WO2009123140A1 - Alliage cu/ni/si à utiliser dans un matériau de ressort électriquement conducteur - Google Patents

Alliage cu/ni/si à utiliser dans un matériau de ressort électriquement conducteur Download PDF

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Publication number
WO2009123140A1
WO2009123140A1 PCT/JP2009/056540 JP2009056540W WO2009123140A1 WO 2009123140 A1 WO2009123140 A1 WO 2009123140A1 JP 2009056540 W JP2009056540 W JP 2009056540W WO 2009123140 A1 WO2009123140 A1 WO 2009123140A1
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WIPO (PCT)
Prior art keywords
alloy
bending
boundary
mass
boundaries
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PCT/JP2009/056540
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English (en)
Japanese (ja)
Inventor
直文 前田
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日鉱金属株式会社
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Publication date
Application filed by 日鉱金属株式会社 filed Critical 日鉱金属株式会社
Priority to KR1020107016770A priority Critical patent/KR101249107B1/ko
Priority to CN2009801115071A priority patent/CN101981212A/zh
Publication of WO2009123140A1 publication Critical patent/WO2009123140A1/fr

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

Definitions

  • the present invention relates to a Cu—Ni—Si based alloy used for a conductive spring material for electronic parts, and is particularly used for electronic parts such as connectors, terminals, relays, switches, etc., and has a balance of strength, bending workability and conductivity.
  • the present invention relates to an excellent Cu—Ni—Si alloy.
  • Corson As electronic devices have become smaller and lighter in recent years, terminals and connectors have become smaller and thinner, requiring strength and bending workability. Instead of conventional solid solution strengthened copper alloys such as phosphor bronze and brass, Corson There is an increasing demand for precipitation strengthened copper alloys such as (Cu—Ni—Si) alloys, beryllium copper and titanium copper. Among these, the Corson alloy has an excellent balance between strength and electrical conductivity, and is frequently used for electronic parts such as connectors.
  • Patent Document 1 in a Corson alloy to which Co, Zn, Mn, Cr, and Al are further added, crystal grain growth during solution treatment is suppressed and bending workability is improved.
  • Patent Document 2 the punching workability and the bending workability are improved by adding an appropriate amount of Ti, Zr, Hf or Th to the Corson alloy, and preferably by reducing the crystal grain size.
  • Patent Document 3 the content of S and O in the Corson alloy is limited to less than 0.005%, the content of Sn, Mg, and optionally Zn is optimized, and the crystal grain size is controlled to bend the workability. Has improved.
  • Patent Documents 4 and 5 bending workability and stress are controlled by limiting the S content in the Corson alloy, optimizing the contents of Mg, Sn, and Zn, and controlling the crystal grain size and the crystal grain aspect ratio. Mitigation is improved.
  • Patent Document 6 bending workability is improved by controlling the texture of the Corson alloy and controlling the pole density in the ⁇ 123 ⁇ ⁇ 412> orientation within a specified range.
  • Patent Document 7 the texture of the Corson alloy is controlled, the texture is controlled to satisfy (I (111) + I (311) ) / I (220) > 2.0, and bending workability is improved. Yes.
  • Patent Document 8 the hot rolling and solution treatment conditions in the Corson alloy are adjusted so that the yield point effect does not appear in the tensile strength test, and the bending workability is improved.
  • Patent Document 6 “0016” conditions of cold rolling and solution treatment before solution treatment are adjusted (Patent Document 6 “0019”). In Patent Document 8, bending wrinkle evaluation is also performed.
  • Patent Document 8 “0009” residual Ni—Si grains
  • the amount of Si, hot rolling, and solution treatment conditions are adjusted (Patent Document 8 “0019”).
  • the present inventors have conducted research on bending workability from the viewpoint of grain boundary control of a polycrystalline metal, unlike the prior art, and as a result, they are generated during the heat treatment of Cu-Ni-Si alloys. By controlling the frequency of occurrence of annealing twins, a Cu—Ni—Si alloy having high strength and good bending workability in bending wrinkle evaluation was obtained.
  • the Cu—Ni—Si based alloy of the present invention is suitable for applications such as terminals and connectors as a copper alloy having good bending workability and reduced bending wrinkles while maintaining high strength.
  • Ni, Si form fine particles of an intermetallic compound mainly composed of Ni 2 Si by performing an appropriate heat treatment.
  • the strength of the alloy is significantly increased and at the same time the electrical conductivity is increased.
  • Ni is added in the range of 1.0 to 4.0% by mass, preferably 1.5 to 3% by mass. If Ni is less than 1.0% by mass, sufficient strength cannot be obtained. When Ni exceeds 4.0 mass%, a crack generate
