WO2004022805A1 - Alliage de cuivre extremement resistant - Google Patents

Alliage de cuivre extremement resistant Download PDF

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Publication number
WO2004022805A1
WO2004022805A1 PCT/JP2003/004470 JP0304470W WO2004022805A1 WO 2004022805 A1 WO2004022805 A1 WO 2004022805A1 JP 0304470 W JP0304470 W JP 0304470W WO 2004022805 A1 WO2004022805 A1 WO 2004022805A1
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WIPO (PCT)
Prior art keywords
content
strength
strength copper
alloy
contract
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PCT/JP2003/004470
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English (en)
Japanese (ja)
Inventor
Keiichiro Oishi
Isao Sasaki
Junichi Otani
Original Assignee
Sambo Copper Alloy Co., Ltd.
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Application filed by Sambo Copper Alloy Co., Ltd. filed Critical Sambo Copper Alloy Co., Ltd.
Priority to EP03794057A priority Critical patent/EP1538229A4/fr
Priority to JP2004534086A priority patent/JP3961529B2/ja
Priority to US10/478,454 priority patent/US20040234412A1/en
Priority to KR1020037010919A priority patent/KR100565979B1/ko
Priority to AU2003236001A priority patent/AU2003236001A1/en
Publication of WO2004022805A1 publication Critical patent/WO2004022805A1/fr

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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/025—Composite material having copper as the basic material

Definitions

  • the present invention relates to a high-strength copper used as a lead for electric, electronic, communication, information, H-law devices, automobiles, etc., such as leads, switches, connectors, relays, and sliding pieces. is there.
  • high-strength copper shelves are used for electrical, electronic, communication, information, tn-law equipment, automobiles, and other leads, switches, connectors, relays, and sliding pieces.
  • extremely strict glue improvement is also required for genuine materials such as leads, switches, connectors and so on.
  • the spring contact part of the connector is a force that can be shelved.
  • the high-strength copper that constitutes such an ultra-thin plate requires a high degree of strength in order to reduce its thickness.
  • high-strength copper ⁇ generally includes beryllium copper, titanium copper, aluminum grape, rye gong, nickel silver, brass and brass power with Sn, Ni added s well-known power s .
  • the HI-like high-role alloy has the following problems and cannot meet the above requirements.
  • beryllium copper the copper ⁇
  • those with the highest strength is always detrimental to beryllium Ca?
  • Human body in particular, a beryllium vapor poles also very dangerous in molten ⁇ any
  • waste disposal beryllium copper ⁇ or products containing them especially incineration
  • initial cost power s very high required dissolution equipment used to «. Therefore, there is a problem in economical efficiency including cost, in combination with the necessity of solution treatment in the final stage for obtaining predetermined characteristics.
  • Titanium copper has the second highest strength than beryllium copper, but since titanium is active, expensive melting equipment is required, which is a problem in quality improvement during melting. Therefore, as in the case of beryllium copper, there is a problem in economy due to the necessity of solution treatment in the final stage of $ 3 ⁇ 4t.
  • aluminum Wl same because the aluminum is tongue 143 ⁇ 4 prime, is that the force s difficult to obtain a ⁇ a ⁇ , also there is a solderability also problems such as bad.
  • Rinjindo and Yoshiro are made of tandem fiber because of their high hot workability and difficulty in hot work. Therefore, productivity is high and energy costs are high!
  • high-strength representative varieties such as Ringen for spring and nickel white for spring contain a large amount of expensive Sn and Ni, which poses a problem in economics.
  • Brass and brass to which Si and Ni are added are ⁇ ffi.
  • the strength is unsatisfactory, and there is a problem in corrosion resistance (stress corrosion IJ and ⁇ ! & Corrosion). It is unsuitable as a product structure for improving performance.
  • crystal grains can be refined by recrystallizing ⁇ depending on the added element, and the crystal grains (recrystallized grains) can be refined to a certain size ij ⁇ or less by 0.2%
  • the strength mainly of the steel can be remarkably improved, and the strength increases as the size of the crystal tree decreases.
  • various experiments were conducted on the list of added elements in the refinement of crystal grains, and the addition of Si to Cu_Zn alloy has the effect of increasing the number of nucleus sites, and furthermore, the effect of Cu— The addition of C 0 to Zn—Si alloy has the effect of suppressing the rice grain length.
  • the present invention has been made based on such findings, and is excellent in mechanical properties, strength, corrosion resistance, and the like.
  • This is a new high-strength copper alloy that has no problem in terms of economic efficiency. It can be used especially as a component for various equipment that is becoming smaller, more compact, and more sophisticated.
  • the purpose is to provide a high-strength copper with extremely high ⁇ m properties that can be used for a wide range of applications.
  • the present invention is mainly used as a material that requires high strength (plate material, strip material, wire material, etc.) or a processed material thereof (press-formed product, bent product, etc.).
  • first invention copper ⁇ a material that requires high strength
  • first invention copper ⁇ a processed material thereof
  • products and parts that can use the first invention copper ⁇ as a genius can be used in electronic devices used in wide-area, small-sized telecommunications, personal computers, etc., which are required to be thin-walled and carnized.
  • connectors Specifically, connectors, relays, switches, sockets, panels, gears, pins, washers, game coins, keys, tumblers, buttons, and hotspots are available. Clamps, fasteners, diaphragms, bellows, sliding pieces, bearings, sliding pieces for volumes, bushings, fuse grips, lead frames, counterweights, etc.
