WO2010126046A1 - Cu-Ni-Si-Mg-BASED ALLOY HAVING IMPROVED ELECTRICAL CONDUCTIVITY AND BENDABILITY - Google Patents
Cu-Ni-Si-Mg-BASED ALLOY HAVING IMPROVED ELECTRICAL CONDUCTIVITY AND BENDABILITY Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/08—Alloys based on copper with lead as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/10—Alloys based on copper with silicon as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
Definitions
- the present invention relates to a Cu—Ni—Si—Mg based alloy suitable as a conductive spring material for connectors, terminals, relays, switches and the like.
- Copper alloys for electronic materials used for terminals, connectors, and the like are required to have both high strength, high electrical conductivity, and thermal conductivity as basic characteristics. In addition to these characteristics, bending workability, stress relaxation resistance, heat resistance, adhesion to plating, etching workability, press punching, and corrosion resistance are required. From the viewpoint of high strength and high conductivity, the amount of age-hardened copper alloys has increased in recent years as an alloy for electronic materials, replacing solid solution strengthened copper alloys represented by conventional phosphor bronze, brass, etc. Yes.
- Mg is more easily oxidized than other additive elements, and therefore reacts with oxygen in the molten metal to become an oxide and float on the molten metal. Therefore, considering the amount of Mg loss due to oxidation, Mg is usually added excessively.
- the Ni—Si—Mg compound (precipitate X) is a primary crystal in this alloy system, it first crystallizes in the cast ingot.
- the conventional Cu—Ni—Si -The Mg component of the Mg-based alloy is in a state of being dissolved in the base material, and is usually not present as the precipitate X.
- the presence of Mg inhibits electrons from passing through the metal lattice. It was difficult to obtain the same high electrical conductivity as that of the Cu—Ni—Si alloy.
- conductive spring materials such as connectors, terminals, relays, and switches are required to have smaller and severe bending and strength while maintaining high conductivity.
- the present inventor has improved the prior art in which Mg is completely dissolved in a Cu—Ni—Si—Mg based alloy after the homogenization heat treatment, and adjusted the casting conditions and the homogenization heat treatment conditions to adjust the specific size. It was discovered that while the Mg-containing precipitate X has in the alloy, the precipitate Y exhibits an excellent effect by keeping the same size and distribution as the conventional one. Based on the knowledge, the size, preferably the amount and the ratio of each of the Ni—Si—Mg compound (precipitate X) and the Ni—Si compound (precipitate Y) are adjusted, and Cu having excellent conductivity and bendability according to the present invention. A Ni—Si—Mg alloy was completed.
- the present invention is as follows.
- a Cu—Ni—Si—Mg based alloy comprising Ni—Si—Mg precipitate X and Ni—Si precipitate Y, the average particle size of the precipitate X being 0.05 to 3.0 ⁇ m,
- the Cu—Ni—Si—Mg alloy of the present invention retains the same high strength, high conductivity, good bending workability and stress relaxation properties as the Cu—Ni—Si alloy, and is excellent at high temperatures. Excellent heat-resistant plating peelability.
- FIG. 2 is a schematic of a two-stage homogenization heat treatment, showing the temperature history of the material being processed.
- Ni concentration in the Cu—Ni—Si—Mg based alloy of the present invention if the Ni concentration is less than 1.0% by mass, the precipitate X or Y does not sufficiently precipitate, and the desired strength cannot be obtained. . If the Ni concentration exceeds 4.5% by mass, coarse precipitates are likely to be formed in the casting ingot, and cracks are likely to occur during hot rolling.
- Si concentration The additive concentration of Si is 0.16 to 1.13 mass%.
- the amount of Si is less than 0.16% by mass, the precipitate X or Y does not sufficiently precipitate and the amount of Ni solid solution increases, so that high conductivity cannot be obtained.
- the amount of Si exceeds 1.13% by mass, the Si concentration on the surface of the base material increases, so that the heat-resistant plating peelability deteriorates.
- Mg concentration When the Mg concentration is less than 0.05% by mass, the intended stress relaxation resistance (resistance to creep deformation), which is the effect of adding Mg, cannot be obtained. When it exceeds 0.30 mass%, the size of the precipitate X is large or the number of the precipitates X is large, so that hot workability is deteriorated. Moreover, since the amount of solid solution Mg increases, conductivity is inferior.
- the precipitate X (Ni—Si—Mg precipitate) refers to a precipitate (second phase particle) containing Ni, Si and Mg formed in the copper alloy of the present invention.
- the Mg ratio in the precipitate X is usually about 0.5 to 16% by mass. When the amount is less than 0.5% by mass, the presence of Mg cannot be detected by component analysis and cannot be distinguished from the precipitate Y (Ni—Si precipitate). Therefore, in the present invention, a precipitate containing Ni and Si and having a Mg ratio of less than 0.5% is treated as a precipitate Y.
- the amount of Mg in the precipitates X was within 16% by mass with the alloy composition of the present invention and the particle sizes of the target precipitates X and Y.
- the precipitate X and precipitate Y of the present invention are crystallized products during casting and also precipitates during aging treatment.
- the presence of the precipitate X reduces the Mg concentration of the base material and improves the conductivity, and pinning of the crystal growth is caused by the presence of the precipitate X remaining in the solution treatment after the homogenization heat treatment. It has a good effect as an effect, and an average crystal grain size finer than that of the conventional example can be obtained.
- the average particle size of the precipitate X of the present invention is 0.05 to 3.0 ⁇ m, more preferably 0.50 to 3.0 ⁇ m.
- the average particle size is less than 0.05 ⁇ m, the size of the precipitate is too small to contribute to the strength, and the amount of Mg dissolved in the matrix increases, so that the intended conductivity cannot be obtained.
- the average particle size of the precipitate X exceeds 3.0 ⁇ m, the precipitate becomes coarse and does not contribute to the strength, and hot cracking is likely to occur, resulting in poor workability.
- the precipitate X having a particle size exceeding 10 ⁇ m exists, the bending workability is remarkably deteriorated.
- the number of precipitates X in the alloy of the present invention is preferably 1.0 ⁇ 10 3 to 1.0 ⁇ 10 5 per square mm in cross section perpendicular to the rolling direction.
- the number of the precipitates X is less than 10 3 , the number is too small, so that even if the precipitates X are precipitated, they do not contribute to the improvement of conductivity and bendability.
- the number of the precipitates X exceeds 10 5
- Ni and Si that should form the precipitates Y are consumed, and the precipitates Y are not formed sufficiently, and the Cu—Ni—Si based alloy inherently high Strength cannot be secured.
- the precipitate X of the present invention is mainly derived from precipitates generated during alloy casting.
- the homogenization heat treatment was performed by heating in the next process of casting, and all precipitates were dissolved.
- this homogenization heat treatment condition is controlled, and the crystallized matter is left so that the desired size and number of precipitates X can be obtained while homogenizing the cast structure of the ingot.
- the precipitate X has a high melting point, even though it undergoes a solution heat treatment step and an aging step after the homogenization heat treatment, the particle size slightly changes due to diffusion of the heat effect, but does not disappear.
- Precipitate Y (Ni-Si precipitate) refers to a precipitate (second phase particle) containing Ni and Si formed in the copper alloy of the present invention, and its normal composition is represented by Ni 2 Si or the like.
