WO2018079050A1 - アルミニウム合金線、アルミニウム合金撚線、被覆電線、及び端子付き電線 - Google Patents
アルミニウム合金線、アルミニウム合金撚線、被覆電線、及び端子付き電線 Download PDFInfo
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- 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
- H01B1/023—Alloys based on aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
- C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
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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
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium 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
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/05—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0006—Apparatus or processes specially adapted for manufacturing conductors or cables for reducing the size of conductors or cables
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0013—Apparatus or processes specially adapted for manufacturing conductors or cables for embedding wires in plastic layers
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/08—Several wires or the like stranded in the form of a rope
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
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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
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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
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
Definitions
- the present invention relates to an aluminum alloy wire, an aluminum alloy twisted wire, a covered electric wire, and a terminal-attached electric wire.
- This application claims priority based on Japanese Patent Application No. 2016-213155 dated Oct. 31, 2016 and Japanese Patent Application No. 2017-074235 dated Apr. 04, 2017. All descriptions described in the above Japanese application are incorporated.
- Patent Document 1 discloses an aluminum alloy wire that is an ultrathin wire composed of an Al—Mg—Si alloy and has high strength, high conductivity, and excellent elongation.
- the aluminum alloy wire of the present disclosure is An aluminum alloy wire composed of an aluminum alloy,
- the aluminum alloy contains Mg in an amount of 0.03% by mass to 1.5% by mass and Si in an amount of 0.02% by mass to 2.0% by mass, and Mg / Si is 0.5 to 3. 5 or less, and the balance consists of Al and inevitable impurities,
- the dynamic friction coefficient is 0.8 or less.
- the aluminum alloy twisted wire of the present disclosure is A plurality of the aluminum alloy wires of the present disclosure are twisted together.
- the covered wire of the present disclosure is A covered electric wire comprising a conductor and an insulating coating covering the outer periphery of the conductor,
- the conductor includes the aluminum alloy twisted wire of the present disclosure described above.
- the electric wire with terminal of the present disclosure is The covered electric wire according to the present disclosure described above and a terminal portion attached to an end of the covered electric wire.
- Wires for various applications such as wiring of various electrical devices such as wire harnesses, industrial robots, etc. mounted on equipment such as automobiles and airplanes, and wiring of buildings, etc. are impacted when the equipment is used or installed. Or repeated bends.
- Specific examples include (1) to (3) below.
- An electric wire wired to an industrial robot may be repeatedly bent or twisted.
- an object is to provide an aluminum alloy wire having excellent impact resistance and fatigue characteristics. Another object is to provide an aluminum alloy stranded wire, a coated electric wire, and a terminal-attached electric wire having excellent impact resistance and fatigue characteristics.
- the aluminum alloy wire of the present disclosure, the aluminum alloy twisted wire of the present disclosure, the covered electric wire of the present disclosure, and the electric wire with a terminal of the present disclosure are excellent in impact resistance and fatigue characteristics.
- the inventors of the present invention manufactured aluminum alloy wires under various conditions, and studied aluminum alloy wires excellent in impact resistance and fatigue characteristics (difficult to break against repeated bending).
- a wire made of an aluminum alloy having a specific composition containing Mg and Si in a specific range, and particularly subjected to an aging treatment has high strength (for example, high tensile strength and 0.2% proof stress), and is electrically conductive. High rate and excellent conductivity.
- the knowledge that it was hard to be disconnected by repeated bending when this wire was slippery was obtained. It has been found that such an aluminum alloy wire can be produced, for example, by smoothing the surface of the wire or adjusting the amount of lubricant on the surface of the wire.
- the present invention is based on these findings. First, the contents of the embodiments of the present invention will be listed and described.
- An aluminum alloy wire according to an aspect of the present invention is: An aluminum alloy wire composed of an aluminum alloy, The aluminum alloy contains Mg in an amount of 0.03% by mass to 1.5% by mass and Si in an amount of 0.02% by mass to 2.0% by mass, and Mg / Si is 0.5 to 3. 5 or less, and the balance consists of Al and inevitable impurities, The dynamic friction coefficient is 0.8 or less.
- the above aluminum alloy wire (hereinafter also referred to as Al alloy wire) is made of an aluminum alloy having a specific composition (hereinafter also referred to as Al alloy), and is subjected to aging treatment in the manufacturing process. As a result, it has high strength, is hard to break even when subjected to repeated bending, and has excellent fatigue characteristics. When the elongation at break is high and the toughness is high, the impact resistance is also excellent.
- the above-mentioned Al alloy wire has a small coefficient of dynamic friction, for example, if a twisted wire is formed, the strands are slippery and can move smoothly when bent or the like, and each strand is difficult to break. Excellent fatigue properties. Therefore, the Al alloy wire is excellent in impact resistance and fatigue characteristics.
- the above-described form has a small surface roughness, so the dynamic friction coefficient tends to be small, and is particularly excellent in fatigue characteristics.
- a lubricant is attached to the surface of the aluminum alloy wire, and a form in which the adhesion amount of C derived from the lubricant is more than 0 and 30% by mass or less is mentioned.
- the lubricant adhering to the surface of the Al alloy wire is considered to be a residue of the lubricant used at the time of wire drawing or twisting in the manufacturing process. Since such a lubricant typically contains carbon (C), the adhesion amount of the lubricant is represented by the adhesion amount of C here.
- C carbon
- the above-described form is more excellent in fatigue characteristics because the lubricant existing on the surface of the Al alloy wire can be expected to reduce the dynamic friction coefficient. Moreover, the said form is excellent also in corrosion resistance with a lubricant.
- the said form is that the amount (C amount) of lubricant which exists in the surface of an Al alloy wire satisfy
- the cross section of the aluminum alloy wire from the surface layer region from the surface to the depth direction of 30 ⁇ m, take a rectangular surface layer bubble measurement region having a short side length of 30 ⁇ m and a long side length of 50 ⁇ m, The form whose total cross-sectional area of the bubble which exists in a surface layer bubble measurement area
- region is 2 micrometers 2 or less is mentioned.
- the cross section of the aluminum alloy wire refers to a cross section cut along a plane orthogonal to the axial direction (longitudinal direction) of the aluminum alloy wire.
- the above form has few bubbles present on the surface layer. For this reason, even when subjected to impact or repeated bending, the bubbles are unlikely to become the starting point of cracking, and cracks due to the bubbles are unlikely to occur. Since it is difficult for surface cracks to occur, cracks from the surface of the wire to the inside or breakage can be reduced, and fatigue characteristics and impact resistance are superior. In addition, since the above Al alloy wire is less likely to be cracked due to bubbles, depending on the composition and heat treatment conditions, the tensile strength, 0.2% proof stress, and elongation at break when a tensile test is performed. At least one selected from the group tends to be higher and has excellent mechanical properties.
- the bubble content is in a specific range
- a rectangular internal bubble measurement region having a short side length of 30 ⁇ m and a long side length of 50 ⁇ m is taken so that the center of the rectangle overlaps the center of the aluminum alloy wire
- a mode in which the ratio of the total cross-sectional area of the bubbles existing in the internal bubble measurement region to the total cross-sectional area of the bubbles existing in the surface bubble measurement region is 1.1 or more and 44 or less can be mentioned.
- the above-mentioned form since the ratio of the above-mentioned total cross-sectional area is 1.1 or more, there are many bubbles present inside compared to the surface layer of the Al alloy wire, but the above-mentioned total cross-sectional area ratio is within a specific range. In order to satisfy, it can be said that there are few bubbles inside. Therefore, the above-described form is more excellent in impact resistance and fatigue characteristics because cracks are less likely to propagate from the surface of the wire through the air bubbles, even when subjected to impacts or repeated bending, and is less likely to break.
- Examples include a hydrogen content of 8.0 ml / 100 g or less.
- the present inventors examined the contained gas component for the Al alloy wire containing bubbles, and obtained the knowledge that it contained hydrogen. Therefore, it is considered that one factor of bubbles in the Al alloy wire is hydrogen. In the above-described embodiment, it can be said that the number of bubbles is small because the hydrogen content is small, and disconnection due to the bubbles is difficult to occur, and the impact resistance and fatigue characteristics are excellent.
- average area of crystallized substances present in the surface layer crystallization measurement region include forms is 0.05 .mu.m 2 or more 3 [mu] m 2 or less.
- the crystallized substance is typically a compound or a single element containing at least one of Mg and Si, which are additive elements, and has an area of 0.05 ⁇ m 2 or more in the cross section of the Al alloy wire here. (The equivalent circle diameter in the same area has 0.25 ⁇ m or more).
- those having an area of less than 0.05 ⁇ m 2 typically 0.2 ⁇ m or less in equivalent circle diameter, and more finer than 0.15 ⁇ m are used as precipitates.
- the above-mentioned form is superior in impact resistance and fatigue characteristics because the crystallized material existing in the surface layer of the Al alloy wire is fine and the crystallized material is unlikely to become a starting point of cracking.
- the above-described form may contribute to the suppression of the growth of crystal grains of the Al alloy due to the presence of a crystallized substance of a certain size although it is fine. Even when the crystal grains are fine, it is possible to expect improvement in impact resistance and fatigue characteristics.
- the size of the crystallized product is in a specific range, A form in which the number of crystallized substances existing in the surface layer crystallization measurement region is more than 10 and 400 or less.
- the number of the fine crystallized substances present on the surface layer of the Al alloy wire satisfies the specific range described above, so that the crystallized substances are less likely to be the starting point of cracking and are attributed to the crystallized substances. It is easy to reduce the progress of cracking, and it is excellent in impact resistance and fatigue characteristics.
- the size of the crystallized product is in a specific range
- a rectangular internal crystallization measurement region having a short side length of 50 ⁇ m and a long side length of 75 ⁇ m is taken so that the center of the rectangle overlaps the center of the aluminum alloy wire
- average area of crystallized substances present in the inner crystallization measurement region include forms is 0.05 .mu.m 2 or more 40 [mu] m 2 or less.
- the crystallized substance existing in the Al alloy wire is also fine, it is easier to reduce breakage caused by the crystallized substance and is excellent in impact resistance and fatigue characteristics.
- the above form is excellent in impact resistance and fatigue characteristics because the crystal grains are fine and excellent in flexibility.
- the work hardening index satisfies a specific range, when the terminal part is attached by pressure bonding or the like, an improvement in the fixing force of the terminal part by work hardening can be expected. Therefore, the said form can be utilized suitably for the conductor to which terminal parts, such as an electric wire with a terminal, are attached.
- the said form when the thickness of the surface oxide film satisfies a specific range, when the terminal portion is attached, there are few oxides (what constitutes the surface oxide film) interposed between the terminal portion and the excessive amount. In addition to preventing an increase in connection resistance due to the inclusion of oxides, it is excellent in corrosion resistance. Therefore, the said form can be utilized suitably for the conductor to which terminal parts, such as an electric wire with a terminal, are attached. In this case, it is possible to construct a connection structure that is excellent in impact resistance and fatigue characteristics, and also has low resistance and excellent corrosion resistance.
- Examples include a tensile strength of 150 MPa or more, a 0.2% proof stress of 90 MPa or more, a breaking elongation of 5% or more, and a conductivity of 40% IACS or more.
- the above-mentioned form has high tensile strength, 0.2% proof stress, and elongation at break, excellent mechanical properties, excellent impact resistance and fatigue properties, and also has high electrical conductivity and electrical properties. Excellent. Since the 0.2% proof stress is high, the above form is also excellent in the adhesion to the terminal portion.
- the aluminum alloy twisted wire according to one aspect of the present invention is A plurality of the aluminum alloy wires according to any one of (1) to (13) above are twisted together.
- Each strand constituting the aluminum alloy stranded wire (hereinafter sometimes referred to as an Al alloy stranded wire) is composed of an Al alloy having a specific composition as described above.
- a stranded wire is generally more flexible than a single wire having the same conductor cross-sectional area, and each strand is difficult to break even when subjected to impact or repeated bending.
- the dynamic friction coefficient of each strand is small, the strands easily slip when subjected to impact or repeated bending, and are not easily broken due to friction between the strands. From these points, the Al alloy stranded wire is excellent in impact resistance and fatigue characteristics. Since each strand is excellent in mechanical properties as described above, the Al alloy twisted wire tends to have at least one selected from tensile strength, 0.2% yield strength, and elongation at break, Excellent mechanical properties.
- the layer core diameter means the diameter of a circle connecting the centers of all the strands included in each layer when the stranded wire has a multilayer structure.
- the twisting pitch satisfies a specific range, and when bending or the like, the strands are not easily twisted so that they are not easily broken. Easy to install. Therefore, in addition to being excellent in fatigue characteristics, the above form can be suitably used for a conductor to which a terminal portion such as a terminal-attached electric wire is attached.
- the covered electric wire according to one aspect of the present invention is A covered electric wire comprising a conductor and an insulating coating covering the outer periphery of the conductor,
- the conductor includes the aluminum alloy stranded wire according to (14) or (15).
- the above-mentioned covered electric wire includes a conductor constituted by the above-described Al alloy stranded wire excellent in impact resistance and fatigue characteristics, it is excellent in impact resistance and fatigue characteristics.
- An electric wire with a terminal according to one aspect of the present invention is: The covered electric wire according to (16) above and a terminal portion attached to an end of the covered electric wire.
- the above-mentioned electric wire with a terminal is excellent in impact resistance and fatigue characteristics because it is composed of a covered electric wire provided with a conductor constituted by the above-described Al alloy wire or Al alloy twisted wire excellent in impact resistance and fatigue properties.
- the aluminum alloy wire (Al alloy wire) 22 of the embodiment is a wire made of an aluminum alloy (Al alloy), and is typically used for a conductor 2 of an electric wire (FIG. 1).
- the Al alloy wire 22 is a single wire, a stranded wire formed by twisting a plurality of Al alloy wires 22 (the Al alloy stranded wire 20 of the embodiment), or a compression formed by compressing a stranded wire into a predetermined shape. It is used in the state of a stranded wire (another example of the Al alloy stranded wire 20 of the embodiment).
- FIG. 1 illustrates an Al alloy twisted wire 20 in which seven Al alloy wires 22 are twisted together.
- the Al alloy wire 22 of the embodiment has a specific composition in which the Al alloy contains Mg and Si in a specific range, and the dynamic friction coefficient of the Al alloy wire 22 is small.
- the Al alloy constituting the Al alloy wire 22 of the embodiment contains Mg of 0.03% to 1.5%, Si of 0.02% to 2.0%, and Mg / This is an Al—Mg—Si based alloy in which Si is 0.5 or more and 3.5 or less and the balance is Al and inevitable impurities.
- the Al alloy wire 22 of the embodiment has a dynamic friction coefficient of 0.8 or less.
- the Al alloy wire 22 of the embodiment having the above-mentioned specific composition and specific surface properties is high strength by receiving an aging treatment or the like in the manufacturing process, it can reduce breakage due to friction. Excellent impact resistance and fatigue characteristics. This will be described in more detail below. Details of a method for measuring each parameter such as a coefficient of dynamic friction and details of the above-described effects will be described in test examples.
- the Al alloy wire 22 of the embodiment is composed of an Al—Mg—Si alloy, and Mg and Si are present in solid solution, and are excellent in strength because they are present as crystallized substances and precipitates.
- Mg is an element having a high strength improvement effect, and it is contained in a specific range simultaneously with Si. Specifically, Mg is contained by 0.03% or more and Si is contained by 0.02% or more. The strength can be effectively improved. The higher the content of Mg and Si, the higher the strength of the Al alloy wire. By including Mg in a range of 1.5% or less and Si in a range of 2.0% or less, the conductivity caused by the inclusion of Mg and Si.
- the Mg content is 0.1% to 2.0%, further 0.2% to 1.5%, 0.3% to 0.9%
- the Si content can be 0.1% or more and 2.0% or less, further 0.1% or more and 1.5% or less, and 0.3% or more and 0.8% or less.
- the ratio of the mass of Mg to the mass of Si is preferably 0.5 or more and 3.5 or less, 0.8 or more and 3.5 or less, and further 0.8 or more and 2. More preferably, it is 7 or less.
- the Al alloy constituting the Al alloy wire 22 of the embodiment includes one or more elements selected from Fe, Cu, Mn, Ni, Zr, Cr, Zn, and Ga (hereinafter, a summary) in addition to Mg and Si. May be referred to as element ⁇ ).
- Fe and Cu have little decrease in conductivity and can improve strength.
- Mn, Ni, Zr, and Cr have a large decrease in conductivity, the effect of improving the strength is high.
- Zn has little decrease in electrical conductivity and has a certain degree of strength improvement effect.
- Ga has an effect of improving strength. Excellent fatigue properties due to improved strength.
- Fe, Cu, Mn, Zr, and Cr have a crystal refinement effect.
- each enumerated element When it has a fine crystal structure, it is excellent in toughness such as elongation at break, and it is easy to bend due to excellent flexibility, so that it can be expected to improve impact resistance and fatigue characteristics.
- the content of each enumerated element is 0% to 0.5%, and the total content of the enumerated elements is 0% to 1.0%.
- the above-described strength improvement effect and impact resistance It is easy to obtain the effect of improving the property and fatigue characteristics. Examples of the content of each element include the following.
- the strength tends to be improved as the amount increases, and the conductivity tends to increase as the amount decreases.
- the amount of each element added is adjusted so that the content of these elements becomes a desired amount. Adjust it. That is, the content in each additive element described above is a total amount including elements contained in the aluminum ingot used as a raw material, and does not necessarily mean the additive amount.
- the Al alloy constituting the Al alloy wire 22 of the embodiment can contain at least one element of Ti and B in addition to Mg and Si.
- Ti and B have the effect of making the Al alloy crystal finer during casting.
- a cast material having a fine crystal structure as a raw material, the crystal grains are likely to become fine even when subjected to processing such as rolling or wire drawing or heat treatment including aging treatment after casting.
- the Al alloy wire 22 having a fine crystal structure is less likely to break when subjected to impact or repeated bending as compared with a coarse crystal structure, and is excellent in impact resistance and fatigue characteristics.
- the refinement effect tends to increase in the order of the inclusion of B alone, the inclusion of Ti alone, and the inclusion of both Ti and B.
