WO2009104615A1 - 銅合金材 - Google Patents

銅合金材 Download PDF

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WO2009104615A1
WO2009104615A1 PCT/JP2009/052718 JP2009052718W WO2009104615A1 WO 2009104615 A1 WO2009104615 A1 WO 2009104615A1 JP 2009052718 W JP2009052718 W JP 2009052718W WO 2009104615 A1 WO2009104615 A1 WO 2009104615A1
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mass
copper alloy
alloy material
strength
compound
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PCT/JP2009/052718
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English (en)
French (fr)
Japanese (ja)
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清慈 廣瀬
立彦 江口
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古河電気工業株式会社
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Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to EP09712614A priority Critical patent/EP2256219A4/en
Priority to CN200980105393XA priority patent/CN101946014A/zh
Priority to JP2009554332A priority patent/JPWO2009104615A1/ja
Publication of WO2009104615A1 publication Critical patent/WO2009104615A1/ja
Priority to US12/858,217 priority patent/US20100310413A1/en
Priority to US13/175,068 priority patent/US20110259480A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

Definitions

  • the present invention relates to a copper alloy material.
  • copper-based materials such as phosphor bronze, red brass, brass, etc., which are excellent in electrical conductivity and thermal conductivity, have been widely used as materials for electric / electronic devices.
  • copper-based materials such as phosphor bronze, red brass, brass, etc.
  • various properties are also required for copper-based materials applied thereto.
  • the main characteristics required of copper-based materials are mechanical properties, electrical conductivity, and bending formability to achieve product functions, and stress relaxation to obtain reliability during product use. Characteristics and fatigue properties are required.
  • high strength alloys such as titanium copper and beryllium copper having good fatigue strength have been used for members that require reliability such as fatigue properties.
  • High-strength alloys such as titanium copper and beryllium copper are more expensive than copper alloys such as phosphor bronze, and in beryllium copper, metal beryllium is harmful to the human body.
  • Alternative materials are desired.
  • Cu—Ni—Si alloys (Corson alloys), which are relatively inexpensive to manufacture and excellent in balance between strength and electrical conductivity, have attracted attention and have been used as copper alloys for connectors.
  • the Cu—Ni—Si based alloy is a precipitation type alloy that forms and precipitates precipitates composed of Ni and Si, and has a very high ability to strengthen.
  • the object of the present invention is to provide terminals, connectors, and switches for electrical and electronic equipment having high strength, excellent bending workability and stress relaxation resistance, and excellent fatigue characteristics. It is to provide a copper alloy material suitable for a relay or the like.
  • the present inventors have studied copper alloy materials suitable for electric / electronic component applications, and formed a precipitate-free zone (PFZ) near the crystal grain boundary in the copper alloy during aging treatment.
  • Precipitation zone is lower in strength than in the grains, so when processing or repeated stress is applied to copper alloy, deformation occurs preferentially and deteriorates bending workability and fatigue characteristics. It was found that it can be made harmless if it is narrowed.
  • PFZ precipitate-free zone
  • Ni is included in a range of 1.8 to 5.0 mass%
  • Si is included in a range of 0.3 to 1.7 mass%
  • the Ni / Si content ratio Ni / Si is 3.0 to 6.0.
  • W represents the width (nm) of the precipitation-free zone (PFZ)
  • L represents the particle diameter (nm) of the compound on the grain boundary)
  • ⁇ 2> The copper alloy material according to ⁇ 1>, further containing 0.01 to 0.20 mass% of Mg, ⁇ 3>
  • (II) Mn is 0.01 to 0.5 mass%
  • the Cu—Ni—Si based copper alloy material of the present invention is a copper alloy material having higher strength and superior bending workability, stress relaxation resistance and fatigue characteristics as compared with the prior art.
  • FIG. 1 is a transmission electron micrograph of the vicinity of a crystal grain boundary including a precipitation-free zone as an example of the copper alloy material of the present invention.
  • FIG. 2 is an explanatory diagram of how to determine the width W of the precipitation-free zone and the particle diameter L of the compound on the grain boundary defined in the present invention.
