WO2011105585A1 - アルミニウム合金導体 - Google Patents
アルミニウム合金導体 Download PDFInfo
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- WO2011105585A1 WO2011105585A1 PCT/JP2011/054398 JP2011054398W WO2011105585A1 WO 2011105585 A1 WO2011105585 A1 WO 2011105585A1 JP 2011054398 W JP2011054398 W JP 2011054398W WO 2011105585 A1 WO2011105585 A1 WO 2011105585A1
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- intermetallic compound
- aluminum alloy
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- alloy conductor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/023—Alloys based on aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
- B21C1/003—Drawing materials of special alloys so far as the composition of the alloy requires or permits special drawing methods or sequences
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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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 conductor used as a conductor of an electric wiring body.
- the cross-sectional area of a pure aluminum conductor needs to be about 1.5 times that of a pure copper conductor, but the weight is still about half that of copper. is there.
- the above% IACS represents the electrical conductivity when the resistivity 1.7241 ⁇ 10 ⁇ 8 ⁇ m of universal standard annealed copper (International Annealed Copper Standard) is 100% IACS.
- a material having higher strength has better fatigue characteristics. Therefore, a high-strength aluminum conductor may be applied.
- the wire harness is required to be easily handled (installation work on the vehicle body) at the time of installation, the tensile break elongation is generally 10. Often, a dull material (annealed material) that can be secured at least% is used.
- the aluminum conductor used for the electric wiring body of the moving body is a material having excellent bending fatigue resistance in addition to the strength required for handling and mounting, and the conductivity necessary for flowing a large amount of electricity. Is required.
- Patent Document 1 Representative examples of aluminum conductors used for electric wiring bodies of moving bodies include those described in Patent Documents 1 to 4.
- the inventions described in any of the patent documents have further problems to be solved. Since the invention of Patent Document 1 does not perform finish annealing, it cannot secure the flexibility required for the mounting work on the vehicle body.
- the invention of Patent Document 2 discloses finish annealing, and the conditions are such that the intermetallic compound can be controlled so as to improve the bending fatigue resistance and conductivity while maintaining excellent flexibility. Is different. Since the invention of Patent Document 3 contains a large amount of Si, the intermetallic compound cannot be appropriately controlled, causing disconnection during wire drawing.
- the invention of Patent Document 4 contains 0.01 to 0.5% of antimony (Sb), and is a technology that is being replaced with an alternative product from the viewpoint of environmental load.
- Sb antimony
- An object of the present invention is to provide an aluminum alloy conductor having sufficient electrical conductivity and tensile strength, and excellent in flexibility, bending fatigue resistance, and the like.
- the inventors have made various studies, and for the aluminum alloy to which a specific additive element is added, by controlling the production conditions such as casting cooling rate, intermediate annealing, and finish annealing, the particle diameters and areas of the three types of intermetallic compounds. It has been found that an aluminum alloy conductor having excellent bending fatigue resistance, strength, flexibility and electrical conductivity can be produced by controlling the rate, and the present invention has been completed based on this finding.
- the present invention provides the following solutions.
- (1) Aluminum containing Fe of 0.4 to 1.5 mass%, Mg of 0.1 to 0.3 mass%, and Si of 0.04 to 0.3 mass%, the balance being Al and inevitable impurities
- An alloy conductor There are three types of intermetallic compounds A, B, C in the conductor, The particle size of the intermetallic compound A is in the range of 0.1 ⁇ m to 2 ⁇ m, The particle size of the intermetallic compound B is in the range of 0.03 ⁇ m or more and less than 0.1 ⁇ m, The particle size of the intermetallic compound C is in the range of 0.001 ⁇ m or more and less than 0.03 ⁇ m, The area ratio a of the intermetallic compound A, the area ratio b of the intermetallic compound B, and the area ratio c of the intermetallic compound C in an arbitrary range in the conductor are 1% ⁇ a ⁇ 9%, An aluminum alloy conductor characterized by satisfying 1% ⁇ b ⁇ 6%, 1% ⁇ c
- An aluminum alloy conductor comprising the balance Al and inevitable impurities,
- intermetallic compounds A, B, C in the conductor,
- the particle size of the intermetallic compound A is in the range of 0.1 ⁇ m to 2 ⁇ m
- the particle size of the intermetallic compound B is in the range of 0.03 ⁇ m or more and less than 0.1 ⁇ m
- the particle size of the intermetallic compound C is in the range of 0.001 ⁇ m or more and less than 0.03 ⁇ m
- the area ratio a of the intermetallic compound A, the area ratio b of the intermetallic compound B, and the area ratio c of the intermetallic compound C in an arbitrary range in the conductor are 1% ⁇ a ⁇ 9%
- An aluminum alloy conductor characterized by satisfying 1% ⁇ b ⁇ 8.5%, 1% ⁇ c ⁇ 10%
- a continuous energization heat treatment including a rapid heating and rapid cooling process is performed at the end of the conductor manufacturing process, so that the crystal grain size in the vertical cross section in the wire drawing direction is 1 to 10 ⁇ m (1) or The aluminum alloy conductor according to (2).
- the aluminum alloy conductor according to any one of (1) to (3) which has a tensile strength of 100 MPa or more and a conductivity of 55% IACS or more.
- the aluminum alloy conductor according to any one of (1) to (5) which has a recrystallized structure.
- the aluminum alloy conductor of the present invention is excellent in strength, flexibility and electrical conductivity, and is useful as a battery cable, harness or motor conductor mounted on a moving body, doors and trunks that require excellent bending fatigue resistance, It can be suitably used for a bonnet or the like.
- a preferred first embodiment of the present invention contains 0.4 to 1.5 mass% of Fe, 0.1 to 0.3 mass% of Mg, and 0.04 to 0.3 mass% of Si,
- An aluminum alloy conductor composed of the balance Al and inevitable impurities There are three types of intermetallic compounds A, B, C in the conductor,
- the particle size of the intermetallic compound A is in the range of 0.1 ⁇ m to 2 ⁇ m
- the particle size of the intermetallic compound B is in the range of 0.03 ⁇ m or more and less than 0.1 ⁇ m
- the particle size of the intermetallic compound C is in the range of 0.001 ⁇ m or more and less than 0.03 ⁇ m
- the area ratio a of the intermetallic compound A, the area ratio b of the intermetallic compound B, and the area ratio c of the intermetallic compound C in an arbitrary range in the conductor are 1% ⁇ a ⁇ 9%, 1% ⁇ b ⁇ 6%, 1% ⁇ c ⁇ 10% is satisfied.