- the Precipitate Y is formed by solution treatment in the manufacturing process, Ni and Si are sufficiently dissolved in the base material, and precipitated from the base material by aging treatment, in the same manner as in the manufacture of ordinary Corson alloy. To do.
- the particle size and density can be controlled by these heat treatment conditions.
- the average particle size of the precipitate Y is 0.01 to 0.10 ⁇ m, preferably 0.05 to 0.10 ⁇ m.
- the number of precipitates Y is preferably 1 ⁇ 10 8 to 1 ⁇ 10 11, more preferably 1 ⁇ 10 9 to 1 ⁇ 10 11 , and if the number is less than 1 ⁇ 10 8 , the number of precipitates is Does not contribute to strength because it is small. On the other hand, when the number of precipitates exceeds 1 ⁇ 10 11, bending workability is lowered.
- Additive elements other than Ni, Si and Mg Cr, P, Mn, Ag, Co and Mo are effective in improving strength and heat resistance, and As and Sb are effective in improving plating peelability.
- Al, Hf, Zr, Ti, C, Fe, In, Ta, Sn, and Zn are effective in preventing the coarsening of the crystal grain size in the solution treatment. If the addition amount of these elements is less than 0.01% by mass, the effect of addition cannot be obtained, and if it exceeds 2.0% by mass, the conductivity is lowered.
- the manufacturing method of the copper alloy of the present invention is a general manufacturing process (melting / casting ⁇ homogenization heat treatment ⁇ hot rolling ⁇ intermediate cold rolling ⁇ intermediate solution forming ⁇ final cooling) with a precipitation strengthened copper alloy. Hot rolling ⁇ intermediate cold rolling ⁇ intermediate solution rolling ⁇ aging ⁇ final cold rolling), but the homogenization heat treatment conditions are adjusted within the process. Thus, the target copper alloy is manufactured. In addition, about intermediate rolling and intermediate solution forming, you may repeat several times as needed. In order to produce the copper alloy of the present invention, it is important to strictly control the conditions for the homogenization heat treatment, the solution treatment, and the annealing.
- the Ni—Si—Mg precipitate X generated by casting is left so as to be within the scope of the present invention, and the Ni—Si precipitate Y must be sufficiently removed.
- the solution treatment it is desirable that Ni and Si are sufficiently solid-solubilized so that the precipitate Y does not exist.
- the condition may be such that the remaining precipitate X does not disappear.
- the last aging what is necessary is just the conditions which precipitate Y with a small average particle diameter fully precipitates, and this conditions may be the same as the conventional aging conditions.
- the homogenization is performed in order to eliminate the Ni—Si precipitate Y generated by casting and to adjust the Ni—Si—Mg precipitate X within the scope of the present invention.
- Heat treatment is preferably performed in two stages. In that case, the atmosphere temperature in the furnace is set to 800 ° C. or more and less than 890 ° C. as the first stage of homogenization heat treatment, and is held for 0.5 to 2.5 hours after the material temperature reaches the set temperature.
- the atmospheric temperature in the furnace was set to 890 ° C. to 980 ° C. as the second stage homogenization heat treatment, and the material temperature was It is preferable to perform hot rolling immediately after holding for 0.5 to 1.2 hours after reaching the set temperature.
- the first and second stage heating may be performed continuously in one furnace, and is performed by moving from the first stage heat treatment zone to the second stage heat treatment zone. An outline of the temperature history of the material of this two-stage homogenization heat treatment is shown in FIG.
- the ingot in order to prevent the temperature of the ingot from decreasing in a separate furnace, it may be inserted into the second stage furnace as soon as it is taken out from the first stage furnace, and the second stage heating may be started.
- the first stage holding temperature is less than 800 ° C.
- the Ni—Si precipitate Y does not sufficiently dissolve, and the precipitate X remains with a large average particle size, while at 890 ° C. or higher, the precipitate X also solidifies. Dissolve and disappear.
- the second stage holding temperature is less than 890 ° C., the precipitate X does not disappear, but the particles of the precipitate X may remain large, and some of the precipitate Y remains without being dissolved. there's a possibility that.
- the precipitate X may be completely dissolved.
- heating is performed by a known means such as a burner or a dielectric. When heating, care is taken to keep the output energy and the ingot weight in the furnace constant. If the ingot weight is light even at the same set temperature, it will be overheated, and if the ingot weight is heavy, there is a risk that the heating will be insufficient.
- the Ni—Si—Mg-based precipitate X is hardly changed by maintaining the atmospheric temperature in the first stage furnace of the homogenization heat treatment at 800 ° C. or more and less than 890 ° C. for 0.5 to 2.5 hours.
- the average particle diameter of the Ni—Si based precipitate Y is small.
- the second stage heat treatment at 890 ° C. to 980 ° C. for 0.5 to 1.2 hours, the average particle size of the Ni—Si—Mg based precipitate X becomes small, and part of it Although it disappears, the remaining precipitates X have a predetermined size and number, while all the Ni—Si based precipitates Y that have remained after the first heat treatment disappear.
- Ni—Si—Mg based precipitates X exist to the end in size and number after hot rolling.
- a predetermined size and number of Ni—Si-based precipitates Y are precipitated by solution treatment and cold rolling and by aging treatment.
- intermediate rolling and intermediate solution forming are performed by appropriately selecting the number of times and the order within the range of the object of the present invention. If the degree of work in the final pass of the intermediate rolling is less than 30%, the number of precipitates Y is reduced because the amount of dislocations that are the starting points of precipitation Y is reduced, and the strength is lowered. On the other hand, when the degree of work exceeds 99%, the amount of dislocations increases and the number of precipitates Y increases, but the average particle size of the precipitates Y becomes too small and the strength decreases. Therefore, it is preferable that the intermediate rolling work degree in the final pass is 30% to 99%.
- the intermediate solution treatment is sufficiently performed to eliminate the precipitate Y as much as possible by dissolving the crystallized particles during melt casting and the precipitated particles after hot rolling.
- the solution treatment temperature is less than 500 ° C.
- the solid solution is insufficient and the desired strength cannot be obtained.
- the solution treatment temperature exceeds 850 ° C.
- the material may be dissolved. Therefore, it is preferable to perform a solution treatment in which the material temperature is heated to 500 ° C. to 850 ° C.
- the solution treatment time is preferably 60 seconds to 2 hours.
- the time is short at a high temperature and at a low temperature. It must be long. For example, in the present invention, 1 hour is desirable at 600 ° C. and 2 to 3 minutes to 30 minutes at 750 ° C.
- the cooling rate after the solution treatment is generally rapidly cooled so that the solid solution component does not precipitate as second phase particles (precipitate Y).
- the degree of work of final rolling is 0 to 50%, preferably 5 to 20%. If it exceeds 50%, the bending workability deteriorates.
- the final aging step of the present invention is performed in the same manner as in the prior art, and fine second-phase particles (including the precipitate Y and, optionally, the precipitate X) within the scope of the present invention are uniformly precipitated.
- Example 1 Manufacture of copper alloy
- 5 kg of high purity copper was dissolved.
- predetermined amounts of Ni, Si and Mg were added to adjust the molten copper temperature to 1200 ° C.
- the molten metal was cast into a mold to produce an ingot having a width of 65 mm and a thickness of 20 mm.
- the sample was cut out from the ingot and the quantity of the structural element was analyzed by the fluorescent X ray analysis. Next, this ingot was subjected to homogenization heat treatment described in Table 1, and then hot-rolled to a thickness of 8 mm.