- the content When Ti is contained, the content is 0% or more and 0.05% or less, and further 0.005% or more and 0.05% or less.
- B When B is contained, the content is 0% or more and 0.005% or less. Furthermore, when it is 0.001% or more and 0.005% or less, a crystal refining effect can be obtained, and a decrease in conductivity due to the inclusion of Ti or B can be reduced. Considering the balance between the crystal refinement effect and the conductivity, the Ti content is 0.01% or more and 0.04% or less, further 0.03% or less, and the B content is 0.002% or more and 0.0. 004% or less.
- the mass ratio of Mg / Si is preferably 0.5 or more and 3.5 or less.
- the Al alloy wire 22 of the embodiment has a dynamic friction coefficient of 0.8 or less.
- the friction between the strands is small and the strand They are slippery and each strand can move smoothly.
- the coefficient of dynamic friction is large, the friction between the strands is large, and when subjected to repeated bending, the strands are likely to break due to this friction, and as a result, the stranded wires are easily broken.
- the Al alloy wire 22 having a dynamic friction coefficient of 0.8 or less can reduce the friction between the strands, particularly when used for a stranded wire, is not easily broken even when subjected to repeated bending, and has excellent fatigue characteristics. Even when subjected to an impact, it can be expected that the strands slide to make it difficult to break the strands by relaxing the impact.
- the smaller the dynamic friction coefficient the more the fracture caused by friction can be reduced, and it is preferably 0.7 or less, more preferably 0.6 or less, and 0.5 or less.
- the dynamic friction coefficient tends to be small when, for example, the surface of the Al alloy wire 22 is smoothed, a lubricant is attached to the surface of the Al alloy wire 22 or both of them are satisfied.
- the Al alloy wire 22 of the embodiment one having a surface roughness of 3 ⁇ m or less can be given.
- the Al alloy wire 22 having such a small surface roughness tends to have a small dynamic friction coefficient, and when used as a strand of stranded wire as described above, the friction between the strands can be reduced, and the fatigue characteristics are excellent. . In some cases, an improvement in impact resistance can be expected.
- the surface roughness is, for example, by using a wire drawing die with a surface roughness of 3 ⁇ m or less, or adjusting the amount of lubricant during wire drawing to have a smooth surface. , Easy to get smaller. If the lower limit of the surface roughness is 0.01 ⁇ m, and further 0.03 ⁇ m, it is expected to be easily mass-produced industrially.
- a lubricant adheres to the surface of the Al alloy wire 22, and the amount of C derived from this lubricant is greater than 0 and 30% by mass or less.
- the lubricant adhering to the surface of the Al alloy wire 22 is considered to be a lubricant (typically an oil agent) used in the manufacturing process as described above.
- the Al alloy wire 22 in which the adhesion amount of C satisfies the above range tends to have a small dynamic friction coefficient due to adhesion of the lubricant, and the dynamic friction coefficient tends to decrease as the amount increases in the above range.
- the dynamic friction coefficient is small, when the Al alloy wire 22 is used as a stranded wire as described above, the friction between the strands can be reduced, and the fatigue characteristics are excellent. In some cases, an improvement in impact resistance can be expected. Moreover, it is excellent also in corrosion resistance by adhesion of a lubricant.
- the smaller the above range the smaller the lubricant interposed between the conductor 2 and the terminal portion 4 when the terminal portion 4 (FIG. 2) is attached to the end portion of the conductor 2 composed of the Al alloy wire 22. In this case, it is possible to prevent an increase in connection resistance between the conductor 2 and the terminal portion 4 due to excessive lubricant.
- the adhesion amount of C can be 0.5% by mass or more and 25% by mass or less, and further 1% by mass or more and 20% by mass or less.
- the amount of lubricant used during wire drawing or twisting, heat treatment conditions, etc. may be adjusted so that the amount of C deposited becomes a desired amount. This is because the lubricant is reduced or removed depending on the heat treatment conditions.
- a surface oxide film having a thickness of 1 nm or more and 120 nm or less can be cited.
- heat treatment such as aging treatment
- an oxide film may exist on the surface of the Al alloy wire 22. Since the thickness of the surface oxide film is as thin as 120 nm or less, the oxide interposed between the conductor 2 and the terminal portion 4 when the terminal portion 4 is attached to the end portion of the conductor 2 composed of the Al alloy wire 22 is reduced. Less.
- the corrosion resistance of the Al alloy wire 22 can be enhanced.
- the thinner the above range the more the increase in the connection resistance can be reduced, and the thicker the corrosion resistance can be enhanced.
- the surface oxide film can be 2 nm to 115 nm, further 5 nm to 110 nm, and further 100 nm.
- the thickness of the surface oxide film can be adjusted and changed depending on, for example, heat treatment conditions. In particular, when the oxygen concentration in the atmosphere is high (for example, air atmosphere), the surface oxide film is easily thickened, and when the oxygen concentration is low (for example, inert gas atmosphere, reducing gas atmosphere), the surface oxide film is easily thinned.
- a surface layer region 220 having a depth of 30 ⁇ m from the surface thereof, that is, an annular region having a thickness of 30 ⁇ m is taken.
- a rectangular surface layer bubble measurement region 222 shown by a broken line in FIG. 3 having a short side length S of 30 ⁇ m and a long side length L of 50 ⁇ m is taken.
- the short side length S corresponds to the thickness of the surface layer region 220.
- a tangent line T is taken for an arbitrary point (contact point P) on the surface of the Al alloy wire 22.
- a straight line C having a length of 30 ⁇ m in the normal direction of the surface is taken from the contact P toward the inside of the Al alloy wire 22. If the Al alloy wire 22 is a round wire, a straight line C is taken toward the center of this circle.
- a straight line parallel to the straight line C and having a length of 30 ⁇ m is defined as a short side 22S.
- a straight line passing through the contact point P and extending along the tangent line T and having a length of 50 ⁇ m so that the contact point P becomes an intermediate point is defined as a long side 22L.
- the total cross-sectional area of bubbles present in the surface bubble measurement region 222 is 2 ⁇ m 2 or less. Since there are few air bubbles in the surface layer, it is easy to reduce cracks originating from air bubbles when subjected to impacts or repeated bending, and as a result, the progress of cracks from the surface layer to the inside can also be reduced, and breakage caused by air bubbles can be reduced. Can be reduced. Therefore, this Al alloy wire 22 is excellent in impact resistance and fatigue characteristics.
- the total area of the bubbles is large, there may be coarse bubbles or a large number of fine bubbles, and the bubbles may become the starting point of cracks, or cracks may easily progress, and impact resistance It is inferior in property and fatigue characteristics.
- the total cross-sectional area of the bubbles, the bubbles smaller less, since it is excellent in impact resistance and fatigue properties by reducing breakage caused by air bubbles 1.9 .mu.m 2 or less, further 1.8 .mu.m 2 or less, 1. 2 ⁇ m 2 or less is preferable, and the closer to 0, the more preferable.
- the bubbles tend to decrease when the hot water temperature is lowered during the casting process.
- the cooling rate at the time of casting especially the cooling rate in a specific temperature range to be described later is increased, it is less and tends to be smaller.
- the measurement region of the bubbles in the surface layer can be a fan shape as shown in FIG.
- the bubble measurement region 224 is indicated by a bold line so that it can be easily understood.
- a surface layer region 220 having a depth of 30 ⁇ m from the surface thereof, that is, an annular region having a thickness t of 30 ⁇ m is taken.
- a fan-shaped region (referred to as a bubble measurement region 224) having an area of 1500 ⁇ m 2 is taken.
- the central angle ⁇ of the fan-shaped region having an area of 1500 ⁇ m 2 is obtained.
- the bubble measurement area 224 can be extracted. If the total cross-sectional area of the bubbles present in the fan-shaped bubble measurement region 224 is 2 ⁇ m 2 or less, the Al alloy wire 22 having excellent impact resistance and fatigue characteristics can be obtained for the reasons described above. Taking both the above-mentioned rectangular surface bubble measurement area and fan-shaped bubble measurement area, and the total area of the bubbles present in both is 2 ⁇ m 2 or less, the wire material is excellent in impact resistance and fatigue characteristics. It is expected to improve the reliability of
- the Al alloy wire 22 of the embodiment there may be mentioned one having few air bubbles in the inside in addition to the surface layer.
- a rectangular region referred to as an internal bubble measurement region
- This internal bubble measurement region is taken such that the center of this rectangle overlaps the center of the Al alloy wire 22.
- the center of the inscribed circle is the center of the Al alloy wire 22 (the same applies hereinafter).
- the ratio of the total cross-sectional area Sib of the bubbles existing in the internal bubble measurement region to the total cross-sectional area Sfb of bubbles existing in the measurement region (Sib / Sfb) is 1.1 or more and 44 or less.
- solidification generally proceeds from the surface of the metal toward the inside. Therefore, when the gas in the atmosphere is dissolved in the molten metal, the gas tends to escape to the outside of the metal on the metal surface layer, but the gas is easily trapped and remains inside the metal.
- the ratio Sib / Sfb is more preferably 40 or less, more preferably 30 or less, 20 or less, or 15 or less because the smaller the ratio Sib / Sfb, the smaller the number of bubbles present inside, and the better the impact resistance and fatigue characteristics. If the ratio Sib / Sfb is 1.1 or more, it is considered that the Al alloy wire 22 with few bubbles can be manufactured without excessively reducing the hot water temperature and is suitable for mass production. It is considered that mass production is easy when the ratio Sib / Sfb is about 1.3 to 6.0.
- the Al alloy wire 22 of the embodiment there is a material in which fine crystallized material is present to some extent on the surface layer.
- the short side length is 50 ⁇ m from the surface layer region up to 50 ⁇ m in the depth direction from the surface, that is, the annular region having a thickness of 50 ⁇ m
- the long side length is A rectangular region (referred to as a surface crystallization measurement region) of 75 ⁇ m is taken.
- the short side length corresponds to the thickness of the surface layer region.
- the average area of the crystallized substances existing in the surface layer crystallization measurement region is 0.05 ⁇ m 2 or more and 3 ⁇ m 2 or less.
- the cross section of the Al alloy wire 22 has an area of 3750 ⁇ m 2 from the annular region having a thickness of 50 ⁇ m.
- a fan-shaped region (referred to as a crystallization measurement region) is taken, and an average area of crystallized substances existing in the fan-shaped crystallization measurement region is 0.05 ⁇ m 2 or more and 3 ⁇ m 2 or less.
- the rectangular surface layer crystallization measurement region and the fan-shaped crystallization measurement region have the short side length S of 50 ⁇ m and the long side length L in the same manner as the surface layer bubble measurement region 222 and the fan-shaped bubble measurement region 224 described above.
- the thickness t may be changed to 50 ⁇ m and the area may be changed to 3750 ⁇ m 2 .
- the average area of the crystallization substances present in both is 0.05 ⁇ m 2 or more and 3 ⁇ m 2 or less, It is expected to improve the reliability as a wire with excellent impact and fatigue characteristics. Even if there are a plurality of crystallized substances on the surface layer, the average size of each crystallized substance is 3 ⁇ m 2 or less, so cracks originating from each crystallized substance when subjected to impact or repeated bending.
- this Al alloy wire 22 is excellent in impact resistance and fatigue characteristics.
- the average area of the crystallized material is large, coarse crystallized material that becomes a starting point of cracking is likely to be included, and the impact resistance and fatigue characteristics are poor.
- the average size of each crystallized product is 0.05 ⁇ m 2 or more, the decrease in conductivity due to the solid solution of additive elements such as Mg and Si is reduced, and the growth of crystal grains is suppressed. You can expect effects such as.
- the average area is easily reduced cracking smaller, 2.5 [mu] m 2 or less, further 2 [mu] m 2 or less, and preferably 1 [mu] m 2 or less.
- the average area can be 0.08 ⁇ m 2 or more, and further 0.1 ⁇ m 2 or more.
- the crystallized product tends to be small when the additive elements such as Mg and Si are reduced or the cooling rate at the time of casting is increased.
- the number of products is preferably more than 10 and 400 or less. Since there are not too many crystallized substances satisfying the above-mentioned specific size of 400 or less, it is difficult for the crystallized substance to become a starting point of cracking, and the progress of cracking due to the crystallized substance is also easily reduced. Therefore, the Al alloy wire 22 is more excellent in impact resistance and fatigue characteristics. The smaller the number, the easier it is to reduce the occurrence of cracks.
- the number may be 15 or more, and further 20 or more.
- the total area of the crystallized substances present in the measurement region having an area of 3 ⁇ m 2 or less is: It is preferably 50% or more, more preferably 60% or more and 70% or more, based on the total area of all the crystallized substances present in the measurement region.
- a fine crystallized substance is present to some extent not only on the surface layer but also inside the Al alloy wire 22.
- a rectangular region referred to as an internal crystallization measurement region
- the internal crystallization measurement region is set so that the center of the rectangle overlaps the center of the Al alloy wire 22.
- Average area of crystallized substances present inside crystallisation measurement region is 0.05 .mu.m 2 or more 40 [mu] m 2 or less.
- the crystallized material is formed in the casting process and may be divided by plastic processing after casting, the size present in the cast material is also in the Al alloy wire 22 having the final wire diameter. It is substantially easy to maintain. In the casting process, since solidification proceeds from the surface of the metal toward the inside as described above, the state in which the temperature inside the metal is higher than that of the surface is easily maintained for a long time. Tends to be larger than the crystallized material of the surface layer. On the other hand, since the Al alloy wire 22 of this form has fine crystallized material present therein, it is easier to reduce the breakage caused by the crystallized material and is excellent in impact resistance and fatigue characteristics.
- the average area is preferably smaller from the viewpoint of reducing fracture, and is preferably 20 ⁇ m 2 or less, more preferably 10 ⁇ m 2 or less, particularly preferably 5 ⁇ m 2 or less and 2.5 ⁇ m 2 or less. From the viewpoint of causing a certain amount of objects to exist, the average area can be 0.08 ⁇ m 2 or more, and further 0.1 ⁇ m 2 or more.
- Al alloy wire 22 of the embodiment an Al alloy having an average crystal grain size of 50 ⁇ m or less can be cited.
- the Al alloy wire 22 having a fine crystal structure is easy to bend, is excellent in flexibility, and hardly breaks when subjected to impact or repeated bending.
- the Al alloy wire 22 of the embodiment is also excellent in impact resistance and fatigue characteristics in combination with a small dynamic friction coefficient. As described above, when there are few bubbles in the surface layer, and preferably crystallized matter is small, the impact resistance and fatigue characteristics are excellent.
- the average crystal grain size is preferably 45 ⁇ m or less, more preferably 40 ⁇ m or less, and 30 ⁇ m or less because the smaller the average crystal grain size, the easier the bending and the like, and the better the impact resistance and fatigue characteristics.
- the crystal grain size tends to become fine if, for example, Ti, B, or the element ⁇ includes an element that has a refinement effect as described above.
- Al alloy wire 22 of the embodiment one having a hydrogen content of 8.0 ml / 100 g or less can be cited.
- One factor of bubbles is considered to be hydrogen as described above. If the Al content of the Al alloy wire 22 is less than or equal to 8.0 ml per mass of 100 g, the Al alloy wire 22 has fewer bubbles and can reduce breakage due to the bubbles as described above. Since it is considered that the smaller the hydrogen content is, the smaller the bubbles are, and therefore it is preferably 7.8 ml / 100 g or less, more preferably 7.6 ml / 100 g or less, and 7.0 ml / 100 g or less.
- the hydrogen in the Al alloy wire 22 is cast in an atmosphere containing water vapor such as an air atmosphere, so that the water vapor in the atmosphere is dissolved in the molten metal, and this dissolved hydrogen remains. Therefore, the hydrogen content tends to decrease when, for example, the hot water temperature is lowered to reduce the dissolution of gas from the atmosphere. Further, the hydrogen content tends to decrease when Cu is contained.
- Al alloy wire 22 of the embodiment one having a work hardening index of 0.05 or more can be given.
- the work hardening index is as large as 0.05 or more, for example, a compression twisted wire obtained by compression-molding a twisted wire obtained by twisting a plurality of Al alloy wires 22 or a conductor 2 (single wire, twisted wire) composed of the Al alloy wire 22 is used.
- the Al alloy wire 22 is easy to work harden when it is subjected to plastic working such as crimping the terminal portion 4 to the end of the wire or the compression stranded wire.
- the strength can be increased by work hardening, and the terminal portion 4 can be firmly fixed to the conductor 2.
- the Al alloy wire 22 having a large work hardening index can constitute the conductor 2 excellent in the fixing property of the terminal portion 4.
- the larger the work hardening index the higher the strength due to work hardening can be expected, so 0.08 or more, and more preferably 0.1 or more.
- the work hardening index tends to increase as the elongation at break increases. Therefore, to increase the work hardening index, for example, the kind and content of additive elements, heat treatment conditions, etc. are adjusted to increase the elongation at break.
- the Al alloy wire 22 having a specific structure in which the size of the crystallized material satisfies the specific range described above and the average crystal grain size satisfies the specific range described above has a work hardening index of 0.05 or more. easy. Therefore, the work hardening index can also be adjusted by adjusting the type and content of additive elements, heat treatment conditions, and the like using the structure of the Al alloy as an index.
- the Al alloy wire 22 of the embodiment is composed of the Al alloy having the specific composition described above, and is typically subjected to a heat treatment such as an aging treatment, so that the tensile strength and the O.D. In addition to 2% yield strength and excellent strength, it has high conductivity and excellent conductivity. Depending on the composition and production conditions, the elongation at break can be high and the toughness can be excellent. Quantitatively, the Al alloy wire 22 has a tensile strength of 150 MPa or more, a 0.2% proof stress of 90 MPa or more, a breaking elongation of 5% or more, and a conductivity of 40% IACS or more. Therefore, one satisfying at least one selected from the above can be mentioned.
- the Al alloy wire 22 that satisfies two of the items to be listed, and further three items, particularly all four items, is excellent in impact resistance and fatigue characteristics, and is excellent in conductivity.
- Such an Al alloy wire 22 can be suitably used as a conductor of an electric wire.
- the breaking elongation can be made 6% or more, further 7% or more and 10% or more.