- the reason why the Fe content is set to 0.4 to 1.5 mass% is mainly to use various effects of the Al—Fe intermetallic compound. Fe dissolves only 0.05 mass% in aluminum at 655 ° C., and is even less at room temperature. The remainder crystallizes or precipitates as an intermetallic compound such as Al—Fe, Al—Fe—Si, Al—Fe—Si—Mg. This crystallized product or precipitate acts as a crystal grain refining material, and improves strength and bending fatigue resistance. If the Fe content is too small, these effects are insufficient, and if it is too much, the crystallized material becomes coarse and the wire drawing workability is poor, the desired bending fatigue resistance cannot be obtained, and the flexibility also decreases. . Moreover, it will be in a supersaturated solid solution state and electrical conductivity will also fall.
- the Fe content is preferably 0.6 to 1.3 mass%, more preferably 0.8 to 1.1 mass%.
- the Mg content is set to 0.1 to 0.3 mass% because Mg is strengthened by solid solution in the aluminum base material, and part of it forms precipitates with Si. This is because strength, bending fatigue resistance, and heat resistance can be improved. If the content of Mg is too small, the effect is insufficient, and if it is too large, the conductivity and flexibility are decreased. Moreover, when there is much content of Mg, yield strength will become excess, a moldability and twist property will deteriorate, and workability will worsen.
- the Mg content is preferably 0.15 to 0.28 mass%, more preferably 0.2 to 0.28 mass%.
- the Si content is set to 0.04 to 0.3 mass% because, as described above, Si forms a compound with Mg to improve strength, bending fatigue resistance, and heat resistance. It is for showing. If the Si content is too small, the effect is insufficient, while if it is too large, the conductivity and flexibility are lowered, the moldability and twistability are deteriorated, and the workability is deteriorated. In addition, the precipitation of Si alone during the heat treatment process during the production of the wire causes disconnection.
- the Si content is preferably 0.1 to 0.3 mass%, more preferably 0.15 to 0.25 mass%.
- Fe is 0.4 to 1.5 mass%
- Mg is 0.1 to 0.3 mass%
- Si is 0.04 to 0.3 mass%
- Zr is 0. 0.01 to 0.4 mass%
- an aluminum alloy conductor comprising the balance Al and inevitable impurities
- intermetallic compounds A, B, C in the conductor
- the particle size of the intermetallic compound A is in the range of 0.1 ⁇ m to 2 ⁇ m
- the particle size of the intermetallic compound B is in the range of 0.03 ⁇ m or more and less than 0.1 ⁇ m
- the particle size of the intermetallic compound C is in the range of 0.001 ⁇ m or more and less than 0.03 ⁇ m
- the area ratio a of the intermetallic compound A, the area ratio b of the intermetallic compound B, and the area ratio c of the intermetallic compound C in an arbitrary range in the conductor are 1% ⁇ a ⁇ 9%, 1% ⁇ b ⁇ 8.5%, 1% ⁇ c
- the alloy composition includes 0.01 to 0.4 mass% of Zr in addition to the alloy composition of the first embodiment described above.
- Zr forms an intermetallic compound with Al, and forms a solid solution in Al, thereby contributing to the improvement of the strength and heat resistance of the aluminum alloy conductor. If the Zr content is too small, the effect cannot be expected. If the Zr content is too large, the melting temperature becomes high and it becomes difficult to form a drawn wire. In addition, the conductivity and flexibility are lowered, and the bending fatigue resistance is also deteriorated.
- the Zr content is preferably 0.1 to 0.35 mass%, more preferably 0.15 to 0.3 mass%.
- Other alloy compositions and their actions are the same as in the first embodiment described above.
- the aluminum alloy conductor of the present invention the aluminum having the desired excellent bending fatigue resistance, strength, and conductivity by defining the size (particle diameter) and area ratio of the intermetallic compound in addition to the above components.
- An alloy conductor can be obtained.
- the present invention contains three kinds of intermetallic compounds having different particle diameters at a predetermined area ratio.
- an intermetallic compound is particles, such as a crystallized substance and a precipitate, which exist in crystal grains.
- the crystallized material is mainly formed during melt casting, and the precipitate is formed by intermediate annealing and finish annealing, for example, particles such as Al—Fe, Al—Fe—Si, and Al—Zr.
- the area ratio represents the ratio of intermetallic compounds contained in the present alloy in terms of area, and can be calculated as described in detail below based on a photograph observed by TEM.
- the intermetallic compound A is mainly composed of Al—Fe, and a part thereof includes Al—Fe—Si, Al—Zr and the like. These intermetallic compounds work as crystal grain refiners and improve strength and bending fatigue resistance.
- the reason why the area ratio a of the intermetallic compound A is 1% ⁇ a ⁇ 9% is that these effects are insufficient if the amount is too small, and if the amount is too large, disconnection is likely to occur due to the intermetallic compound. Flexural fatigue characteristics cannot be obtained and flexibility is also reduced.
- the intermetallic compound B is mainly composed of Al—Fe—Si and Al—Zr. These intermetallic compounds improve strength and bending fatigue resistance by precipitation.
- the area ratio b of the intermetallic compound B is 1% ⁇ b ⁇ 6% in the first embodiment and 1% ⁇ b ⁇ 8.5% in the second embodiment. This is because it is insufficient, and if it is too much, it causes disconnection due to excessive precipitation. Also, flexibility is reduced.
- the intermetallic compound C increases the strength and greatly improves the bending fatigue resistance. The reason why the area ratio c of the intermetallic compound C is set to 1% ⁇ c ⁇ 10% is that if the amount is too small, these effects are insufficient, and if the amount is too large, disconnection is caused by excessive precipitation. Also, flexibility is reduced.