  • the additive concentration (mass%) of Si is set to 1/6 to 1/4 of the additive concentration (mass%) of Ni. If the Si addition concentration is less than 1/6 of the Ni addition concentration, the strength is reduced. If the Si addition concentration is more than 1/4 of the Ni addition concentration, not only does not contribute to the strength, but the conductivity is reduced due to excessive Si.
  • Mg has the effect of improving the stress relaxation characteristics and hot workability, but if it exceeds 0.2% by mass, the castability (decrease in casting surface quality), hot workability, and plating heat-resistant peelability deteriorate. Therefore, the Mg concentration is defined to be 0.2% or less.
  • Sn and Zn have an effect of improving strength and heat resistance, Sn further has an effect of improving stress relaxation resistance, and Zn has an effect of improving heat resistance of solder joints. Sn is added in the range of 0.2 to 1% by mass, and Zn is added in the range of 0.2 to 1% by mass. If it is below the above range, the desired effect cannot be obtained, and if it exceeds, the conductivity is lowered.
  • Co and Cr have the effect of forming a compound with Si and improving the strength by precipitation. Further, Co has an effect of preventing coarsening of crystal grains during heat treatment, and Cr has an effect of improving heat resistance. Co is added in the range of 1 to 1.5% by mass, and Cr is added in the range of 0.05 to 0.2% by mass. If it is below the above range, the desired effect cannot be obtained, and if it exceeds, the conductivity is lowered.
  • the metal material is usually an aggregate of crystal grains having various crystal orientations, that is, a polycrystalline body, and a boundary, that is, a crystal grain boundary exists in the metal material due to a difference in arrangement of atoms.
  • Grain boundaries are classified into large-angle grain boundaries, small-angle grain boundaries, and sub-grain boundaries depending on the orientation difference between adjacent crystal grains.
  • a grain boundary refers to a large-angle grain boundary whose orientation difference between adjacent crystal grains is 15 ° or more.
  • crystal grain boundaries are classified into random grain boundaries and corresponding grain boundaries depending on the consistency between adjacent crystal grains.
  • Annealing twins generated by thermomechanical processing of a Cu—Ni—Si based alloy are the corresponding grain boundaries of ⁇ 3 and have high consistency between crystal grains.
  • the ⁇ value is an index indicating the consistency of the grain boundary.
  • the ratio of twin boundaries in all boundaries is controlled to be 15% or more and 60% or less, preferably 30% or more and 60% or less. Workability is improved. If it is less than 15%, the desired bending workability cannot be obtained, and if it exceeds 60%, the crystal grains at the time of solution forming become coarse and the strength decreases.
  • EBSP Electro Back Scattering Pattern
  • FESEM Field Emission Scanning Electron Microscope
  • This method is a method of analyzing crystal orientation based on a backscattered electron diffraction pattern (Kikuchi pattern) generated when an electron beam is obliquely applied to a sample surface. After analyzing the crystal orientation by this method, the orientation difference between adjacent crystal orientations can be obtained, and the ratio of the random grain boundaries and the corresponding grain boundaries (grain boundary character distribution) can be determined.
  • the crystal grain boundary means a boundary where the orientation difference between adjacent crystal grains is 15 ° or more, and does not include a small-angle grain boundary or a sub-grain boundary.
  • the twins in the present invention are annealing twins, and are twins that are generated accompanying recrystallization generated by annealing after rolling.
  • the occurrence frequency of twins correlates with the stacking fault energy of the material.
  • the stacking fault energy is reduced by increasing the amount of solute Ni / Si (more precisely, increasing the amount of solute Si). Therefore, in order to increase the twin boundary frequency, the amount of solid solution Ni / Si may be increased to lower the stacking fault energy before the final recrystallization annealing (corresponding to the solution treatment in the present invention).
  • the present invention by increasing the cooling rate during casting, the number and grain size of Ni-Si crystals are reduced, and further, the annealing conditions for high temperature and long time are within the limits where cracks do not occur in the hot rolling process.
  • the amount of solid solution Ni / Si was increased as compared with the conventional method, and the desired twin boundary frequency was obtained.
  • the Corson alloy of the present invention is manufactured by a general manufacturing process that combines solution treatment, cold rolling, and aging treatment after “melting, casting ⁇ hot rolling ⁇ facing”, and straightening after final cold rolling.
  • annealing is performed or solution treatment is also performed by hot rolling.
  • Annealing twins are generated along with recrystallization during solution treatment.