  • the present invention does not require strength mainly for the copper required for the first invention copper alloy, but requires a highly balanced strength and conductivity.
  • the purpose is to share high-strength copper (hereinafter referred to as the “second invention copper alloy”) as a material (plate material, strip material, wire material, etc.) or as a material for caro (press-formed product, bent product, etc.).
  • the second invention copper alloy high-strength copper
  • products and parts that can be decorated with the second invention copper ⁇ as a genius include various equipment parts for automobiles, information products that require conductivity,
  • the present invention mainly relates to a drawn wire material (a target wire material having a circular cross section, a cross-sectional work shape (square, polygonal) which requires the same high strength as the first invention copper ⁇ .
  • the purpose is to share a high-strength drama (hereinafter referred to as the "third invention copper") that is shelved in the haze as a deformed wire (such as hexagonal ⁇ ) or its karoe (bent processed product).
  • the products and parts that can use the third invention copper as a genius are parts of medical equipment, parts of wisteria, parts of wisteria, parts of luster, trees, parts for leisure, various m parts for automobiles, etc.
  • connectors There are two types: electronic devices, electronic devices, electronic devices, and connectors. Specifically, connectors, keys, headers, nails (such as nails for play equipment), washers, pins, screws, coil springs, lead screws, Shafts for copying, wire mesh (cooling device using wire mesh or seawater, filters for seawater intake and outlet in small M white, etc.), sliding pieces, bearings, bolts, etc. can be mentioned.
  • the mean binding Akiratsubu ⁇ D is 0, 3 ⁇ m ⁇ D ⁇ 3.5 m (preferably 0.3 m ⁇ D ⁇ 2.5 m, more preferably 0.3 m ⁇ D ⁇ 2 m) None has, it is an ⁇ that the 0. 2% K3 ⁇ 4 force s 250 N / mm 2 or more in the recrystallized state (preferably 300 N / mm 2 or higher).
  • the third invention copper ⁇ is composed of 66-76 ma ss% (preferably 68-75.5 mass%) of Cu and 21-33 ma ss% (preferably 22-31111335%) of 2] 1 and 0. 5 to 2 ma ss% (preferably 0.8 to 1.8 ma ss%, more preferably:!
  • the average grain size D is 0.3 ⁇ m ⁇ D ⁇ 3.5 m (preferably 0.3 m ⁇ D ⁇ 3 m, It is preferably 0.3 m ⁇ D2.5 m), and the 0.2% movement in the recrystallized state is 250 N / mm 2 or more (preferably 300 N / mm 2 ⁇ W is defined as W.
  • the average crystal grain size of 0% and 0.2% in the copper alloy is resistant to recrystallization of a part or all of the alloy structure.
  • the average grain size of the material (hereinafter referred to as “recrystallized material”) obtained by the last recrystallization treatment (hereinafter referred to as “final crystallization process”) is 0.2%. It is specified by.
  • the recrystallization process is performed only once, it is needless to say that the process is the: 11 winter recrystallization process and the evacuation is a crystal material.
  • Jomei copper alloy is in a preferred form of difficulty
  • the lump is processed into a dog by plastic karoe including hot working (j ⁇ 3 ⁇ 4, extrusion, forging, etc.) and ⁇ or cold working o, wire drawing.
  • Recrystallized material obtained by recrystallization treatment (final recrystallization treatment) by quenching (final recrystallization, etc.) mainly the first and second invention copper alloys are rolled materials, and the third invention Copper alloy is a wire drawing material
  • a cold-worked material obtained by cold-working (j, drawing) the recrystallized material of the above (1) to a predetermined dog mainly, the first and second invention copper are brilliant,
  • the third invention copper alloy is a wire drawn material
  • copper alloy in order to further improve the characteristics, 0.005 to 0.5 ma ss% (preferably 0.01 to 0.3 ma ss%, more preferably 0.02 to 0 2ma ss%) C
  • the Sn content is a value obtained by dividing the Si content by the content, and S i / Sn is 1.5 or more (preferably S i / S n ⁇ 2, more preferably S i / S n n ⁇ 3).
  • copper alloy 0.005 to 0.3 mass% (preferably 0.01 to 0.2 mass%) Fe and / or 0.005 to 0.3 mass% (preferably 0. .01 to 0.2 mass%) may further be contained as a co-element of Co or as a co-addition element with Co.
  • the Fe content or the Ni content is determined in consideration of the Si content (when co-added with C 0, the Si content and the Co content).
  • the content of Fe and Ni is the value obtained by dividing the synonymous content including the case where Co is contained by the content of Si (Fe + N i + Co) / S i is 0.005.
  • the total content (F e + N i + C 0) determined is 0.005 to 0.55 mass% (preferably 0.01 to 0.35 mass%, more preferably Is 0.02 to 0.25ma ss%).
  • the Co content and the Sn content are determined in consideration of the relationship with the Si content. That is, within the above range, the Co content is a value obtained by dividing the Co content by the Si content.
  • the Sn content is a value obtained by dividing the Si content by the Sn content within the above-mentioned range, and the value S i / Sn is 0.5 or less (preferably, S i / S n ⁇ 0.4, Preferably, f i is set so that S iZSn ⁇ 0.3).
  • copper instead of or together with Co, Q.005 to 0.3mass% (more preferably 0.01 to 0.2mass%) Fe and / or 0.005mass%.
  • Ni of 0.3 to 0.3 mass% (more preferably 0.01 to 0.2 mass%) can be contained.
  • the Fe content * X and the Ni content are determined in consideration of the Si content (when co-added with Co, the Si content and the Co content).