- the Al alloy wire 22 is typically used for the conductor 2, the higher the electrical conductivity is, the more preferable it is, and it is more preferable that it is 45% IACS or more, 48% IACS or more, 50% IACS or more.
- the Al alloy wire 22 preferably has a high 0.2% proof stress. This is because when the tensile strength is the same, the higher the 0.2% proof stress, the better the adhesion to the terminal portion 4.
- the 0.2% proof stress can be 95 MPa or more, further 100 MPa or more, 130 MPa or more.
- the Al alloy wire 22 has a sufficiently large 0.2% yield strength, high strength, and is difficult to break. Excellent adherence to 4.
- Tensile strength, 0.2% proof stress, elongation at break, and conductivity can be changed by adjusting, for example, the type and content of additive elements and manufacturing conditions (such as wire drawing conditions and heat treatment conditions). For example, when there are many additive elements, there exists a tendency for tensile strength and 0.2% yield strength to become high, and when there are few additive elements, there exists a tendency for electrical conductivity to become high.
- the cross-sectional shape of the Al alloy wire 22 of the embodiment can be appropriately selected depending on the application.
- the round line whose cross-sectional shape is circular is mentioned (refer FIG. 1).
- a square line whose cross-sectional shape is a quadrangle such as a rectangle may be used.
- the Al alloy wire 22 constitutes a strand of the above-described compression stranded wire, it is typically an irregular shape in which a circular shape is crushed.
- the Al alloy wire 22 is a square line or the like, a rectangular area is easy to use, and if the Al alloy wire 22 is a round line or the like, a rectangular area is also usable. Any of the fan-shaped regions may be used.
- the shape of the wire drawing die, the shape of the die for compression molding, and the like may be selected so that the cross-sectional shape of the Al alloy wire 22 becomes a desired shape.
- the size (cross-sectional area, wire diameter (diameter) or the like in the case of a round wire) of the Al alloy wire 22 of the embodiment can be appropriately selected according to the application.
- the wire diameter of Al alloy wire 22 is 0.2 mm or more and 1.5 mm or less.
- the wire diameter of Al alloy wire 22 is 0.1 mm or more and 3.6 mm or less. Since the Al alloy wire 22 is a high-strength wire, it is expected that the Al alloy wire 22 can be suitably used for smaller diameter applications such as a wire diameter of 0.1 mm to 1.0 mm.
- the Al alloy wire 22 of the embodiment can be used as a strand of stranded wire as shown in FIG.
- the Al alloy twisted wire 20 of the embodiment is formed by twisting a plurality of Al alloy wires 22 together. Since the Al alloy twisted wire 20 is formed by twisting a plurality of strands (Al alloy wire 22) having a small cross-sectional area compared to a single Al alloy wire having the same conductor cross-sectional area, it is excellent in flexibility. Easy to bend. Moreover, even if the Al alloy wire 22 which is each strand is thin by being twisted together, it is excellent in intensity
- the Al alloy twisted wire 20 of the embodiment uses the Al alloy wire 22 having a specific surface property that the coefficient of dynamic friction is small as the strand, the strands are easily slipped and can be bent smoothly and repeatedly. The wire is difficult to break when subjected to bending.
- the Al alloy twisted wire 20 is excellent in impact resistance and fatigue characteristics, particularly in fatigue characteristics, even when the Al alloy wire 22 as an element wire is not easily broken even when subjected to impact or repeated bending. Excellent.
- the Al alloy wire 22 which is each strand is selected from the above-mentioned surface roughness, C adhesion amount, bubble content, hydrogen content, size and number of crystallized substances, and crystal grain size. If at least one item satisfies the specific range described above, the impact resistance and fatigue characteristics are further improved.
- the number of twisted Al alloy twisted wires 20 can be appropriately selected, and examples thereof include 7, 11, 16, 19, 37, and the like.
- the twist pitch of the Al alloy twisted wire 20 can be selected as appropriate, when the twist pitch is 10 times or more the layer core diameter of the Al alloy twisted wire 20, a terminal portion is formed at the end of the conductor 2 composed of the Al alloy twisted wire 20. It is difficult to disperse when attaching 4, and the workability of attaching the terminal portion 4 is excellent.
- the twist pitch is 40 times or less of the above layer core diameter, the strands are not easily twisted when bent or the like, so that they are difficult to break and have excellent fatigue characteristics.
- the twisting pitch can be 15 to 35 times, more preferably 20 to 30 times the layer core diameter.
- the Al alloy twisted wire 20 can be a compression twisted wire that has been further subjected to compression molding. In this case, it is possible to make the wire diameter smaller than in a state where the wires are simply twisted together, or to change the outer shape to a desired shape (for example, a circle).
- a desired shape for example, a circle.
- compositions, structure, surface properties, surface oxide film thickness, hydrogen content, C adhesion amount, mechanical properties and electrical properties of each Al alloy wire 22 constituting the Al alloy twisted wire 20 are as follows:
- the specification of the Al alloy wire 22 used before twisting is substantially maintained.
- the thickness of the surface oxide film, the amount of C deposited, the mechanical characteristics, and the electrical characteristics may change depending on reasons such as the use of a lubricant during twisting or heat treatment after twisting.
- the twisting conditions may be adjusted so that the specification of the Al alloy twisted wire 20 has a desired value.
- the Al alloy wire 22 of the embodiment and the Al alloy twisted wire 20 (which may be a compression stranded wire) of the embodiment can be suitably used as a conductor for electric wires. It can be used for either a bare conductor not provided with an insulating coating and a conductor of a covered electric wire provided with an insulating coating.
- the covered electric wire 1 of the embodiment includes a conductor 2 and an insulating coating 3 that covers the outer periphery of the conductor 2, and the conductor 2 includes the Al alloy wire 22 of the embodiment or the Al alloy twisted wire 20 of the embodiment.
- this covered electric wire 1 includes the conductor 2 composed of the Al alloy wire 22 and the Al alloy twisted wire 20 that are excellent in impact resistance and fatigue characteristics, it is excellent in impact resistance and fatigue characteristics.
- the insulating material constituting the insulating coating 3 can be selected as appropriate. Examples of the insulating material include polyvinyl chloride (PVC), a non-halogen resin, a material excellent in flame retardancy, and the like, and known materials can be used.
- the thickness of the insulating coating 3 can be appropriately selected within a range having a predetermined insulating strength.
- the covered electric wire 1 according to the embodiment can be used for electric wires for various purposes such as wiring of various electric devices such as wire harnesses and industrial robots mounted on devices such as automobiles and airplanes, and wiring of buildings.
- the terminal portion 4 is typically attached to the end portion of the covered electric wire 1.
- the electric wire with terminal 10 according to the embodiment includes the covered electric wire 1 according to the embodiment and a terminal portion 4 attached to an end of the covered electric wire 1. Since the electric wire with terminal 10 includes the covered electric wire 1 that is excellent in impact resistance and fatigue characteristics, it is excellent in impact resistance and fatigue characteristics.
- the terminal portion 4 includes a female or male fitting portion 42 at one end, an insulation barrel portion 44 that grips the insulating coating 3 at the other end, and a wire that grips the conductor 2 at the intermediate portion.
- the crimp terminal provided with the barrel part 40 is illustrated. Examples of the other terminal portions 4 include a melted type in which the conductor 2 is melted and connected.
- the crimp terminal is crimped to the end portion of the conductor 2 exposed by removing the insulating coating 3 at the end portion of the covered electric wire 1, and is electrically and mechanically connected to the conductor 2.
- the Al alloy wire 22 or the Al alloy twisted wire 20 constituting the conductor 2 has a high work hardening index as described above, the cross-sectional area of the attachment portion of the crimp terminal in the conductor 2 is locally reduced. However, it is excellent in strength by work hardening. Therefore, for example, the conductor 2 is less likely to break in the vicinity of the terminal portion 4 even when subjected to an impact when the terminal portion 4 is connected to the connection target of the covered electric wire 1 or further subjected to repeated bending after the connection.
- This terminal-attached electric wire 10 is excellent in impact resistance and fatigue characteristics.
- the Al alloy wire 22 and the Al alloy twisted wire 20 constituting the conductor 2 are interposed between the conductor 2 and the terminal portion 4 when the adhesion amount of C is small as described above or the surface oxide film is thin. Electrical insulators (such as lubricants containing C and oxides constituting the surface oxide film) can be reduced, and the connection resistance between the conductor 2 and the terminal portion 4 can be reduced. Therefore, this electric wire with terminal 10 is excellent in impact resistance and fatigue characteristics, and also has a low connection resistance.
- the terminal-attached electric wire 10 includes one terminal portion (not shown) for the plurality of covered electric wires 1 in addition to a form in which one terminal portion 4 is attached to each covered electric wire 1.
- a form is mentioned.
- the electric wire with terminal 10 is easy to handle.
- the Al alloy wire 22 of the embodiment typically undergoes heat treatment (including aging treatment) at an appropriate time in addition to basic processes such as casting, intermediate processing such as (hot) rolling and extrusion, and wire drawing. Can be manufactured. Known conditions and the like can be referred to for basic process and aging treatment conditions.
- the Al alloy twisted wire 20 of the embodiment can be manufactured by twisting a plurality of Al alloy wires 22 together. Known conditions can be referred to for the twisting conditions and the like.
- the Al alloy wire 22 of the embodiment having a small dynamic friction coefficient can be manufactured mainly by adjusting the wire drawing conditions and heat treatment conditions as described later.
- the above-described Al alloy wire 22 with few bubbles in the surface layer is easy to manufacture, for example, when the hot water temperature is lowered in the casting process. It is possible to reduce the dissolution of gas in the atmosphere in the molten metal, and it is possible to produce a cast material with a molten metal with a small amount of dissolved gas.
- the dissolved gas include hydrogen as described above, and it is considered that this hydrogen was decomposed and contained in the atmosphere.
- the air bubbles existing in the surface layer or inside of the Al alloy wire 22 having the final wire diameter can be within the specific range described above.
- the Al alloy wire 22 having a low hydrogen content can be manufactured.
- the position of the bubbles trapped inside the Al alloy changes or the size of the bubbles Is considered to be small to some extent.
- the total content of bubbles present in the cast material is large, the total content of bubbles present in the surface layer and inside the Al alloy wire of the final wire diameter, hydrogen, It is considered that the content of sucrose tends to increase (it remains substantially maintained). Therefore, it is proposed that the hot water temperature be lowered to sufficiently reduce bubbles contained in the cast material itself.
- a specific hot water temperature for example, a liquidus temperature of Al alloy or higher and lower than 750 ° C. may be mentioned. Since the dissolved gas can be reduced and the bubbles of the cast material can be reduced as the hot water temperature is lower, it is preferably 748 ° C. or lower, and more preferably 745 ° C. or lower. On the other hand, when the hot water temperature is high to some extent, the additive element is easily dissolved, so that the hot water temperature can be 670 ° C. or higher, and further 675 ° C. or higher.
- the cooling rate in the casting process In addition to lowering the hot water temperature, increasing the cooling rate in the casting process, particularly the cooling rate in a specific temperature range from the hot water temperature to 650 ° C. to some extent, can easily prevent an increase in dissolved gas from the atmosphere.
- the specific temperature range is mainly a liquid phase range, where hydrogen and the like are easily dissolved and dissolved gas is likely to increase.
- the dissolved gas inside the metal during solidification is easily discharged into the atmosphere outside because the cooling rate in the specific temperature range is not too fast.
- the cooling rate is preferably 1 ° C./second or more, more preferably 2 ° C./second or more, and 4 ° C./second or more.
- the cooling rate is 30 ° C./second or less, further less than 25 ° C./second, 20 ° C./second or less, 20 ° C./second or less, 15 ° C./second or less, 10 It can be set to ° C./second or less. Since the cooling rate is not too fast, it is suitable for mass production. Depending on the cooling rate, a supersaturated solid solution can be obtained. In this case, the solution treatment may be omitted in the steps after casting, or may be performed separately.
- the specific temperature region is mainly a liquid phase region, and if the cooling rate in the liquid phase region is increased, the crystallization product generated during solidification can be easily reduced.
- the hot water temperature is lowered as described above, if the cooling rate is too high, particularly when it is 25 ° C./second or more, a crystallized product is not easily generated, and the amount of solid solution of the additive element increases. It is considered that the conductivity is lowered and it becomes difficult to obtain the pinning effect of the crystal grains due to the crystallized product.
- the cooling rate is preferably more than 1 ° C./second, more preferably 2 ° C./second or more, although it depends on the contents of additive elements such as Mg, Si, and element ⁇ . From the above, it is more preferable that the hot water temperature is 670 ° C. or higher and lower than 750 ° C., and the cooling rate from the hot water temperature to 650 ° C. is lower than 20 ° C./second.
- the cooling rate of the casting process is increased within the above-mentioned range, it is easy to obtain a cast material having a fine crystal structure, it is easy to dissolve the additive element to some extent, and DAS (Dendrite Arm Spacing) can be easily reduced (for example, The effect of 50 ⁇ m or less, and further 40 ⁇ m or less) can be expected.
- DAS Digitalendrite Arm Spacing
- Continuous casting enables continuous production of long cast materials and facilitates faster cooling rates.
- reduction of bubbles, suppression of coarse crystals, refinement of crystal grains and DAS, addition of added elements can be expected.
- the cast material is typically subjected to wire drawing with an intermediate processed material subjected to plastic processing (intermediate processing) such as (hot) rolling or extrusion. It is also possible to subject the continuous cast rolled material (an example of an intermediate processed material) to wire drawing by performing hot rolling continuously after continuous casting. Skinning and heat treatment can be performed before and after the plastic working. By skinning, the surface layer where bubbles or surface scratches may exist can be removed. Examples of the heat treatment here include those for the purpose of homogenizing or solutionizing the Al alloy.
- the conditions for the homogenization treatment are, for example, the atmosphere is air or a reducing atmosphere, the heating temperature is about 450 ° C. to 600 ° C. (preferably 500 ° C.
- the holding time is 1 hour to 10 hours (preferably 3 hours or more).
- slow cooling at a cooling rate of 1 ° C./min or less.
- the material (intermediate work material) that has undergone plastic working such as rolling as described above is subjected to wire drawing (cold) until a predetermined final wire diameter is obtained, thereby forming a wire drawing material.
- the wire drawing is typically performed using a wire drawing die. Moreover, it carries out using a lubricant. As described above, by using a wire drawing die having a small surface roughness, for example, 3 ⁇ m or less, and by further adjusting the amount of lubricant applied, the surface roughness is 3 ⁇ m or less.
- An Al alloy wire 22 can be manufactured. By appropriately replacing with a wire drawing die having a small surface roughness, a wire drawing material having a smooth surface can be continuously produced.
- the surface roughness of the wire drawing die can be easily measured by using, for example, the surface roughness of the wire drawing material as an alternative value.
- the coating amount of the lubricant or adjusting the heat treatment conditions described later it is possible to manufacture the Al alloy wire 22 in which the adhesion amount of C on the surface of the Al alloy wire 22 satisfies the specific range described above.
- the Al alloy wire 22 of the embodiment in which the coefficient of dynamic friction satisfies the specific range described above can be manufactured.
- the wire drawing degree may be appropriately selected according to the final wire diameter.
- twisting process In the case of manufacturing the Al alloy twisted wire 20, a plurality of wires (drawn wire or heat treated material that has been heat-treated after drawing) are prepared, and these are prepared at a predetermined twist pitch (for example, 10 times the layer core diameter). 40 times). A lubricant may be used at the time of twisting.
- a predetermined twist pitch for example, 10 times the layer core diameter. 40 times.
- a lubricant may be used at the time of twisting.
- the Al alloy stranded wire 20 is a compression stranded wire, it is compression molded into a predetermined shape after twisting.
- Heat treatment can be performed on a wire drawing material or the like at any time during or after the wire drawing step.
- the intermediate heat treatment performed in the middle of wire drawing includes, for example, one for the purpose of removing distortion introduced during wire drawing and improving workability.
- Examples of the heat treatment after the wire drawing step include those for the solution treatment and those for the aging treatment. It is preferable to perform heat treatment for at least aging treatment.
- aging treatment precipitates containing additive elements such as Mg and Si in the Al alloy and, depending on the composition, the element ⁇ (for example, Zr) are dispersed in the Al alloy, the strength is improved by age hardening, and the solid solution element This is because the conductivity can be improved by the reduction.
- the time for performing the heat treatment includes at least one time during drawing, after drawing (before twisting), after twisting (before compression molding), and after compression molding.
- Heat treatment may be performed at a plurality of times.
- the solution treatment is performed before (but not immediately before) the aging treatment.
- the intermediate heat treatment or solution treatment described above is performed in the middle of wire drawing or before twisting, the workability can be improved and the wire drawing or twisting can be easily performed.
- the heat treatment conditions may be adjusted so that the properties after the heat treatment satisfy a desired range.
- the Al alloy wire 22 having a work hardening index satisfying the specific range described above can be manufactured.
- the amount of lubricant before the heat treatment is measured, and the heat treatment conditions can be adjusted so that the residual amount after the heat treatment becomes a desired value. The higher the heating temperature or the longer the holding time, the smaller the residual amount of lubricant tends to be.
- Either heat treatment can be performed continuously by supplying the heat treatment target to a heating vessel such as a pipe furnace or electric furnace, or batch processing in which the heat treatment target is enclosed in a heating vessel such as an atmospheric furnace. it can.
- a heating vessel such as a pipe furnace or electric furnace
- batch processing in which the heat treatment target is enclosed in a heating vessel such as an atmospheric furnace.
- the continuous treatment for example, the temperature of the wire is measured with a non-contact type thermometer, and the control parameters are adjusted so that the characteristics after the heat treatment are within a predetermined range.
- Specific conditions for batch processing include, for example, the following. (Solution treatment)
- the heating temperature is about 450 ° C. to 620 ° C. (preferably 500 ° C.
