zn、In、Ni、Co、Zr及びCrからなる群から選ばれる少なくとも1種の元素が0.05質量%よりも少ない場合は不可避不純物と見做す。
本発明の銅合金線材は、<101>集合組織が全体の10%以上であることを特徴としている。<101>集合組織が全体の20%以上であることが好ましい。ここで、<101>集合組織が全体の10%以上であるとは、線材の長手方向(伸線方向)に垂直な断面を該断面の法線方向からEBSD法で観察した際に、<101>方位を有する結晶粒の面積率が全測定面積の10%以上であることをいう。銅合金線に、従来通常の条件によって引抜加工、熱処理を行うと、<100>集合組織と<111>集合組織が発達する。しかし、本発明者は、様々な組織を持つ銅合金極細線材について検討を重ねた結果、<101>集合組織が全体の10%以上を満たす銅合金線材が、伸びに優れコイル成形性にも優れた特性を発揮することを見い出した。また、<101>集合組織が多すぎると強度不足となる場合があるため、<101>集合組織が全体の40%以下であることが好ましい。
本発明における上記結晶方位の観察と解析には、EBSD法を用いる。EBSDとは、Electron BackScatter Diffractionの略で、走査電子顕微鏡(SEM)内で試料に電子線を照射したときに生じる反射電子菊池線回折を利用した結晶方位解析技術のことである。
本発明での特性をさらに向上させるために平均結晶粒径は0.2~5.0μmが好ましい。平均結晶粒径が小さすぎる場合、結晶粒が過剰に微細であるため加工硬化能が低下し、伸びが若干低下する場合がある。一方、平均結晶粒径が大きすぎる場合、不均一変形を生じやすくなり、やはり伸びが低下してしまう場合がある。
本発明の銅合金線材の製造方法について説明する。
前記のとおり、本発明の銅合金線材の形状は、丸線に限定されず、角線や平角線としても良いので、これらについて以下に説明する。なお、本発明の銅合金線材は、加工上がり材ではなく、焼鈍上がり材である。
まず、本発明の銅合金丸線材の製造方法は、例えば、鋳造、冷間加工(具体的には冷間伸線加工であり、中間冷間加工ともいう。)、中間焼鈍、最終冷間加工及び最終焼鈍の各工程からなる。ここで、冷間加工と中間焼鈍とは、必要に応じてこの順で行えばよく、これらをこの順で2回以上繰り返して行ってもよい。冷間加工と中間焼鈍とを繰り返す回数は、特に制限されるものではないが、通常1回~5回であり、好ましくは2回~4回である。鋳塊サイズと最終線径が近い場合(例えば、鋳塊から最終線径までの加工度で0.5~4の範囲の場合、つまり、鋳塊サイズが小さいもしくは最終線径が太い場合)は必ずしも中間焼鈍を必要とせずに省略することができる。この場合、中間焼鈍後の中間伸線としての冷間加工も省略する。
坩堝にてCuとAg、Sn、Mg、Zn、In、Ni、Co、Zr、Crの添加元素を溶解し鋳造する。溶解するときの坩堝の雰囲気は酸化物の生成を防止するために真空もしくは窒素やアルゴンなどの不活性ガス雰囲気とすることが好ましい。鋳造方法には特に制限はなく、例えば横型連続鋳造機やUpcast法などの連続鋳造伸線法を用いることができる。これらの連続鋳造伸線法によれば、鋳造から伸線の工程を連続して行うことによって、通常直径φ8~23mm程度の荒引線が得られる。一方、連続鋳造伸線法によらない場合には、鋳造によって得たビレット(鋳塊)を伸線加工に付すことによって、同様に直径φ8~23mm程度の荒引線を得る。
この荒引線に対して冷間加工と熱処理(中間焼鈍)を必要に応じて少なくとも1回ずつこの順で繰り返して行ってもよい。これらの冷間加工と熱処理(中間焼鈍)を施すことによって、直径が通常φ0.06~1mm程度の細径線を得る。
各々の冷間加工は、加工度(η)が0.5以上4以下の範囲内で線材(細径線)を得るように行う。ここで、加工度(η)は、加工前の線材の断面積をS0、加工後の線材の断面積をS1とした時に、η=ln(S0/S1)で定義される。この加工度が小さすぎる場合は、加工後の熱処理(中間焼鈍)によって強度、伸びが十分発現せず、また、工程数が増えてしまうためエネルギー消費量が大きくなる為に製造効率が悪く、好ましくない。また、加工度が大きすぎる場合は、<101>集合組織の配向性(前記の<101>方位を有する結晶粒の面積率)が10%未満と小さくなって、代わりに<111>集合組織が多くなってしまい、仕上焼鈍(最終焼鈍)後の組織にも影響を与え伸びが低くなる。