  • the total content (Fe + Ni + Co) power s 0.005 to 0.55 mass% (preferably 0.01 to 0.35 mass%, more preferably 0.02 to 0.25 mass%) %) Is desirable.
  • coppers, P, Sb, As, Sr, Mg, Y, Cr, La, Ti, Mn, Zr , In, Hf can contain one or more elements scaled down. The content of each of these elements is determined in the range of 0.003 to 0.3 mass%, as follows:
  • copper ⁇ in order to further improve the characteristic I production, 0.005 to 0.3 mass% (preferably 0.01 to 0.2 mass%, more preferably 0.1 mass%). 02-0.15ma ss%) and / or 0.03-lma ss% (preferably 0.05-0.7ma ss%, more preferably 0.05-0.5ma ss%) the sn, it is preferable to assume that further form a ⁇ 1 Makoto containing.
  • the Sn content is a value obtained by dividing the Si content by the content, S 1311 is 1 or more (preferably S i / Sn ⁇ 1.5, more preferably S i / Sn ⁇ 2). Is determined as follows.
  • copper ⁇ as an element of Co or as a co-addition element with Co, 0.005 to 0.3mass% (preferably 0.01 to 0.2mass%) of Fe and And / or 0.05% to 0.3mass% (preferably 0.01 to 0.2mass%) of Ni can be contained 5 '.
  • An alloy fiber can be further contained so that the total content thereof is 0.005 to 0.25 mass%.
  • the thickness is preferably not more than 2.5 ⁇ m.
  • the average crystal ⁇ Keeping D less than 2 m is considered to be powerful.
  • the movement also improves.
  • the minimum of the average crystal t3 ⁇ 4 ⁇ is 0.3 m, which is less than 0.3 ⁇ m. Things are expected to be difficult to obtain at the level.
  • the first to third invention copper ⁇ , in order to secure a resistance to 250 N / mm 2 or more (preferably 300 N / mm 2 or more), 0.3 m ⁇ D ⁇ It is said that it is necessary to have a recrystallized basket of 3.5 m. In other words, the average result in the recrystallized state (the state after the final recrystallization process)! It is necessary that the particle size D is 0.3 m ⁇ D ⁇ 3.5 ⁇ m and 0.2% K 250 is 250 N / mm 2 or more. In the case where the second and third invention copper alloys are required to have higher strength, it is considered that the copper alloy has a thickness of 0.
  • the first invention copper alloy which has higher strength than the second and third invention coppers, and which is also used for required applications, has a capacity of 0.3; m ⁇ D ⁇ 2.5 ⁇ More preferably, it should be set to 0.3 m ⁇ D ⁇ 2 / m.
  • the first to third invention copper ⁇ realizes the refinement of crystal grains as described above by recrystallization by an appropriate heat treatment ( ⁇ : ⁇ ).
  • Refinement of grains can be achieved by setting the alloy ⁇ J ⁇ described above. That is, No .; -In the third invention copper alloy, Zn, Si lowers the stacking fault energy, increases the dislocation density, and increases the number of nuclei sites (locations) for recrystallization, thereby contributing to the refinement of crystal grains.
  • a function of forming a solid solution in the Cu matrix to contribute to the improvement of the material strength hereinafter, both functions are referred to as “crystal thinning 'strength improving function”
  • the first and second invention copper ⁇ , which are mainly shelved as a brilliant product or a processed material thereof, in order to achieve the functions of crystal thinning and strength improvement due to the inclusion of Zn in 5 minutes, It is necessary that the Zn content be 4 mass% or more, and in order to exhibit the function more effectively, in the first invention copper alloy for which the strength is greatly improved, 6 mass% or more (preferably 7 mass%) is required. mass% or more), and in the second invention copper, which is considered to be slightly inferior in strength to the first invention copper, at least 5 mass% (preferably 6 mass% or more).
  • the Zn content is reduced to 19 ma ss% in the first invention copper alloy. Lower (preferably 15 mass% or less, more preferably 13 mass% or less), and in the second invention copper ⁇ , 17 mass% or less (preferably 13 mass% or less, more preferably 11.5 mass% or less) It is necessary to keep it.
  • the function of improving the crystal densification 'strength by containing Si is exhibited with i being much smaller than that of Zn, but is due to mutual use with Zn.
  • S i can respond to co-addition with Zn, and has an action force s that suppresses one life.
  • the addition of iifij of Si reduces the conductivity.
  • the first invention copper ⁇ to the strength improvement ⁇ TO AkiraTatsuki ⁇ raw eye, it is necessary that force s to keep and the S i content 0. 5 ma ss% or more, 0. It should be at least 9 mass% (more preferably 1.3 mass% m ⁇ ).
  • the Si content is preferably set to 2.3 ma ss% or less, more preferably 2.2 ma ss% or less.
  • the Si content in the second invention copper alloy, which emphasizes the balance between strength and conductivity, the Si content must be at least 0.1% in order to exhibit the crystal-densification effect necessary for obtaining the predetermined strength. It is important to keep it at 0.2 ma ss% or more.
  • the Si content in order to maintain the electrical conductivity in consideration of the balance between strength and strength, it is necessary to keep the Si content to 0.8 mass% or less. To ensure electrical conductivity, it should be 0.6 mass% or less (more preferably, 0.5 mass% or less) Preferably.
  • the force required to balance the effect of crystallization by co-addition of Zn and Si with the strength of 14% of stress corrosion It is not sufficient to determine the Zn, Si content individually ⁇ : within the above range, and the relationship between Zn, Si content is specified by Zn_2_5 ⁇ Si. Then, it is necessary to determine the value of the relational expression within a certain range.