- the holding time is 0.005 seconds to 5 hours (preferably 0.01 seconds to 3 hours), Rapid cooling (intermediate heat treatment) heating temperature at a cooling rate of 100 ° C./min or more, 200 ° C./min or more, heating temperature of 250 ° C. or more and 550 ° C. or less, heating time of 0.01 seconds or more and 5 hours or less (aging treatment) heating temperature of 100 ° C to 300 ° C, 140 ° C to 250 ° C, holding time of 4 hours to 20 hours, further 16 hours or less
- Examples of the atmosphere during the heat treatment include an atmosphere having a relatively high oxygen content such as an air atmosphere, or a low oxygen atmosphere having a lower oxygen content than the air.
- the atmosphere control is unnecessary, but the surface oxide film is easily formed thick (for example, 50 nm or more). For this reason, in the case of an air atmosphere, if the continuous treatment is performed to easily shorten the holding time, it is easy to manufacture the Al alloy wire 22 in which the thickness of the surface oxide film satisfies the specific range described above.
- Examples of the low oxygen atmosphere include a vacuum atmosphere (reduced pressure atmosphere), an inert gas atmosphere, and a reducing gas atmosphere.
- Examples of the inert gas include nitrogen and argon.
- the reducing gas examples include hydrogen gas, a hydrogen mixed gas containing hydrogen and an inert gas, and a mixed gas of carbon monoxide and carbon dioxide.
- the atmosphere control is required in a low oxygen atmosphere, the surface oxide film can be easily thinned (for example, less than 50 nm). Therefore, in the case of a low oxygen atmosphere, when the batch process is easy to control the atmosphere, the Al alloy wire 22 in which the thickness of the surface oxide film satisfies the specific range described above, preferably the thickness of the surface oxide film is more It is easy to manufacture a thin Al alloy wire 22.
- the degree of wire drawing from a material obtained by subjecting a continuously cast material to plastic processing such as rolling or a continuous cast rolled material to a wire drawing material of the final wire diameter is 80% or more, and the wire drawing material of the final wire diameter or twisted
- heat treatment especially aging treatment
- heat treatment may be performed during the wire drawing.
- Other methods for adjusting the thickness of the surface oxide film include exposing the drawn wire with the final wire diameter in the presence of high-temperature and high-pressure hot water, applying water to the drawn wire with the final wire diameter, and continuous treatment in the atmosphere.
- a drying step may be provided after water cooling.
- the surface oxide film tends to be thickened by exposure to hot water or application of water. By drying after the above-described water cooling, formation of a boehmite layer due to water cooling is prevented, and the surface oxide film tends to be thin.
- degreasing can be performed simultaneously with cooling.
- the lubricant is added so that the predetermined adhering amount is obtained. Can be applied. At this time, the adhesion amount of the lubricant can be adjusted using the adhesion amount of C and the dynamic friction coefficient as an index.
- the degreasing treatment can use a known method, and can also serve as cooling as described above.
- the coated electric wire 1 of the embodiment prepares the Al alloy wire 22 or the Al alloy stranded wire 20 (which may be a compression stranded wire) of the embodiment constituting the conductor 2, and forms the insulating coating 3 on the outer periphery of the conductor 2 by extrusion or the like Can be manufactured.
- Known conditions can be referred to for the extrusion conditions and the like.
- the electric wire with terminal 10 of the embodiment can be manufactured by removing the insulating coating 3 at the end portion of the covered electric wire 1 to expose the conductor 2 and attaching the terminal portion 4.
- each manufacturing method performs the process which attached
- Sample No. 1 to No. 71, no. 101 to No. 106, no. 111 to No. Reference numeral 119 denotes a sample manufactured by the manufacturing method C.
- Sample No. 72 to No. Reference numeral 77 denotes a sample manufactured in order from manufacturing methods A, B, and D.
- the specific manufacturing process of the manufacturing method C is demonstrated.
- the same steps as manufacturing method C are performed under the same conditions.
- the intermediate heat treatment is a continuous treatment using a high frequency induction heating method (wire temperature: about 300 ° C.).
- the conditions of the solution treatment of the manufacturing method G are batch processing of 540 degreeC x 3 hours.
- Pure aluminum 99.7 mass% or more Al is prepared and melted as a base, and the contents of additive elements shown in Tables 1 to 4 are shown in Tables 1 to 4 in the obtained molten metal (molten aluminum).
- the molten aluminum alloy is prepared by adding the amount (mass%).
- the continuously cast rolled material is produced by continuously performing casting and hot rolling using a belt-wheel type continuous casting rolling machine and a prepared molten Al alloy to obtain a wire rod having a diameter of 9.5 mm.
- the billet cast material is produced by pouring a molten Al alloy into a predetermined fixed mold and cooling it. After homogenizing the billet cast material, hot rolling is performed to produce a ⁇ 9.5 mm wire rod (rolled material).
- Tables 5 to 8 show the type of casting method (continuous cast rolled material is indicated as “continuous” and billet cast material is indicated as “billet”), molten metal temperature (° C.), cooling rate during casting process (from hot water temperature to 650 ° C.) The average cooling rate of [deg.] C./sec. The cooling rate was changed by adjusting the cooling state using a water cooling mechanism or the like.
- the wire rod is subjected to solution treatment (batch treatment) under conditions of 530 ° C. ⁇ 5 hours, followed by cold wire drawing to draw a wire with a wire diameter of ⁇ 0.3 mm, a wire with a diameter of ⁇ 0.25 mm.
- a wire rod and a wire rod having a wire diameter of ⁇ 0.32 mm are produced.
- the wire drawing is performed using a wire drawing die and a commercially available lubricant (carbon oil).
- the wire drawing dies to be used are prepared with different surface roughnesses and appropriately changed, and the surface roughness of the wire drawing material of each sample is adjusted by adjusting the amount of lubricant used.
- Sample No. 115 uses a wire drawing die having the largest surface roughness.
- an aging treatment is performed to produce an aging material (Al alloy wire).
- the solution treatment is a high-frequency induction heating type continuous treatment, and the wire temperature is measured with a non-contact infrared thermometer, and the energization conditions are controlled so that the wire temperature becomes 300 ° C. or higher.
- the aging treatment is a batch treatment using a box furnace, and is performed in the temperature (° C.), time (time (H)), and atmosphere shown in Tables 5 to 8.
- Sample No. No. 116 performs a boehmite treatment (100 ° C. ⁇ 15 minutes) after an aging treatment in an air atmosphere (“*” is added to the atmosphere column in Table 8).
- the obtained aging material having a wire diameter of ⁇ 0.3 mm was subjected to a bending test, and the number of times until breakage was measured.
- the bending test was measured using a commercially available repeated bending tester.
- a bending strain of 0.3% is applied to the wire of each sample
- repeated bending is performed with a load of 12.2 MPa applied.
- Three or more bending tests were performed for each sample, and the average (times) is shown in Table 9 to Table 12. It can be said that the more the number of times until breakage is, the more difficult it is to break by repeated bending, and the better the fatigue characteristics.
- the obtained wire diameter ⁇ 0.25 mm or wire diameter ⁇ 0.32 mm (not subjected to the above-mentioned aging treatment and solution treatment immediately before aging, and production methods B, F and G are not subjected to aging treatment) )
- a commercially available lubricant oil containing carbon
- a twisted wire using seven wires having a wire diameter of 0.25 mm is prepared.
- the compression twisted wire which further compression-molded the twisted wire using seven wires with a wire diameter of ⁇ 0.32 mm is produced.
- the cross-sectional area of the stranded wire and the cross-sectional area of the compression stranded wire are both 0.35 mm 2 (0.35 sq).
- the twist pitch is 20 mm (about 40 times the core diameter when using a wire drawing material with a wire diameter of 0.25 mm, and about 32 times the core diameter when using a wire drawing material with a wire diameter of 0.32 mm). .
- Solution treatment and aging treatment are applied to the obtained stranded wire and compression stranded wire in this order (production methods B, F, and G are only aging treatment). All the heat treatment conditions are the same as the heat treatment conditions applied to the 0.3 mm wire drawing material described above, the solution treatment is a continuous treatment of a high frequency induction heating method, and the aging treatment is a batch treatment performed under the conditions shown in Tables 5 to 8. Yes (see above for * in sample No. 116).
- the obtained aging stranded wire is used as a conductor, and an insulating coating (thickness 0.2 mm) is formed on the outer periphery of the conductor with an insulating material (here, a halogen-free insulating material) to produce a coated electric wire.
- an insulating material here, a halogen-free insulating material
- the amount of at least one of the lubricant during wire drawing and the lubricant during twisting is adjusted so that the lubricant remains to some extent after the aging treatment.
- Sample No. No. 29 uses a larger amount of lubricant than the other samples.
- 117 has the largest usage amount of a lubricant.
- Sample No. 114 performs a degreasing process after an aging treatment.
- Sample No. No. 113 has an aging temperature of 300 ° C. and a holding time of 50 hours, and is aging at a higher temperature and longer time than other samples.
- a strand (Al alloy wire) to be the sample S is horizontally arranged on the counterpart material 150 so as to be orthogonal to the counterpart material 150 and parallel to the long side direction of the one surface of the pedestal 100.
- a weight 110 (in this case, 200 g) having a predetermined mass is arranged on the intersection of the sample S and the counterpart material 150 so that the intersection is not displaced.
- a pulley is arranged in the middle of the sample S, one end of the sample S is pulled upward along the pulley, and the tensile force (N) is measured by an autograph or the like.
- the average load when the sample S and the counterpart material 150 move up to 100 mm after starting the relative displacement motion is defined as a dynamic friction force (N).
- a value (dynamic friction force / normal force) obtained by dividing the dynamic friction force by a normal force (2N in this case) generated by the mass of the weight 110 is defined as a dynamic friction coefficient.
- the lubricant adheres to the surface of the Al alloy wire constituting the conductor provided for the covered electric wire, the lubricant is insulated at the contact point with the insulating coating on the Al alloy wire when the insulating coating is removed. There is a possibility that the adhesion amount of C cannot be measured appropriately.
- the adhesion amount of C can be accurately measured. It can be measured well.
- a central strand that is not in contact with the insulating coating is used as a measurement target.
- a portion that is not in contact with the insulation coating can also be set as a measurement target.
- the insulation coating is removed to make only the conductor, the stranded wire or the compressed stranded wire constituting the conductor is unwound, and the surface oxide film of each strand is as follows. Measured. Here, the thickness of the surface oxide film of each element wire (Al alloy wire) is examined. For each sample, the thickness of the surface oxide film on the total of seven strands was examined, and the value obtained by averaging the thickness of the surface oxide film on the total of seven strands was defined as the thickness (nm) of the surface oxide film. 17 to Table 20.
- Cross section polisher (CP) processing is performed to take a cross section of each strand, and the cross section is observed by SEM.
- the thickness is measured using this SEM observation image.
- the analysis in the depth direction is separately performed by X-ray photoelectron spectroscopy (ESCA). Repeat to measure.
- Tables 13 to 16 show the total area A ( ⁇ m 2 ) as a value obtained by averaging the total cross-sectional areas of the bubbles in the total seven measurement regions.
- a fan-shaped bubble measurement region having an area of 1500 ⁇ m 2 is taken from an annular surface layer region having a thickness of 30 ⁇ m, and evaluation is performed using the above-described rectangular surface bubble measurement region.
- the total area B ( ⁇ m 2 ) of the bubbles in the fan-shaped bubble measurement region was determined.
- the results are shown in Tables 13 to 16.
- the measurement of the total cross-sectional area of the bubbles can be easily performed by performing image processing such as binarization processing on the observed image and extracting the bubbles from the processed image. The same applies to a crystallized substance to be described later.
- a rectangular internal bubble measurement region having a short side length of 30 ⁇ m and a long side length of 50 ⁇ m is taken.
- the internal bubble measurement region is taken so that the center of the rectangle overlaps the center of each Al alloy wire.
- the ratio “internal / surface layer” of the total cross-sectional area of the bubbles existing in the internal bubble measurement region to the total cross-sectional area of the bubbles existing in the surface layer bubble measurement region is obtained.
- a total of seven surface bubble measurement areas and internal bubble measurement areas are taken to determine the ratio “internal / surface layer”.
- Tables 13 to 16 show values obtained by averaging the ratio “inside / surface layer” in the seven measurement regions in total as the ratio “inside / surface layer A”.
- the ratio “internal / surface layer B” in the above-described fan-shaped bubble measurement region was determined in the same manner as in the case of evaluation in the rectangular surface bubble measurement region described above, and the results are shown in Tables 13 to 16 .
- Crystal grain size in accordance with JIS G 0551 (steel-microscopic test method of grain size, 2013), a test line is drawn on the SEM observation image, and the test line is divided at each crystal grain.
- the length to be used is defined as the crystal grain size (cutting method).
- the length of the test line is such that ten or more crystal grains are divided by the test line.
- Three test lines are drawn on one cross section to obtain each crystal grain size, and the average value of these crystal grain sizes is shown in Table 13 to Table 16 as the average crystal grain size ( ⁇ m). .
- the average of the area of the crystallization product is obtained. That is, the average of the areas of crystallized substances in a total of seven measurement regions is obtained for one sample.
- Table 13 to Table 16 show the average area A ( ⁇ m 2 ) as a mean value of the average of the crystallized areas in the total of seven measurement regions.
- the number of crystallized substances in a total of seven surface crystallization measurement regions was examined, and the value obtained by averaging the number of crystallized substances in a total of seven measurement regions was defined as the number A (pieces). To Table 16 below.
- each surface layer crystallization measurement region is examined, and the total area of those having an area of 3 ⁇ m 2 or less is examined.
- the ratio of the total area of 3 ⁇ m 2 or less is obtained.
- Tables 13 to 16 show the area ratio A (%) as an average value of the ratio of the total area in the total seven measurement regions.
- a sector-shaped crystallization measurement region having an area of 3750 ⁇ m 2 is taken from an annular surface layer region having a thickness of 50 ⁇ m, and evaluation is performed using the above-described rectangular surface crystallization measurement region.
- the average area B ( ⁇ m 2 ) of the crystallization product in the fan-shaped crystallization measurement region was determined.
- the area ratio B (%) was determined.
- the average area (inside) of 70 was 2 ⁇ m 2 , 3 ⁇ m 2 , and 1 ⁇ m 2 in order.
- the hydrogen content is measured by an inert gas melting method. Specifically, a sample is put into a graphite crucible in an argon stream, and heated and melted to extract hydrogen together with other gases. The extracted gas is passed through a separation column to separate hydrogen from other gases, measured with a thermal conductivity detector, and the hydrogen content is determined by quantifying the hydrogen concentration.
- terminal fixation power (N) was evaluated.
- N terminal fixation power
- a terminal portion attached to one end of a terminal-attached electric wire is held by a terminal chuck, the insulating coating at the other end of the covered electric wire is removed, and the conductor portion is held by the conductor chuck.
- the maximum load (N) at break was measured using a general-purpose tensile testing machine, and this maximum load (N) was evaluated as the terminal fixing force (N). To do.
- Specimen No. 2 composed of an Al—Mg—Si alloy having a specific composition containing Mg and Si in a specific range and appropriately including a specific element ⁇ in a specific range and subjected to an aging treatment.
- 1 to No. 77 (hereinafter sometimes collectively referred to as an aging sample group)
- Al alloy wire is sample No. 101 to No.
- the evaluation parameter value of impact resistance is high and 4 J / m or more as compared with the Al alloy wire of 106 (hereinafter sometimes referred to collectively as a comparative sample group).
- the Al alloy wires of the aging sample group have a high elongation at break and a high number of bendings.
- the Al alloy wire of the aging sample group has excellent impact resistance and excellent fatigue characteristics in a balanced manner as compared with the Al alloy wire of the comparative sample group.
- the aging sample group is excellent in mechanical characteristics and electrical characteristics, that is, has high tensile strength, high electrical conductivity, high elongation at break, and here, 0.2% proof stress is also high.
- the Al alloy wires of the aging sample group satisfy a tensile strength of 150 MPa or more, a 0.2% proof stress of 90 MPa or more, a breaking elongation of 5% or more, and a conductivity of 40% IACS or more.
- the ratio “strength / tensile” between the tensile strength and the 0.2% proof stress is also high, being 0.5 or more.
- the Al alloy wires of the aging sample group are also excellent in adhesion to the terminal portion (40 N or more).
- the Al alloy wire of the aging sample group has a work hardening index as large as 0.05 or more (Tables 9 to 11), so that the effect of improving the strength by work hardening when crimping a crimp terminal is good. It is thought that it was obtained.
- the Al alloy wire of the aging sample group has a small coefficient of dynamic friction. Quantitatively, the dynamic friction coefficient is 0.8 or less, and many samples are 0.5 or less. Thus, since the dynamic friction coefficient is small, it is thought that the strands which comprise a twisted wire are easy to slip, and it is hard to disconnect when repeated bending is performed. Therefore, sample no. No. 41 single wire (wire diameter 0.3 mm) and sample no. About the following stranded wire produced using the Al alloy wire of 41 composition, the frequency
- the Al alloy wire of the aging sample group has a small surface roughness. Quantitatively, the surface roughness is 3 ⁇ m or less, many samples are 2.5 ⁇ m or less, and there are samples of 2 ⁇ m or less or 1 ⁇ m or less.
- 115 Table 20. Sample No. having the same composition. 20 (Table 18, Table 10) and Sample No. 115 (Table 20, Table 12), sample No. No. 20 has a smaller coefficient of dynamic friction and a smaller surface roughness, more flexing times, and better impact resistance. From this, it is considered that a small dynamic friction coefficient contributes to improvement of fatigue characteristics and impact resistance. Moreover, it can be said that reducing the surface roughness is effective in reducing the dynamic friction coefficient.
- the adhesion amount of C is 1% by mass or more (Sample No. 41 (Table 14 and Table 18) and Sample No. 114 (see Table 16 and Table 20)), as shown in Table 17 to Table 19, it can be said that the dynamic friction coefficient tends to be small. Even when the surface roughness is relatively large, it can be said that the dynamic friction coefficient tends to be small due to the larger amount of C attached (see, for example, Sample No. 22 (Tables 14 and 18)). Further, as shown in Table 21, it can be seen that the corrosion resistance is excellent when the lubricant adheres to the surface of the Al alloy wire. If the amount of adhesion of the lubricant (the amount of adhesion of C) is too large, the connection resistance with the terminal portion is increased, so that it is considered that a certain amount, particularly 30% by mass or less, is preferable.