バッチ式の熱処理は処理時間、コストがかかるため生産性に劣るが、温度や保持時間の制御が行いやすいため特性の制御を行いやすい。これに対して、連続式の熱処理は伸線加工工程と連続で熱処理が行えるため生産性に優れるが、極短時間で熱処理を行う必要があるため熱処理温度と時間を正確に制御し特性を安定して実現させることが必要である。それぞれの熱処理方法は以上のように長所と短所があるため、目的に沿った熱処理方法を選択する。なお、一般に、熱処理温度が高いほど短時間で、熱処理温度が低いほど長時間で熱処理を行う。
まず、通電加熱式は、伸線工程の途中に電極輪を設け、電極輪間を通過する銅合金線材に電流を流し、銅合金線材自身に発生するジュール熱によって熱処理を行う方法である。
次に、雰囲気内走間熱処理式は、伸線の途中に加熱用容器を設け、所定の温度に加熱された加熱用容器雰囲気の中に銅合金線材を通過させ熱処理を行う方法である。
いずれの熱処理方法も銅合金線材の酸化を防止するために不活性ガス雰囲気下で行うことが好ましい。
以下、前記通電加熱式と雰囲気内走間熱処理式の2種類の連続式熱処理で行う中間焼鈍をそれぞれ、電流焼鈍、走間焼鈍と略記する。このいずれかの熱処理による中間焼鈍が不十分な熱処理であると、十分な歪の除去と再結晶ができずに<111>の加工集合組織が残存してしまうため、最終製品で十分な伸びを発現することができない。
必要により前記冷間加工と中間焼鈍が施された線材に対して、仕上冷間加工を施して、所望の線径とする。この仕上冷間加工も、前記中間の冷間加工と同様に、銅合金線材の加工度(η)が0.5以上4以下となる範囲内で行う。加工度が小さすぎる場合は、十分な加工を与えられないため銅合金線材の加工硬化が不十分となり、仕上焼鈍(最終焼鈍)後に得られる銅合金線材の強度が不十分となってしまう。一方、加工度が大きすぎる場合は、仕上焼鈍後に<101>集合組織を10%以上得ることができず、十分な伸びを得ることができない。好ましくは、仕上冷間加工は加工度が0.5以上3以下となる範囲内で行い、さらに好ましくは、仕上冷間加工は加工度(η)が0.5以上2以下となる範囲内で行う。この好ましい加工度で仕上冷間加工を行うことによって、<101>集合組織を10%以上とするとともに、伸び25%以上というより優れた銅合金線材を得ることができる。
上記仕上冷間加工(最終冷間加工)工程により所望のサイズまで伸線加工した銅合金線材に対して、最終熱処理として再結晶温度以上で仕上焼鈍を施す。この熱処理もまた、軟化処理に相等するものである。仕上焼鈍をバッチ式で行う場合は、300~800℃で30分~2時間の熱処理を行う。一方、仕上焼鈍を連続式で行う場合は、400~850℃で0.1~5秒の熱処理を行う。特に、Ag、Zrといった耐熱性を高める元素を添加した場合は、バッチ式の場合は400~800℃で30分~2時間の熱処理を行い、一方、連続式の場合は500~850℃で0.1~5秒の熱処理を行う。前述のとおり、合金組成によって具体的な熱処理温度は異なるが、仕上焼鈍温度は再結晶温度以上である。
前記仕上焼鈍の熱処理は、好ましくは再結晶温度以上で(再結晶温度+200℃)以下、より好ましくは再結晶温度以上で(再結晶温度+100℃)以下、さらに好ましくは再結晶温度以上で(再結晶温度+50℃)以下の範囲で行う。最終熱処理(最終焼鈍)の温度を高くし過ぎると強度が低下してしまう。さらに、(再結晶温度+200℃)よりも高い温度で熱処理すると結晶粒の粗大化を引き起こして伸びが低下してしまう。