- the respective alloy compositions are set in the above-described ranges. There is a need. And it is realizable by controlling appropriately a casting cooling rate, intermediate annealing temperature, finish annealing conditions, etc.
- the casting cooling rate is an average cooling rate from the start of solidification of the aluminum alloy ingot to 200 ° C.
- a method for changing the cooling rate for example, the following three methods can be cited. That is, (1) change the size (thickness) of the iron mold, (2) provide a water cooling mold on the lower surface of the mold and forcibly cool (the cooling speed also changes by changing the amount of water), (3) the amount of molten metal cast Change. If the casting cooling rate is too slow, the Al—Fe-based crystallized product becomes coarse, and the desired structure cannot be obtained, and cracking tends to occur. If it is too fast, excessive dissolution of Fe occurs and the desired structure cannot be obtained, leading to a decrease in conductivity. In some cases, casting cracks can also occur.
- the casting cooling rate is usually 1 to 20 ° C./second, preferably 5 to 15 ° C./second.
- the intermediate annealing temperature is the temperature at which heat treatment is performed during wire drawing.
- the intermediate annealing is performed mainly to regain the flexibility of the wire that has been hardened by wire drawing. If the intermediate annealing temperature is too low, the recrystallization is insufficient and the yield strength becomes excessive, so that flexibility cannot be secured, and there is a high possibility that the wire will not be obtained due to the subsequent wire drawing. When too high, it will be in an over-annealed state, recrystallization grain coarsening will occur and flexibility will fall remarkably, and the possibility that a wire will not be obtained due to breakage in the subsequent wire drawing will increase.
- the intermediate annealing temperature is usually 300 to 450 ° C, preferably 350 to 450 ° C.
- the time for the intermediate annealing is usually 30 minutes or more. This is because if it is less than 30 minutes, the time required for the formation and growth of recrystallized grains is insufficient, and the flexibility of the wire cannot be recovered. Preferably it is 1 to 6 hours.
- the average cooling rate from the heat treatment temperature during intermediate annealing to 100 ° C. is not particularly specified, but is preferably 0.1 to 10 ° C./min.
- the finish annealing is performed, for example, by continuous energization heat treatment in which annealing is performed by Joule heat generated from itself by passing an electric current through a wire that passes through two electrode wheels.
- the continuous energization heat treatment includes rapid heating and rapid cooling steps, and can be annealed by controlling the wire temperature and time. Cooling is performed by passing the wire continuously through water after rapid heating. If the wire temperature during annealing is too low or too high, or if one or both of the annealing times are too short or too long, the desired structure cannot be obtained.
- the wire temperature during annealing is too low, if one or both of the annealing time is too short, the necessary flexibility when mounting on the vehicle is not obtained, if the wire temperature during annealing is too high, In one or both of cases where the annealing time is too long, the strength is lowered and the bending fatigue resistance is also deteriorated. That is, using the mathematical expression represented by the wire temperature y (° C.) and the annealing time x (seconds), 24x ⁇ 0.6 +402 ⁇ y ⁇ 17x ⁇ 0.6 within the range of 0.03 ⁇ x ⁇ 0.55. It is necessary that the annealing conditions satisfy +502.
- the wire temperature represents the temperature immediately before passing through the water, which is the highest in the wire.
- finish annealing includes rapid heating and quenching processes in addition to continuous energization heat treatment, for example, running annealing in which the wire continuously anneals through an annealing furnace maintained at a high temperature, and the wire in the magnetic field. It may be induction heating that passes and anneals continuously.
- the annealing conditions are not the same as those for continuous energization heat treatment because the atmosphere and heat transfer coefficient are different, but even in the case of running annealing and induction heating, including these rapid heating and quenching processes, the prescribed intermetallic compound
- finish annealing conditions thermal history
- the aluminum alloy conductor of the present invention having a precipitation state can be obtained.
- the crystal grain size in the vertical cross section in the wire drawing direction of the aluminum alloy conductor is 1 to 10 ⁇ m.
- the reason for this is that if the particle size is too small, the partially recrystallized structure remains and the tensile elongation at break is remarkably reduced, and if it is too large, a coarse structure is formed and the deformation behavior becomes non-uniform, and similarly the tensile break This is because the elongation is lowered and the strength is significantly lowered.
- the crystal grain size is preferably 1 to 8 ⁇ m.
- the aluminum alloy conductor of the present invention has a tensile strength (TS) of 100 MPa or more and a conductivity of 55% IACS or more, preferably a tensile strength of 100 to 180 MPa and a conductivity of 55 to 65% IACS, more preferably tensile.
- the strength is 100 to 170 MPa and the conductivity is 57 to 63% IACS.
- Tensile strength and electrical conductivity have contradictory properties. The higher the tensile strength, the lower the electrical conductivity, and conversely, pure aluminum with a low tensile strength has a higher electrical conductivity.
- the conductivity is desirably 55% IACS or more.
- the aluminum alloy conductor of the present invention has sufficient flexibility. This can be obtained by performing the above-described finish annealing.
- the tensile elongation at break is used as an index of flexibility, preferably 10% or more. The reason for this is that, if the tensile elongation at break is too small, it is difficult to handle the electrical wiring body (for example, the mounting work to the vehicle body) as described above. In addition, if the tensile elongation at break is too large, the strength is insufficient and weak at the time of handling, which may cause disconnection.
- the tensile elongation at break is more preferably 10% to 40%, still more preferably 10 to 30%.
- the aluminum alloy conductor of the present invention includes [1] melting, [2] casting, [3] hot or cold processing (groove roll processing, etc.), [4] wire drawing, [5] heat treatment (intermediate annealing), It can be manufactured through steps of [6] wire drawing and [7] heat treatment (finish annealing).
- the aluminum alloy conductor of the present invention produced by heat treatment as described above has a recrystallized structure.
- the recrystallized structure is a structure state composed of crystal grains with few lattice defects such as dislocations introduced by plastic working. By having a recrystallized structure, tensile elongation at break and electrical conductivity are recovered, and sufficient flexibility can be obtained.