  • the conditions from the above casting to hot rolling are within the following range. It is preferable to sufficiently dissolve Ni and Si before the final recrystallization annealing, that is, the solution treatment.
  • the ingot cooling rate during casting is set to 300 to 500 ° C./min to suppress the crystallization of coarse Ni—Si particles during casting cooling.
  • a speed exceeding the ingot cooling rate of 500 ° C./min is not practical from the viewpoint of cost.
  • annealing is performed at a heating temperature of 940 to 1000 ° C., preferably 950 to 980 ° C. for a heating time of 3 to 6 hours to dissolve Ni—Si particles remaining in the ingot, and then hot rolling is performed. If the heating temperature is less than 940 ° C. or less than 3 hours, the solid solution of the remaining Ni—Si particles is insufficient.
  • annealing at a high temperature exceeding 1000 ° C. during hot rolling increases the risk of hot rolling cracks. Annealing exceeding 6 hours becomes an excessive annealing for a desired effect in the above temperature range, which is not preferable from the viewpoint of cost.
  • the material temperature at the end of hot rolling is 650 ° C. or higher. If it is lower than 650 ° C., the amount of Ni 2 Si precipitated during hot rolling increases, and a sufficient amount of solid solution Ni ⁇ Si cannot be secured, so the twin boundary frequency decreases.
  • cold rolling at a workability of 85% or more is performed, and a solution treatment (in this case, final recrystallization annealing) is performed at 700 to 820 ° C. for 5 seconds to 30 minutes, and then 350 to Aging is performed at 550 ° C. for 2 to 30 hours. Further, cold rolling is performed at a working degree of 5% to 50%.
  • Example production The electrolytic copper was melted, and a predetermined amount of the additive element was put into an atmospheric melting furnace, and the molten metal was stirred. Then, the hot water was poured into the mold at a casting temperature of 1250 ° C. to obtain an ingot. By changing the water cooling conditions of the mold, the ingot cooling rate during casting was adjusted to the conditions in the table. The ingot cooling rate at the time of casting is an average cooling rate (° C./min) until the ingot temperature reaches from 1100 ° C. to 500 ° C. after the molten metal solidifies. Next, this ingot was processed and heat-treated in the following order to obtain a sample having a plate thickness of 0.25 mm.
  • the ingot was annealed and hot-rolled under the conditions in the table to finish the plate thickness to a predetermined thickness, and then water-cooled.
  • the surface oxide scale was removed by chamfering.
  • Cold rolling was performed to a plate thickness of 0.3 mm.
  • Solution treatment for 1 minute was performed at the solution temperature in the table.
  • An aging treatment was performed under the condition of 450 ° C. ⁇ 10 h.
  • the aging material was cold-rolled to 0.25 mm. About the said material, the EBSP measurement regarding the twin boundary, the tensile test, and the W bending test were implemented according to the following reference
  • twin boundary An EBSP (Electron Back Scattering Pattern) method using FESEM (Field Emission Scanning Electron Microscope) was used as a method for obtaining the twin boundary ratio. After analyzing the crystal orientation by this method, the orientation difference between adjacent crystal orientations was determined, and the grain boundary character distribution was determined. The observation magnification was 1000 times, and the total observation field was 2 mm 2 . Corresponding grain boundaries are represented using ⁇ values, and twin boundaries correspond to ⁇ 3 corresponding grain boundaries. The ratio (%) of twin boundaries is calculated by (total length of corresponding grain boundaries ⁇ 3) / (total length of crystal grain boundaries) ⁇ 100.
  • the crystal grain boundary in a formula refers to the boundary from which the orientation difference between adjacent crystal grains becomes 15 degrees or more, and does not include a small grain boundary and a subgrain boundary.
  • Examples of the Ni—Si based copper alloy A (Cu-2% Ni-0.5% Si-0.1% Mg) according to the present invention are shown in Table 1.
  • Examples of the Ni—Si based copper alloy B (Cu—1.6% Ni—0.4% Si—0.4% Sn—0.5% Zn) according to the present invention are shown in Table 2.
  • Examples of Ni—Si based copper alloy C (Cu—1.6% Ni—0.4% Si) according to the present invention are shown in Table 3.
  • Comparative Examples 1, 8 and 15 since the cooling rate during casting was less than 300 ° C./min, coarse Ni—Si grain crystallized products were generated in the ingot, and the solid solution amounts of Ni and Si in the parent phase decreased. Since the stacking fault energy does not decrease sufficiently, the twin boundary frequency was less than 15%.
  • Example production The electrolytic copper was melted, and a predetermined amount of the additive element was introduced into the atmospheric melting furnace so as to have a desired composition shown in Table 4, and the molten metal was stirred. Then, it poured out into the casting_mold