次に、本発明の銅合金平角線材の製造方法は、平角線加工工程を有する以外は、前記丸線材の製造方法と同様である。具体的には、本発明の銅合金平角線材の製造方法は、例えば、鋳造、冷間加工(冷間伸線)、平角線加工、最終熱処理(最終焼鈍)の各工程をこの順に施してなる。必要に応じて、冷間加工と平角線加工の間に中間焼鈍(中間熱処理)を入れても良いことも、前記丸線材の製造方法と同様である。鋳造、冷間加工、中間焼鈍、最終焼鈍の各工程の加工・熱処理の各条件とそれらの好ましい条件や、冷間加工と中間焼鈍の繰り返し回数も丸線材の製造方法と同様である。
平角線加工の前までは、丸線材の製造と同様にして、鋳造で得た鋳塊に冷間加工(伸線加工)を施して丸線形状の荒引線を得て、必要により中間焼鈍を施す。平角線加工としては、こうして得た丸線(荒引線)に、圧延機による冷間圧延、カセットローラーダイスによる冷間圧延、プレス、引抜加工等を施す。この平角線加工により、幅方向(TD)断面形状を長方形に加工して、平角線の形状とする。この圧延等は、通常1~5回のパスによって行う。圧延等の際の各パスでの圧下率と合計圧下率は、特に制限されるものではなく、所望の平角線サイズが得られるように適宜設定すればよい。ここで、圧下率とは平角線加工を行った時の圧延方向の厚さの変化率であり、圧延前の厚さをt1、圧延後の厚さをt2とした時、圧下率(%)は{1-(t2/t1)}×100で表される。また、本発明において平角線加工での加工度ηはη=ln(t1/t2)と定義する。例えば、この合計圧下率は、10~90%とし、各パスでの圧下率は、10~50%とすることができる。ここで、本発明において、平角線の断面形状には特に制限はないが、アスペクト比は通常1~50、好ましくは1~20、さらに好ましくは2~10である。アスペクト比(下記のw/tとして表わされる)とは、平角線の幅方向(TD)断面(つまり、長手方向に垂直な断面)を形成する長方形の短辺に対する長辺の比である。平角線のサイズとしては、平角線材の厚さtは前記幅方向(TD)断面を形成する長方形の短辺に等しく、平角線材の幅wは前記幅方向(TD)断面を形成する長方形の長辺に等しい。平角線材の厚さtは、通常0.1mm以下、好ましくは0.07mm以下、より好ましくは0.05mm以下である。平角線材の幅wは、通常1mm以下、好ましくは0.7mm以下、さらに好ましくは0.5mm以下である。
この平角線材を厚さ方向に巻線加工する場合、本発明による丸線材と同様に、高い引張強度、伸び、導電率を発現することができる。ここで、平角線材を厚さ方向に巻線加工するとは、平角線材の幅wをコイルの幅として、平角線をコイル状に巻きつけることをいう。
さらに、角線材を製造する場合には、前記平角線材の製造方法において、幅方向(TD)断面が正方形(w=t)となるように設定すればよい。
前記の製造方法に代えて、所定の合金組成の板材または条材を製造し、これらの板または条をスリットして、所望の線幅の平角線材または角線材を得ることができる。
この製造工程として、例えば、鋳造、熱間圧延、冷間圧延、仕上焼鈍、スリット加工からなる方法がある。必要に応じて冷間圧延の途中に中間焼鈍を入れても良い。スリット加工は場合によっては仕上焼鈍の前に行っても良い。
以上で説明した本発明の製造方法によって、<101>組織の面積率が全体の10%以上、好ましくは20%以上(通常40%以下)である銅合金線材を得ることができる。本発明の銅合金線材は、好ましくは260MPa以上、さらに好ましくは300MPa以上の引張強さを有する。引張強度が小さすぎる場合には、細径化したときの強度が足りず、耐屈曲疲労特性に劣ることがある。引張強さの上限値には特に制限はないが、通常400MPa以下である。また、本発明の銅合金線材は、好ましくは20%以上、さらに好ましくは30%以上の伸び(引張破断伸び)を有する。伸びが小さすぎる場合には、コイルを成形する際に破断等の不具合が生じてしまうことがある。伸びの上限値には特に制限はないが、通常40%以下である。
本発明の銅合金線材の線径または線材の厚さには、特に制限はないが、好ましくは0.1mm以下、さらに好ましくは0.07mm以下、より好ましくは0.05mm以下である。線径または線材の厚さの下限値には特に制限はないが、現在の技術では通常0.01mm以上である。