- Examples 1 to 14 Comparative Examples 101 to 114, 201, 202 Fe, Mg, Si and Al, or Fe, Mg, Si, Zr and Al in amounts (mass%) shown in Table 1-1 and Table 2-1, using a Properti type continuous casting and rolling mill, Rolling was performed while continuously casting with a water-cooled mold to obtain a rod of about 10 mm ⁇ .
- the casting cooling rate at this time is 1 to 20 ° C./second (including 0.2 ° C./second and 50 ° C./second in the comparative example).
- the surface is peeled to 9 to 9.5 mm ⁇ , and this is drawn to 2.6 mm ⁇ .
- the cold-drawn processed material was heated to 300 to 450 ° C. (including 200 ° C. and 550 ° C. in the comparative example) for 0.5 to 4 hours (
- the intermediate annealing was performed (including 0.1 hour), and in Examples 1 to 12, Comparative Examples 101 to 114, 201, and 202, up to 0.31 mm ⁇ , and in Example 13 to 0.37 mm ⁇ .
- wire drawing was performed to 0.43 mm ⁇ .
- continuous energization heat treatment was performed at a temperature of 477 to 629 ° C. (including 465 ° C. in the comparative example) for a time of 0.03 to 0.54 seconds. The temperature was measured with a fiber-type radiation thermometer (manufactured by Japan Sensor Co., Ltd.) immediately above the water surface where the temperature of the wire became highest.
- (A) Crystal grain size The cross section of the specimen cut out perpendicular to the wire drawing direction was filled with resin, and after mechanical polishing, electrolytic polishing was performed.
- the electrolytic polishing conditions are: an ethanol solution containing 20% perchloric acid, a liquid temperature of 0 to 5 ° C., a voltage of 10 V, a current of 10 mA, and a time of 30 to 60 seconds.
- anodic finishing was performed using 2% borohydrofluoric acid under the conditions of a voltage of 20 V, a current of 20 mA, and a time of 2 to 3 minutes. This structure was photographed with an optical microscope of 200 to 400 times, and the particle size was measured by a crossing method.
- an average particle size was obtained by arbitrarily drawing a straight line on the photographed photo, and measuring the number of intersections of the length of the straight line and the grain boundary. The particle size was evaluated by changing the length and number of lines so that 50 to 100 particles could be counted.
- (B) Dimension (particle diameter) and area ratio of intermetallic compound The wires of Examples and Comparative Examples were made into thin films by an electrolytic polishing thin film method (twin jet polishing method), and a magnification of 6000 using a transmission electron microscope (TEM). An arbitrary range was observed at ⁇ 30000 times.
- an electron beam was focused on the intermetallic compound to detect an intermetallic compound such as an Al—Fe, Al—Fe—Si, or Al—Zr system.
- the size of the intermetallic compound was judged from the scale of the photographed photo, and the shape was calculated by converting it into an equivalent volume sphere.
- the area ratios a, b, and c of the intermetallic compounds are about 5 to 10 for the intermetallic compound A, 20 to 50 for the intermetallic compound B, and about the intermetallic compound C based on the photographed photographs.
- the area ratio is calculated by using the sample thickness of the thin piece as a reference thickness of 0.15 ⁇ m. If the sample thickness is different from the reference thickness, convert the sample thickness to the reference thickness, that is, by multiplying the area ratio calculated based on the photographed (reference thickness / sample thickness) The area ratio can be calculated. In this example and the comparative example, the sample thickness was calculated by observing the interval of the equal thickness stripes observed from the photograph, and was about 0.15 ⁇ m in all the samples.
- (C) Tensile strength (TS) and tensile elongation at break Three pieces each were tested according to JIS Z 2241 and the average value was determined.
- the strain amplitude can be determined by the wire diameter of the wire rod 1 and the bending radii of the bending jigs 2 and 3 shown in FIG. 1, the wire diameter of the wire rod 1 and the bending radii of the bending jigs 2 and 3 are arbitrarily set and bent. It is possible to conduct a fatigue test. By using a double-bending bending fatigue tester manufactured by Fujii Seiki Co., Ltd. (currently Fujii Co., Ltd.) and using a jig that gives a bending strain of ⁇ 0.17% to the wire, repeated bending is performed. The number of return breaks was measured. The number of repeated ruptures was measured four by four and the average value was determined. As shown in the explanatory view of FIG.
- the wire 1 was inserted with a gap of 1 mm between the bending jigs 2 and 3, and repeatedly moved in such a manner as to be along the jigs 2 and 3.
- One end of the wire was fixed to a holding jig 5 so that it could be bent repeatedly, and a weight 4 of about 10 g was hung from the other end. Since the holding jig 5 moves during the test, the wire 1 fixed to the holding jig 5 also moves and can be bent repeatedly. The repetition is performed under the condition of 1.5 Hz (1.5 reciprocations per second), and when the wire specimen 1 breaks, the weight 4 falls and stops counting.
- the number of times of opening and closing per day is 10 and the use for 15 years is assumed, the number of times of opening and closing is 54750 times (calculated as 365 days a year).
- the actually used electric wire is not a single wire but has a stranded wire structure, and since the coating process is performed, the burden on the electric wire conductor becomes a fraction.
- the number of repeated fractures of 60000 times or more that can ensure sufficient bending fatigue resistance as an evaluation value for a single wire is preferred, and more preferably 80000 times or more.
- Comparative Examples 101 to 107 the additive component of the aluminum alloy is outside the scope of the present invention.
- Fe is too small, so that there are few intermetallic compounds A and B, and the tensile strength and the number of repeated fractures are poor.
- Comparative Example 102 since there was too much Fe, it disconnected during the wire drawing process.
- Comparative Example 103 since there is too little Mg, there are few intermetallic compounds C, and the number of times of repeated fracture is bad.
- Comparative Example 104 since there is too much Mg, there are many intermetallic compounds C, and the number of repeated fractures and electrical conductivity are bad.
- Comparative Example 105 since there is too little Si, there are few intermetallic compounds C, and the number of times of repeated fracture is bad. In the comparative example 106, since there was too much Si, it disconnected during the wire drawing process. In Comparative Example 7, since there is too much Zr, there are many intermetallic compounds B, and the electrical conductivity and the number of repeated fractures are poor. Comparative Examples 108 to 114 and Comparative Examples 201 to 202 indicate that the area ratio of the intermetallic compound in the aluminum alloy conductor is out of the range of the present invention or is broken during the production. Here, an example is shown in which the aluminum alloy conductor defined by the present invention is not obtained depending on the production conditions of the aluminum alloy.