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)

Abstract

L’invention concerne un alliage à base de Cu/Ni/Si qui contient du Ni en une quantité représentant de 1,0 à 4,0 % en poids et du Si dans une concentration représentant de 1/6 à 1/4 de celle du Ni, la densité des limites jumelées (limites Σ3) vaut de 15 à 60 % des toutes les limites de grain. L’alliage peut contenir en outre 0,2 % ou moins de Mg, 0,2 à 1 % de Sn, 0,2 à 1 % de Zn, 1 à 1,5 % de Co, et/ou 0,05 à 0,2 % de Cr.
PCT/JP2009/056540 2008-03-31 2009-03-30 Alliage cu/ni/si à utiliser dans un matériau de ressort électriquement conducteur WO2009123140A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020107016770A KR101249107B1 (ko) 2008-03-31 2009-03-30 도전성 스프링재에 사용되는 Ｃｕ-Ｎｉ-Ｓｉ 계 합금
CN2009801115071A CN101981212A (zh) 2008-03-31 2009-03-30 用于导电性弹性材料的Cu-Ni-Si系合金

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008093847 2008-03-31
JP2008-093847 2008-03-31

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WO2009123140A1 true WO2009123140A1 (fr) 2009-10-08

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JP (1) JP4596493B2 (fr)
KR (1) KR101249107B1 (fr)
CN (1) CN101981212A (fr)
TW (1) TWI443204B (fr)
WO (1) WO2009123140A1 (fr)

Cited By (1)

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EP2377959A1 (fr) 2010-04-05 2011-10-19 Dowa Metaltech Co., Ltd. Feuille d'alliage en cuivre, procédé de fabrication de feuille d'alliage en cuivre et composant électrique/électronique