  • the first invention copper alloy needs to have Zn ⁇ 2.5 ⁇ S i ⁇ 0mass%, and Zn ⁇ 2.5 ⁇ S i ⁇ lm ass% (preferably Zn-2.5 ⁇ S i ⁇ 2 mass%), and in the second copper alloy ⁇ , Zn-2.5 ''S i ⁇ 2ma ss%, and Zn—2.5 ⁇ S i ⁇ 4ma ss% (more preferably, Zn—2.5 ⁇ S i ⁇ 5ma ss%).
  • any of the first and second invention copper alloys when Zn ⁇ 2.5 ⁇ S i> 15 ma ss%, stress corrosion ij is significantly generated, so that Zn, S i It is necessary to determine the content so that Zn-2.5 ⁇ S i ⁇ 15 ma ss%.
  • stress corrosion ij is significantly generated, so that Zn-2.5 ⁇ S i ⁇ 15 ma ss%.
  • ftj S i ⁇ l 2ma ss% more preferably, Zn-2.5 ⁇ S i ⁇ 9ma ss% for the first invention copper, Z n-2.5 ⁇ S i ⁇ 10 mass% for the second invention copper ⁇
  • Is preferably determined.
  • the Zn content is, as in the first and second invention copper, naturally, taking into account the strength improvement function.
  • the third invention copper is mainly used as a drawn wire or a processed product thereof, so it is necessary to take hot extrudability into consideration.
  • 2 invention should be a large amount in comparison with the copper alloy, in order to ensure a sufficient hot extrudability is that the force 5 must be a 21 mass% or more.
  • the copper alloy of the third invention is inferior in stress corrosion cracking resistance due to its high Zn content compared with the copper of the first and second inventions.
  • Zn content is low, use as Itoizumi ⁇ , stress rot resistance: f! J Can s power.
  • copper in order to secure a necessary and sufficient stress KusaKen U Re 143 ⁇ 4 Pi cold workability as wires or the like, mosquitoes can put Z n content as 33 mass% or less? Required is there. That is, if the Zn content exceeds 33mass%, the / 3 phase and the ⁇ phase are easily drawn, which gives bad workability to cold workability and stress decay: 1'43 ⁇ 4 ⁇ 1 »& Corrosion is also a problem.
  • the Zn content is preferably set to 31 mass% or less.
  • copper ⁇ it is necessary to consider the Cu content in order to ensure hot extrudability and cold workability. If the Cu content is less than 66 mass%, the / 3 phase and the ⁇ phase ⁇ to facilitate, cold workability becomes a problem, if it exceeds 76 mass% to the contrary, the hot extrusion force s difficult. Therefore, it is necessary to keep the Cu content at 66-76 ma ss%, and to ensure sufficient cold workability and hot extrudability, it is important to keep the Cu content at 68-75.5 ma ss%. .
  • the Si content needs to be 0.5 mass% or more, as in the first invention copper, mainly for the function of improving the crystal thinning 'strength.
  • the material is a drawn wire, it is preferably 0.8 mass% or more, and more preferably 1 mass% or more.
  • the Si content exceeds 2 mass%, a phase and foveals, which are factors inhibiting cold workability, precipitate. Therefore, in order to ensure the cold Karoe resistance, it is necessary to the S i content is 2 mass% or less, considering that contained in Z 11 months? Multimeric, 1. 8 mass% or less More preferably, it is more preferably 1.7 mass% or less.
  • the crystal grains grow as the 3 ⁇ 4J rises or as ⁇ !
  • the recrystallized grains at the beginning of the recrystallization process will start to grow by the end of the recrystallization process in winter, and will grow considerably when the set recrystallizes to. Therefore, in order to uniformly distribute fine recrystallized grains in the swelling, it is preferable to suppress the growth of recrystallized grains during the recrystallization process.
  • Co has a function of controlling such recrystallized grains, and this is the reason why Co is added to the first to third invention coppers.
  • Co bonds with Si to form fine precipitates such as Co 2 Si of about 0.01 ⁇ m), thereby suppressing the growth of crystal grains.
  • To be grain growth ⁇ function forces volatilized by Co is that mosquito? Necessary to the a C 0 content 0. 005 mass% or more.
  • the amount of Co added does not contribute to the formation of the above-mentioned precipitates, but the solid solution of c3 ⁇ 4 of ⁇ 3 ⁇ 4 improves the matrix and improves the stress relaxation characteristics. Will be.
  • the C 0 content of 0.01 to 0.01 of the first to third copper alloys must be reduced. It is preferably set to not less than mass%, more preferably not less than 0.02 mass%.
  • the first and second invention copper alloys even if Co is added in excess of 0.5 mass%, and in the third invention copper alloy, Co is added in excess of 0.3 mass%. Nevertheless, the required effect of suppressing the formation of crystal grains and improving the effect of stress reduction are clear and do not improve any further, and are economically wasteful. There is a possibility that bending workability may be deteriorated due to excessive formation or excessive amount of precipitates.
  • the Co content needs to be 0.5 mass% or less in the first and second invention copper alloys, and 0.3 mass% or less in the third invention copper ⁇ .
  • the first and second invention copper require 0.3 ma. s Force to be kept at 3% or less Force, more preferably force to be 0.2 mass% or less, and more preferably force to be 0.2 mass% or less for the third invention copper alloy More preferably, it is set to 0.15 mass% or less.