- Ni—Si and Ni—Si—Mg precipitates formed during casting remain.
- the oxidized scale on the hot-rolled plate surface was ground and removed, and then cold-rolled to a plate thickness of 0.2 mm.
- the surface oxide film was removed by chemical polishing after heating at 750 to 800 ° C. for 20 seconds and quenching in water. Thereafter, cold rolling with a workability of 25% was performed, and the aging treatment was performed at 460 ° C. for 7.5 hours in an inert atmosphere.
- the use of EDS (energy dispersive X-ray analysis) of FE-SEM confirms that Ni and Si, or Ni, Si and Mg are contained as the components of the precipitate to be measured. It confirmed by analyzing a component with respect to all the deposits.
- the distinction between the precipitates X and Y is a precipitate containing Ni, Si, and Mg because of the problem of detection accuracy.
- the presence or absence of Ni—Si—Mg precipitates X having an average particle size of 10 ⁇ m or more was confirmed.
- the particle size was the length of the longest part of the precipitate in the photograph taken with FE-SEM.
- the average grain size is obtained by a simple average obtained by adding all crystal grain sizes in the observation area and dividing by the number of crystal grains.
- Tensile strength No. 13B test piece defined in JIS Z 2201 (2003) was collected in a direction in which the tensile direction was parallel to the rolling direction. Using this test piece, a tensile test was performed according to JIS Z 2241 (2003) to obtain a tensile strength.
- the preferable tensile strength aimed at in the present invention is 760 MPa or more.
- the stress relaxation was measured until the sample was 150 ° C. and showed a certain relaxation rate. Since a substantially constant stress relaxation rate was exhibited in about 1000 hours, this value was taken as the stress relaxation rate.
- the stress relaxation rate after 150 ° C. ⁇ 1000 h of a commonly used Corson alloy is about 10%. Therefore, in the evaluation of each of the following invention examples and comparative examples, those having a stress relaxation rate of 9% or less were considered to have good stress relaxation resistance at high temperatures.
- the first stage homogenization heat treatment is 800 ° C. to less than 890 ° C. ⁇ 2 hours
- the second stage heat treatment is 890 ° C. to 980 ° C. ⁇ 0.5 to 1.2 h.
- the precipitate X had no coarse grains exceeding 10 ⁇ m and the average particle diameter was 0.05 to 3.0 ⁇ m, and all the precipitate Y was dissolved and disappeared.
- the precipitate Y could be precipitated under aging conditions such that the average particle diameter was 0.01 to 0.10 ⁇ m.
- high strength, high conductivity, good bending workability and stress relaxation were obtained.
- Comparative Examples 11 to 15 the homogenization heat treatment was performed in one stage.
- Comparative Example 11 since the homogenization heat treatment temperature was as low as 870 ° C., the size of the precipitate X was not reduced by the heat treatment, and coarse precipitates X of 10 ⁇ m or more remained in the product.
- the precipitate Y having a large size before the homogenization heat treatment remains without disappearing at the homogenization heat treatment temperature of 870 ° C.
- the precipitate Y remaining after hot rolling after the homogenizing heat treatment does not disappear even after solution treatment, rolling, and aging treatment (the same conditions as in Invention Examples 1 to 10).
- Comparative Example 11 has poor bending workability due to the presence of large precipitates X, and the strength is inferior due to the small number of precipitates Y. Furthermore, since a large amount of Mg is present in a large number of precipitates X, the amount of solid solution Mg is reduced and the stress relaxation characteristics are also poor.
- Comparative Examples 12 and 13 since the homogenization heat treatment temperature is higher than that in Comparative Example 11, there is no coarse precipitate X of 10 ⁇ m or more, but since the time is relatively short, the average particle size of the precipitate X is 3.0 ⁇ m or less. The precipitate Y having a large size did not disappear even after the homogenization heat treatment. As a result, Comparative Examples 12 and 13 were inferior in strength because the average particle size of the precipitate Y exceeded 0.10 ⁇ m and the number was small, and the stress relaxation characteristics were also poor because the number of precipitates X was large and the average particle size was large. .
- the average particle size of the precipitate Y is The number of precipitates Y was less than 0.10 ⁇ m. As a result, the strength was inferior.
- Comparative Example 17 since the time for the second stage homogenization heat treatment is too short, coarse precipitates X remain after hot rolling, and the average particle size of the precipitates X exceeds 3.0 ⁇ m, and the size Large precipitates Y remained, but the total number of precipitates Y was small. As a result, the strength, bending workability, and stress relaxation characteristics were inferior.
- the heat treatment time in the second stage is too long, so the average particle size of the precipitate X is less than 0.05 ⁇ m, the number is small, and the conductivity is inferior.
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Abstract
Description
高強度および高導電性の観点から、近年電子材料用合金としては、従来のりん青銅、黄銅等に代表される固溶強化型銅合金に替わり、時効硬化型銅合金の使用量が増加している。時効硬化型銅合金では、溶体化処理された過飽和固溶体を時効処理することにより、微細な析出物が均一に分散して合金の強度が高くなると同時に、銅中に固溶している添加元素量が減少して導電性が向上する。このため、強度、バネ性などの機械的特性に優れ、しかも電気伝導性、熱伝導性が良好な材料が得られる。この時効硬化型銅合金のうち、Cu-Ni-Si系合金はコルソン合金として知られ、高強度と高導電性とを併せ持つ代表的な銅合金であり、電子機器用材料として実用化されている。この銅合金では、銅マトリックス中に微細なNi-Si系金属間化合物(析出物Y)が粒子状に析出することにより強度と導電性が上昇する。 Copper alloys for electronic materials used for terminals, connectors, and the like are required to have both high strength, high electrical conductivity, and thermal conductivity as basic characteristics. In addition to these characteristics, bending workability, stress relaxation resistance, heat resistance, adhesion to plating, etching workability, press punching, and corrosion resistance are required.
From the viewpoint of high strength and high conductivity, the amount of age-hardened copper alloys has increased in recent years as an alloy for electronic materials, replacing solid solution strengthened copper alloys represented by conventional phosphor bronze, brass, etc. Yes. In age-hardened copper alloys, by aging the solution-treated supersaturated solid solution, fine precipitates are uniformly dispersed to increase the strength of the alloy, and at the same time, the amount of additive elements dissolved in copper Decreases and conductivity is improved. For this reason, it is possible to obtain a material having excellent mechanical properties such as strength and spring property and excellent electrical conductivity and thermal conductivity. Among these age-hardening type copper alloys, Cu—Ni—Si based alloys are known as Corson alloys, and are representative copper alloys having both high strength and high conductivity, and have been put into practical use as materials for electronic devices. . In this copper alloy, fine Ni—Si intermetallic compounds (precipitates Y) precipitate in the form of particles in the copper matrix, thereby increasing strength and conductivity.