  • the copper alloy material means a copper alloy processed into a specific shape such as a plate material, a strip material, or a foil by a rolling process.
  • Ni 2 Si phase is mainly formed to improve strength and conductivity.
  • the Ni content is 1.8 to 5.0 mass%, preferably 2.0 to 4.8 mass%.
  • the reason for specifying in this way is that if the content is less than 1.8 mass%, sufficient strength as a copper alloy for connector use cannot be obtained, and if it is more than 5.0 mass%, the strength is increased during casting or hot working. This is because the formation of a compound that does not contribute to the improvement occurs, and the strength corresponding to the content cannot be obtained, and the hot workability is deteriorated and adversely affects.
  • the Si content is 0.3 to 1.7 mass%, preferably 0.35 to 1.6 mass%.
  • the reason for specifying in this way is that when the Si amount is less than 0.3 mass%, the strength improvement by the aging treatment is insufficient and sufficient strength cannot be obtained, and the Si content is more than 1.7 mass%.
  • the amount is too large, the same problem as in the case where the amount of Ni is large is caused, and the conductivity is lowered. Since Ni and Si mainly form a Ni 2 Si phase, there is an optimum ratio of Ni and Si in order to improve the strength.
  • the hot workability is deteriorated at 0.005 mass% or more, so the content is specified to be less than 0.005 mass%. In particular, less than 0.002 mass% is preferable.
  • Mg magnesium
  • the amount is 0.01-0.20 mass%.
  • Mg greatly improves the stress relaxation properties, but adversely affects bending workability.
  • the Mg content is preferably as large as 0.01 mass% or more, but if it exceeds 0.20 mass%, the bending workability does not satisfy the required characteristics.
  • it is 0.05 to 0.15 mass%.
  • tin (Sn) in the copper alloy.
  • the amount is 0.05 to 1.5 mass%. Sn interacts with Mg to improve the stress relaxation characteristics, but the effect is not as great as with Mg. If Sn is less than 0.05 mass%, the effect is not sufficiently exhibited, and if it exceeds 1.5 mass%, the conductivity is significantly lowered. Preferably, it is 0.1 to 0.7 mass%.
  • the copper alloy contains zinc (Zn).
  • Zn slightly improves the bending workability. By containing Zn in an amount of 0.2 to 1.5 mass%, even if Mg is added up to a maximum of 0.20 mass%, a level of bending workability that is practically satisfactory can be obtained.
  • Zn improves the adhesion and migration characteristics of Sn plating and solder plating. If the amount of Zn is less than 0.2 mass%, the effect cannot be sufficiently obtained, and if it exceeds 1.5 mass%, the conductivity is lowered. Preferably, it is 0.3 to 1.0 mass%.
  • the copper alloy may be any one of scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), molybdenum (Mo), and silver (Ag). Two or more kinds can be added in a total amount of 0.005 to 0.3 mass%. Sc, Y, Ti, Zr, Hf, V, and Mo have an effect of forming a compound with Ni or Si and suppressing the coarsening of the crystal grain size. The addition amount can be added in the above range which does not deteriorate the properties such as strength and conductivity. Ag improves heat resistance and strength, and at the same time, prevents coarsening of crystal grains and improves bending workability. If the Ag amount is less than 0.005 mass%, the effect cannot be sufficiently obtained, and even if added over 0.3 mass%, there is no adverse effect on the characteristics, but the cost increases. From these viewpoints, the content of Ag is preferably within the above range.
  • Manganese (Mn) has an effect of improving hot workability, and it is effective to add 0.01 to 0.5 mass% to such an extent that conductivity is not deteriorated.
  • Cobalt (Co) like Ni, has a function of forming a compound with Si to improve the strength, so it is preferable to contain 0.05 to 2.0 mass% of Co. If the content is less than 0.05 mass%, the effect cannot be sufficiently obtained. If the content exceeds 2.0 mass%, crystallization / precipitates that do not contribute to the strength exist after the solution treatment, and bending workability deteriorates. .