  • Co has a close relationship with Si in reducing the crystal grain size
  • the Co content should be adjusted so that the ratio Co / S i to the Si content becomes 0.005 or more in the first and third invention copper alloys. It is important to determine the second invention copper so that it becomes 0.02 or more. That is, if Co / Si does not reach these values, the composition of the above-mentioned copper alloy is small and the effect of controlling the formation of crystal grains is not controlled. Ii ⁇ It is difficult to obtain the required strength.
  • Co / Si is 0.01 or more in the first and third invention coppers, More preferably, it is 0.02 or more. Further, in the second invention copper, it is preferably 0.04 or more, more preferably 0.06 or more.
  • the value 0 should be determined so that the Co / Si force s becomes a certain value or more as described above in relation to the Si content, but the Co / Si force is more than necessary. If it becomes larger, the above mentioned products will be coarsened and increased in volume, impeding bending workability. For example, if Co / Si exceeds 0.4 in the first invention copper ⁇ , which is a thigh, and 0.4 in the third invention copper, which is a wire drawing material or a product material thereof, bending occurs. Workability sharply decreases.
  • the upper limit of Co / S i is compared with this point and the effect of Co crystal elimination P ⁇ ! :
  • the decision should be made in consideration of the intended use of the copper and the ⁇ jg and ⁇ ⁇ 1 dogs.
  • the range of Co / Si is as follows: It is determined. That is, the upper limit of the Co / S i is first invention copper ⁇ near connexion is that force necessary to the C o / S i ⁇ 0. 5, CoZS i ⁇ 0.
  • Fe and Ni exhibit the same crystal 3 ⁇ 43 ⁇ control effect as Co (more precisely, the effect of Fe and Ni is less than or equal to C 0). It was but ', connexion, Fe Ni, it forces s is contained in the t 3 ⁇ 4 element of Co' can. Of course, by co-adding Fe and Ni with C 0, a further improvement in the above effects can be expected. It is expensive to add Fe and Z or Ni instead of or together with C0.
  • the second In the invention copper alloy it is 0.02 to 1.5 (preferably 0.04 to 1, more preferably 0.06 to 0.5), and in the third invention copper, it is 0.005 to 0.4 (preferably 0.4 to 0.5). 01 to 0.2, more preferably 0.02 to 0.15).
  • Fe and Ni can be f elements of Co and exert the same function as Co. Therefore, when two or more of Fe, Ni and Co are added together, However, their total content should be equal to the content when only Co is added to the insects (the content of self-edited Co).
  • the upper limit of the co-added content (total content) of Fe, Ni, and Co is higher than the Co content in consideration of solid solution and precipitation. Can be increased by about 0.05 mass%. From this point, when two or more of Fe, Ni, and Co are co-added, the total content (Fe + Ni + Co) and the upper limit of the Co content are set to 0. It was determined that it was desirable to increase the range by 05 mass%. That is, the total content (F e + ⁇ i + C 0) force s of the first and second invention copper ⁇ is 0.005 to 0.55 ma ss% (preferably 0.01 to 0.
  • 35 ma ss% 35 ma ss%, more preferably 0.02 to 0.25 ma ss%), and in the third invention copper alloy, 0.005 to 0.35 mass s% (preferably 0.01 to 0.25 ma ss%). And more preferably 0.02 to 0.2 mass%).
  • the Sn content must be at least 0.03 mass% in order to fully exhibit the function to improve the performance of the matrix and the properties of the matrix, stress relaxation characteristics, corrosion resistance, and abrasion resistance. It should be at least mass%.
  • the Sn content exceeds 1.5% in the first invention copper ⁇ , which is a copper alloy, and exceeds 1 mass% in the third invention copper ⁇ , which is a wire drawing material, bending workability is increased. It drops sharply. Therefore, in order to ensure bending workability, it is necessary that the Sn content be 1.5 mAs s% or less in the first invention copper and 1 mA s s% or less in the third invention copper.
  • the content of 311 should be set to 0.7 mass% or less. It is the power to keep it below 5mass%.
  • the strength is improved by adding Sn, the crystal is refined, improvement of the stress relaxation characteristics, anti-stress corrosion ⁇ Y is resistance, corrosion resistance, it is preferable to improve the abrasion resistance, for which is that the force? necessary to the the Sn content 0. 2ma ss% or more, 1 mass% or less depending on the required strength It is also important to keep it above 1.2mass 3%.
  • the Sn content must be 3 mass% or less in order to ensure such calo workability. In order to ensure better hot workability and bending workability, 2.6 ma ss % Or less, and more preferably 2.5 mass% or less.
  • the Sn content is determined to be S i / S n ⁇ 1 for the same reason as described above. must, in order to sufficiently ensure the ductility is S i / Sn ⁇ l. 5 and to keep it forces operators preferred, it forces s to keep the S i / Sn ⁇ 2.
  • copper having a high Zn content particularly, P, Sb and 83 are added for the purpose of improving hemp lead corrosion resistance and stress corrosion resistance.
  • the effect of P, Sb, and As, which are excited for such a purpose, is hardly exhibited when the excitation is less than 0.005%, as in the above case.
  • the P content exceeds 0.2 mass%, the bending workability in the cold state will be degraded. Therefore, when P, Sb, and As are purified in the third invention copper ⁇ , the content is 0.005 to 0.2 mass%. It is important that the total content when two or more of P, Sb, and As are added together is set to 0.005 to 0.25 mass%.
  • the process is as follows. It will be a shelf for 20 minutes to 10 hours at C.