- the evaluation results using the rectangular measurement area A and the evaluation results using the fan-shaped measurement area B are referred to.
- the Al alloy wire of the aging sample group has a total area of bubbles of 2.0 ⁇ m 2 or less in the surface layer. 111, no. 118, no. Less than 119 Al alloy wire. Paying attention to the bubbles on the surface layer, sample No. 20 and sample no. 111, sample no. 47 and sample no. 118, sample no. 71 and sample no. 119 is compared. Sample No. with few bubbles 20, no. 47, no. It can be seen that No.
- the sample No. 111, no. 118, no. In the case of the Al alloy wire of 119, it is considered that when subjected to impact or repeated bending, the bubbles become the starting point of cracking and easily break. From this, it can be said that impact resistance and fatigue characteristics can be improved by reducing bubbles in the surface layer of the Al alloy wire. Further, as shown in Table 13 to Table 15, the Al alloy wire of the aging sample group has a sample No. shown in Table 16 whose hydrogen content is shown in Table 16. 111, no. 118, no. Less than 119 Al alloy wire.
- the Al alloy wire of the aging sample group has few bubbles present not only in the surface layer but also inside. Quantitatively, the ratio of the total area of bubbles “inside / surface layer” is 44 or less, here 35 or less, many samples are 20 or less, and further 10 or less. 112 (Table 16). Sample No. having the same composition. 20 and sample no. In comparison with Sample No. 112, the sample No. No. 20 has more flexing times (Tables 10 and 12) and higher impact resistance parameter values (Tables 18 and 20). One reason for this is that Sample No.
- the Al alloy wire of the aging sample group has a certain amount of fine crystals on the surface layer. Quantitatively, the average area is 3 ⁇ m 2 or less, and many samples are 2 ⁇ m 2 or less, and further 1.5 ⁇ m 2 or less. Further, the number of such fine crystallized substances is more than 10 and 400 or less, here 350 or less, many samples are 300 or less, and there are 200 or less and 100 or less samples. Sample No. having the same composition. 20 (Table 10, Table 18) and Sample No. 112 (Table 12 and Table 20), sample No. 1 in which fine crystallized substances are present to some extent on the surface layer. No. 20 has a larger number of flexing times and higher impact resistance parameter values.
- the crystallized matter present in the surface layer is fine, so that it is difficult to become a starting point of cracking and is excellent in impact resistance and fatigue characteristics. Presence of fine crystallized materials to some extent is considered to be one factor for improving fatigue properties by suppressing crystal growth and facilitating bending.
- the “area ratio” in Tables 13 to 15 most of the crystallized substances existing in the surface layer (here, 70% or more, many are 80% or more, and further 85% or more) are 3 ⁇ m 2. Since it was the following, and it was a crystallized product of a fine and uniform size, it is thought that it was hard to become the starting point of a crack.
- the crystallized matter existing not only in the surface layer but also in the inside is small (40 ⁇ m 2 or less) as described above, the crystallized product becomes a starting point of cracking, or the surface layer is formed through the crystallized product. It can be considered that cracking progresses from the inside to the inside, and is excellent in impact resistance and fatigue characteristics.
- the cooling rate in a specific temperature range should be increased to some extent (here, more than 0.5 ° C / second, and more than 1 ° C / second). , Preferably less than 25 ° C./second, and more preferably less than 20 ° C./second).
- the Al alloy wire of the aging sample group has a small crystal grain size.
- the average crystal grain size is 50 ⁇ m or less, many samples are 35 ⁇ m or less, further 30 ⁇ m or less, and some samples are 20 ⁇ m or less. It is smaller than 113 (Table 16).
- Sample No. having the same composition. 20 (Table 10) and Sample No. 113 (Table 12), sample No. 20 is about twice as many times of bending. Therefore, it is considered that the small crystal grain size contributes particularly to improvement of fatigue characteristics.
- the Al alloy wire of the aging sample group has a surface oxide film, but is thin (refer to Sample No. 116 in Table 20) and is 120 nm or less. Therefore, it is considered that these Al alloy wires can reduce an increase in connection resistance with the terminal portion and can construct a low resistance connection structure. Further, it is considered that providing the surface oxide film with an appropriate thickness (here, 1 nm or more) contributes to the improvement of the above-described corrosion resistance. In addition, from this test, it can be said that the surface oxide film is likely to be thick when the heat treatment such as aging treatment is performed in the air atmosphere or the condition that the boehmite layer can be formed, and is thin when the atmosphere is low oxygen.
- an Al alloy wire made of an Al—Mg—Si alloy having a specific composition and subjected to an aging treatment which has a small dynamic friction coefficient, has high strength, high toughness, and high electrical conductivity. In addition to excellent connection strength with the part, it also has excellent impact resistance and fatigue characteristics.
- Such an Al alloy wire is expected to be suitably used as a conductor of a covered electric wire, particularly a conductor of a terminal-attached electric wire to which a terminal portion is attached.
- the present invention is not limited to these exemplifications, but is defined by the scope of the claims, and is intended to include all modifications within the scope and meaning equivalent to the scope of the claims.
- the composition of the alloy of Test Example 1 the cross-sectional area of the wire, the number of twisted strands, and the production conditions (hot water temperature, cooling rate during casting, heat treatment time, heat treatment conditions, etc.) can be changed as appropriate.
- [Appendix 3] The aluminum alloy wire according to [Appendix 1] or [Appendix 2], wherein a lubricant is attached to a surface of the aluminum alloy wire, and an adhesion amount of C derived from the lubricant is more than 0 and 30% by mass or less.
- [Appendix 4] In the cross section of the aluminum alloy wire, a 1500- ⁇ m 2 fan-shaped bubble measurement region is taken from the annular surface layer region in the depth direction from the surface to 30 ⁇ m, and the total number of bubbles present in the fan-shaped bubble measurement region The aluminum alloy wire according to any one of [Appendix 1] to [Appendix 3] having a cross-sectional area of 2 ⁇ m 2 or less.
- [Appendix 11] The aluminum alloy wire according to any one of [Appendix 1] to [Appendix 10], which has a work hardening index of 0.05 or more.
- [Appendix 12] The aluminum alloy wire according to any one of [Appendix 1] to [Appendix 11], wherein a thickness of a surface oxide film of the aluminum alloy wire is 1 nm or more and 120 nm or less.
- the aluminum alloy further includes one or more elements selected from Fe, Cu, Mn, Ni, Zr, Cr, Zn, and Ga, each in an amount of 0% by mass to 0.5% by mass, and 0% by mass in total.
- the aluminum alloy wire according to any one of [Appendix 1] to [Appendix 12], which is contained in an amount of 1.0% by mass or less.
- [Appendix 14] [Appendix 1] to [Appendix 13], wherein the aluminum alloy further contains at least one element of Ti of 0% by mass to 0.05% by mass and B of 0% by mass to 0.005% by mass.
- the aluminum alloy wire as described in any one.
- [Appendix 15] One or more selected from a tensile strength of 150 MPa or more, a 0.2% proof stress of 90 MPa or more, a breaking elongation of 5% or more, and a conductivity of 40% IACS or more.
- [Appendix 16] An aluminum alloy stranded wire formed by twisting a plurality of the aluminum alloy wires according to any one of [Appendix 1] to [Appendix 15].
- [Appendix 17] The aluminum alloy twisted wire according to [Appendix 16], wherein the twist pitch is 10 to 40 times the layer core diameter of the aluminum alloy twisted wire.
- [Appendix 18] A covered electric wire comprising a conductor and an insulating coating covering the outer periphery of the conductor, The said conductor is a covered electric wire provided with the aluminum alloy twisted wire as described in [Appendix 16] or [Appendix 17].
- Mg is contained in an amount of 0.03 to 1.5 mass%
- Si is contained in an amount of 0.02 to 2.0 mass%
- Mg / Si is 0.5 to 3.5 in terms of mass ratio.
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Abstract
Description
本出願は、2016年10月31日付の日本国出願の特願2016-213155に基づく優先権、及び2017年04月04日付の日本国出願の特願2017-074235に基づく優先権を主張し、前記日本国出願に記載された全ての記載内容を援用するものである。
アルミニウム合金から構成されるアルミニウム合金線であって、
前記アルミニウム合金は、Mgを0.03質量%以上1.5質量%以下、Siを0.02質量%以上2.0質量%以下含有し、質量比でMg/Siが0.5以上3.5以下であり、残部がAl及び不可避不純物からなり、
動摩擦係数が0.8以下である。
上記の本開示のアルミニウム合金線を複数撚り合わせてなる。
導体と、前記導体の外周を覆う絶縁被覆とを備える被覆電線であって、
前記導体は、上記の本開示のアルミニウム合金撚線を備える。
上記の本開示の被覆電線と、前記被覆電線の端部に装着された端子部とを備える。
電線に備える導体などに利用される線材として、耐衝撃性に優れる上に、疲労特性にも優れるアルミニウム合金線が望まれている。
(1)自動車用ワイヤーハーネスに備える電線では、電線を接続対象に取り付ける際などで端子部近傍に衝撃が与えられること(特許文献1)、その他、自動車の走行状態によって突発的な衝撃が与えられること、自動車の走行時の振動によって繰り返しの曲げが与えられることなどが考えられる。
(2)産業用ロボットに配線される電線では、繰り返しの曲げや捻回などが与えられることなどが考えられる。