  • Chromium (Cr) precipitates finely in copper and contributes to strength improvement, and forms a compound with Si or Ni and Si, and the group of Sc, Y, Ti, Zr, Hf, V, and Mo described above. Similarly, there is an effect of suppressing the coarsening of the crystal grain size. When it is added, if less than 0.005 mass%, the effect cannot be sufficiently obtained, and if it exceeds 1.0 mass%, bending workability deteriorates.
  • the tensile strength TS in the rolling parallel direction (LD) of the copper alloy material having the above composition is defined. Since both hot rolling and cold rolling are performed in the same direction in the production process of the copper alloy material, the rolling directions are the same. In applications such as terminals, connectors, and relays, the strength of the copper alloy material is necessary to maintain the spring property, but the bending workability deteriorates when the strength is significantly improved by processing or the like. Further, when the Ni and Si contents are increased in the Cu—Ni—Si based alloy, the strength is increased, but even with the Ni and Si contents described above, the cost increases if they are increased unnecessarily.
  • Ni and Si contents suitable for each strength region exist within the above-described Ni and Si content ranges, and the formula (1) has been derived.
  • the Si content has an optimum region for the ratio of Ni and Si content as described above, and can be defined by the Ni content C as a representative.
  • the tensile strength TS is too small, it means that the contents of Ni and Si are large with respect to the strength, which increases the cost.
  • the tensile strength TS is too large, it means that the strength is remarkably improved by processing or the like, and the bending workability is deteriorated.
  • TS is obtained according to JIS Z 2241.
  • TS is preferably (130 ⁇ C + 350) ⁇ TS ⁇ (130 ⁇ C + 600).
  • the average crystal grain size d (mm) of the crystal grains of the base material of the copper alloy material is 0.001 ⁇ d ⁇ 0.020.
  • the reason for prescribing the average crystal grain size d to be 0.001 mm or more and 0.020 mm or less is that when the average crystal grain size d is less than 0.001 mm, the recrystallized structure is mixed (a structure in which crystal grains having different sizes are mixed).
  • the average crystal grain size d exceeds 0.020 mm, stress concentration near the grain boundary is promoted during bending, and the following precipitation-free zone (PFZ) and This is because the bending workability deteriorates with the compound on the grain boundary.
  • PFZ precipitation-free zone
  • the crystal grain size d is a value measured based on JIS H 0501 (cutting method).
  • the number of measurements for determining the crystal grain size d is 1000 or more.
  • the average crystal grain size d (mm) is preferably 0.001 ⁇ d ⁇ 0.015.
  • the non-precipitation zone (PFZ) is a region that is formed near the grain boundary in the course of aging treatment and no precipitate is present.
  • FIG. 1 is a transmission electron micrograph in the vicinity of a grain boundary including a precipitation-free zone of one example of the copper alloy material of the present invention.
  • the non-precipitation zone (PFZ) is an area where no precipitate is present, and thus is relatively softer than in the crystal grains. Therefore, when deformation or repetitive stress is applied to the copper alloy material, the deformation progresses preferentially, and becomes a starting point of cracking and a starting point of fatigue failure due to accumulation of dislocations. Therefore, the weakness of the copper alloy structure is reduced when the PFZ width W is narrow.
  • the width W (nm) of the precipitation-free zone is W ⁇ 150 (150 nm or less), the bending workability and fatigue characteristics are not greatly affected.
  • the PFZ width W is obtained by photographing a transmission electron micrograph at 50,000 magnifications in two fields around the grain boundary of a copper alloy plate with the (100) plane of the beam incident direction, and at five locations per field of view. The PFZ width is measured and set to the average value of a total of 10 locations. W is preferably 0 to 100 nm.
  • the compound on the crystal grain boundary is mainly an intermetallic compound, and is harder than in the crystal grain and the non-precipitated zone.
  • a difference in strength occurs between the hard compound and the surrounding structure, dislocations tend to accumulate in the copper alloy structure near the compound, and become the starting point of cracking and the starting point of fatigue failure . Therefore, the smaller the compound on the grain boundary, the less the brittleness of the copper alloy structure.
  • the average particle diameter L (nm) of the compound on the grain boundary is 10 ⁇ L ⁇ 800. If the average particle diameter L of the compound is 800 nm or less, the bending workability and the deterioration of fatigue characteristics are not greatly affected.