  • Such «management is usually Roh Tutsi force 5 carried out in the manner ', If no ⁇ time mosquitoes 3 ⁇ 4, those that have been recrystallized in the early stages of YuzuruMakoto force s, if C o crystal growth Sip braking effect forces volatilized by adding Even if it does, it may grow slowly and prevent uniform refinement of the crystal grains.
  • m is added to C by performing a treatment (rapidly high ⁇ 3 ⁇ 4 ⁇ heat treatment) at a higher temperature (a material temperature for growth) than that of a general;
  • a treatment rapidly high ⁇ 3 ⁇ 4 ⁇ heat treatment
  • the growth of the initial recrystallized grains can be prevented, and the crystal grains can be satisfactorily reduced by recrystallization. That is, by applying high thermal energy in a short period of time, recrystallization can be performed almost simultaneously in more nucleation sites in a short period of time, and there is no time allowance for crystal growth.
  • mm a treatment for example, a higher temperature (a material temperature for growth) than that of a general
  • Roe material is heated at 450 ⁇ 750 ° C, 1 ⁇ : L0000 seconds with rice cake. It is to make it.
  • the first to third invention copper alloys can be used as a recrystallized material of (1), a cold-worked material of (2) or a product processed material of (3) or (4), as described in is the force s, by keeping adding the following processing in the ⁇ extent, can be force s further improve the alloy particular strength.
  • the caloric work rate for example, by setting the caloric work rate to 30% or more (preferably 60% or more) in the cold working before obtaining the recrystallized material, specifically, the customer material referred to in (1) can be used.
  • the step of obtaining or by performing cold working with a wire drawing ratio of 30% or more (preferably 60% or more) the grain refinement is improved, and the strength improvement due to the grain refinement is improved.
  • the image material to be finally recrystallized is a material having a small average crystal string ⁇ (average crystal before recrystallization ⁇ ).
  • 3 ⁇ 4 ⁇ is 2 It should be less than 0 ⁇ m (preferably less than 10 ⁇ m). The smaller the average crystal tree before recrystallization, the more the location of the nucleus of recrystallization in the subsequent yielding increases, especially the higher the standing density at the grain boundary, the more likely it is to be a nucleus site.
  • the average crystal grain size is, the higher the strength is. Therefore, the energy required for the high-strength game is high, the cost is high, and it takes 3 ⁇ 4jt time. Therefore, the average crystal tree Holy of ⁇ material referred to in paragraph (1), it forces decide in view of the knitted his own machining rate? Preferable. In the case where the strength of the recrystallized material is insufficient when used, the recrystallized material is subjected to cold ⁇ or cold drawing at a working rate of 10 to 60% to achieve higher strength. Can be obtained.
  • the knitting material when the knitting material is obtained, if a single pass of rolling or drawing and working roving is performed, the reduction and drawing ratios must be increased (15% or more (preferably 25% or more). )) Power to keep. This is because the shearing strain and nucleation sites are increased by the reduction of the draft and the elongation and the cold working, and further refinement of the crystal grains can be realized.
  • the rolling process is performed by a / W ⁇ roll or a roll with an extremely low angle, or the wire drawing process is performed with a wire drawing die with a large die angle or a wire drawing die with an extremely small die angle. It is also important to increase the number of nucleation sites or local strain energies and to realize further finer recrystallized grains.
  • the Jomei copper alloy is subjected to an appropriate treatment that does not recrystallize (" ⁇ , 150 to 600 ° C, 1 second to 4 hours in a restaurant). by placing the spring limit I class Pi, it can be force s significantly improve the mosquitoes bamboo mouth characteristics.
  • cold working material including cold working material referred to in (4)
  • the processed material of (4) is subjected to Mi treatment, for example, at 200 ° C. for 2 hours, or at 600 ° C. for 3 seconds.
  • the copper ⁇ of the stringiness shown in Tables 1 to 4 was dissolved in the atmosphere to obtain a prism ⁇ ⁇ fiber having a thickness of 35 mm, a width of 80 mm, and a length of 200 mm. Then, the ingot was hot-rolled (at 4 passes) at 850 ° C to obtain an intermediate plate having a thickness of 6 mm, which was then pickled, and further cold-processed into a final plate having a thickness of 1 mm. By subjecting each final sheet to 100% recrystallization (hereinafter referred to as “recrystallized Sg”), it is heat-treated ('otun) for one hour, that is, the complete recrystallization of the knitting is performed. Thus, the first brilliant copper No.
  • Difficult Example 2 the copper of ⁇ shown in Tables 5 to 8 was dissolved in air, and the thickness was 35 mm and the width was 35 mm.
  • Example 3 ⁇ of Itosei shown in Tables 9 to 12 was dissolved in the atmosphere to obtain a cylindrical longevity lump having a diameter of 95 mm and a length of 180 mm.
  • the lump was heated to 780 ° C and extruded (500 t) to obtain a diameter of 12 mm.