(3)建築物に配線される電線では、布設時に作業者が突発的に強く引っ張ったり、誤って落下させたりして衝撃が与えられること、コイル状に巻き取られた線材から巻き癖を除去するために波打つように振ることで繰り返しの曲げが与えられることなどが考えられる。
従って、電線に備える導体などに利用されるアルミニウム合金線には、衝撃だけでなく、繰り返しの曲げが与えられた場合でも、断線し難いことが望まれる。
上記の本開示のアルミニウム合金線、上記の本開示のアルミニウム合金撚線、上記の本開示の被覆電線、上記の本開示の端子付き電線は、耐衝撃性及び疲労特性に優れる。
本発明者らは、種々の条件でアルミニウム合金線を製造して、耐衝撃性、疲労特性(繰り返しの曲げに対する断線し難さ)に優れるアルミニウム合金線を検討した。Mg及びSiを特定の範囲で含むという特定の組成のアルミニウム合金から構成され、特に時効処理が施された線材は、高強度(例えば、引張強さや0.2%耐力が高い)であり、導電率が高く導電性にも優れる。更に、この線材が滑り易いものであると、繰り返しの曲げによっても断線し難いとの知見を得た。このようなアルミニウム合金線は、例えば線材の表面を平滑にしたり、線材表面の潤滑剤量を調整したりするなどによって製造できる、との知見を得た。本願発明は、これらの知見に基づくものである。最初に本願発明の実施形態の内容を列記して説明する。
アルミニウム合金から構成されるアルミニウム合金線であって、
前記アルミニウム合金は、Mgを0.03質量%以上1.5質量%以下、Siを0.02質量%以上2.0質量%以下含有し、質量比でMg/Siが0.5以上3.5以下であり、残部がAl及び不可避不純物からなり、
動摩擦係数が0.8以下である。
表面粗さが3μm以下である形態が挙げられる。
前記アルミニウム合金線の表面に潤滑剤が付着しており、この潤滑剤に由来するCの付着量が0超30質量%以下である形態が挙げられる。
前記アルミニウム合金線の横断面において、その表面から深さ方向に30μmまでの表層領域から、短辺長さが30μmであり、長辺長さが50μmである長方形の表層気泡測定領域をとり、前記表層気泡測定領域に存在する気泡の合計断面積が2μm2以下である形態が挙げられる。
アルミニウム合金線の横断面とは、アルミニウム合金線の軸方向(長手方向)に直交する面で切断した断面をいう。
前記アルミニウム合金線の横断面において、短辺長さが30μmであり、長辺長さが50μmである長方形の内部気泡測定領域をこの長方形の中心が前記アルミニウム合金線の中心に重なるようにとり、前記表層気泡測定領域に存在する気泡の合計断面積に対する前記内部気泡測定領域に存在する気泡の合計断面積の比が1.1以上44以下である形態が挙げられる。
水素の含有量が8.0ml/100g以下である形態が挙げられる。
前記アルミニウム合金線の横断面において、その表面から深さ方向に50μmまでの表層領域から、短辺長さが50μmであり、長辺長さが75μmである長方形の表層晶出測定領域をとり、前記表層晶出測定領域に存在する晶出物の平均面積が0.05μm2以上3μm2以下である形態が挙げられる。
晶出物とは、代表的には添加元素であるMg及びSiの少なくとも一方などを含む化合物や単体元素などであり、ここではAl合金線の横断面において0.05μm2以上の面積を有するもの(同一面積における円相当径では0.25μm以上を有するもの)とする。上記化合物のうち、0.05μm2未満の面積を有するもの、代表的には円相当径で0.2μm以下、更に0.15μm以下のより微細なものを析出物とする。
前記表層晶出測定領域に存在する晶出物の個数が10個超400個以下である形態が挙げられる。
前記アルミニウム合金線の横断面において、短辺長さが50μmであり、長辺長さが75μmである長方形の内部晶出測定領域をこの長方形の中心が前記アルミニウム合金線の中心に重なるようにとり、前記内部晶出測定領域に存在する晶出物の平均面積が0.05μm2以上40μm2以下である形態が挙げられる。
前記アルミニウム合金の平均結晶粒径が50μm以下である形態が挙げられる。
加工硬化指数が0.05以上である形態が挙げられる。
前記アルミニウム合金線の表面酸化膜の厚さが1nm以上120nm以下である形態が挙げられる。
引張強さが150MPa以上であり、0.2%耐力が90MPa以上であり、破断伸びが5%以上であり、導電率が40%IACS以上である形態が挙げられる。
上記(1)から(13)のいずれか一つに記載のアルミニウム合金線を複数撚り合わせてなる。
撚りピッチが前記アルミニウム合金撚線の層心径の10倍以上40倍以下である形態が挙げられる。
層心径とは、撚線が多層構造である場合、各層に含まれる全ての素線の中心を連ねる円の直径をいう。
導体と、前記導体の外周を覆う絶縁被覆とを備える被覆電線であって、
前記導体は、上記(14)又は(15)に記載のアルミニウム合金撚線を備える。
上記(16)に記載の被覆電線と、前記被覆電線の端部に装着された端子部とを備える。
以下、適宜、図面を参照して、本願発明の実施の形態を詳細に説明する。図中、同一符号は同一名称物を示す。以下の説明において元素の含有量は、質量%を示す。
(概要)
実施形態のアルミニウム合金線(Al合金線)22は、アルミニウム合金(Al合金)から構成される線材であり、代表的には、電線の導体2などに利用される(図1)。この場合、Al合金線22は、単線、又は複数のAl合金線22が撚り合わされてなる撚線(実施形態のAl合金撚線20)、又は撚線が所定の形状に圧縮成形されてなる圧縮撚線(実施形態のAl合金撚線20の別例)の状態で利用される。図1では7本のAl合金線22が撚り合わされたAl合金撚線20を例示する。実施形態のAl合金線22は、Al合金がMg及びSiを特定の範囲で含むという特定の組成を有すると共に、Al合金線22の動摩擦係数が小さい。詳しくは、実施形態のAl合金線22を構成するAl合金は、Mgを0.03%以上1.5%以下、Siを0.02%以上2.0%以下含有し、質量比でMg/Siが0.5以上3.5以下であり、残部がAl及び不可避不純物からなるAl-Mg-Si系合金である。また、実施形態のAl合金線22は、動摩擦係数が0.8以下である。上述の特定の組成を有すると共に特定の表面性状を有する実施形態のAl合金線22は、製造過程で時効処理などを受けることで高強度である上に、摩擦に起因する破断も低減できるため、耐衝撃性、疲労特性にも優れる。
以下、より詳細に説明する。なお、動摩擦係数などといった各パラメータの測定方法の詳細、上述の効果の詳細は試験例で説明する。
実施形態のAl合金線22は、Al-Mg-Si系合金で構成されて、Mg及びSiが固溶して存在すると共に、晶出物及び析出物として存在することで強度に優れる。Mgは強度の向上効果が高い元素であり、Siと同時に特定の範囲で含有することで、具体的にはMgを0.03%以上かつSiを0.02%以上含有することで、時効硬化による強度の向上を効果的に図ることができる。Mg及びSiの含有量が高いほど、Al合金線の強度を高められ、Mgを1.5%以下かつSiを2.0%以下の範囲で含むことで、Mg及びSiの含有に起因する導電率や靭性の低下を招き難く、高い導電率や高い靭性などを有したり、伸線加工時に断線し難く、製造性にも優れたりする。強度、靭性、導電率のバランスを考慮して、Mgの含有量を0.1%以上2.0%以下、更に0.2%以上1.5%以下、0.3%以上0.9%以下、Siの含有量を0.1%以上2.0%以下、更に0.1%以上1.5%以下、0.3%以上0.8%以下とすることができる。
(Fe)0.01%以上0.25%以下、更に0.01%以上0.2%以下
(Cu,Mn,Ni,Zr,Cr,Znのそれぞれ)0.01%以上0.5%以下、更に0.01%以上0.3%以下
(Ga)0.005%以上0.1%以下、更に0.005%以上0.05%以下
(1)Mgを0.03%以上1.5%以下、Siを0.02%以上2.0%以下、Feを0.01%以上0.25%以下含有し、残部がAl及び不可避不純物。
(2)Mgを0.03%以上1.5%以下、Siを0.02%以上2.0%以下、Feを0.01%以上0.25%以下、Cu,Mn,Ni,Zr,Cr,Zn,及びGaから選択される1種以上の元素を合計で0.01%以上0.3%以下含有し、残部がAl及び不可避不純物。
(3)上記(1)又は(2)において、0.005%以上0.05%以下のTi及び0.001%以上0.005%以下のBの少なくとも一方の元素を含有する。
・動摩擦係数
実施形態のAl合金線22は動摩擦係数が0.8以下である。動摩擦係数がこのように小さいAl合金線22を例えば撚線の素線に用いて、この撚線に繰り返しの曲げを与えた場合に素線(Al合金線22)間の摩擦が小さくて素線同士が滑り易く、各素線が滑らかに動ける。ここで、動摩擦係数が大きいと、素線間の摩擦が大きく、繰り返しの曲げを受けた場合、この摩擦に起因して素線が破断し易くなり、結果として撚線が断線し易くなる。動摩擦係数が0.8以下であるAl合金線22は、特に撚線に用いられた場合に素線間の摩擦を小さくでき、繰り返しの曲げを受けても破断し難く、疲労特性に優れる。衝撃を受けた場合でも素線同士が滑ることで、衝撃を緩和して素線が破断し難くなることが期待できる。動摩擦係数は小さいほど、摩擦に起因する破断を低減でき、0.7以下、更に0.6以下、0.5以下であることが好ましい。動摩擦係数は、例えば、Al合金線22の表面を平滑にしたり、Al合金線22の表面に潤滑剤を付着したり、これら双方を満たしたりすると、小さくなり易い。
実施形態のAl合金線22の一例として、表面粗さが3μm以下であるものが挙げられる。表面粗さがこのように小さいAl合金線22は、動摩擦係数が小さくなる傾向にあり、上述のように撚線の素線に用いた場合に素線間の摩擦を小さくでき、疲労特性に優れる。場合によっては耐衝撃性の向上も期待できる。表面粗さは小さいほど、動摩擦係数が小さくなり易く、上記素線間の摩擦を小さくし易いことから、2.5μm以下、更に2μm以下、1.8μm以下であることが好ましい。表面粗さは、例えば、伸線ダイスの表面粗さが3μm以下のものを用いたり、伸線時の潤滑剤量を多めに調整したりするなど、平滑な表面を有するように製造することで、小さくなり易い。表面粗さの下限を0.01μm、更に0.03μmとすると、工業的に量産し易いと期待される。
実施形態のAl合金線22の一例として、Al合金線22の表面に潤滑剤が付着しており、この潤滑剤に由来するCの付着量が0超30質量%以下であるものが挙げられる。Al合金線22の表面に付着する潤滑剤とは、上述のように製造過程で用いる潤滑剤(代表的には油剤)が残存したものと考えられる。Cの付着量が上記範囲を満たすAl合金線22は、潤滑剤の付着によって動摩擦係数が小さくなり易く、上記範囲で多いほど、動摩擦係数が小さくなる傾向にある。動摩擦係数が小さいことで、上述のようにAl合金線22を撚線の素線に用いた場合に素線間の摩擦を小さくでき、疲労特性に優れる。場合によっては耐衝撃性の向上も期待できる。また、潤滑剤の付着によって耐食性にも優れる。上記範囲で少ないほど、Al合金線22から構成される導体2の端部に端子部4(図2)を取り付けた場合に、導体2と端子部4間に介在する潤滑剤を少なくできる。この場合、過度の潤滑剤の介在に伴う導体2と端子部4間の接続抵抗の増大を防止できる。摩擦低減と接続抵抗の増大抑制とを考慮すると、Cの付着量を0.5質量%以上25質量%以下、更に1質量%以上20質量%以下とすることができる。Cの付着量が所望の量となるように、例えば、伸線時や撚線時における潤滑剤の使用量や、熱処理条件などを調整することが挙げられる。熱処理条件によっては潤滑剤が低減、除去されるからである。
実施形態のAl合金線22の一例として、Al合金線22の表面酸化膜の厚さが1nm以上120nm以下であるものが挙げられる。時効処理などの熱処理が施されると、Al合金線22の表面に酸化膜が存在し得る。表面酸化膜の厚さが120nm以下と薄いことで、Al合金線22から構成される導体2の端部に端子部4を取り付けた場合に導体2と端子部4間に介在される酸化物を少なくできる。導体2と端子部4間に電気絶縁物である酸化物の介在量が少ないことで、導体2と端子部4間の接続抵抗の増大を低減できる。一方、表面酸化膜が1nm以上であれば、Al合金線22の耐食性を高められる。上記範囲で薄いほど上記接続抵抗の増大を低減でき、厚いほど耐食性を高められる。接続抵抗の増大抑制と耐食性とを考慮すると、表面酸化膜は、2nm以上115nm以下、更に5nm以上110nm以下、更に100nm以下とすることができる。表面酸化膜の厚さは、例えば、熱処理条件によって調整変化できる。特に雰囲気中の酸素濃度が高いと(例えば大気雰囲気)表面酸化膜を厚くし易く、酸素濃度が低いと(例えば不活性ガス雰囲気、還元ガス雰囲気など)表面酸化膜を薄くし易い。
・気泡
実施形態のAl合金線22の一例として、その表層に存在する気泡が少ないものが挙げられる。具体的にはAl合金線22の横断面において、図3に示すようにその表面から深さ方向に30μmまでの表層領域220、即ち厚さ30μmの環状の領域をとる。この表層領域220から、短辺長さSが30μmであり、長辺長さLが50μmである長方形の表層気泡測定領域222(図3では破線で示す)をとる。短辺長さSは表層領域220の厚さに相当する。詳しくは、Al合金線22の表面の任意の点(接点P)について接線Tをとる。接点PからAl合金線22の内部に向かって、表面の法線方向に長さが30μmである直線Cをとる。Al合金線22が丸線であれば、この円の中心に向かって直線Cをとる。直線Cと平行な直線であって長さが30μmの直線を短辺22Sとする。接点Pを通り、接線Tに沿った直線であって、接点Pが中間点となるように長さが50μmである直線をとり、この直線を長辺22Lとする。表層気泡測定領域222にAl合金線22が存在しない微小な空隙(ハッチング部分)gが生じることを許容する。この表層気泡測定領域222に存在する気泡の合計断面積が2μm2以下である。表層に気泡が少ないことで、衝撃や繰り返しの曲げを受けた場合などに気泡を起点とする割れを低減し易く、ひいては表層から内部への割れの進展も低減できて、気泡に起因する破断を低減できる。そのため、このAl合金線22は、耐衝撃性や疲労特性に優れる。一方、気泡の合計面積が大きければ、粗大な気泡が存在したり、微細な気泡が多数存在したりして、気泡が割れの起点となったり、割れが進展し易くなったりして、耐衝撃性や疲労特性に劣る。他方、気泡の合計断面積は、小さいほど気泡が少なく、気泡に起因する破断を低減して耐衝撃性や疲労特性に優れることから、1.9μm2以下、更に1.8μm2以下、1.2μm2以下であることが好ましく、0に近いほど好ましい。気泡は、例えば、鋳造過程で湯温を低めにすると少なくなり易い。加えて鋳造時の冷却速度、特に後述する特定の温度域の冷却速度を速めるとより少なく、小さくなり易い。
実施形態のAl合金線22の一例として、表層に微細な晶出物がある程度存在するものが挙げられる。具体的にはAl合金線22の横断面において、その表面から深さ方向に50μmまでの表層領域、即ち厚さ50μmの環状の領域から、短辺長さが50μmであり、長辺長さが75μmである長方形の領域(表層晶出測定領域と呼ぶ)をとる。短辺長さは表層領域の厚さに相当する。この表層晶出測定領域に存在する晶出物の平均面積が0.05μm2以上3μm2以下である。Al合金線22が丸線である場合や実質的に丸線と見做せる場合などでは、Al合金線22の横断面において、上述の厚さ50μmの環状の領域から、3750μm2の面積を有する扇型の領域(晶出測定領域と呼ぶ)をとり、この扇型の晶出測定領域に存在する晶出物の平均面積が0.05μm2以上3μm2以下である。長方形の表層晶出測定領域や扇型の晶出測定領域は、上述の表層気泡測定領域222や扇型の気泡測定領域224と同様にして、短辺長さSを50μm、長辺長さLを75μmに代えたり、厚さtを50μm、面積を3750μm2に代えたりしてとるとよい。上述の長方形の表層晶出測定領域と扇型の晶出測定領域との双方をとり、この双方に存在する晶出物の平均面積がいずれも0.05μm2以上3μm2以下であると、耐衝撃性や疲労特性に優れる線材としての信頼性を高められると期待される。表層に複数の晶出物が存在しても、各晶出物の平均の大きさが3μm2以下であるため、衝撃や繰り返しの曲げを受けた場合などに各晶出物を起点とする割れを低減し易く、ひいては表層から内部への割れの進展も低減できて、晶出物に起因する破断を低減できる。そのため、このAl合金線22は、耐衝撃性や疲労特性に優れる。一方、晶出物の平均面積が大きければ、割れの起点となるような粗大な晶出物を含み易く、耐衝撃性や疲労特性に劣る。他方、各晶出物の平均の大きさが0.05μm2以上であるため、Mg,Siなどの添加元素の固溶に起因する導電率の低下を低減したり、結晶粒の成長を抑制したりするなどの効果が期待できる。上記平均面積は、小さいほど割れを低減し易く、2.5μm2以下、更に2μm2以下、1μm2以下であることが好ましい。晶出物をある程度存在させる観点からは、上記平均面積を0.08μm2以上、更に0.1μm2以上とすることができる。晶出物は、例えば、Mg,Siなどの添加元素を少なくしたり、鋳造時の冷却速度を速めたりすると小さくなり易い。
実施形態のAl合金線22の一例として、Al合金の平均結晶粒径が50μm以下であるものが挙げられる。微細な結晶組織を有するAl合金線22は曲げなどを行い易く、柔軟性に優れて、衝撃や繰り返しの曲げを受けた場合などで破断し難い。実施形態のAl合金線22は、動摩擦係数が小さいことも相俟って、この形態は耐衝撃性、疲労特性に優れる。上述のように表層に気泡が少なく、好ましくは晶出物も小さい場合には、耐衝撃性、疲労特性により優れる。上記平均結晶粒径は、小さいほど曲げなどを行い易く、耐衝撃性、疲労特性に優れることから、45μm以下、更に40μm以下、30μm以下であることが好ましい。結晶粒径は、組成や製造条件にもよるが、例えば上述のようにTiやB、元素αのうち微細化効果がある元素を含むと、微細になり易い。
実施形態のAl合金線22の一例として、水素の含有量が8.0ml/100g以下であるものが挙げられる。気泡の一要因は、上述のように水素であると考えられる。Al合金線22について質量100gあたりに対する水素の含有量が8.0ml以下であれば、このAl合金線22は気泡が少なく、上述のように気泡に起因する破断を低減できる。水素の含有量は少ないほど、気泡が少ないと考えられることから、7.8ml/100g以下、更に7.6ml/100g以下、7.0ml/100g以下であることが好ましく、0に近いほど好ましい。Al合金線22中の水素は、大気雰囲気などの水蒸気を含む雰囲気で鋳造を行うことで雰囲気中の水蒸気が溶湯に溶解し、この溶存水素が残存していると考えられる。そのため、水素の含有量は、例えば、湯温を低めにして雰囲気からのガスの溶解を低減すると少なくなり易い。また、水素の含有量は、Cuを含有すると少なくなる傾向にある。
・加工硬化指数
実施形態のAl合金線22の一例として、加工硬化指数が0.05以上であるものが挙げられる。加工硬化指数が0.05以上と大きいことで、例えば複数のAl合金線22を撚り合わせた撚線を圧縮成形した圧縮撚線としたり、Al合金線22から構成される導体2(単線、撚線、圧縮撚線のいずれでもよい)の端部に端子部4を圧着したりするといった塑性加工を施した場合に、Al合金線22は加工硬化し易い。圧縮成形や圧着などの塑性加工によって断面積が減少した場合でも、加工硬化によって強度を高められ、導体2に端子部4を強固に固着できる。このように加工硬化指数が大きいAl合金線22は、端子部4の固着性に優れる導体2を構成できる。加工硬化指数は大きいほど、加工硬化による強度の向上が期待できることから、0.08以上、更に0.1以上が好ましい。加工硬化指数は、破断伸びが大きいほど大きくなり易い。そのため、加工硬化指数を大きくするには、例えば添加元素の種類や含有量、熱処理条件などを調整して破断伸びを高めることが挙げられる。晶出物の大きさが上述の特定の範囲を満たすと共に、平均結晶粒径が上述の特定の範囲を満たすという特定の組織を有するAl合金線22は、加工硬化指数が0.05以上を満たし易い。そのため、Al合金の組織を指標として、添加元素の種類や含有量、熱処理条件などを調整することでも、加工硬化指数を調整できる。
実施形態のAl合金線22は、上述した特定の組成のAl合金で構成され、代表的には時効処理などの熱処理を施されることで、引張強さや0.2%耐力が高く強度に優れる上に導電率が高く導電性にも優れる。組成や製造条件などによっては、破断伸びが高く靭性にも優れるものとすることができる。定量的には、Al合金線22は、引張強さが150MPa以上であること、0.2%耐力が90MPa以上であること、破断伸びが5%以上であること、導電率が40%IACS以上であることから選択される一つ以上を満たすものが挙げられる。列挙する事項のうち二つの事項、更に三つの事項、特に四つ全ての事項を満たすAl合金線22は、耐衝撃性、疲労特性により優れたり、導電性にも優れたりする。このようなAl合金線22は、電線の導体として好適に利用できる。