しかし、近年の製品小型化に従い、コネクタ、端子、リレー、スイッチ等の導電性バネ材には、高い導電性を保持しつつ、より小さく厳しい曲げ及び強度が要求されている。 In the production of a Cu—Ni—Si—Mg alloy, Mg is more easily oxidized than other additive elements, and therefore reacts with oxygen in the molten metal to become an oxide and float on the molten metal. Therefore, considering the amount of Mg loss due to oxidation, Mg is usually added excessively. On the other hand, since the Ni—Si—Mg compound (precipitate X) is a primary crystal in this alloy system, it first crystallizes in the cast ingot. However, since the precipitate X is dissolved in the homogenization heat treatment performed to make the heterogeneous structure of the metal internal structure after casting uniform, and then the solution treatment is also performed, the conventional Cu—Ni—Si -The Mg component of the Mg-based alloy is in a state of being dissolved in the base material, and is usually not present as the precipitate X. In the conventional Cu—Ni—Si—Mg-based alloy in which Mg is excessively added and solidly dissolved in this manner, the presence of Mg inhibits electrons from passing through the metal lattice. It was difficult to obtain the same high electrical conductivity as that of the Cu—Ni—Si alloy.
However, in accordance with recent miniaturization of products, conductive spring materials such as connectors, terminals, relays, and switches are required to have smaller and severe bending and strength while maintaining high conductivity.
本発明は、下記のとおりである。
(1)1.0~4.5質量%のNi、0.16~1.13質量%のSi、及び0.05~0.30質量%のMgを含有し、残部がCu及び不可避的不純物からなるCu-Ni-Si-Mg系合金であり、Ni-Si-Mg析出物X及びNi-Si析出物Yを含み、析出物Xの平均粒径が0.05~3.0μmであり、粒径が10μmを超える析出物Xが存在せず、かつ析出物Yの平均粒径が0.01~0.10μmである銅合金。
(2)上記析出物Xは圧延方向に直角な断面1平方mm当たり1.0×103~1.0×105個含まれる(1)の銅合金。
(3)上記析出物Yは圧延方向に直角な断面1平方mm当たり1.0×108~1.0×1011個含まれる(1)又は(2)の銅合金。
(4)Cr、P、Mn、Ag、Co、Mo、As、Sb、Al、Hf、Zr、Ti、C、Fe、In、Ta、Sn及びZnの群から選ばれた少なくとも一種を合計で0.01~2.0質量%含む上記いずれかの銅合金。 The present inventor has improved the prior art in which Mg is completely dissolved in a Cu—Ni—Si—Mg based alloy after the homogenization heat treatment, and adjusted the casting conditions and the homogenization heat treatment conditions to adjust the specific size. It was discovered that while the Mg-containing precipitate X has in the alloy, the precipitate Y exhibits an excellent effect by keeping the same size and distribution as the conventional one. Based on the knowledge, the size, preferably the amount and the ratio of each of the Ni—Si—Mg compound (precipitate X) and the Ni—Si compound (precipitate Y) are adjusted, and Cu having excellent conductivity and bendability according to the present invention. A Ni—Si—Mg alloy was completed.
The present invention is as follows.
(1) Containing 1.0 to 4.5 mass% Ni, 0.16 to 1.13 mass% Si, and 0.05 to 0.30 mass% Mg, the balance being Cu and inevitable impurities A Cu—Ni—Si—Mg based alloy comprising Ni—Si—Mg precipitate X and Ni—Si precipitate Y, the average particle size of the precipitate X being 0.05 to 3.0 μm, A copper alloy in which no precipitate X having a particle size exceeding 10 μm is present and the average particle size of the precipitate Y is 0.01 to 0.10 μm.
(2) The copper alloy according to (1), wherein the precipitate X is contained in an amount of 1.0 × 10 3 to 1.0 × 10 5 per square mm in cross section perpendicular to the rolling direction.
(3) The copper alloy according to (1) or (2), wherein the precipitate Y is included in an amount of 1.0 × 10 8 to 1.0 × 10 11 per square mm of the cross section perpendicular to the rolling direction.
(4) At least one selected from the group consisting of Cr, P, Mn, Ag, Co, Mo, As, Sb, Al, Hf, Zr, Ti, C, Fe, In, Ta, Sn, and Zn is 0 in total. Any one of the above copper alloys containing 0.01 to 2.0% by mass.
本発明のCu-Ni-Si-Mg系合金では、Ni濃度が1.0質量%未満であると析出物X又はYが充分に析出しないため目的とする強度が得られない。Ni濃度が4.5質量%を超えると、鋳造インゴット中に粗大な析出物が形成され易く、熱間圧延で割れが発生しやすくなる。 (1) Ni concentration In the Cu—Ni—Si—Mg based alloy of the present invention, if the Ni concentration is less than 1.0% by mass, the precipitate X or Y does not sufficiently precipitate, and the desired strength cannot be obtained. . If the Ni concentration exceeds 4.5% by mass, coarse precipitates are likely to be formed in the casting ingot, and cracks are likely to occur during hot rolling.
Siの添加濃度は、0.16~1.13質量%とする。Si量が0.16質量%未満になると、析出物X又はYが充分に析出せずNi固溶量が増大するため高い導電性が得られない。Si量が1.13質量%を超えると、母材表面のSi濃度が増大するため耐熱めっき剥離性が悪化する。 (2) Si concentration The additive concentration of Si is 0.16 to 1.13 mass%. When the amount of Si is less than 0.16% by mass, the precipitate X or Y does not sufficiently precipitate and the amount of Ni solid solution increases, so that high conductivity cannot be obtained. When the amount of Si exceeds 1.13% by mass, the Si concentration on the surface of the base material increases, so that the heat-resistant plating peelability deteriorates.
Mg濃度が0.05質量%未満では、目的とするMg添加効果である耐応力緩和特性(クリープ変形に対する耐性)が得られない。0.30質量%を超えると、析出物Xのサイズが大きく又は個数が多くなるため熱間加工性が悪化する。また、固溶Mg量が増大するため導電性が劣る。 (3) Mg concentration When the Mg concentration is less than 0.05% by mass, the intended stress relaxation resistance (resistance to creep deformation), which is the effect of adding Mg, cannot be obtained. When it exceeds 0.30 mass%, the size of the precipitate X is large or the number of the precipitates X is large, so that hot workability is deteriorated. Moreover, since the amount of solid solution Mg increases, conductivity is inferior.
析出物X(Ni-Si-Mg析出物)は、本発明の銅合金中に形成されたNi、Si及びMgを含有する析出物(第二相粒子)をいう。析出物X中のMg割合は、通常0.5~16質量%程度である。0.5質量%未満の場合、成分分析ではMgの存在が検出できず析出物Y(Ni-Si析出物)との区別が不可能である。そのため、本発明ではNi及びSiを含む析出物であってMg割合が0.5%未満のものは析出物Yとして扱う。多数の析出物Xを分析した結果、本発明の合金組成及び目的とする析出物X及びYの粒径であると、析出物X中のMg量は16質量%以内であった。
本発明の析出物X及び析出物Yは、鋳造時の晶出物であり時効処理時の析出物でもある。本発明では析出物Xを存在させることにより、母材のMg濃度が低下して導電性が改善され、均質化熱処理後の溶体化処理でも残存する析出物Xの存在により結晶粒成長に対するピン止め効果として良い影響を与え、従来例より細かい平均結晶粒径を得ることができる。 (4) Precipitate X (Ni—Si—Mg precipitate)
The precipitate X (Ni—Si—Mg precipitate) refers to a precipitate (second phase particle) containing Ni, Si and Mg formed in the copper alloy of the present invention. The Mg ratio in the precipitate X is usually about 0.5 to 16% by mass. When the amount is less than 0.5% by mass, the presence of Mg cannot be detected by component analysis and cannot be distinguished from the precipitate Y (Ni—Si precipitate). Therefore, in the present invention, a precipitate containing Ni and Si and having a Mg ratio of less than 0.5% is treated as a precipitate Y. As a result of analyzing a large number of precipitates X, the amount of Mg in the precipitates X was within 16% by mass with the alloy composition of the present invention and the particle sizes of the target precipitates X and Y.