- Comparative Example 108 the finish annealing was not performed, so the wire was broken during the wire drawing.
- Comparative Example 109 the casting cooling rate is too high, the intermetallic compound A is small, the intermetallic compound B is large, and the electrical conductivity and the number of repeated fractures are poor.
- Comparative Examples 110 to 112 since the finish annealing was not performed, the wire was broken during the wire drawing.
- Comparative Example 113 since it was in an unannealed state due to insufficient softening in the final annealing step and no intermetallic compound was observed, the tensile elongation at break was poor.
- Comparative Example 114 since the finish annealing temperature was too high, the amount of intermetallic compound C was small, and the tensile strength, the number of repeated breaks, and the tensile break elongation were poor. Comparative Examples 201 to 202 are examples in which finish annealing was performed using a batch annealing furnace, but the amount of intermetallic compound C was small and the number of repeated fractures was poor. On the other hand, in Examples 1 to 14, aluminum alloy conductors excellent in tensile strength, electrical conductivity, tensile fracture elongation (flexibility), and number of repeated fractures (flexural fatigue resistance) were obtained.
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Abstract
Description
アルミニウムの比重は銅の約1/3、アルミニウムの導電率は銅の約2/3(純銅を100%IACSの基準とした場合、純アルミニウムは約66%IACS)であり、純アルミニウムの導体に純銅の導体と同じ電流を流すためには、純アルミニウムの導体の断面積を純銅の導体の約1.5倍にする必要があるが、それでも重量では銅に比べて約半分と有利な点がある。
なお、上記の%IACSとは、万国標準軟銅(International Annealed Copper Standard)の抵抗率1.7241×10-8Ωmを100%IACSとした場合の導電率を表したものである。
一般に強度の高い材料ほど疲労特性は良好と言われている。そこで、強度の高いアルミニウム導体を適用すればよいが、ワイヤーハーネスはその設置時の取り回し(車体への取り付け作業)がしやすいことが要求されているために、一般的には引張破断伸びが10%以上確保できる鈍し材(焼鈍材)が使われていることが多い。
特許文献1の発明は、仕上げ焼鈍を行なっていないため、車体での取り付け作業時に必要な柔軟性が確保できない。
特許文献2の発明は、仕上げ焼鈍の開示があるが、その条件は、優れた柔軟性を保持したまま、耐屈曲疲労特性や導電率等を向上させるように金属間化合物を制御可能な条件とは異なる。
特許文献3の発明は、Siを多く含んでいるため、金属間化合物を適切に制御することができず、伸線加工などの際に断線の原因となる。
特許文献4の発明は、アンチモン(Sb)を0.01~0.5%含んでおり、環境負荷の観点から、代替製品に置き換えられつつある技術である。
(1)Feを0.4~1.5mass%と、Mgを0.1~0.3mass%と、Siを0.04~0.3mass%とを含有し、残部Alと不可避不純物からなるアルミニウム合金導体であって、
前記導体中に3種類の金属間化合物A、B、Cが存在し、
前記金属間化合物Aの粒子径は0.1μm以上2μm以下の範囲であり、
前記金属間化合物Bの粒子径は0.03μm以上0.1μm未満の範囲であり、
前記金属間化合物Cの粒子径は0.001μm以上0.03μm未満の範囲であり、
前記導体中の任意の範囲における、前記金属間化合物Aの面積率a、前記金属間化合物Bの面積率b、および前記金属間化合物Cの面積率cが、それぞれ1% ≦ a ≦ 9%、1% ≦ b ≦ 6%、1% ≦ c ≦ 10%を満足することを特徴とするアルミニウム合金導体。
(2)Feを0.4~1.5mass%と、Mgを0.1~0.3mass%と、Siを0.04~0.3mass%と、Zrを0.01~0.4mass%とを含有し、残部Alと不可避不純物からなるアルミニウム合金導体であって、
前記導体中に3種類の金属間化合物A、B、Cが存在し、
前記金属間化合物Aの粒子径は0.1μm以上2μm以下の範囲であり、
前記金属間化合物Bの粒子径は0.03μm以上0.1μm未満の範囲であり、
前記金属間化合物Cの粒子径は0.001μm以上0.03μm未満の範囲であり、