  • Comparative Example 1 a first comparative example of feathers ⁇ feN 0.401 to N 0.422 shown in Table 13 was obtained by the same process as in 1 m. Further, as Comparative Example 2, the same second comparative example 0.423 to No. 431 shown in Table 14 were obtained by the same steps as in the third cutting example. Note that the first comparative example ⁇ feN o. 40 l to No. 407 are the same fibers as JIS standard C2100, C2200, C2300, C2400, C2600, C2680 and C4250, respectively, and the second comparative example Alloy Nos. 423 and N 0.424 have the same integrity as JIS standard C 2600 and C 2700, respectively. In Tables 1 to 12, ⁇ ⁇ ⁇ in “(Co + Fe + Ni) ZSi” for those containing Co but not Fe or Ni should be read as “Co / Si”. And
  • the first invention copper ⁇ No. 101 to No. 186, No. 102A, No. 107A, No. 111A, No. 154A, No. 180A
  • the second invention copper No. 20 l to No. No. 281, No. 202 A, No. 209 A, No. 25 OA, No. 265 A and 3rd invention copper No. 301-No. 397, No. 302 A, No. 314 A, No. 338 A and 1st and 2nd Comparative Example ⁇ Recrystallization of No. 40 1 to No. 43 1 (excluding No. 421, No. 425, No. 427, No. 431 which abandoned the production) Average crystal 3 ⁇ 4 D (m ) was measured based on a section using an optical image (JI S-H0501). The results were as shown in Tables 15 to 26.
  • the conductivity was measured. The results were as shown in Tables 15 to 20 and 25.
  • the conductivity (% IACS) is the percentage ratio of the value obtained by dividing the volume resistivity (17.241 (10-9 ⁇ ⁇ ⁇ ⁇ ) equivalent to that of the international standard by the mechanical ratio of the ⁇ . I can do it.
  • the first invention copper ⁇ No. 101 to No. 186, No. 102A, No. 107A, No. 11A, No. 1 54A, No. 180A and the second invention copper ⁇ ⁇ No. 201 to No. 281, No. 202 A, No. 209 A, No. 25 OA, No. 265 A and the first comparative example No. 401 to No. 422 (excluding No. 421)
  • Tensile tests were performed using an Ammsler ⁇ ability tester, and K3 ⁇ 4 (0.2% ⁇ ]), tensile and elongation were measured.
  • ⁇ is cold-rolled (30% thigh) to a thickness of 0.7 mm, and its pressure resistance (hereinafter referred to as “micro-roe material”) is subjected to the same tensile test as above to obtain a 0.2, the tensile strength and elongation were measured, and the bending workability was evaluated, and the test was conducted to confirm the strength and strength.
  • the results were as shown in Tables 15 to 20 and 25.
  • the first invention copper ⁇ No. 101 to No. 186, No. 102 A, No. 107 A, No. 11 A, No. 154A, No. 180 A and the second invention
  • the impeached wood obtained by rolling copper ⁇ No. 201 to No. 281, No. 202 A, No. 209 A, No. 25 OA, No. 265A by 30% is also a high impregnated material according to the present invention. It goes without saying that it is high-strength copper.
  • the bendable basket was cut from the impeached material perpendicular to the thigh direction!
  • the dough was bent into a W dog and the degree of bending R / t ( R: curvature radius (mm) on the inner circumference side at the bent part, t: (mm)).
  • R curvature radius (mm) on the inner circumference side at the bent part, t: (mm)
  • the stress decay test was carried out using a sample vessel and a sample night specified in JIS H3250.
  • a cage with stress decay resistance J was used.
  • ⁇ ⁇ '' those with a stress relaxation rate of 20% or less after 75 hours exposure are indicated by ⁇ ⁇ '' as having excellent corrosion resistance: Even if the amount exceeds 30%, those that are 20% or less after 30 hours exposure are indicated by “ ⁇ ” as having good corrosion cracking resistance (no problem), and the stress relaxation rate after 12 hours exposure
  • the bending workability of the basket is determined by bending the material to 90 degrees through the V block, and the degree of bending when a crack occurs R / d (R: inner circumferential side in the bent part)
  • ⁇ ⁇ '' the degree of bending when a crack occurs.
  • Tables 15 to 26 show that the first to third invention copper alloys have finer crystal grains than those of the first and second comparative examples which do not have ⁇ the can force s achieved are those mechanical properties and bending workability, and the like significantly increases of ⁇ Ru the containing excited, plate even in conventional high strength Application for hardly decorative in ⁇ , elongated member, wires, etc. that force 3 ⁇ 4 are those that can be force s to I 3 ⁇ 43 ⁇ 4 to as

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Abstract

Alliage de cuivre extrêmement résistant possédant des propriétés mécaniques excellentes, ainsi que des caractéristiques optimisées d'adaptabilité au traitement, de résistance à la corrosion et de productivité. Cet alliage consiste en un matériau laminé dont la composition contient 4 à 19 % massique de zinc, 0,5 à 2,5 % massique de silicium, le reste étant constitué par du cuivre. Les teneurs en zinc et en silicium répondent au rapport ≤ Zn - 2,5 . Si ≤ 15 ( % massique). Ce matériau possède une structure cristalline dont le diamètre moyen de grain D est de 0,3 à 3,5 νm et la limite d'élasticité à 0,2 % est égale ou supérieure à 250 N/mm2 en l'état de recristallisation.