The precipitate X and precipitate Y of the present invention are crystallized products during casting and also precipitates during aging treatment. In the present invention, the presence of the precipitate X reduces the Mg concentration of the base material and improves the conductivity, and pinning of the crystal growth is caused by the presence of the precipitate X remaining in the solution treatment after the homogenization heat treatment. It has a good effect as an effect, and an average crystal grain size finer than that of the conventional example can be obtained.
析出物Y(Ni-Si析出物)は、本発明の銅合金中に形成されたNi及びSiを含有する析出物(第二相粒子)をいい、通常の組成はNi2Si等で表される。
析出物Yは、通常のコルソン合金の製造と同様に、製造工程中で溶体化処理を行いNiとSiを母材に充分固溶させておいて、時効処理により母材から析出させることにより生成する。また、粒径や密度はこれらの熱処理条件により制御を行うことができる。析出物Yの平均粒径は、0.01~0.10μm、好ましくは0.05~0.10μmである。析出物Yの平均粒径が0.01μm未満の場合は、大きさが小さ過ぎるために強度に寄与しない。一方、析出物Yの平均粒径が0.10μm以上の場合には粗大であるため強度への寄与をしなくなる。なお、粒径が3.0μmを超える析出物Yが存在する場合には、強度及び応力緩和性が悪化しやすい。
析出物Yの個数は、好ましくは1×108~1×1011個、更に好ましくは1×109~1×1011個であり、1×108個未満の場合には、析出物の数が少ないために強度に寄与しない。一方、析出物の個数が1×1011個を超える場合には曲げ加工性を低下させる。 (5) Precipitate Y (Ni-Si precipitate)
Precipitate Y (Ni-Si precipitate) refers to a precipitate (second phase particle) containing Ni and Si formed in the copper alloy of the present invention, and its normal composition is represented by Ni 2 Si or the like. The
Precipitate Y is formed by solution treatment in the manufacturing process, Ni and Si are sufficiently dissolved in the base material, and precipitated from the base material by aging treatment, in the same manner as in the manufacture of ordinary Corson alloy. To do. The particle size and density can be controlled by these heat treatment conditions. The average particle size of the precipitate Y is 0.01 to 0.10 μm, preferably 0.05 to 0.10 μm. When the average particle size of the precipitate Y is less than 0.01 μm, the size is too small and does not contribute to the strength. On the other hand, when the average particle size of the precipitate Y is 0.10 μm or more, the precipitate Y is coarse and does not contribute to the strength. In addition, when the precipitate Y with a particle size exceeding 3.0 μm exists, the strength and the stress relaxation property are likely to deteriorate.
The number of precipitates Y is preferably 1 × 10 8 to 1 × 10 11, more preferably 1 × 10 9 to 1 × 10 11 , and if the number is less than 1 × 10 8 , the number of precipitates is Does not contribute to strength because it is small. On the other hand, when the number of precipitates exceeds 1 × 10 11, bending workability is lowered.
Cr、P、Mn、Ag、Co及びMoは強度の改善と耐熱性の向上に効果があり、As、Sbはめっき剥離性の改善に効果があり、Al、Hf、Zr、Ti、C、Fe、In、Ta、Sn及びZnは溶体化処理における結晶粒径の粗大化防止に効果がある。
これら元素の添加量は0.01質量%未満では添加効果が得られず、2.0質量%を超えると導電性が低下してしまう。 (6) Additive elements other than Ni, Si and Mg Cr, P, Mn, Ag, Co and Mo are effective in improving strength and heat resistance, and As and Sb are effective in improving plating peelability. , Al, Hf, Zr, Ti, C, Fe, In, Ta, Sn, and Zn are effective in preventing the coarsening of the crystal grain size in the solution treatment.
If the addition amount of these elements is less than 0.01% by mass, the effect of addition cannot be obtained, and if it exceeds 2.0% by mass, the conductivity is lowered.
本発明の銅合金の製造方法は、析出強化型銅合金で一般的な製造プロセス(溶解・鋳造→均質化熱処理→熱間圧延→中間冷間圧延→中間溶体化→最終冷間圧延→時効、又は、溶解・鋳造→均質化熱処理→熱間圧延→中間冷間圧延→中間溶体化→時効→最終冷間圧延)を使用するが、その工程内で均質化熱処理条件を調整して目的の銅合金を製造する。なお、中間圧延、中間溶体化については、必要に応じて複数回繰り返してもよい。
本発明の銅合金を製造するには、均質化熱処理条件、溶体化処理及び焼鈍の条件を厳密に制御することが重要である。すなわち、均質化熱処理では、鋳造で発生したNi-Si-Mg析出物Xは本発明の範囲内となるように残し、Ni-Si析出物Yは充分になくす条件で行われなければならない。なお、溶体化処理では、NiとSiが十分に固溶して、析出物Yが存在しない条件が望ましいが、残った析出物Xが消滅しないような条件であればよい。最後の時効については、平均粒径が小さな析出物Yが充分に析出する条件であればよく、この条件は従来の時効条件と同様でよい。 (7) Manufacturing Method The manufacturing method of the copper alloy of the present invention is a general manufacturing process (melting / casting → homogenization heat treatment → hot rolling → intermediate cold rolling → intermediate solution forming → final cooling) with a precipitation strengthened copper alloy. Hot rolling → intermediate cold rolling → intermediate solution rolling → aging → final cold rolling), but the homogenization heat treatment conditions are adjusted within the process. Thus, the target copper alloy is manufactured. In addition, about intermediate rolling and intermediate solution forming, you may repeat several times as needed.
In order to produce the copper alloy of the present invention, it is important to strictly control the conditions for the homogenization heat treatment, the solution treatment, and the annealing. That is, in the homogenization heat treatment, the Ni—Si—Mg precipitate X generated by casting is left so as to be within the scope of the present invention, and the Ni—Si precipitate Y must be sufficiently removed. In the solution treatment, it is desirable that Ni and Si are sufficiently solid-solubilized so that the precipitate Y does not exist. However, the condition may be such that the remaining precipitate X does not disappear. About the last aging, what is necessary is just the conditions which precipitate Y with a small average particle diameter fully precipitates, and this conditions may be the same as the conventional aging conditions.