本発明の銅合金線材の用途は、特に制限されないが、例えば、携帯電話、スマートフォンなどに使用されているスピーカコイルに用いられる極細線であるマグネットワイヤ等が挙げられる。
鋳造材は、0.1~4質量%のAg、並びに/または、各々の含有量として0.05~0.3質量%のSn、Mg、Zn、In、Ni、Co、Zr及びCrからなる群から選ばれる少なくとも1種を含有し、残部がCuと不可避的不純物からなる表1-1、2-1、2-6、2-11、4-1に示した種々の合金組成を有する本発明例(実施例)の銅合金素材と、表1-1、2-1、2-6、2-11、4-1に示した種々の合金組成を有する比較例の銅合金素材とを、それぞれ横型連続鋳造方法でφ8~22mmの鋳塊(荒引線)に鋳造した。
この荒引線に冷間加工(中間冷間伸線)、中間焼鈍(中間熱処理)、最終冷間加工(仕上冷間伸線)及び最終焼鈍(仕上熱処理)をこの順に施して、各々表中に示した各種線径の、各丸線材サンプル(供試材)を作成した。
中間焼鈍、最終焼鈍の熱処理は、バッチ焼鈍、電流焼鈍、走間焼鈍の3パターンから選ばれるいずれかの方式で実施し、いずれも窒素雰囲気下で行った。各表中には、行った熱処理の方式を「バッチ」、「電流」、「走間」と示した。当該熱処理の熱処理温度と熱処理時間を各欄に示した。なお、中間焼鈍及び最終焼鈍は、熱処理1→熱処理2→熱処理3→…として、行った順に示した。「熱処理X」として示した「X」が何回目(第X回目)に行った焼鈍であるかの順番(番号)を示す。この内、最後に行った熱処理が最終焼鈍である。各表に示した試験例では、中間焼鈍を1回から4回行った場合と、中間焼鈍を1回も行わなかった場合とがある。各試験例において「熱処理X」の項の「線径」欄に示した値は、当該第X回目の熱処理に付す直前の冷間加工(中間冷間加工または最終冷間加工)後の線材の線径である。この冷間加工(中間冷間加工または最終冷間加工)における加工度を「加工度」の欄に示した。
表1-2、2-4、2-9、2-14には、当該最終に施した冷間加工(最終冷間加工)における加工度を「最終加工での加工度」の欄に示した。
表3-1に示した種々の合金組成を有する本発明例(実施例)の銅合金と比較例の銅合金とを用いて、前記丸線材と同様にして、但し、鋳塊を冷間加工(伸線)して得た荒引線に中間焼鈍(表中の熱処理1)を付した後、少なくとも1回ずつの冷間加工(伸線)と中間焼鈍(表中の熱処理2→熱処理3→熱処理4)に付した後に、平角線加工を施してから仕上焼鈍(表中の熱処理3、熱処理4、熱処理5のいずれか)を施して、平角線材サンプルを作製した。
平角線加工は、表3-3~3-4に示したように、各平角線加工前に線径φ(mm)であった丸線を、厚さt(mm)×幅w(mm)のサイズの平角線に冷間圧延によって加工した。
表3-4には、最終に施した冷間加工(仕上冷間伸線)における加工度を「最終加工での加工度」の欄に示した。
以上のようにして得た丸線材と平角線材のサンプルについて、各種特性を試験、評価した。
このように、本発明によれば、熱処理温度と加工度を適正に制御することで<101>集合組織を制御することができて、より高いレベルの強度と伸びを有するとともに、コイル特性にも優れた銅合金線材を得ることができる。
表中、「最終加工での加工度」の欄には、「熱処理1~5」の内、最終に行った熱処理x(x回目、x=最終)の直前に行った最終の仕上冷間加工(x回目、x=最終)における加工度を示した。
表3中、平角線加工後のサイズを厚さt(mm)×幅w(mm)で示した。「熱処理2、熱処理3または熱処理4」の内、最終に行った中間熱処理x(x回目、x=最終)後の線径φ(mm)の丸線に対して、平角線加工を「熱処理3、熱処理4または熱処理5」の欄に示した加工度で施した。最後に行った「熱処理3、熱処理4または熱処理5」の欄に示した熱処理が最終熱処理(最終焼鈍)である。
なお、平角線材の場合にも、前記丸線材の場合と同様の結果が得られる。
Claims (8)
- Agを0.1~4.0質量%含有し、残部がCuと不可避的不純物からなる銅合金線材であって、