  • the average particle diameter L of the compound is preferably 500 nm or less.
  • the compound existing at the crystal grain boundary has an effect of suppressing the movement of the crystal grain and keeping the crystal grain size fine. Therefore, the particle diameter L is 10 nm or more, preferably 30 nm or more.
  • the average particle diameter L of the compound on the grain boundary is obtained by taking a transmission electron micrograph at 50000 magnifications at five fields with the grain boundary of the copper alloy material aligned with the (100) plane of the beam. The major axis and minor axis of one compound are measured, the average is the particle diameter of the compound, and the particle diameters of 20 compounds are averaged.
  • FIG. 2 is an explanatory view schematically showing how to obtain the width W of the precipitation-free zone and the particle diameter L of the compound on the grain boundary in the present invention.
  • 1 is a crystal grain boundary
  • 2 is a compound on the crystal grain boundary
  • 3 is a Ni 2 Si precipitate in the crystal grain.
  • the width W of the precipitation-free zone is obtained by measuring the distance from the crystal grain boundary 1 to the boundary of the range formed by one crystal grain.
  • the average particle diameter L of the compound on the grain boundary is obtained by measuring the major axis and minor axis of the compound 2 on the grain boundary, setting the average as the particle diameter of the compound, and further averaging the particle diameters of 20 compounds. Desired.
  • Crystal grains, precipitation-free zones, and grain boundary compounds interact with each other when a deformation or repeated stress is applied to a copper alloy. Therefore, it is not sufficient that the average crystal grain size d, the width W of the precipitation-free zone, and the average grain size L of the grain boundary compound satisfy the above-mentioned regulations. Can be relaxed.
  • the preferable manufacturing method of the copper alloy material which concerns on this invention is demonstrated.
  • Casting is performed by a general semi-continuous casting method, such as a so-called DC (direct chill) casting method.
  • the ingot is hot-rolled at a temperature of 600 to 1000 ° C. immediately after, for example, homogenization treatment at a temperature of 850 to 1000 ° C. for 0.5 to 6 hours.
  • cold rolling is performed in a timely manner.
  • Precipitates formed during cooling after hot rolling tend to be coarse, and coarse compounds of 1000 nm or more remain on the grain boundaries of the final product, which may deteriorate bending workability and fatigue characteristics.
  • dough rolling after chamfering the oxide film. In the dough rolling, it is preferable to perform rolling to a plate thickness that can obtain a predetermined processing rate in the cold processing after the next step.
  • the subsequent solution treatment is performed by determining the temperature according to the Ni content C. It is preferable to carry out in a range where the actual temperature Tst (° C.) of the material satisfies the equation (5). 54 ⁇ C + 625 ⁇ Tst ⁇ 54 ⁇ C + 725 (5)
  • the higher the solution treatment temperature the smaller the average particle diameter L of the precipitates on the grain boundaries, the narrower the width W of the precipitation-free zone, and the better solute state is obtained, and the aging in the subsequent steps. High strength can be obtained in the process.
  • Tst exceeds the upper limit formula, the crystal grains become coarse and the average crystal grain size d does not satisfy the above range, and the bending workability may be deteriorated.
  • Tst is less than the lower limit formula, a dislocation structure due to cold working in the raw rolling may remain and bend workability may deteriorate.
  • the subsequent aging treatment uniformly disperses and precipitates the Ni 2 Si compound in the copper alloy, thereby improving the strength and electrical conductivity. It is preferable to use a batch type furnace and hold at an actual temperature of 350 to 600 ° C. for 0.5 to 12 hours. If the temperature during the aging treatment is lower than 350 ° C., it takes a long time to obtain a sufficient amount of deposited Ni 2 Si, resulting in an increase in cost or insufficient tensile strength and electrical conductivity. If the temperature during the aging treatment is higher than 600 ° C., coarse Ni 2 Si is formed in the crystal grains and the strength is lowered, and the width W of the precipitation-free zone is expanded in the vicinity of the grain boundary. Therefore, bending workability and fatigue characteristics are improved.