1段目の保持温度が800℃未満ではNi-Si析出物Yが充分に固溶せず、析出物Xは平均粒径が大きいまま残存し、一方、890℃以上では、析出物Xも固溶して消失してしまう。また、2段目の保持温度が890℃未満では、析出物Xは消失しないが、析出物Xの粒子が大きいまま残存する可能性があり、一部の析出物Yも固溶せずに残存する可能性がある。一方、2段目の保持温度が980℃を超えると析出物Xが全て固溶してしまう可能性がある。
この均質化熱処理では、バーナーや誘電体等の公知の手段により加熱が行われる。加熱に際しては、出力エネルギー及び炉内のインゴット重量をそれぞれ一定に保つように注意する。同一設定温度でもインゴット重量が軽い場合には加熱し過ぎになり、インゴット重量が重い場合には加熱が不充分になる危険性がある。 In the melting / casting step, raw materials such as electrolytic copper, Ni, Si, and Mg are melted to obtain a molten metal having a desired composition and cast into an ingot. In the homogenization heat treatment and hot rolling of the ingot, in order to eliminate the Ni—Si precipitate Y generated by casting and to adjust the Ni—Si—Mg precipitate X within the scope of the present invention, the homogenization is performed. Heat treatment is preferably performed in two stages. In that case, the atmosphere temperature in the furnace is set to 800 ° C. or more and less than 890 ° C. as the first stage of homogenization heat treatment, and is held for 0.5 to 2.5 hours after the material temperature reaches the set temperature. Further, in order to reduce the average particle size of the remaining coarse Ni—Si—Mg precipitate X, the atmospheric temperature in the furnace was set to 890 ° C. to 980 ° C. as the second stage homogenization heat treatment, and the material temperature was It is preferable to perform hot rolling immediately after holding for 0.5 to 1.2 hours after reaching the set temperature. The first and second stage heating may be performed continuously in one furnace, and is performed by moving from the first stage heat treatment zone to the second stage heat treatment zone. An outline of the temperature history of the material of this two-stage homogenization heat treatment is shown in FIG. Alternatively, in order to prevent the temperature of the ingot from decreasing in a separate furnace, it may be inserted into the second stage furnace as soon as it is taken out from the first stage furnace, and the second stage heating may be started.
When the first stage holding temperature is less than 800 ° C., the Ni—Si precipitate Y does not sufficiently dissolve, and the precipitate X remains with a large average particle size, while at 890 ° C. or higher, the precipitate X also solidifies. Dissolve and disappear. In addition, when the second stage holding temperature is less than 890 ° C., the precipitate X does not disappear, but the particles of the precipitate X may remain large, and some of the precipitate Y remains without being dissolved. there's a possibility that. On the other hand, if the second stage holding temperature exceeds 980 ° C., the precipitate X may be completely dissolved.
In this homogenization heat treatment, heating is performed by a known means such as a burner or a dielectric. When heating, care is taken to keep the output energy and the ingot weight in the furnace constant. If the ingot weight is light even at the same set temperature, it will be overheated, and if the ingot weight is heavy, there is a risk that the heating will be insufficient.
中間溶体化は、溶解鋳造時の晶出粒子や、熱間圧延後の析出粒子を固溶させてできるかぎり析出物Yをなくすために充分に行う。例えば、溶体化処理温度が500℃未満だと固溶が不充分であり、所望の強度を得ることが出来ない。一方、溶体化処理温度が850℃を超えると材料が溶解する可能性がある。従って、材料温度を500℃~850℃に加熱する溶体化処理を行うのが好ましい。溶体化処理の時間は60秒~2時間とするのが好ましい。 After the hot rolling, intermediate rolling and intermediate solution forming are performed by appropriately selecting the number of times and the order within the range of the object of the present invention. If the degree of work in the final pass of the intermediate rolling is less than 30%, the number of precipitates Y is reduced because the amount of dislocations that are the starting points of precipitation Y is reduced, and the strength is lowered. On the other hand, when the degree of work exceeds 99%, the amount of dislocations increases and the number of precipitates Y increases, but the average particle size of the precipitates Y becomes too small and the strength decreases. Therefore, it is preferable that the intermediate rolling work degree in the final pass is 30% to 99%.
The intermediate solution treatment is sufficiently performed to eliminate the precipitate Y as much as possible by dissolving the crystallized particles during melt casting and the precipitated particles after hot rolling. For example, when the solution treatment temperature is less than 500 ° C., the solid solution is insufficient and the desired strength cannot be obtained. On the other hand, when the solution treatment temperature exceeds 850 ° C., the material may be dissolved. Therefore, it is preferable to perform a solution treatment in which the material temperature is heated to 500 ° C. to 850 ° C. The solution treatment time is preferably 60 seconds to 2 hours.
溶体化処理後の冷却速度は、一般的には固溶成分が第二相粒子(析出物Y)として析出しないように急冷する。
最終圧延の加工度は0~50%、好ましくは5~20%である。50%を超えると曲げ加工性が低下する。
本発明の最終時効工程は、従来技術と同様に行われ、本発明の範囲内の微細な第二相粒子(析出物Y及び、場合によっては析出物Xも含む)を均一に析出させる。 As a relation between the solution treatment temperature and time, in order to obtain the same heat treatment effect (for example, the same average particle diameter of the precipitate Y), it is common sense that the time is short at a high temperature and at a low temperature. It must be long. For example, in the present invention, 1 hour is desirable at 600 ° C. and 2 to 3 minutes to 30 minutes at 750 ° C.
The cooling rate after the solution treatment is generally rapidly cooled so that the solid solution component does not precipitate as second phase particles (precipitate Y).
The degree of work of final rolling is 0 to 50%, preferably 5 to 20%. If it exceeds 50%, the bending workability deteriorates.
The final aging step of the present invention is performed in the same manner as in the prior art, and fine second-phase particles (including the precipitate Y and, optionally, the precipitate X) within the scope of the present invention are uniformly precipitated.
高周波誘導炉を用い5kgの高純度銅を溶解した。溶銅表面を木炭片で覆った後、所定量のNi、SiおよびMgを添加し、溶銅温度を1200℃に調整した。その後、溶湯を金型に鋳込み、幅65mm、厚み20mmのインゴットを製造した。製造したインゴットの成分については、JIS H1292に従い、インゴットからサンプルを切り出し、蛍光X線分析により構成元素の量を分析した。
次に、このインゴットを表1に記載された均質化熱処理を行った後、厚さ8mmまで熱間圧延した。この段階でも、鋳造時に生成したNi-SiとNi-Si-Mgの析出物は残留している。上記熱間圧延された板表面の酸化スケ-ルを研削除去した後、板厚0.2mmまで冷間圧延した。溶体化処理として750℃~800℃で20秒間加熱し水中で急冷した後、化学研磨により表面酸化膜を除去した。その後、加工度25%の冷間圧延を行い、時効処理として不活性雰囲気において460℃で7.5時間加熱した。 Example 1 (Manufacture of copper alloy)
Using a high frequency induction furnace, 5 kg of high purity copper was dissolved. After covering the molten copper surface with charcoal pieces, predetermined amounts of Ni, Si and Mg were added to adjust the molten copper temperature to 1200 ° C. Thereafter, the molten metal was cast into a mold to produce an ingot having a width of 65 mm and a thickness of 20 mm. About the component of the manufactured ingot, according to JISH1292, the sample was cut out from the ingot and the quantity of the structural element was analyzed by the fluorescent X ray analysis.
Next, this ingot was subjected to homogenization heat treatment described in Table 1, and then hot-rolled to a thickness of 8 mm. Even at this stage, Ni—Si and Ni—Si—Mg precipitates formed during casting remain. The oxidized scale on the hot-rolled plate surface was ground and removed, and then cold-rolled to a plate thickness of 0.2 mm. As a solution treatment, the surface oxide film was removed by chemical polishing after heating at 750 to 800 ° C. for 20 seconds and quenching in water. Thereafter, cold rolling with a workability of 25% was performed, and the aging treatment was performed at 460 ° C. for 7.5 hours in an inert atmosphere.