実施形態のAl合金線22の横断面形状は、用途などに応じて適宜選択できる。例えば、横断面形状が円形である丸線が挙げられる(図1参照)。その他、横断面形状が長方形などの四角形である角線などが挙げられる。Al合金線22が上述の圧縮撚線の素線を構成する場合には、代表的には円形が押し潰された異形状である。上述の気泡や晶出物を評価するときの測定領域は、Al合金線22が角線などであれば長方形の領域が利用し易く、Al合金線22が丸線などであれば長方形の領域でも扇型の領域でもいずれを利用してもよい。Al合金線22の横断面形状が所望の形状となるように、伸線ダイスの形状、圧縮成形用のダイスの形状などを選択するとよい。
実施形態のAl合金線22の大きさ(横断面積、丸線の場合には線径(直径)など)は、用途などに応じて適宜選択できる。例えば、自動車用ワイヤーハーネスなどの各種のワイヤーハーネスに備えられる電線の導体に利用する場合、Al合金線22の線径は0.2mm以上1.5mm以下であることが挙げられる。例えば、建築物などの配線構造を構築する電線の導体に利用する場合、Al合金線22の線径は0.1mm以上3.6mm以下であることが挙げられる。Al合金線22は高強度線材であることから、線径が0.1mm以上1.0mm以下といったより細径の用途などにも好適に利用できると期待される。
実施形態のAl合金線22は、図1に示すように撚線の素線に利用できる。実施形態のAl合金撚線20は、複数のAl合金線22を撚り合わせてなる。Al合金撚線20は、同じ導体断面積を有する単線のAl合金線と比較して断面積が小さい複数の素線(Al合金線22)を撚り合わせて構成されるため、可撓性に優れ、曲げなどを行い易い。また、撚り合わせられることで、各素線であるAl合金線22が細くても、撚線全体として強度に優れる。更に、実施形態のAl合金撚線20は、動摩擦係数が小さいという特定の表面性状を有するAl合金線22を素線とするため、素線同士が滑り易く、曲げなどを滑らかに行えて、繰り返しの曲げを受けた場合などに素線が破断し難い。これらのことからAl合金撚線20は、衝撃や繰り返しの曲げを受けた場合などでも、各素線であるAl合金線22が破断し難く、耐衝撃性及び疲労特性に優れ、特に疲労特性に優れる。各素線であるAl合金線22は、上述した表面粗さ、Cの付着量、気泡の含有量、水素の含有量、晶出物の大きさや個数、及び結晶粒径の大きさから選択される少なくとも一つの事項が上述の特定の範囲を満たすと、耐衝撃性、疲労特性に更に優れる。
実施形態のAl合金線22や実施形態のAl合金撚線20(圧縮撚線でもよい)は、電線用導体に好適に利用できる。絶縁被覆を備えていない裸導体、絶縁被覆を備える被覆電線の導体のいずれにも利用できる。実施形態の被覆電線1は、導体2と、導体2の外周を覆う絶縁被覆3とを備え、導体2として、実施形態のAl合金線22、又は実施形態のAl合金撚線20を備える。この被覆電線1は、耐衝撃性、疲労特性に優れるAl合金線22やAl合金撚線20から構成される導体2を備えるため、耐衝撃性、疲労特性に優れる。絶縁被覆3を構成する絶縁材料は、適宜選択できる。上記絶縁材料は、例えば、ポリ塩化ビニル(PVC)やノンハロゲン樹脂、難燃性に優れる材料などが挙げられ、公知のものが利用できる。絶縁被覆3の厚さは所定の絶縁強度を有する範囲で適宜選択できる。
実施形態の被覆電線1は、自動車や飛行機などの機器に載置されるワイヤーハーネス、産業用ロボットなどといった各種の電気機器の配線、建築物などの配線など、各種の用途の電線に利用できる。ワイヤーハーネスなどに備えられる場合、代表的には、被覆電線1の端部には端子部4が取り付けられる。実施形態の端子付き電線10は、図2に示すように実施形態の被覆電線1と、被覆電線1の端部に装着された端子部4とを備える。この端子付き電線10は、耐衝撃性、疲労特性に優れる被覆電線1を備えるため、耐衝撃性、疲労特性に優れる。図2では、端子部4として、一端に雌型又は雄型の嵌合部42を備え、他端に絶縁被覆3を把持するインシュレーションバレル部44を備え、中間部に導体2を把持するワイヤバレル部40を備える圧着端子を例示する。その他の端子部4として、導体2を溶融して接続する溶融型のものなどが挙げられる。
(概要)
実施形態のAl合金線22は、代表的には、鋳造、(熱間)圧延や押出などの中間加工、伸線という基本工程に加えて、適宜な時期に熱処理(時効処理を含む)を行うことで製造できる。基本工程や時効処理の条件などは公知の条件などを参照できる。実施形態のAl合金撚線20は、複数のAl合金線22を撚り合わせることで製造できる。撚り合せ条件などは公知の条件を参照できる。動摩擦係数が小さい実施形態のAl合金線22は、後述するように主として伸線条件や熱処理条件を調整することで製造できる。
上述した表層に気泡が少ないAl合金線22は、例えば、鋳造過程において湯温を低めにすると製造し易い。溶湯に雰囲気中のガスが溶解することを低減でき、溶存ガスが少ない溶湯で鋳造材を製造できる。溶存ガスとしては、上述のように水素が挙げられ、この水素は雰囲気中の水蒸気が分解したもの、雰囲気中に含まれていたものと考えられる。溶存水素などの溶存ガスが少ない鋳造材を素材とすることで、圧延や伸線などの塑性加工、時効処理などの熱処理を施しても、鋳造以降においてAl合金に溶存ガスに起因する気泡が少ない状態を維持し易い。その結果、最終線径のAl合金線22の表層や内部に存在する気泡を上述の特定の範囲にすることができる。また、上述のように水素の含有量が少ないAl合金線22を製造できる。鋳造過程以降の工程、例えば、皮剥ぎ、塑性変形を伴う加工(圧延、押出、伸線など)を行うことで、Al合金の内部に閉じ込められた気泡の位置が変化したり、気泡の大きさがある程度小さくなったりすると考えられる。しかし、鋳造材に存在する気泡の合計含有量が多ければ、位置変動や大きさ変動があっても、最終線径のAl合金線において、表層や内部に存在する気泡の合計含有量や、水素の含有量が多くなり易い(実質的に維持されたままである)と考えられる。そこで、湯温を低くして、鋳造材自体に含まれる気泡を十分に少なくすることを提案する。
鋳造材に、代表的には(熱間)圧延や押出などの塑性加工(中間加工)を施した中間加工材を伸線に供することが挙げられる。連続鋳造に連続して熱間圧延を行って、連続鋳造圧延材(中間加工材の一例)を伸線に供することもできる。上記塑性加工の前後に皮剥ぎや熱処理を行うことができる。皮剥ぎを行うことで、気泡や表面キズなどが存在し得る表層を除去できる。ここでの熱処理は、例えば、Al合金の均質化や溶体化などを目的とするものが挙げられる。均質化処理の条件は、例えば、雰囲気が大気又は還元雰囲気、加熱温度が450℃以上600℃以下程度(好ましくは500℃以上)、保持時間が1時間以上10時間以下(好ましくは3時間以上)、冷却速度が1℃/分以下の徐冷、が挙げられる。伸線前の中間加工材に上記の条件で均質化処理を行うと、破断伸びが高く、靭性に優れるAl合金線22を製造し易く、特に中間加工材を連続鋳造圧延材とすると、靭性により優れるAl合金線22を製造し易い。溶体化処理の条件は、後述の条件を利用できる。
上述の圧延などの塑性加工を経た素材(中間加工材)に、所定の最終線径になるまで(冷間)伸線加工を施し、伸線材を形成する。伸線加工は、代表的には伸線ダイスを用いて行う。また、潤滑剤を用いて行う。上述のように伸線ダイスの表面粗さが小さいもの、例えば3μm以下のものを利用することで、更に潤滑剤の塗布量を調整することで、表面粗さが3μm以下という平滑な表面を有するAl合金線22を製造できる。表面粗さが小さい伸線ダイスに適宜交換することで、平滑な表面を有する伸線材を連続して製造できる。伸線ダイスの表面粗さは、例えば伸線材の表面粗さを代替値として利用すると、測定が容易である。潤滑剤の塗布量を調整したり、後述の熱処理条件などを調整したりすることで、Al合金線22の表面におけるCの付着量が上述の特定の範囲を満たすAl合金線22を製造できる。ひいては、動摩擦係数が上述の特定の範囲を満たす実施形態のAl合金線22を製造できる。伸線加工度は、最終線径に応じて適宜選択するとよい。
Al合金撚線20を製造する場合には、複数の線材(伸線材、又は伸線後に熱処理を施した熱処理材)を用意し、これらを所定の撚りピッチ(例えば、層心径の10倍~40倍)で撚り合わせる。撚り合せ時に潤滑剤を用いてもよい。Al合金撚線20を圧縮撚線とする場合には、撚り合せ後に所定の形状に圧縮成形する。
伸線途中及び伸線工程以降の任意の時期の伸線材などに熱処理を行うことができる。伸線途中に行う中間熱処理は、例えば、伸線加工時に導入された歪みを除去し、加工性を高めることを目的とするものが挙げられる。伸線工程以降の熱処理は、溶体化処理を目的とするもの、時効処理を目的とするものなどが挙げられる。少なくとも時効処理を目的とする熱処理を行うことが好ましい。時効処理によって、Al合金中のMgやSi、組成によっては元素α(例えばZrなど)といった添加元素を含む析出物をAl合金中に分散させて、時効硬化による強度の向上、及び固溶元素の低減による導電率の向上を図ることができるからである。その結果、高強度及び高靭性で、耐衝撃性、疲労特性にも優れるAl合金線22やAl合金撚線20を製造できる。熱処理を行う時期は、伸線途中、伸線後(撚線前)、撚線後(圧縮成形前)、圧縮成形後の少なくとも一つの時期が挙げられる。複数の時期に熱処理を行ってもよい。溶体化処理を行う場合、溶体化処理は、時効処理よりも前(直前でなくてもよい)に行う。伸線途中や撚線前に上述の中間熱処理や溶体化処理などを行うと、加工性を高められて、伸線加工や撚り合せなどを行い易い。熱処理後の特性が所望の範囲を満たすように熱処理条件を調整するとよい。例えば破断伸びが5%以上を満たすように熱処理を行うことで、加工硬化指数が上述の特定の範囲を満たすAl合金線22を製造することもできる。また、熱処理前の潤滑剤量を測定しておき、熱処理後の残存量が所望の値となるように熱処理条件を調整することもできる。加熱温度が高いほど、又は保持時間が長いほど潤滑剤の残存量が少なくなる傾向にある。
(溶体化処理)加熱温度が450℃以上620℃以下程度(好ましくは500℃以上6000℃以下)、保持時間が0.005秒以上5時間以下(好ましくは0.01秒以上3時間以下)、冷却速度が100℃/分以上、更に200℃/分以上の急冷
(中間熱処理)加熱温度が250℃以上550℃以下、加熱時間が0.01秒以上5時間以下
(時効処理)加熱温度が100℃以上300℃以下、更に140℃以上250℃以下、保持時間が4時間以上20時間以下、更に16時間以下
その他、表面酸化膜の厚さの調整方法として、最終線径の伸線材を高温高圧の熱水の存在下に曝すこと、最終線径の伸線材に水を塗布すること、大気雰囲気の連続処理で熱処理後に水冷する場合に水冷後に乾燥工程を設けることなどが挙げられる。熱水に曝したり、水を塗布したりすることで表面酸化膜が厚くなる傾向にある。上記の水冷後に乾燥させることで、水冷に起因するベーマイト層の形成を防止して、表面酸化膜が薄くなる傾向にある。水冷の冷媒として、水にエタノールを添加したものを用いると、冷却と同時に脱脂も行える。
実施形態の被覆電線1は、導体2を構成する実施形態のAl合金線22又はAl合金撚線20(圧縮撚線でもよい)を用意し、導体2の外周に絶縁被覆3を押出などによって形成することで製造できる。押出条件などは公知の条件を参照できる。
実施形態の端子付き電線10は、被覆電線1の端部において、絶縁被覆3を除去して導体2を露出させ、端子部4を取り付けることで製造できる。
Al合金線を種々の条件で作製して特性を調べた。また、このAl合金線を用いてAl合金撚線を作製し、更にこのAl合金撚線を導体とする被覆電線を作製し、その端部に圧着端子を取り付けて得られた端子付き電線の特性を調べた。
(製法A)WR⇒伸線⇒熱処理(溶体化)⇒時効
(製法B)WR⇒熱処理(溶体化)⇒伸線⇒時効
(製法C)WR⇒熱処理(溶体化)⇒伸線⇒熱処理(溶体化)⇒時効
(製法D)WR⇒皮剥ぎ⇒伸線⇒中間熱処理⇒伸線⇒熱処理(溶体化)⇒時効
(製法E)WR⇒熱処理(溶体化)⇒皮剥ぎ⇒伸線⇒中間熱処理⇒伸線⇒熱処理(溶体化)⇒時効
(製法F)WR⇒伸線⇒時効
(製法G)WR⇒熱処理(溶体化、バッチ)⇒伸線⇒時効
得られた線径φ0.3mmの時効材について、引張強さ(MPa)、0.2%耐力(MPa)、破断伸び(%)、加工硬化指数、導電率(%IACS)を測定した。また、引張強さに対する0.2%耐力の比「耐力/引張」を求めた。これらの結果を表9から表12に示す。
得られた線径φ0.3mmの時効材について、屈曲試験を行い、破断までの回数を測定した。屈曲試験は、市販の繰り返し曲げ試験機を用いて測定した。ここでは、各試料の線材に0.3%の曲げ歪みが加えられる治具を使用して、12.2MPaの負荷を印加した状態で繰り返しの曲げを行う。試料ごとに3本以上の屈曲試験を行い、その平均(回)を表9から表12に示す。破断までの回数が多いほど、繰り返しの曲げによって破断し難く、疲労特性に優れるといえる。
・動摩擦係数
得られた各試料の被覆電線について、絶縁被覆を除去して導体のみとし、導体を構成する撚線又は圧縮撚線を解いて素線にばらして各素線(Al合金線)を試料として、以下のようにして動摩擦係数を測定した。その結果を表17から表20に示す。図5に示すように直方体状の台座100を用意し、台座100の表面のうち、長方形の一面の短辺方向に平行するように相手材150となる素線(Al合金線)を載置して、相手材150の両端を固定する(固定箇所は図示せず)。相手材150に直交するように、かつ台座100の上記一面の長辺方向に平行するように、試料Sとなる素線(Al合金線)を相手材150の上に水平に配置する。試料Sと相手材150との交差箇所の上に所定の質量の錘110(ここでは200g)を配置し、交差箇所がずれないようにする。この状態で、試料Sの途中に滑車を配置し、滑車に沿って試料Sの一端を上方に引っ張り、オートグラフなどによって引張力(N)を測定する。試料Sと相手材150とが相対ずれ運動を開始した後から100mmまで移動したときの平均荷重を動摩擦力(N)とする。この動摩擦力を、錘110の質量によって生じる法線力(ここでは2N)で除した値(動摩擦力/法線力)を動摩擦係数とする。
得られた各試料の被覆電線について、絶縁被覆を除去して導体のみとし、導体を構成する撚線又は圧縮撚線を解いて素線にばらして各素線(Al合金線)を試料として、市販の三次元光学プロファイラー(例えば、ZYGO社製NewView7100)を用いて表面粗さ(μm)を測定した。ここでは、各素線(Al合金線)に対して、85μm×64μmの長方形の領域について、算術平均粗さRa(μm)を求める。試料ごとに、合計7個の領域における算術平均粗さRaを調べ、合計7個の領域における算術平均粗さRaを平均した値を表面粗さ(μm)として、表17から表20に示す。
得られた各試料の被覆電線について、絶縁被覆を除去して導体のみとし、導体を構成する撚線又は圧縮撚線を解いて、中心素線の表面に付着する潤滑剤に由来するCの付着量を調べた。Cの付着量(質量%)は、SEM-EDX(エネルギー分散型X線分析)装置を用いて、電子銃の加速電圧を5kVとして測定した。その結果を表13から表16に示す。なお、被覆電線に備える導体を構成するAl合金線の表面に潤滑剤が付着している場合、絶縁被覆を除去する際に、Al合金線における絶縁被覆との接触箇所では、潤滑剤が絶縁被覆に付着して除去され、Cの付着量を適切に測定できない可能性がある。一方、被覆電線に備える導体を構成するAl合金線について、その表面におけるCの付着量を測定する場合、Al合金線における絶縁被覆と接触していない箇所を対象とすると、Cの付着量を精度よく測定できると考えられる。そこで、ここでは7本のAl合金線が同心撚りされてなる撚線又は圧縮撚線において、絶縁被覆に接触していない中心素線を測定対象とする。中心素線の外周を囲む外周素線のうち、絶縁被覆に接触していない箇所を測定対象にすることもできる。
得られた各試料の被覆電線について、絶縁被覆を除去して導体のみとし、導体を構成する撚線又は圧縮撚線を解いて、各素線の表面酸化膜を以下のようして測定した。ここでは、各素線(Al合金線)の表面酸化膜の厚さを調べる。試料ごとに合計7本の素線における表面酸化膜の厚さを調べ、この合計7本の素線における表面酸化膜の厚さを平均した値を表面酸化膜の厚さ(nm)として、表17から表20に示す。クロスセクションポリッシャー(CP)加工を施して、各素線の断面をとり、断面をSEM観察する。50nm程度を超える比較的厚い酸化膜については、このSEM観察像を用いて厚さを測定する。SEM観察において、50nm程度以下の比較的薄い酸化膜を有する場合には、別途、X線光電子分光分析(ESCA)によって深さ方向の分析(スパッタリングとエネルギー分散型X線分析(EDX)による分析とを繰り返す)を行って測定する。
・気泡
得られた各試料の被覆電線について、横断面をとり、導体(Al合金線から構成される撚線又は圧縮撚線、以下同様)を走査型電子顕微鏡(SEM)で観察して、表層及び内部の気泡、結晶粒径を調べた。ここでは、導体を構成する各Al合金線について、その表面から深さ方向に30μmまでの表層領域から、短辺長さ30μm×長辺長さ50μmである長方形の表層気泡測定領域をとる。つまり、一つの試料について、撚線を構成していた7本のAl合金線のそれぞれから、一つの表層気泡測定領域をとり、合計7個の表層気泡測定領域をとる。そして、各表層気泡測定領域に存在する気泡の合計断面積を求める。試料ごとに、合計7個の表層気泡測定領域における気泡の合計断面積を調べる。この合計7個の測定領域における気泡の合計断面積を平均した値を合計面積A(μm2)として、表13から表16に示す。
上述の長方形の表層気泡測定領域に代えて、厚さ30μmの環状の表層領域から、面積が1500μm2である扇型の気泡測定領域をとり、上述の長方形の表層気泡測定領域で評価した場合と同様にして、扇型の気泡測定領域における気泡の合計面積B(μm2)を求めた。その結果を表13から表16に示す。
なお、気泡の合計断面積の測定は、観察像に二値化処理などの画像処理を施して、処理像から気泡を抽出すると容易に行える。後述する晶出物についても同様である。
また、上記横断面において、JIS G 0551(鋼-結晶粒度の顕微鏡試験方法、2013年)に準拠して、SEM観察像に試験線を引き、各結晶粒において、試験線を分断する長さを結晶粒径とする(切断法)。試験線の長さは、この試験線によって10個以上の結晶粒が分断される程度とする。一つの横断面に対して、3本の試験線を引いて、各結晶粒径を求め、これらの結晶粒径を平均した値を平均結晶粒径(μm)として、表13から表16に示す。
得られた各試料の被覆電線について、横断面をとり、導体を金属顕微鏡で観察して、表層及び内部の晶出物を調べた。ここでは、導体を構成する各Al合金線について、その表面から深さ方向に50μmまでの表層領域から、短辺長さ50μm×長辺長さ75μmである長方形の表層晶出測定領域をとる。つまり、一つの試料について、撚線を構成していた7本のAl合金線のそれぞれから、一つの表層晶出測定領域をとり、合計7個の表層晶出測定領域をとる。そして、各表層晶出測定領域に存在する晶出物の面積及び個数をそれぞれ求める。表層晶出測定領域ごとに、晶出物の面積の平均を求める。つまり、一つの試料について、合計7個の測定領域における晶出物の面積の平均を求める。そして、試料ごとに、この合計7個の測定領域における晶出物の面積の平均を更に平均した値を平均面積A(μm2)として、表13から表16に示す。
また、試料ごとに、合計7個の表層晶出測定領域における晶出物の個数を調べ、合計7個の測定領域における晶出物の個数を平均した値を個数A(個)として、表13から表16に示す。
更に、各表層晶出測定領域に存在する晶出物のうち、面積が3μm2以下であるものの合計面積を調べ、各表層晶出測定領域に存在する全ての晶出物の合計面積に対する面積が3μm2以下であるものの合計面積の割合を求める。試料ごとに、合計7個の表層晶出測定領域における上記合計面積の割合を調べる。この合計7個の測定領域における上記合計面積の割合を平均した値を面積割合A(%)として表13から表16に示す。
得られた各試料の被覆電線について、絶縁被覆を除去して導体のみとし、導体100gあたりの水素の含有量(ml/100g)を測定した。その結果を表13から表16に示す。水素の含有量は、不活性ガス溶融法によって測定する。詳しくは、アルゴン気流中で黒鉛るつぼ中に試料を投入し、加熱溶融して水素を他のガスと共に抽出する。抽出したガスを分離カラムに通して水素を他のガスと分離し、熱伝導度検出器で測定して、水素の濃度を定量することで水素の含有量を求める。
得られた各試料の被覆電線について、特許文献1を参照して、耐衝撃性(J/m)を評価した。概略を述べると、評点間距離が1mである試料の先端に錘を取り付け、この錘を1m上方に持ち上げた後、自由落下させ、試料が断線しない最大の錘の質量(kg)を測定する。この錘の質量に重力加速度(9.8m/s2)と落下距離1mとをかけた積値を落下距離(1m)で除した値を耐衝撃性の評価パラメータ(J/m又は(N・m)/m)とする。求めた耐衝撃性の評価パラメータを導体断面積(ここでは0.35mm2)で除した値を単位面積当たりの耐衝撃性の評価パラメータ(J/m・mm2)として、表17から表20に示す。
得られた各試料の端子付き電線について、特許文献1を参照して、端子固着力(N)を評価した。概略を述べると、端子付き電線の一端に取り付けられた端子部を端子チャックで挟持し、被覆電線の他端の絶縁被覆を除去して、導体部分を導体チャックで挟持する。両チャックで両端を挟持した各試料の端子付き電線について、汎用の引張試験機を用いて破断時の最大荷重(N)を測定し、この最大荷重(N)を端子固着力(N)として評価する。求めた最大荷重を導体断面積(ここでは0.35mm2)で除した値を単位面積当たりの端子固着力(N/mm2)として、表17から表20に示す。