  • the aging treatment may be performed twice because it has a function of reducing the width W of the precipitation-free zone.
  • the aging treatment temperature is divided into the temperature range 1: 350 to 450 ° C. and the temperature range 2: 450 to 600 ° C., and the temperature range 1 and the temperature range. It is preferable to perform the process in 2 once each. At this time, the order of performing the processing in the temperature range 1 and the temperature range 2 may be either first. It is desirable to carry out in a relatively long time of 4 to 12 hours in the temperature range 1 and in a relatively short time of 0.5 to 6 hours in the temperature range 2. In order to promote precipitation of the Ni 2 Si compound between the two aging treatments, cold rolling of 50% or less may be performed.
  • finish cold rolling is performed for the purpose of improving the tensile strength.
  • the tensile strength after the aging treatment is sufficient, it is not necessary to introduce finish cold rolling.
  • the rolling ratio of finish cold rolling is too high, bending workability is deteriorated and stress relaxation resistance is deteriorated. Therefore, the rolling rate of finish rolling is desirably 50% or less.
  • Low temperature annealing performed after finish rolling is performed for the purpose of restoring elongation, bending workability, and spring limit value while maintaining strength to some extent.
  • the low-temperature annealing step may be omitted. It is desirable to perform annealing in a short time of 5 to 60 seconds at an actual temperature of 300 to 600 ° C. If the temperature during annealing is lower than 300 ° C, the elongation, bending workability and recovery of the spring limit value may be insufficient, and if the temperature during annealing is higher than 600 ° C, strength may be reduced.
  • the copper alloy materials of Examples and Comparative Examples of the present invention are formed of copper alloys (alloys Nos. 1 to 25) having chemical compositions shown in Table 1 (the balance is Cu). These copper alloys are melted in a high-frequency melting furnace, cast into ingots having a thickness of 30 mm, a width of 120 mm, and a length of 150 mm, and then the ingots are heated to 980 ° C. and held at this temperature for 1 hour, It was hot-rolled to a thickness of 12 mm and quickly cooled. At this time, Alloy No. Regarding No.
  • alloy no. Regarding No. 19 since the amount of Ni was too large, alloy no. Regarding No. 20, since the amount of S was too large, alloy no. Regarding No. 21, since the amount of Si was too large, alloy no. No. 23 had too much Cr, so alloy no. Regarding 24 and 25, since the total amount of Zr, Ti, and Hf and the total amount of V, Mo, and Y were too large, cracks occurred during hot rolling and the subsequent steps were stopped.
  • both sides were cut 1.5 mm each to remove the oxide film, and then processed to a thickness of 0.16 to 0.50 mm by cold rolling. At this time, Alloy No. Since 22 had too much Sn, edge cracks occurred during cold rolling, and the subsequent steps were stopped. Thereafter, heat treatment was performed at 800 to 950 ° C. for 30 seconds, and immediately cooled at a cooling rate of 15 ° C./second or more.
  • Time aging treatment was applied.
  • a rolling rate of 0% means that no rolling is performed.
  • a heat treatment with two aging treatments was performed, or a heat treatment at 400 ° C. was performed for 4 hours in an inert gas atmosphere, and then for 2 hours at 500 ° C. Either heat treatment was performed, or heat treatment at 500 ° C. for 2 hours followed by heat treatment at 400 ° C. for 4 hours. Details of this will be described later.
  • finish rolling was performed at various rolling rates, and the final thickness was adjusted to 0.15 mm.
  • a low temperature annealing treatment was performed at 400 to 600 ° C. for 30 seconds to produce copper alloy materials of Examples and Comparative Examples, and the following various properties were evaluated.
  • the average crystal grain size of (a) was calculated based on the crystal grain size measured by the cutting method (JIS H 0501) defined by JIS.
  • the measurement cross section of the crystal grain size was measured in a cross section parallel to the final cold rolling direction.
  • the crystal structure of the copper alloy plate is magnified 1000 times with a scanning electron microscope to take a photograph, a 200 mm line segment is drawn on the photograph, the number n of crystal grains cut by the line segment is counted, and [200 mm / (n ⁇ 1000)].