PCT/JP2003/004470 2002-09-09 2003-04-08 Alliage de cuivre extremement resistant WO2004022805A1 (fr)

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EP03794057A EP1538229A4 (fr) 2002-09-09 2003-04-08 Alliage de cuivre extremement resistant
JP2004534086A JP3961529B2 (ja) 2002-09-09 2003-04-08 高強度銅合金
US10/478,454 US20040234412A1 (en) 2002-09-09 2003-04-08 High-strength copper alloy
KR1020037010919A KR100565979B1 (ko) 2002-09-09 2003-04-08 고강도 동합금
AU2003236001A AU2003236001A1 (en) 2002-09-09 2003-04-08 High-strength copper alloy

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WO2007148712A1 (fr) * 2006-06-23 2007-12-27 Ngk Insulators, Ltd. Alliage laminé à base de cuivre et son procédé de fabrication
JP4913910B1 (ja) * 2011-01-29 2012-04-11 サンエツ金属株式会社 パチンコ釘用伸線材の製造方法
JP2012153961A (ja) * 2011-01-28 2012-08-16 Mitsui Sumitomo Metal Mining Brass & Copper Co Ltd 銅−亜鉛合金板条及び銅−亜鉛合金板条の製造方法
WO2013042678A1 (fr) * 2011-09-20 2013-03-28 三菱伸銅株式会社 Feuille d'alliage de cuivre et procédé de production de feuille d'alliage de cuivre
US9303300B2 (en) 2005-09-30 2016-04-05 Mitsubishi Shindoh Co., Ltd. Melt-solidified substance, copper alloy for melt-solidification and method of manufacturing the same
US9328401B2 (en) * 2004-08-10 2016-05-03 Mitsubishi Shindoh Co., Ltd. Copper alloy casting having excellent machinability, strength, wear resistance and corrosion resistance and method of casting the same
WO2016170992A1 (fr) * 2015-04-21 2016-10-27 株式会社オートネットワーク技術研究所 Fil en alliage de cuivre, toron en alliage de cuivre, câble électrique gainé et faisceau de câbles
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US10570483B2 (en) 2004-08-10 2020-02-25 Mitsubishi Shindoh Co., Ltd. Copper-based alloy casting in which grains are refined
US10017841B2 (en) 2004-08-10 2018-07-10 Mitsubishi Shindoh Co., Ltd. Copper alloy casting and method of casting the same
US9328401B2 (en) * 2004-08-10 2016-05-03 Mitsubishi Shindoh Co., Ltd. Copper alloy casting having excellent machinability, strength, wear resistance and corrosion resistance and method of casting the same
US9303300B2 (en) 2005-09-30 2016-04-05 Mitsubishi Shindoh Co., Ltd. Melt-solidified substance, copper alloy for melt-solidification and method of manufacturing the same
JP2007169790A (ja) * 2005-12-22 2007-07-05 Viega Gmbh & Co Kg 媒体水又は飲料水運搬作業用の低マイグレーション部品
WO2007148712A1 (fr) * 2006-06-23 2007-12-27 Ngk Insulators, Ltd. Alliage laminé à base de cuivre et son procédé de fabrication
EP2042613A1 (fr) * 2006-06-23 2009-04-01 NGK Insulators, Ltd. Alliage laminé à base de cuivre et son procédé de fabrication
US8211249B2 (en) 2006-06-23 2012-07-03 Ngk Insulators, Ltd. Copper base rolled alloy and manufacturing method therefor
EP2042613A4 (fr) * 2006-06-23 2013-03-13 Ngk Insulators Ltd Alliage laminé à base de cuivre et son procédé de fabrication
JP5263525B2 (ja) * 2006-06-23 2013-08-14 日本碍子株式会社 銅基圧延合金の製造方法
JP2012153961A (ja) * 2011-01-28 2012-08-16 Mitsui Sumitomo Metal Mining Brass & Copper Co Ltd 銅−亜鉛合金板条及び銅−亜鉛合金板条の製造方法
JP4913910B1 (ja) * 2011-01-29 2012-04-11 サンエツ金属株式会社 パチンコ釘用伸線材の製造方法
US9133535B2 (en) 2011-09-20 2015-09-15 Mitsubishi Shindoh Co., Ltd. Copper alloy sheet and method of manufacturing copper alloy sheet
US9080227B2 (en) 2011-09-20 2015-07-14 Mitsubishi Shindoh Co., Ltd. Copper alloy sheet and method of manufacturing copper alloy sheet
KR101476592B1 (ko) 2011-09-20 2014-12-24 미쓰비시 신도 가부시키가이샤 구리 합금판 및 구리 합금판의 제조방법
WO2013042678A1 (fr) * 2011-09-20 2013-03-28 三菱伸銅株式会社 Feuille d'alliage de cuivre et procédé de production de feuille d'alliage de cuivre
WO2016170992A1 (fr) * 2015-04-21 2016-10-27 株式会社オートネットワーク技術研究所 Fil en alliage de cuivre, toron en alliage de cuivre, câble électrique gainé et faisceau de câbles
WO2019171951A1 (fr) * 2018-03-09 2019-09-12 Ｄｏｗａメタルテック株式会社 Tôle d'alliage de cuivre et procédé pour la fabriquer
JP2019157175A (ja) * 2018-03-09 2019-09-19 Ｄｏｗａメタルテック株式会社 銅合金板材およびその製造方法
JP7195054B2 (ja) 2018-03-09 2022-12-23 Ｄｏｗａメタルテック株式会社 銅合金板材およびその製造方法
US11591673B2 (en) 2018-03-09 2023-02-28 Dowa Metaltech Co., Ltd. Copper alloy plate and method for producing same

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KR100565979B1 (ko) 2006-03-30
AU2003236001A1 (en) 2004-03-29
TW593703B (en) 2004-06-21
TW200404102A (en) 2004-03-16
US20040234412A1 (en) 2004-11-25
JPWO2004022805A1 (ja) 2005-12-22
EP2230323A1 (fr) 2010-09-22
KR20040041539A (ko) 2004-05-17
CN1516748A (zh) 2004-07-28
JP3961529B2 (ja) 2007-08-22
EP1538229A4 (fr) 2005-08-03
EP1538229A1 (fr) 2005-06-08

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