前記導体中の任意の範囲における、前記金属間化合物Aの面積率a、前記金属間化合物Bの面積率b、および前記金属間化合物Cの面積率cが、それぞれ1% ≦ a ≦ 9%、1% ≦ b ≦ 8.5%、1% ≦ c ≦ 10%を満足することを特徴とするアルミニウム合金導体。
(3)前記導体の製造工程の最後に急熱、急冷の工程を含む連続通電熱処理を施されることにより、伸線方向の垂直断面における結晶粒径が1~10μmとなされる(1)または(2)に記載のアルミニウム合金導体。
(4)引張強度が100MPa以上、及び導電率が55%IACS以上である(1)~(3)のいずれか1項に記載のアルミニウム合金導体。
(5)引張破断伸びが10%以上である(1)~(4)のいずれか1項に記載のアルミニウム合金導体。
(6)再結晶組織を有する(1)~(5)のいずれか1項に記載のアルミニウム合金導体。
(7)前記導体が移動体内で、バッテリーケーブル、ハーネス、またはモータ用線材として用いられることを特徴とする(1)~(6)のいずれか1項に記載のアルミニウム合金導体。
(8)前記導体が車両、電車、または航空機に用いられることを特徴とする(1)~(7)のいずれか1項に記載のアルミニウム合金導体。
前記導体中に3種類の金属間化合物A、B、Cが存在し、
前記金属間化合物Aの粒子径は0.1μm以上2μm以下の範囲であり、
前記金属間化合物Bの粒子径は0.03μm以上0.1μm未満の範囲であり、
前記金属間化合物Cの粒子径は0.001μm以上0.03μm未満の範囲であり、
前記導体中の任意の範囲における、前記金属間化合物Aの面積率a、前記金属間化合物Bの面積率b、および前記金属間化合物Cの面積率cが、それぞれ1% ≦ a ≦ 9%、1% ≦ b ≦ 6%、1% ≦ c ≦ 10%を満足する。
前記導体中に3種類の金属間化合物A、B、Cが存在し、
前記金属間化合物Aの粒子径は0.1μm以上2μm以下の範囲であり、
前記金属間化合物Bの粒子径は0.03μm以上0.1μm未満の範囲であり、
前記金属間化合物Cの粒子径は0.001μm以上0.03μm未満の範囲であり、
前記導体中の任意の範囲における、前記金属間化合物Aの面積率a、前記金属間化合物Bの面積率b、および前記金属間化合物Cの面積率cが、それぞれ1% ≦ a ≦ 9%、1% ≦ b ≦ 8.5%、1% ≦ c ≦ 10%を満足する。
その他の合金組成とその作用については上述の第1の実施態様と同様である。
本発明は前記第1及び第2の実施態様に示すように粒子径の異なる3種類の金属間化合物をそれぞれ所定の面積率で含有する。ここで、金属間化合物とは、結晶粒内に存在する、晶出物、析出物などの粒子である。主として、晶出物は溶解鋳造時に形成され、析出物は中間焼鈍及び仕上げ焼鈍で形成される、例えば、Al-Fe、Al-Fe-Si、Al-Zr等の粒子である。なお、面積率は本合金に含まれる金属間化合物の割合を面積で表したものであり、TEMにより観察した写真を基に、以下に詳述するようにして算出できる。
金属間化合物Aは主にAl-Feにより構成され、一部にAl-Fe-Si、Al-Zr等が含まれる。これらの金属間化合物は結晶粒の微細化材として働くと共に、強度、及び耐屈曲疲労特性を向上させる。金属間化合物Aの面積率aを1% ≦ a ≦ 9%としたのは、少なすぎるとこれらの効果が不十分であり、多すぎると金属間化合物を起因として断線が起こりやすく、目的の耐屈曲疲労特性が得られず、柔軟性も低下する。
金属間化合物Bは主にAl-Fe-Si、Al-Zrにより構成される。これらの金属間化合物は析出により強度、及び耐屈曲疲労特性を向上させる。金属間化合物Bの面積率bを第1の実施態様では1% ≦ b ≦ 6%、第2の実施態様では1% ≦ b ≦ 8.5%としたのは、少なすぎるとこれらの効果が不十分であり、多すぎると析出過剰により断線の原因となるためである。また柔軟性も低下する。
金属間化合物Cは、強度を高め、耐屈曲疲労特性を大幅に向上させる。金属間化合物Cの面積率cを1% ≦ c ≦ 10%としたのは、少なすぎるとこれらの効果が不十分であり、多すぎると析出過剰により断線の原因となるためである。また柔軟性も低下する。
なお、仕上げ焼鈍は連続通電熱処理の他に、急熱、急冷過程を含む、例えば、高温に保持した焼鈍炉中を線材が連続的に通過して焼鈍させる走間焼鈍や、磁場中を線材が連続的に通過して焼鈍させる誘導加熱でもよい。雰囲気や熱伝達率が異なるため焼鈍条件は連続通電熱処理と同一条件ではないが、これらの急熱、急冷過程を含む、走間焼鈍や誘導加熱の場合であっても、所定の金属間化合物の析出状態を有してなる本発明のアルミニウム合金導体が得られるように、代表例としての前記の連続通電熱処理における焼鈍条件を参考に仕上げ焼鈍条件(熱履歴)を適切に制御することで、本発明のアルミニウム合金導体を作製することができる。
本発明ではアルミニウム合金導体の伸線方向の垂直断面における結晶粒径を1~10μmとする。この理由は、粒径が小さすぎると部分再結晶組織が残存して引張破断伸びが著しく低下するためであり、大きすぎると粗大な組織を形成して変形挙動が不均一となり、同様に引張破断伸びが低下、さらに強度が著しく低下するためである。結晶粒径は、好ましくは1~8μmである。
本発明のアルミニウム合金導体は、引張強度(TS)が100MPa以上、及び導電率が55%IACS以上であり、好ましくは引張強度が100~180MPa及び導電率が55~65%IACS、より好ましくは引張強度が100~170MPa及び導電率が57~63%IACSである。
引張強度と導電率は相反する性質のものであり、引張強度が高いほど導電率が低く、逆に引張強度が低い純アルミニウムは導電率が高い。アルミニウム合金導体を考えた場合、引張強度が100MPa未満では、取り扱いを含めて強度不足であり、工業用導体として使用することが難しい。動力線に用いる場合には数十A(アンペア)の高電流が流れるため、導電率は55%IACS以上であることが望まれる。
本発明のアルミニウム合金導体は、十分な柔軟性を有する。これは前述の仕上げ焼鈍を行なうことにより得ることができる。柔軟性の指標として前述の通り、引張破断伸びを用い、好ましくは10%以上とする。この理由は、引張破断伸びが小さすぎると前述の通り電気配線体設置時の取り回し(例えば車体への取り付け作業)がしにくくなるためである。また、引張破断伸びが大きすぎると強度不足となり取り回し時に弱々しく、断線の原因になりうるため、50%以下であることが望ましい。引張破断伸びはより好ましくは10%~40%であり、更に好ましくは10~30%である。