  • the number of crystal grains cut by the line segment is less than 20
  • the number n of crystal grains cut by the line segment having a length of 200 mm is counted in a 500 ⁇ photograph, and obtained from the formula [200 mm / (n ⁇ 500)]. It was.
  • the crystal grain size d is shown by rounding the average of the four values of the major axis and the minor axis obtained in the cross sections A and B to an integer multiple of 0.005 mm.
  • the width of the precipitation-free zone in (b) was determined by taking two views of a transmission electron micrograph at a magnification of 50,000 times in the vicinity of the grain boundary of the copper alloy plate and aligning the incident direction of the beam with the (100) plane.
  • the PFZ widths of the places were measured, and the average value of a total of 10 places was defined as the width W of the precipitation-free zone and rounded to an integer multiple of 10 nm.
  • the particle diameter of the compound on the grain boundary in (c) is a total of 20 grains of a copper alloy plate taken at five fields of view at 50,000 times with the incident direction of the beam aligned with the (100) plane. The particle size of the compound was measured. The major axis and minor axis of one compound were measured, and the average was taken as the particle diameter of the compound. Furthermore, the particle diameter of 20 compounds was averaged, and the average particle diameter L of the compound on the grain boundary of the copper alloy plate was rounded to an integer multiple of 10 nm.
  • the tensile strength of (d) was determined according to JIS Z 2241 using a No. 5 test piece described in JIS Z 2201. A test was performed in a direction parallel to the rolling direction. The electrical conductivity of (e) was determined according to JIS H 0505.
  • a 90 ° bending jig with an inner bending radius of 0.15 mm is used, and the ratio R / t of bending radius (mm) / plate thickness (mm) is 1.0.
  • a 90 ° W bending test was conducted, and a case where no crack occurred in the bent portion was judged as good ( ⁇ ), and a case where a crack occurred was judged as poor ( ⁇ ).
  • G For stress relaxation resistance, a cantilever type of the Japan Copper and Brass Association Technical Standard (JBMA-T309) is adopted, and the load stress is set so that the maximum surface stress is 80% of the proof stress. The stress relaxation rate was obtained by holding in a bath for 1000 hours.
  • the fatigue characteristics of (h) were collected in accordance with JIS Z 2273 by performing a double-bending plane bending fatigue test.
  • the test piece was a strip with a width of 10 mm, and the parallel direction of the rolling and the length direction of the test piece were matched.
  • the test conditions were the thickness t (mm) of the test piece, the maximum bending stress ⁇ B (MPa) applied to the surface of the test piece, the piece amplitude ⁇ (mm) applied to the test piece, the Young's modulus E (130 GPa) of the alloy, and the fulcrum ⁇
  • the test piece was installed so as to satisfy the above relationship, the maximum bending stress ⁇ B was set to 500 (MPa), and the number N of times when the sample broke was measured. The test and measurement were performed four times, the average value of the number N was determined, and the fatigue life of each test piece was determined.
  • Examples 1-1 to 1-6 and Comparative Examples 1-7 to 1-10 are alloy Nos. 1 and Examples 2-1 and 2-2 are alloy nos. 2 is subjected to different heat treatment and rolling conditions within the above-mentioned range. No. 3 to 18 are alloy nos. It was created from 3-18.
  • the conditions of Examples 1-1 to 1-6 and Comparative Examples 1-7 to 1-10 were as follows. The conditions not described in Examples 1-2 to 1-6 and Comparative Examples 1-7 to 1-10 were the same as those in Example 1-1. ⁇ Process of Example> Example 1-1: After solution treatment at 875 ° C., aging treatment was performed at 500 ° C.
  • Example 1-2 In place of the aging treatment of Example 1-1, two aging treatments were performed in which treatment at 400 ° C. for 4 hours was followed by treatment at 500 ° C. for 2 hours.
  • Example 1-3 Instead of the aging treatment of Example 1-1, two aging treatments were performed in which treatment at 500 ° C. for 2 hours was followed by treatment at 400 ° C. for 4 hours.
  • Example 1-4 Solution treatment was performed at 885 ° C.