得られた各試料の被覆電線について、絶縁被覆を除去して導体のみとし、導体を構成する撚線又は圧縮撚線を解いて素線にばらして、任意の1本の素線を試料として塩水噴霧試験を行って、腐食の有無を目視確認にて調べた。その結果を表21に示す。塩水噴霧試験の条件は、5質量%濃度のNaCl水溶液を用い、試験時間を96時間とする。表21には、Cの付着量が15質量%である試料No.43、Cの付着量が0質量%であり、潤滑剤が実質的に付着していない試料No.114、Cの付着量が40質量%であり、潤滑剤が過剰に付着している試料No.117について、抜粋して示す。なお、試料No.1からNo.77の試料については、試料No.43と同様の結果であった。
表13から表15に示すように、時効試料群のAl合金線は、表面に潤滑剤が付着していると、特にCの付着量が1質量%以上であると(試料No.41(表14、表18)と、試料No.114(表16、表20)との比較参照)、表17から表19に示すように動摩擦係数が小さくなり易いといえる。表面粗さが比較的大きい場合でもCの付着量がより多いことで動摩擦係数が小さくなり易いといえる(例えば、試料No.22(表14,表18)参照)。また、表21に示すように、Al合金線の表面に潤滑剤が付着していることで耐食性に優れることが分かる。潤滑剤の付着量(Cの付着量)が多過ぎると、端子部との接続抵抗の増大を招くことから、ある程度少ないこと、特に30質量%以下が好ましいと考えられる。
以下の気泡、晶出物に関する事項については、長方形の測定領域Aを用いた評価結果、扇形の測定領域Bを用いた評価結果を参照する。
(1)表13から表15に示すように時効試料群のAl合金線は、表層に存在する気泡の合計面積が2.0μm2以下であり、表16に示す試料No.111,No.118,No.119のAl合金線に比較して少ない。この表層の気泡に着目して、同じ組成である試料No.20と試料No.111、試料No.47と試料No.118、試料No.71と試料No.119とを比較する。気泡が少ない試料No.20,No.47,No.71の方が、耐衝撃性に優れる上に(表18,表19)、屈曲回数が多く疲労特性にも優れることが分かる(表10,表11)。この理由の一つとして、表層に気泡が多い試料No.111,No.118,No.119のAl合金線では、衝撃や繰り返しの曲げを受けた場合に気泡が割れの起点となって破断し易くなったと考えられる。このことから、Al合金線の表層において、気泡を低減することで、耐衝撃性及び疲労特性を向上できるといえる。また、表13から表15に示すように時効試料群のAl合金線は、水素の含有量が表16に示す試料No.111,No.118,No.119のAl合金線に比較して少ない。このことから、気泡の一要因は水素であると考えられる。試料No.111,No.118,No.119では湯温が高く、溶湯中の溶存ガスが多く存在し易いと考えられ、この溶存ガスに由来する水素が多くなったと考えられる。これらのことから、上記表層の気泡を低減するには、鋳造過程で湯温を低めにすること(ここでは750℃未満)が効果的であるといえる。
その他、試料No.10(表13)と試料No.22からNo.24(表14)との比較などによって、Cuを含有すると、水素を低減し易いことが分かる。
また、この試験では、表13から表15の「面積割合」に示すように表層に存在する晶出物の多く(ここでは70%以上、多くは80%以上、更に85%以上)が3μm2以下であり、微細で均一的な大きさの晶出物であったことからも、割れの起点になり難かったと考えられる。
更に、この試験では、上述のように表層だけでなく内部に存在する晶出物も小さいことからも(40μm2以下)、晶出物が割れの起点になったり、晶出物を介して表層から内部に割れが進展したりすることを低減でき、耐衝撃性及び疲労特性に優れると考えられる。
この試験から、上記晶出物を微細にすると共にある程度存在させるには、特定の温度域での冷却速度をある程度速めにすること(ここでは0.5℃/秒超、更に1℃/秒以上、好ましくは25℃/秒未満、更に20℃/秒未満)が効果的であるといえる。
例えば、試験例1の合金の組成、線材の断面積、撚線の撚り合せ数、製造条件(湯温、鋳造時の冷却速度、熱処理時期、熱処理条件など)を適宜変更できる。
耐衝撃性及び疲労特性に優れるアルミニウム合金線として、以下の構成とすることができる。耐衝撃性及び疲労特性に優れるアルミニウム合金線の製造方法として、例えば、以下が挙げられる。
[付記1]
アルミニウム合金から構成されるアルミニウム合金線であって、
前記アルミニウム合金は、Mgを0.03質量%以上1.5質量%以下、Siを0.02質量%以上2.0質量%以下含有し、質量比でMg/Siが0.5以上3.5以下であり、残部がAl及び不可避不純物からなり、
動摩擦係数が0.8以下であるアルミニウム合金線。
[付記2]
表面粗さが3μm以下である[付記1]に記載のアルミニウム合金線。
[付記3]
前記アルミニウム合金線の表面に潤滑剤が付着しており、この潤滑剤に由来するCの付着量が0超30質量%以下である[付記1]又は[付記2]に記載のアルミニウム合金線。
[付記4]
前記アルミニウム合金線の横断面において、その表面から深さ方向に30μmまでの環状の表層領域から、1500μm2の扇型の気泡測定領域をとり、前記扇型の気泡測定領域に存在する気泡の合計断面積が2μm2以下である[付記1]から[付記3]のいずれか1つに記載のアルミニウム合金線。
[付記5]
前記アルミニウム合金線の横断面において、短辺長さが30μmであり、長辺長さが50μmである長方形の内部気泡測定領域をこの長方形の中心が前記アルミニウム合金線の中心に重なるようにとり、前記扇型の気泡測定領域に存在する気泡の合計断面積に対する前記内部気泡測定領域に存在する気泡の合計断面積の比が1.1以上44以下である[付記4]に記載のアルミニウム合金線。
[付記6]
水素の含有量が8.0ml/100g以下である[付記4]又は[付記5]に記載のアルミニウム合金線。
[付記7]
前記アルミニウム合金線の横断面において、その表面から深さ方向に50μmまでの環状の表層領域から、3750μm2の扇型の晶出測定領域をとり、前記扇型の晶出測定領域に存在する晶出物の平均面積が0.05μm2以上3μm2以下である[付記1]から[付記6]のいずれか1つに記載のアルミニウム合金線。
[付記8]
前記扇型の晶出測定領域に存在する晶出物の個数が10個超400個以下である[付記7]に記載のアルミニウム合金線。
[付記9]
前記アルミニウム合金線の横断面において、短辺長さが50μmであり、長辺長さが75μmである長方形の内部晶出測定領域をこの長方形の中心が前記アルミニウム合金線の中心に重なるようにとり、前記内部晶出測定領域に存在する晶出物の平均面積が0.05μm2以上40μm2以下である[付記7]又は[付記8]に記載のアルミニウム合金線。
[付記10]
前記アルミニウム合金の平均結晶粒径が50μm以下である[付記1]から[付記9]のいずれか1つに記載のアルミニウム合金線。
[付記11]
加工硬化指数が0.05以上である[付記1]から[付記10]のいずれか1つに記載のアルミニウム合金線。
[付記12]
前記アルミニウム合金線の表面酸化膜の厚さが1nm以上120nm以下である[付記1]から[付記11]のいずれか1つに記載のアルミニウム合金線。
[付記13]
前記アルミニウム合金は、更に、Fe、Cu、Mn、Ni、Zr、Cr、Zn、及びGaから選択される1種以上の元素をそれぞれ0質量%以上0.5質量%以下、合計で0質量%以上1.0質量%以下含有する[付記1]から[付記12]のいずれか1つに記載のアルミニウム合金線。
[付記14]
前記アルミニウム合金は、更に、0質量%以上0.05質量%以下のTi及び0質量%以上0.005質量%以下のBの少なくとも一方の元素を含有する[付記1]から[付記13]のいずれか1つに記載のアルミニウム合金線。
[付記15]
引張強さが150MPa以上であること、0.2%耐力が90MPa以上であること、破断伸びが5%以上であること、導電率が40%IACS以上であることから選択される一つ以上を満たす[付記1]から[付記14]のいずれか1つに記載のアルミニウム合金線。
[付記16]
[付記1]から[付記15]のいずれか1つに記載のアルミニウム合金線を複数撚り合わせてなるアルミニウム合金撚線。
[付記17]
撚りピッチが前記アルミニウム合金撚線の層心径の10倍以上40倍以下である[付記16]に記載のアルミニウム合金撚線。
[付記18]
導体と、前記導体の外周を覆う絶縁被覆とを備える被覆電線であって、
前記導体は、[付記16]又は[付記17]に記載のアルミニウム合金撚線を備える被覆電線。
[付記19]
[付記18]に記載の被覆電線と、前記被覆電線の端部に装着された端子部とを備える端子付き電線。
[付記20]
Mgを0.03質量%以上1.5質量%以下、Siを0.02質量%以上2.0質量%以下含有し、質量比でMg/Siが0.5以上3.5以下であり、残部がAl及び不可避不純物からなるアルミニウム合金の溶湯を鋳造して、鋳造材を形成する鋳造工程と、
前記鋳造材に塑性加工を施して中間加工材を形成する中間加工工程と、
前記中間加工材に伸線加工を施して伸線材を形成する伸線工程と、
前記伸線加工の途中又は前記伸線工程以降に熱処理を施す熱処理工程とを備え、
前記伸線工程では、表面粗さが3μm以下の伸線ダイスを用いるアルミニウム合金線の製造方法。
10 端子付き電線
2 導体
20 アルミニウム合金撚線
22 アルミニウム合金線(素線)
220 表層領域
222 表層気泡測定領域
224 気泡測定領域
22S 短辺
22L 長辺
P 接点
T 接線
C 直線
g 空隙
3 絶縁被覆
4 端子部
40 ワイヤバレル部
42 嵌合部
44 インシュレーションバレル部
S 試料
100 台座
110 錘
150 相手材
Claims (17)
- アルミニウム合金から構成されるアルミニウム合金線であって、
前記アルミニウム合金は、Mgを0.03質量%以上1.5質量%以下、Siを0.02質量%以上2.0質量%以下含有し、質量比でMg/Siが0.5以上3.5以下であり、残部がAl及び不可避不純物からなり、
動摩擦係数が0.8以下であるアルミニウム合金線。 - 表面粗さが3μm以下である請求項1に記載のアルミニウム合金線。
- 前記アルミニウム合金線の表面に潤滑剤が付着しており、この潤滑剤に由来するCの付着量が0超30質量%以下である請求項1又は請求項2に記載のアルミニウム合金線。
- 前記アルミニウム合金線の横断面において、その表面から深さ方向に30μmまでの表層領域から、短辺長さが30μmであり、長辺長さが50μmである長方形の表層気泡測定領域をとり、前記表層気泡測定領域に存在する気泡の合計断面積が2μm2以下である請求項1から請求項3のいずれか1項に記載のアルミニウム合金線。
- 前記アルミニウム合金線の横断面において、短辺長さが30μmであり、長辺長さが50μmである長方形の内部気泡測定領域をこの長方形の中心が前記アルミニウム合金線の中心に重なるようにとり、前記表層気泡測定領域に存在する気泡の合計断面積に対する前記内部気泡測定領域に存在する気泡の合計断面積の比が1.1以上44以下である請求項4に記載のアルミニウム合金線。
- 水素の含有量が8.0ml/100g以下である請求項4又は請求項5に記載のアルミニウム合金線。
- 前記アルミニウム合金線の横断面において、その表面から深さ方向に50μmまでの表層領域から、短辺長さが50μmであり、長辺長さが75μmである長方形の表層晶出測定領域をとり、前記表層晶出測定領域に存在する晶出物の平均面積が0.05μm2以上3μm2以下である請求項1から請求項6のいずれか1項に記載のアルミニウム合金線。
- 前記表層晶出測定領域に存在する晶出物の個数が10個超400個以下である請求項7に記載のアルミニウム合金線。
- 前記アルミニウム合金線の横断面において、短辺長さが50μmであり、長辺長さが75μmである長方形の内部晶出測定領域をこの長方形の中心が前記アルミニウム合金線の中心に重なるようにとり、前記内部晶出測定領域に存在する晶出物の平均面積が0.05μm2以上40μm2以下である請求項7又は請求項8に記載のアルミニウム合金線。
- 前記アルミニウム合金の平均結晶粒径が50μm以下である請求項1から請求項9のいずれか1項に記載のアルミニウム合金線。
- 加工硬化指数が0.05以上である請求項1から請求項10のいずれか1項に記載のアルミニウム合金線。
- 前記アルミニウム合金線の表面酸化膜の厚さが1nm以上120nm以下である請求項1から請求項11のいずれか1項に記載のアルミニウム合金線。
- 引張強さが150MPa以上であり、0.2%耐力が90MPa以上であり、破断伸びが5%以上であり、導電率が40%IACS以上である請求項1から請求項12のいずれか1項に記載のアルミニウム合金線。
- 請求項1から請求項13のいずれか1項に記載のアルミニウム合金線を複数撚り合わせてなるアルミニウム合金撚線。
- 撚りピッチが前記アルミニウム合金撚線の層心径の10倍以上40倍以下である請求項14に記載のアルミニウム合金撚線。
- 導体と、前記導体の外周を覆う絶縁被覆とを備える被覆電線であって、
前記導体は、請求項14又は請求項15に記載のアルミニウム合金撚線を備える被覆電線。 - 請求項16に記載の被覆電線と、前記被覆電線の端部に装着された端子部とを備える端子付き電線。
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DE112017005481.8T DE112017005481T5 (de) | 2016-10-31 | 2017-08-28 | Aluminiumlegierungsdraht, Aluminiumlegierungs-Litzendraht, ummantelter elektrischer Draht und mit einer Anschlussklemme ausgestatteter elektrischer Draht |
KR1020227004450A KR102544287B1 (ko) | 2016-10-31 | 2017-08-28 | 알루미늄 합금선, 알루미늄 합금 연선, 피복 전선, 및 단자 부착 전선 |
US16/346,479 US10522263B2 (en) | 2016-10-31 | 2017-08-28 | Aluminum alloy wire, aluminum alloy strand wire, covered electrical wire, and terminal-equipped electrical wire |
CN202110671182.5A CN113409989B (zh) | 2016-10-31 | 2017-08-28 | 铝合金线、铝合金绞合线、包覆电线以及带端子电线 |
CN201780067695.7A CN109923226B (zh) | 2016-10-31 | 2017-08-28 | 铝合金线、铝合金绞合线、包覆电线以及带端子电线 |
JP2018547163A JP7137759B2 (ja) | 2016-10-31 | 2017-08-28 | アルミニウム合金線、アルミニウム合金撚線、被覆電線、及び端子付き電線 |
KR1020197012661A KR102362938B1 (ko) | 2016-10-31 | 2017-08-28 | 알루미늄 합금선, 알루미늄 합금 연선, 피복 전선, 및 단자 부착 전선 |
US16/677,734 US10650936B2 (en) | 2016-10-31 | 2019-11-08 | Aluminum alloy wire, aluminum alloy strand wire, covered electrical wire, and terminal-equipped electrical wire |
US16/842,397 US10796811B2 (en) | 2016-10-31 | 2020-04-07 | Aluminum alloy wire, aluminum alloy strand wire, covered electrical wire, and terminal-equipped electrical wire |
US17/003,394 US11037695B2 (en) | 2016-10-31 | 2020-08-26 | Aluminum alloy wire, aluminum alloy strand wire, covered electrical wire, and terminal-equipped electrical wire |
US17/317,180 US11810687B2 (en) | 2016-10-31 | 2021-05-11 | Aluminum alloy wire, aluminum alloy strand wire, covered electrical wire, and terminal-equipped electrical wire |
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US16/677,734 Continuation US10650936B2 (en) | 2016-10-31 | 2019-11-08 | Aluminum alloy wire, aluminum alloy strand wire, covered electrical wire, and terminal-equipped electrical wire |
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WO2020045401A1 (ja) * | 2018-08-27 | 2020-03-05 | 古河電気工業株式会社 | アルミニウム合金材ならびにこれを用いた編組シールド線、導電部材、電池用部材、締結部品、バネ用部品、構造用部品およびキャブタイヤケーブル |
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JP6112438B1 (ja) | 2016-10-31 | 2017-04-12 | 住友電気工業株式会社 | アルミニウム合金線、アルミニウム合金撚線、被覆電線、及び端子付き電線 |
JP6112437B1 (ja) * | 2016-10-31 | 2017-04-12 | 住友電気工業株式会社 | アルミニウム合金線、アルミニウム合金撚線、被覆電線、及び端子付き電線 |
JP2021150230A (ja) * | 2020-03-23 | 2021-09-27 | 株式会社東芝 | 圧着判定方法 |
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JPWO2020045401A1 (ja) * | 2018-08-27 | 2020-09-03 | 古河電気工業株式会社 | アルミニウム合金材ならびにこれを用いた編組シールド線、導電部材、電池用部材、締結部品、バネ用部品、構造用部品およびキャブタイヤケーブル |
CN112534075A (zh) * | 2018-08-27 | 2021-03-19 | 古河电气工业株式会社 | 铝合金材料以及使用其的编织屏蔽线、导电构件、电池用构件、紧固部件、弹簧用部件、结构用部件及橡胶绝缘电缆 |
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KR102362938B1 (ko) | 2022-02-14 |
US20210272717A1 (en) | 2021-09-02 |
US20200234841A1 (en) | 2020-07-23 |
KR102544287B1 (ko) | 2023-06-15 |
US11810687B2 (en) | 2023-11-07 |
US10796811B2 (en) | 2020-10-06 |
KR20220025192A (ko) | 2022-03-03 |
US11037695B2 (en) | 2021-06-15 |
US20200395143A1 (en) | 2020-12-17 |
US10522263B2 (en) | 2019-12-31 |
KR20190080878A (ko) | 2019-07-08 |
DE112017005481T5 (de) | 2019-07-18 |
CN113409989B (zh) | 2023-02-21 |
US20190267152A1 (en) | 2019-08-29 |
JP7137759B2 (ja) | 2022-09-15 |
US20200075192A1 (en) | 2020-03-05 |
CN113409989A (zh) | 2021-09-17 |
CN109923226A (zh) | 2019-06-21 |
US10650936B2 (en) | 2020-05-12 |
JPWO2018079050A1 (ja) | 2019-09-12 |
CN109923226B (zh) | 2021-07-06 |
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