本発明のアルミニウム合金組成を得るには、Fe、Mg、Si及びAl、またはFe、Mg、Si、Zr及びAlを所望の濃度となるような分量で溶製する。
次いで、例えば、鋳造輪とベルトを組み合わせたプロペルチ式の連続鋳造圧延機を用いて、溶湯を水冷した鋳型で連続的に鋳造しながら圧延を行ない、約10mmφの棒材とする。このときの鋳造冷却速度は上述の通り通常1~20℃/秒である。鋳造及び熱間圧延は、鋳造冷却速度を1~20℃/秒としたビレット鋳造、及び押出法などにより行なってもよい。
次いで、表面の皮むきを実施して、9~9.5mmφとし、これを伸線加工する。ここで、伸線加工前の導体断面積をA0、伸線加工後の導体断面積をA1とすると、η=ln(A0/A1)で表される加工度は、1以上6以下が望ましい。1未満であると、次工程の熱処理時、再結晶粒が粗大化し強度及び引張破断伸びが著しく低下し、断線の原因にもなる。6を越えると、加工硬化しすぎて伸線加工が困難となり、伸線加工中に断線するなど品質の面で問題がある。線材表面の皮むきは、行なうことによって表面の清浄化がなされるが、行なわなくてもよい。
冷間伸線した加工材に中間焼鈍を施す。中間焼鈍の条件は上述の通り通常300~450℃30分以上である。
さらに伸線加工を施す。この際も加工度は前述の理由により1以上6以下が望ましい。
冷間伸線した加工材に連続通電熱処理により仕上げ焼鈍を行なう。焼鈍条件は上述の通り線材温度y(℃)、焼鈍時間x(秒)で表される数式を用いると、0.03≦x≦0.55の範囲で24x-0.6+402 ≦ y ≦ 17x-0.6+502を満たす。
Fe、Mg、Si及びAl、またはFe、Mg、Si、Zr及びAlを表1-1及び表2-1に示す量(質量%)で、プロペルチ式の連続鋳造圧延機を用いて、溶湯を水冷した鋳型で連続的に鋳造しながら圧延を行ない、約10mmφの棒材とした。このときの鋳造冷却速度は1~20℃/秒(比較例では0.2℃/秒、50℃/秒を含む)である。
次いで、表面の皮むきを実施して、9~9.5mmφとし、これを伸線加工して、2.6mmφとする。次に表1-1及び表2-1に示すように、この冷間伸線した加工材に温度300~450℃(比較例では200℃、550℃を含む)で0.5~4時間(比較例では0.1時間を含む)の中間焼鈍を施し、更に、実施例1~12、比較例101~114、201、202では0.31mmφまで、実施励13では0.37mmφまで、実施励14では0.43mmφまで伸線加工を行った。
最後に仕上げ焼鈍として連続通電熱処理を温度477~629℃(比較例では465℃を含む)、時間0.03~0.54秒行なった。温度はファイバ型放射温度計(ジャパンセンサー株式会社製)で線材の温度が最も高くなる水面直上の温度を測定した。
伸線方向に垂直に切り出した供試材の横断面を樹脂で埋め、機械研磨後、電解研磨を行った。電解研磨条件は、研磨液が過塩素酸20%のエタノール溶液、液温は0~5℃、電圧は10V、電流は10mA、時間は30~60秒である。次いで、結晶粒コントラストを得るため、2%ホウフッ化水素酸を用いて、電圧20V、電流20mA、時間2~3分の条件でアノーダイジング仕上げを行なった。この組織を200~400倍の光学顕微鏡で撮影し、交差法による粒径測定を行った。具体的には、撮影された写真に任意に直線を引いて、その直線の長さと粒界が交わる数を測定して平均粒径を求めた。なお、粒径は50~100個が数えられるように直線の長さと本数を変えて評価した。
(b)金属間化合物の寸法(粒子径)及び面積率
実施例および比較例の線材を電解研磨薄膜法(ツインジェット研磨法)にて薄膜にして、透過電子顕微鏡(TEM)を用い、倍率6000~30000倍で任意の範囲を観察した。次いで、エネルギー分散型X線検出器(EDX)を用いて、金属間化合物に電子線を絞り、Al-Fe、Al-Fe-Si、Al-Zr系等の金属間化合物を検出した。
金属間化合物の寸法は撮影された写真のスケールから判断し、形状を等体積球相当に換算して算出した。金属間化合物の面積率a、b、cは、撮影された写真を基に、金属間化合物Aについては約5~10個、金属間化合物Bについては20~50個、金属間化合物Cについては50~100個をカウントできる範囲を設定して、それぞれの金属間化合物の大きさ及び個数から金属間化合物の面積を算出して、ぞれぞれの金属間化合物の面積をカウント対象とした範囲の面積で割って求めた。
面積率は上記薄片の試料厚さを0.15μmを基準厚さとして算出している。試料厚さが基準厚さと異なる場合、試料厚さを基準厚さに換算して、つまり、(基準厚さ/試料厚さ)を撮影された写真を基に算出した面積率にかけることによって、面積率を算出できる。本実施例および比較例では試料厚さは写真から観察された等厚縞の間隔を観測することにより算出し、すべての試料においてほぼ0.15μmであった。
(c)引張強度(TS)及び引張破断伸び
JIS Z 2241に準じて各3本ずつ試験し、その平均値を求めた。
(d)導電率(EC)
長さ300mmの試験片を20℃(±0.5℃)に保持した恒温漕中で、四端子法を用いて比抵抗を各3本ずつ測定し、その平均導電率を算出した。端子間距離は200mmとした。
(e)繰返破断回数
耐屈曲疲労特性の基準として、常温におけるひずみ振幅は±0.17%とした。耐屈曲疲労特性はひずみ振幅によって変化する。ひずみ振幅が大きい場合疲労寿命は短くなり、ひずみ振幅が小さい場合疲労寿命は長くなる。ひずみ振幅は図1記載の線材1の線径と曲げ冶具2、3の曲率半径により決定することができるため、線材1の線径と曲げ冶具2、3の曲率半径は任意に設定して屈曲疲労試験を実施することが可能である。
藤井精機株式会社(現 株式会社フジイ)製の両振屈曲疲労試験機を用い、線材に±0.17%の曲げ歪みが与えられる治具を使用して、繰り返し曲げを実施することにより、繰返破断回数を測定した。繰返破断回数は各4本ずつ測定し、その平均値を求めた。図1の説明図に示すように、線材1を、曲げ治具2及び3の間を1mm空けて挿入し、冶具2及び3に沿わせるような形で繰り返し運動をさせた。線材の一端は繰り返し曲げが実施できるよう押さえ冶具5に固定し、もう一端には約10gの重り4をぶら下げた。試験中は押さえ冶具5が動くため、それに固定されている線材1も動き、繰り返し曲げが実施できる。繰り返しは1.5Hz(1秒間に往復1.5回)の条件で行い、線材の試験片1が破断すると、重り4が落下し、カウントを停止する仕組みになっている。