線材の長手方向に垂直な断面を該断面の法線方向からEBSD法で観察した際に、<101>方位を有する結晶粒の面積率が全測定面積の10%以上である銅合金線材。 - Agを0.1~4.0質量%含有し、Sn、Mg、Zn、In、Ni、Co、ZrおよびCrからなる群から選ばれる少なくとも1種を各々の含有量として0.05~0.30質量%含有し、残部がCuと不可避的不純物からなる銅合金線材であって、
線材の長手方向に垂直な断面を該断面の法線方向からEBSD法で観察した際に、<101>方位を有する結晶粒の面積率が全測定面積の10%以上である銅合金線材。 - Sn、Mg、Zn、In、Ni、Co、ZrおよびCrからなる群から選ばれる少なくとも1種を各々の含有量として0.05~0.30質量%含有し、残部がCuと不可避的不純物からなる銅合金線材であって、
線材の長手方向に垂直な断面を該断面の法線方向からEBSD法で観察した際に、<101>方位を有する結晶粒の面積率が全測定面積の10%以上である銅合金線材。 - 前記<101>方位を有する結晶粒の面積率が全測定面積の20%以上である請求項1~3のいずれか1項に記載の銅合金線材。
- 母材の平均結晶粒径が0.2~5.0μmである請求項1~4のいずれか1項に記載の銅合金線材。
- Agを0.1~4.0質量%含有し、残部がCuと不可避的不純物からなる合金組成を与える銅合金材料を溶解、鋳造して荒引線を得る工程と、
該荒引線に、加工度ηが0.5以上4以下の冷間加工と中間焼鈍を少なくとも1回ずつこの順で繰り返して所定の線径の線材を得る工程と、
その後、該線材に、加工度ηが0.5以上4以下の最終冷間加工と最終焼鈍をこの順で行う工程とを有し、
前記中間焼鈍および前記最終焼鈍は、いずれも、バッチ式で行う場合は不活性ガス雰囲気下において400~800℃(ただし前記銅合金材料の再結晶温度以上)で30分~2時間、または、連続式で行う場合は不活性ガス雰囲気下において500~850℃(ただし前記銅合金材料の再結晶温度以上)で0.1~5秒の熱処理である、銅合金線材の製造方法。 - Agを0.1~4.0質量%含有し、Sn、Mg、Zn、In、Ni、Co、ZrおよびCrからなる群から選ばれる少なくとも1種を各々の含有量として0.05~0.30質量%含有し、残部がCuと不可避的不純物からなる合金組成を与える銅合金材料を溶解、鋳造して荒引線を得る工程と、
該荒引線に、加工度ηが0.5以上4以下の冷間加工と中間焼鈍を少なくとも1回ずつこの順で繰り返して所定の線径の線材を得る工程と、
その後、該線材に、加工度ηが0.5以上4以下の最終冷間加工と最終焼鈍をこの順で行う工程とを有し、
前記中間焼鈍および前記最終焼鈍は、いずれも、バッチ式で行う場合は不活性ガス雰囲気下において400~800℃(ただし前記銅合金材料の再結晶温度以上)で30分~2時間、または、連続式で行う場合は不活性ガス雰囲気下において500~850℃(ただし前記銅合金材料の再結晶温度以上)で0.1~5秒の熱処理である、銅合金線材の製造方法。 - Sn、Mg、Zn、In、Ni、Co、ZrおよびCrからなる群から選ばれる少なくとも1種を各々の含有量として0.05~0.30質量%含有し、残部がCuと不可避的不純物からなる合金組成を与える銅合金材料を溶解、鋳造して荒引線を得る工程と、
該荒引線に、加工度ηが0.5以上4以下の冷間加工と中間焼鈍を少なくとも1回ずつこの順で繰り返して所定の線径の線材を得る工程と、
その後、該線材に、加工度ηが0.5以上4以下の最終冷間加工と最終焼鈍をこの順で行う工程とを有し、
前記中間焼鈍および前記最終焼鈍は、いずれも、バッチ式で行う場合は不活性ガス雰囲気下において300~800℃若しくはZrを含有する場合は400~800℃(ただしいずれの場合も前記銅合金材料の再結晶温度以上)で30分~2時間、または、連続式で行う場合は不活性ガス雰囲気下において400~850℃若しくはZrを含有する場合は500~850℃(ただしいずれの場合も前記銅合金材料の再結晶温度以上)で0.1~5秒の熱処理である、銅合金線材の製造方法。
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