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JP4830048B1 (ja) * 2010-07-07 2011-12-07 三菱伸銅株式会社 深絞り加工性に優れたＣｕ−Ｎｉ−Ｓｉ系銅合金板及びその製造方法
KR102008302B1 (ko) 2010-09-30 2019-08-07 휴렛-팩커드 디벨롭먼트 컴퍼니, 엘.피. 접속한 사용자에게 표시되는 사용자 인터페이스 화면을 생성하는 화상형성장치 및 방법
JP5192536B2 (ja) * 2010-12-10 2013-05-08 三菱伸銅株式会社 深絞り加工性及び耐疲労特性に優れたＣｕ−Ｎｉ−Ｓｉ系銅合金板及びその製造方法
JP5180283B2 (ja) * 2010-12-24 2013-04-10 三菱伸銅株式会社 曲げ加工後の耐疲労特性及びばね特性に優れたＣｕ−Ｎｉ−Ｓｉ系銅合金板及びその製造方法
JP4857395B1 (ja) * 2011-03-09 2012-01-18 Ｊｘ日鉱日石金属株式会社 Ｃｕ−Ｎｉ−Ｓｉ系合金及びその製造方法
JP5534610B2 (ja) * 2011-03-31 2014-07-02 Ｊｘ日鉱日石金属株式会社 Ｃｕ−Ｃｏ−Ｓｉ系合金条
WO2012160684A1 (fr) 2011-05-25 2012-11-29 三菱伸銅株式会社 Tôle d'alliage de cuivre en cu-ni-si présentant une excellente aptitude à l'emboutissage profond et son procédé de production
JP2013098098A (ja) * 2011-11-02 2013-05-20 Otsuka Techno Kk ブレーカ
US9159985B2 (en) * 2011-05-27 2015-10-13 Ostuka Techno Corporation Circuit breaker and battery pack including the same
EP2752498A4 (fr) * 2011-08-29 2015-04-08 Furukawa Electric Co Ltd Matériau en alliage de cuivre et son procédé de fabrication
JP5827530B2 (ja) * 2011-09-16 2015-12-02 三菱伸銅株式会社 優れたばね限界値及び耐応力緩和性を有するせん断加工性が良好なＣｕ−Ｎｉ−Ｓｉ系銅合金板
JP5802150B2 (ja) 2012-02-24 2015-10-28 株式会社神戸製鋼所 銅合金
CN102867562A (zh) * 2012-09-10 2013-01-09 任静儿 一种铜合金
CN102851536A (zh) * 2012-09-10 2013-01-02 任静儿 一种用于导线的铜合金
CN102864332A (zh) * 2012-09-10 2013-01-09 任静儿 一种铜稀土合金
CN102851532A (zh) * 2012-09-10 2013-01-02 顾建 一种用于阀门的铜合金材料
CN102864327A (zh) * 2012-09-10 2013-01-09 任静儿 用于阀门的铜合金材料
CN102851531A (zh) * 2012-09-10 2013-01-02 虞雪君 一种铜锌合金
CN102864331A (zh) * 2012-09-10 2013-01-09 顾建 一种铜合金材料
CN102855957A (zh) * 2012-09-10 2013-01-02 顾建 一种用于导线的铜合金材料
CN102864333A (zh) * 2012-09-10 2013-01-09 顾建 一种铜稀土合金材料
CN102925746B (zh) * 2012-11-29 2014-09-17 宁波兴业鑫泰新型电子材料有限公司 高性能Cu-Ni-Si系铜合金及其制备和加工方法
JP5795030B2 (ja) * 2013-07-16 2015-10-14 株式会社古河テクノマテリアル 耐応力腐食性に優れるＣｕ−Ａｌ−Ｍｎ系合金材料からなる展伸材
CN103643080A (zh) * 2013-12-25 2014-03-19 海门市江滨永久铜管有限公司 高强、高延性、高导电的铜镍硅合金棒材及生产方法
JP6310538B1 (ja) * 2016-12-14 2018-04-11 古河電気工業株式会社 銅合金線棒材およびその製造方法
JP7046032B2 (ja) * 2019-04-11 2022-04-01 Ｊｘ金属株式会社 電子材料用銅合金、電子材料用銅合金の製造方法及び電子部品

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Publication number Priority date Publication date Assignee Title
EP2377959A1 (fr) 2010-04-05 2011-10-19 Dowa Metaltech Co., Ltd. Feuille d'alliage en cuivre, procédé de fabrication de feuille d'alliage en cuivre et composant électrique/électronique
US8992702B2 (en) 2010-04-05 2015-03-31 Dowa Metaltech Co., Ltd Copper alloy sheet, manufacturing method of copper alloy sheet, and electric/electronic component

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KR20100095476A (ko) 2010-08-30
CN101981212A (zh) 2011-02-23
KR101249107B1 (ko) 2013-03-29
JP2009263784A (ja) 2009-11-12
TWI443204B (zh) 2014-07-01
TW200948990A (en) 2009-12-01
JP4596493B2 (ja) 2010-12-08

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