(1)析出物の個数および大きさの測定
圧延方向に直角な断面を、直径1μmのダイヤモンド砥粒を用いた機械研磨により鏡面に仕上げ、FE-SEM(電解放射型走査電子顕微鏡)を用い、400倍の倍率で、長さが0.05mm以上の析出物の個数を計測した。観察面積は60mm2とし観察面積内の析出物の個数を数え上げた。また、計測対象の析出物の成分としてNi及びSi、又はNi、Si及びMgが含まれることを、FE-SEM(電解放射型走査電子顕微鏡)のEDS(エネルギー分散型X線分析)を用いて全ての析出物に対して成分分析することにより確認した。ここで析出物XとYの区別は検出精度の問題からNi、Si及びMgを含む析出物であってもMgの割合が0.5%未満のものは析出物Yとして扱う。
また、平均粒径を計測する際に、平均粒径10μm以上のNi-Si-Mg析出物Xの有無を確認した。粒径はFE-SEMで撮影した写真の析出物の一番長い部分の長さとした。平均粒径は観察面積内すべての結晶粒径を足し、結晶粒の個数で割った単純平均で求めている。 The following evaluation was performed on the sample thus fabricated.
(1) Measurement of the number and size of precipitates A cross section perpendicular to the rolling direction was mirror-finished by mechanical polishing using diamond abrasive grains having a diameter of 1 μm, and an FE-SEM (electrolytic emission scanning electron microscope) was used. The number of precipitates having a length of 0.05 mm or more was measured at a magnification of 400 times. The observation area was 60 mm 2 and the number of precipitates in the observation area was counted. In addition, the use of EDS (energy dispersive X-ray analysis) of FE-SEM (electrolytic emission scanning electron microscope) confirms that Ni and Si, or Ni, Si and Mg are contained as the components of the precipitate to be measured. It confirmed by analyzing a component with respect to all the deposits. Here, the distinction between the precipitates X and Y is a precipitate containing Ni, Si, and Mg because of the problem of detection accuracy.
Further, when measuring the average particle size, the presence or absence of Ni—Si—Mg precipitates X having an average particle size of 10 μm or more was confirmed. The particle size was the length of the longest part of the precipitate in the photograph taken with FE-SEM. The average grain size is obtained by a simple average obtained by adding all crystal grain sizes in the observation area and dividing by the number of crystal grains.
試料から試験片を切り取り、機械研磨と化学エッチングにより表面酸化層を完全に除去した後、4端子法により導電率(%IACS)を測定した。本発明で目的とする好ましい導電率は、45%IACS以上である。 (2) Conductivity measurement of base material A test piece was cut out from a sample, and the surface oxide layer was completely removed by mechanical polishing and chemical etching, and then the conductivity (% IACS) was measured by a four-terminal method. The preferred electrical conductivity aimed at in the present invention is 45% IACS or higher.
JIS H 3130に記載のW曲げ試験を、曲げ半径Rが0になるように行った。試験方向はBad Way(曲げ軸が圧延方向と平行な方向)とした。試験片は幅10mm、長さ30mmの短冊形とした。次に、上記曲げRにてW曲げを行った試験片に対し、光学顕微鏡を用いて曲げ部断面を目視にて観察し、曲げ加工性の良否を判断した。評価基準は次の通りである。○:しわ、亀裂が無い、△:材料表面にしわがある、×:亀裂が発生。 (3) Bending workability The W bending test described in JIS H 3130 was performed so that the bending radius R was zero. The test direction was Bad Way (the direction in which the bending axis was parallel to the rolling direction). The test piece was a strip having a width of 10 mm and a length of 30 mm. Next, the cross section of the bending part was visually observed using an optical microscope for the test piece subjected to W bending with the bending R, and the quality of the bending workability was judged. The evaluation criteria are as follows. ○: No wrinkles or cracks, Δ: Wrinkles on the material surface, ×: Cracks occurred.
引張り方向が圧延方向と平行になる方向に、JIS Z 2201(2003年)に規定された13B号試験片を採取した。この試験片を用いてJIS Z 2241(2003年)に従って引張試験を行い、引張強度を求めた。本発明で目的とする好ましい引張強度は、760MPa以上である。 (4) Tensile strength No. 13B test piece defined in JIS Z 2201 (2003) was collected in a direction in which the tensile direction was parallel to the rolling direction. Using this test piece, a tensile test was performed according to JIS Z 2241 (2003) to obtain a tensile strength. The preferable tensile strength aimed at in the present invention is 760 MPa or more.
高温下での耐応力緩和特性として、応力緩和率(日本伸銅協会(JCBA)の技術標準:JCBA T309)を測定した。この試験は、幅10mmの短冊試験片を片持ちはりに取付け、高温の曲げ状態で所定時間保持後のたわみ変位(自由端における所定位置の変位)を初期状態と比較し、温度によるへたりを評価する方法である。試験後と初期状態のたわみが変わらない場合の応力緩和率の値は0%となり、試験後のたわみが初期状態より大きくなるほど、応力緩和率の値が大きくなる(応力が低下する)。応力緩和率は下式で与えられる(但し、y=所定時間経過後のたわみ変位(mm)、y1=初期たわみ(mm)、y0=設定高さ(mm))。
応力緩和率=(y-y1)/y0×100(%) (5) Stress relaxation property As the stress relaxation property at high temperature, the stress relaxation rate (Technical Standard of Japan Copper and Brass Association (JCBA): JCBA T309) was measured. In this test, a strip test piece having a width of 10 mm is attached to a cantilever beam, the deflection displacement (displacement at a predetermined position at the free end) after being held for a predetermined time in a high temperature bent state is compared with the initial state, and the sag due to temperature is It is a method to evaluate. When the deflection after the test and the initial state does not change, the value of the stress relaxation rate is 0%, and as the deflection after the test becomes larger than the initial state, the value of the stress relaxation rate increases (stress decreases). The stress relaxation rate is given by the following equation (where, y = deflection displacement (mm) after elapse of a predetermined time, y 1 = initial deflection (mm), y 0 = set height (mm)).
Stress relaxation rate = (y−y 1 ) / y 0 × 100 (%)
y0=(2/3)×L×L×σ0/(E×t) Further, the set height y 0 is given by the following equation (where L = target distance (mm), σ 0 = load stress (kg / mm 2 ); 0.2%
y 0 = (2/3) × L × L × σ 0 / (E × t)
一般的に使用されるコルソン合金の150℃×1000h後の応力緩和率は10%程度である。従って、以下の各発明例及び比較例の評価において、応力緩和率が9%以下のものを高温下での耐応力緩和特性が良好であるとみなした。 The stress relaxation was measured until the sample was 150 ° C. and showed a certain relaxation rate. Since a substantially constant stress relaxation rate was exhibited in about 1000 hours, this value was taken as the stress relaxation rate.
The stress relaxation rate after 150 ° C. × 1000 h of a commonly used Corson alloy is about 10%. Therefore, in the evaluation of each of the following invention examples and comparative examples, those having a stress relaxation rate of 9% or less were considered to have good stress relaxation resistance at high temperatures.
発明例1~10については、第1段目の均質化熱処理が800℃から890℃未満×2時間、第2段目の熱処理が890℃~980℃×0.5~1.2hであるので、熱間圧延後では、析出物Xは10μmを超える粗大粒が存在せず、かつ平均粒径が0.05~3.0μmであり、析出物Yはすべて固溶し、消失していた。その後、溶体化・冷間圧延を経て時効処理において、析出物Yを平均粒径が0.01~0.10μmとなるような時効条件にて析出させることができた。その結果、高強度、高導電性、良好な曲げ加工性と応力緩和性を得ることができた。 In the above table, “-*” represents no addition of other elements.