  • Example 1-6 A 10% cold rolling treatment was performed after the solution treatment and before the aging treatment.
  • Comparative Example 1-7 Solution treatment was performed at 950 ° C. Comparative Example 1-8: Solution treatment was performed at 800 ° C. Comparative Example 1-9: The solution treatment was carried out at a treatment temperature of 800 ° C. with a lower temperature increase rate. Comparative Example 1-10: The finish rolling rate was 60%.
  • Comparative Example 1-7 since the value of the crystal grain size d was too large, the bending workability deteriorated. In Comparative Example 1-8, since the value of the width W of the precipitation-free zone was too large, bending workability and fatigue characteristics deteriorated. In Comparative Example 1-9, since the particle diameter L of the compound on the grain boundary was too large, bending workability and fatigue characteristics deteriorated. In Comparative Example 1-10, the bending workability deteriorated because the tensile strength was too high.
  • Comparative Example 14 since the Ni concentration and the Si concentration were too low, the fatigue life was short and the stress relaxation resistance was inferior. In Comparative Example 15, since the Mg concentration was too high, bending workability deteriorated. In Comparative Examples 16 and 17, the conductivity decreased because the Mn and Zn concentrations were too high. In Comparative Example 18, since the Co concentration was too high, the bending workability was poor and the fatigue life was also deteriorated.

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PCT/JP2009/052718 2008-02-18 2009-02-17 銅合金材 WO2009104615A1 (ja)

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Application Number Priority Date Filing Date Title
EP09712614A EP2256219A4 (en) 2008-02-18 2009-02-17 COPPER ALLOY MATERIAL
CN200980105393XA CN101946014A (zh) 2008-02-18 2009-02-17 铜合金材料
JP2009554332A JPWO2009104615A1 (ja) 2008-02-18 2009-02-17 銅合金材
US12/858,217 US20100310413A1 (en) 2008-02-18 2010-08-17 Copper alloy material
US13/175,068 US20110259480A1 (en) 2008-02-18 2011-07-01 Copper alloy material

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JP2008-036694 2008-02-18
JP2008036694 2008-02-18

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WO (1) WO2009104615A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102859016A (zh) * 2010-04-07 2013-01-02 古河电气工业株式会社 铜合金伸展材、铜合金部件和铜合金伸展材的制造方法
US20130167988A1 (en) * 2010-07-07 2013-07-04 Mitsubishi Shindoh Co., Ltd. Cu-Ni-Si-BASED COPPER ALLOY PLATE HAVING EXCELLENT DEEP DRAWING WORKABILITY AND METHOD OF MANUFACTURING THE SAME
JP2013204083A (ja) * 2012-03-28 2013-10-07 Kobe Steel Ltd 曲げ加工性及び耐応力緩和特性に優れる電気電子部品用銅合金板
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CN102859016B (zh) * 2010-04-07 2015-04-08 古河电气工业株式会社 铜合金伸展材、铜合金部件和铜合金伸展材的制造方法
US20130167988A1 (en) * 2010-07-07 2013-07-04 Mitsubishi Shindoh Co., Ltd. Cu-Ni-Si-BASED COPPER ALLOY PLATE HAVING EXCELLENT DEEP DRAWING WORKABILITY AND METHOD OF MANUFACTURING THE SAME
US9435016B2 (en) * 2010-07-07 2016-09-06 Mitsubishi Shindoh Co., Ltd. Cu-Ni-Si-based copper alloy plate having excellent deep drawing workability and method of manufacturing the same
JP2013204083A (ja) * 2012-03-28 2013-10-07 Kobe Steel Ltd 曲げ加工性及び耐応力緩和特性に優れる電気電子部品用銅合金板
JP2016199792A (ja) * 2015-04-10 2016-12-01 古河電気工業株式会社 ばね用銅合金線材、該ばね用銅合金線材の製造方法、並びにばね、該ばねの製造方法
JP2021098887A (ja) * 2019-12-20 2021-07-01 Ｊｘ金属株式会社 積層造形用金属粉末及び該金属粉末を用いて作製した積層造形物

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