1日あたりの開閉回数を10回とし15年間の使用を想定した場合、開閉回数は54750回となる(1年365日として計算)。実際に使用される電線は単線ではなく、撚り線構造となり、さらに被覆処理がされているために電線導体への負担は数分の一となる。単線での評価値として十分な耐屈曲疲労特性が確保できる60000回以上の繰返破断回数が好ましく、より好ましくは80000回以上である。
比較例101~107ではアルミニウム合金の添加成分が本発明の範囲外である。比較例101では、Feが少なすぎるため、金属間化合物AおよびBが少なく、引張強度、繰返破断回数が悪い。比較例102では、Feが多すぎるため、伸線加工中に断線した。比較例103では、Mgが少なすぎるため、金属間化合物Cが少なく、繰返破断回数が悪い。比較例104では、Mgが多すぎるため、金属間化合物Cが多く、繰返破断回数、導電率が悪い。比較例105では、Siが少なすぎるため、金属間化合物Cが少なく、繰返破断回数が悪い。比較例106では、Siが多すぎるため、伸線加工中に断線した。比較例7では、Zrが多すぎるため、金属間化合物Bが多く、導電率及び繰返破断回数が悪い。
比較例108~114および比較例201~202は、アルミニウム合金導体中の金属間化合物の面積率が本発明の範囲外であるか、製造中に断線したものを示す。ここでは、アルミニウム合金の製造条件によって本発明の規定するアルミニウム合金導体が得られなかった例を示す。比較例108では、仕上げ焼鈍を行わなかったため、伸線加工中に断線した。比較例109では、鋳造冷却速度が速すぎて、金属間化合物Aが少なく、金属間化合物Bが多くなり、導電率、繰返破断回数が悪い。比較例110~112では、仕上げ焼鈍を行わなかったため、伸線加工中に断線した。比較例113では仕上げ焼鈍工程での軟化不足が原因で未焼鈍状態となり、金属間化合物が観察されなかったため、引張破断伸びが悪い。比較例114では、仕上げ焼鈍温度が高すぎたために、金属間化合物Cが少なく、引張強度、繰返破断回数、及び引張破断伸びが悪い。比較例201~202はバッチ式焼鈍炉を用いて仕上げ焼鈍を行なった例であるが、金属間化合物Cが少なく、繰返破断回数が悪い。
これに対し実施例1~14では、引張強度、導電率、引張破断伸び(柔軟性)、繰返破断回数(耐屈曲疲労特性)に優れたアルミニウム合金導体が得られた。
2、3 曲げ治具
4 重り
5 押さえ冶具
Claims (8)
- Feを0.4~1.5mass%と、Mgを0.1~0.3mass%と、Siを0.04~0.3mass%とを含有し、残部Alと不可避不純物からなるアルミニウム合金導体であって、
前記導体中に3種類の金属間化合物A、B、Cが存在し、
前記金属間化合物Aの粒子径は0.1μm以上2μm以下の範囲であり、
前記金属間化合物Bの粒子径は0.03μm以上0.1μm未満の範囲であり、
前記金属間化合物Cの粒子径は0.001μm以上0.03μm未満の範囲であり、
前記導体中の任意の範囲における、前記金属間化合物Aの面積率a、前記金属間化合物Bの面積率b、および前記金属間化合物Cの面積率cが、それぞれ1% ≦ a ≦ 9%、1% ≦ b ≦ 6%、1% ≦ c ≦ 10%を満足することを特徴とするアルミニウム合金導体。 - Feを0.4~1.5mass%と、Mgを0.1~0.3mass%と、Siを0.04~0.3mass%と、Zrを0.01~0.4mass%とを含有し、残部Alと不可避不純物からなるアルミニウム合金導体であって、
前記導体中に3種類の金属間化合物A、B、Cが存在し、
前記金属間化合物Aの粒子径は0.1μm以上2μm以下の範囲であり、
前記金属間化合物Bの粒子径は0.03μm以上0.1μm未満の範囲であり、
前記金属間化合物Cの粒子径は0.001μm以上0.03μm未満の範囲であり、
前記導体中の任意の範囲における、前記金属間化合物Aの面積率a、前記金属間化合物Bの面積率b、および前記金属間化合物Cの面積率cが、それぞれ1% ≦ a ≦ 9%、1% ≦ b ≦ 8.5%、1% ≦ c ≦ 10%を満足することを特徴とするアルミニウム合金導体。 - 前記導体の製造工程の最後に急熱、急冷の工程を含む連続通電熱処理を施されることにより、伸線方向の垂直断面における結晶粒径が1~10μmとなされる請求項1または請求項2に記載のアルミニウム合金導体。
- 引張強度が100MPa以上、及び導電率が55%IACS以上である請求項1~3のいずれか1項に記載のアルミニウム合金導体。
- 引張破断伸びが10%以上である請求項1~4のいずれか1項に記載のアルミニウム合金導体。
- 再結晶組織を有する請求項1~5のいずれか1項に記載のアルミニウム合金導体。
- 前記導体が移動体内で、バッテリーケーブル、ハーネス、またはモータ用線材として用いられることを特徴とする請求項1~6のいずれか1項に記載のアルミニウム合金導体。
- 前記導体が車両、電車、または航空機に用いられることを特徴とする請求項1~7のいずれか1項に記載のアルミニウム合金導体。
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WO2013146762A1 (ja) * | 2012-03-29 | 2013-10-03 | 大電株式会社 | 微結晶金属導体及びその製造方法 |
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JP2018070915A (ja) * | 2016-10-25 | 2018-05-10 | 矢崎総業株式会社 | アルミニウム素線、並びにそれを用いたアルミニウム電線及びワイヤーハーネス |
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JP5607855B1 (ja) * | 2013-03-29 | 2014-10-15 | 古河電気工業株式会社 | アルミニウム合金線材、アルミニウム合金撚線、被覆電線、ワイヤーハーネスおよびアルミニウム合金線材の製造方法 |
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