In Invention Examples 1 to 10, the first stage homogenization heat treatment is 800 ° C. to less than 890 ° C. × 2 hours, and the second stage heat treatment is 890 ° C. to 980 ° C. × 0.5 to 1.2 h. After the hot rolling, the precipitate X had no coarse grains exceeding 10 μm and the average particle diameter was 0.05 to 3.0 μm, and all the precipitate Y was dissolved and disappeared. Thereafter, in the aging treatment after solution heat treatment and cold rolling, the precipitate Y could be precipitated under aging conditions such that the average particle diameter was 0.01 to 0.10 μm. As a result, high strength, high conductivity, good bending workability and stress relaxation were obtained.
比較例14、15では、従来技術と同様に析出物X及び析出物Yが全て消失するような条件で均質化熱処理を行った。その後の時効処理で、析出物Yがそれぞれ1.7×108個、1.2×108個析出したため高強度を得ることができたが、析出物Xが存在しないので、母材中のMgの量が過剰となり、導電率が劣った。
比較例16の均質化熱処理では、析出物Xの平均粒径及び最大粒径の制御は可能であった。しかし、第1段目の熱処理温度が低いために、第2段目の温度が900℃でも熱処理前にサイズの大きかった析出物Yは小さくなるが消失しないため、析出物Yの平均粒径は0.10μmを超え、析出物Yの個数も少なかった。その結果、強度が劣った。
比較例17は、第2段目の均質化熱処理の時間が短すぎるため、熱間圧延後にも粗大な析出物Xが残り、析出物Xの平均粒径も3.0μmを超え、さらにサイズの大きな析出物Yが残ったが析出物Y全体の個数は少なかった。その結果、強度、曲げ加工性、応力緩和特性が劣っていた。
比較例18は2段目の熱処理時間が長すぎるため、析出物Xの平均粒径が0.05μm未満となり個数も少なく、導電率が劣っている。 In Comparative Examples 12 and 13, since the homogenization heat treatment temperature is higher than that in Comparative Example 11, there is no coarse precipitate X of 10 μm or more, but since the time is relatively short, the average particle size of the precipitate X is 3.0 μm or less. The precipitate Y having a large size did not disappear even after the homogenization heat treatment. As a result, Comparative Examples 12 and 13 were inferior in strength because the average particle size of the precipitate Y exceeded 0.10 μm and the number was small, and the stress relaxation characteristics were also poor because the number of precipitates X was large and the average particle size was large. .
In Comparative Examples 14 and 15, the homogenization heat treatment was performed under the conditions such that all of the precipitate X and the precipitate Y disappeared as in the prior art. In the subsequent aging treatment, 1.7 × 10 8 precipitates and 1.2 × 10 8 precipitates were precipitated, respectively, so that high strength could be obtained. However, since the precipitate X does not exist, The amount of Mg was excessive and the conductivity was inferior.
In the homogenization heat treatment of Comparative Example 16, the average particle size and maximum particle size of the precipitate X could be controlled. However, since the heat treatment temperature of the first stage is low, the precipitate Y which was large before the heat treatment becomes small but does not disappear even if the temperature of the second stage is 900 ° C. Therefore, the average particle size of the precipitate Y is The number of precipitates Y was less than 0.10 μm. As a result, the strength was inferior.
In Comparative Example 17, since the time for the second stage homogenization heat treatment is too short, coarse precipitates X remain after hot rolling, and the average particle size of the precipitates X exceeds 3.0 μm, and the size Large precipitates Y remained, but the total number of precipitates Y was small. As a result, the strength, bending workability, and stress relaxation characteristics were inferior.
In Comparative Example 18, the heat treatment time in the second stage is too long, so the average particle size of the precipitate X is less than 0.05 μm, the number is small, and the conductivity is inferior.
なお、耐熱めっき剥離性に関しては、発明例は実際の使用上問題が生じない耐熱めっき剥離性を示したが、発明例20は他の実施例に比べて更に優れた耐熱めっき剥離性を示した。 It can be seen from Invention Examples 19 to 22 and Comparative Examples 23 to 30 that the present invention is effective even in alloys in which other elements are added to a Cu—Ni—Mg alloy. In Comparative Examples 23 to 26, the homogenization heat treatment was performed in one stage, and since the precipitate X was not present, the conductivity was low. In Comparative Examples 27 and 28, the number of precipitates Y was small because the first-stage homogenization heat treatment temperature was low, but the average particle size was large. Therefore, it was inferior in tensile strength. In Comparative Examples 29 and 30, the second stage homogenization heat treatment time was short, so the particle size of the precipitate X was large, and coarse precipitates X of 10 μm or more remained in the product, but the number of precipitates Y was small. It was. Therefore, it was inferior in tensile strength, bending workability, and stress relaxation characteristics. Furthermore, in Comparative Example 29, since the number of precipitates X was large, the stress relaxation characteristics were inferior.
In addition, regarding the heat-resistant plating peelability, the invention example showed a heat-resistant plating peelability that does not cause a problem in actual use, but the invention example 20 showed a further excellent heat-resistant plating peelability compared to other examples. .
Claims (4)
- 1.0~4.5質量%のNi、0.16~1.13質量%のSi、及び0.05~0.30質量%のMgを含有し、残部がCu及び不可避的不純物からなるCu-Ni-Si-Mg系合金であり、Ni-Si-Mg析出物X及びNi-Si析出物Yを含み、析出物Xの平均粒径が0.05~3.0μmであり、粒径が10μmを超える析出物Xが存在せず、かつ析出物Yの平均粒径が0.01~0.10μmである銅合金。 Cu containing 1.0 to 4.5% by mass of Ni, 0.16 to 1.13% by mass of Si, and 0.05 to 0.30% by mass of Mg, the balance being Cu and inevitable impurities -Ni-Si-Mg based alloy, including Ni-Si-Mg precipitate X and Ni-Si precipitate Y, the average particle size of the precipitate X being 0.05 to 3.0 μm, A copper alloy in which no precipitate X exceeding 10 μm exists and the average particle size of the precipitate Y is 0.01 to 0.10 μm.
- 上記析出物Xは圧延方向に直角な断面1平方mm当たり1.0×103~1.0×105個含まれる請求項1の銅合金。 2. The copper alloy according to claim 1, wherein the precipitate X is contained in an amount of 1.0 × 10 3 to 1.0 × 10 5 per square mm in cross section perpendicular to the rolling direction.
- 上記析出物Yは圧延方向に直角な断面1平方mm当たり1.0×108~1.0×1011個含まれる請求項1又は2の銅合金。 The copper alloy according to claim 1 or 2, wherein the precipitate Y is contained in an amount of 1.0 x 10 8 to 1.0 x 10 11 per square mm of a cross section perpendicular to the rolling direction.
- Cr、P、Mn、Ag、Co、Mo、As、Sb、Al、Hf、Zr、Ti、C、Fe、In、Ta、Sn及びZnの群から選ばれた少なくとも一種を合計で0.01~2.0質量%含む請求項1~3いずれか1項記載の銅合金。 A total of at least one selected from the group consisting of Cr, P, Mn, Ag, Co, Mo, As, Sb, Al, Hf, Zr, Ti, C, Fe, In, Ta, Sn and Zn is 0.01 to The copper alloy according to any one of claims 1 to 3, comprising 2.0% by mass.
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