EP1245690B1 - Cuivre et alliage de cuivre et procédé de fabrication - Google Patents

Cuivre et alliage de cuivre et procédé de fabrication Download PDF

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Publication number
EP1245690B1
EP1245690B1 EP02006886A EP02006886A EP1245690B1 EP 1245690 B1 EP1245690 B1 EP 1245690B1 EP 02006886 A EP02006886 A EP 02006886A EP 02006886 A EP02006886 A EP 02006886A EP 1245690 B1 EP1245690 B1 EP 1245690B1
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Prior art keywords
copper
alloy
cold rolling
rolling
copper alloy
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German (de)
English (en)
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EP1245690A1 (fr
Inventor
Yasuo Nippon Mining & Metals Co. Ltd Tomioka
Junji c/o Nippon Mining & Metals Co. Ltd Miyake
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Nippon Mining Holdings Inc
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Nikko Metal Manufacturing Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B2003/005—Copper or its alloys

Definitions

  • the present invention relates to copper and to copper alloys having fine crystal grains, and relates to a manufacturing method therefor, and more particularly, the resent invention relates to a technology for enhancing the characteristics in bending or other working when used for electronic devices such as terminals, connectors, and lead frames for semiconductor integrated circuits.
  • Copper alloy Electrical conductivity of copper alloy is inversely related to strength, and when an alloying element is added to enhance the strength, the electrical conductivity is lowered, and therefore alloys which compromise strength and electrical conductivity or price have been used, depending on the application. So far, alloys for enhancing the strength and electrical conductivity have been intensively developed, and generally, copper alloys of precipitation reinforced type containing second phase particles such as Cu-Ni-Si alloy or Cu-Cr-Zr alloy have come to be used as high functional materials which is superior in balance between both.
  • the inventors have accumulated extensive research to solve these problems, and they have discovered that fine crystal grains at a level not known thus far can be obtained by controlling the conditions of the rolling process instead of the conditions of the annealing. That is, in the structure of a material cold rolled with an ordinary cold rolling reduction, when recrystallized by subsequent annealing, the decrease in dislocation density occurs discontinuously when the recrystallized grain boundaries pass a cell, and large crystal grains of uneven size are produced intermittently. This is called static recrystallization.
  • the present invention is made on the basis of these findings, and provides copper and copper alloy comprising: a structure having fine crystal grains with grain size of 1 ⁇ m or less composed of crystal grain boundaries mainly formed of curved portions after a final cold rolling, the structure obtained by dynamic continuous recrystallization caused by the final cold rolling, and an elongation of 2% or more in a tensile test.
  • the present invention also provides a manufacturing method for copper and copper alloy, the method comprising: a final cold rolling with a reduction (true stress) ⁇ , wherein ⁇ is expressed in the following formula and satisfying ⁇ ⁇ 3, thereby obtaining a structure having fine crystal grains with grain size of 1 ⁇ m or less after the final cold rolling, and an elongation of 2% or more in a tensile test.
  • ⁇ ln ( T 0 / T 1 )
  • T 0 plate thickness before rolling
  • T 1 plate thickness after rolling.
  • a high ductility is essential.
  • a fracture elongation in a tensile test is required to be 2% or more at a gauge length of 50 mm.
  • the grain size after final cold rolling must be 1 ⁇ m or less.
  • the grain size and elongation after final cold rolling vary depending on the cold rolling reduction.
  • the value of ⁇ when the value of ⁇ is small, a rolled structure remains, and clear fine crystal grains are not obtained, or if they are obtained, the grain size is large, and the grain boundary sliding does not take place, and favorable ductility is not obtained.
  • the value of ⁇ should be 3 or more in order to obtain a fine grain size of 1 ⁇ m or less.
  • the structure of a material cold rolled by a conventional ordinary cold rolling reduction sometimes had a cell structure due to mutual entangling of dislocations introduced in the crystal grains. In this case, however, since the misorientation among neighboring cells is small, that is, 15° or less, properties as crystal grain boundary are not realized. Accordingly, as shown in Fig. 1, when recrystallized by annealing after cold rolling, as mentioned above, static crystallization takes place, that is, large crystal grains of uneven size are formed intermittently.
  • the crystal grain boundary is largely different from the case of the static recrystallization, and there is no linearity in the grain boundary, and it is a feature that a crystal grain boundary mainly composed of curved portions is formed.
  • This dynamic continuous recrystallization is mostly formed in cold rolling. It is also known that a clearer high angle grain boundary is grown by annealing at intentional low temperatures and bringing it into an ordinary recovery regime. In this case, it is found that the ductility is further enhanced as described below.
  • cold rolling may be performed by plural rolling machines by exchanging rolling machines depending on the range of plate thickness, or pickling or polishing may be performed in order to control the surface properties.
  • the ductility is enhanced, and a further preferable bending properties are obtained.
  • annealing conditions it is necessary to set adequate annealing conditions to such an extent that the product value will not be lost due to extreme decline of strength.
  • the annealing condition differs with the alloy system, but by selecting an appropriate annealing condition in a temperature range of 80 to 500°C and in a range of 5 to 60 minutes, an elongation of 6% or more may be easily obtained, and it is applicable to a severe bend forming.
  • copper alloy of the invention include Cu-Ni-Si alloys having precipitates of intermetallic compounds of Ni and Si such as Ni 2 Si, and the copper alloys comprise Ni: 1.0 to 4.8 mass %, Si: 0.2 to 1.4 mass %, and the balance of Cu.
  • the invention also includes Cu-Cr-Zr alloys having precipitates of pure Cr grains and intermetallic compounds of Cu and Zr, and the copper alloys comprise Cr: 0.02 to 0.4 mass %, Zr: 0.1 to 0.25 mass %, and balance of Cu.
  • These copper alloy may be added with subsidiary components such as one or more of Sn, Fe, Ti, P, Mn, Zn, In, Mg and Ag in a total amount of 0.005 to 2 mass %.
  • copper alloys having second phase particles such as other kinds of precipitates and dispersed particles may be used.
  • the aging temperature was adjusted so that the product strength would be highest in each alloy composition, or in the case of recrystallization, the temperature condition was adjusted so that the grain size would be 5 to 15 ⁇ m.
  • the final cold rolling plates of 0.15 mm in thickness were manufactured and obtained as experiment samples for evaluation. The final cold rolling conditions are also shown in Tables 1 to 3.
  • Test pieces were sampled from the obtained plates, and the materials were tested to evaluate "grain size", “strength”, “elongation”, “bending”, and “electrical conductivity”.
  • the bright fields were observed by a transmission electron microscope, and it was determined by the cut-off method of JIS H 0501 on the obtained photograph.
  • the tensile strength and rupture elongation were measured.
  • "bending” by bend forming using a W-bend testing machine, the bent part was observed by an optical microscope at a magnification of 50 times, and presence or absence of cracking was observed. The mark “o” indicates that cracking is absent, and the mark “x” indicates that cracking is present.
  • the "electrical conductivity” was determined by measuring the electrical conductivity according to a four-point method.
  • Fig. 2 is a transmission electron microscope photograph of sample No. 12 of the invention, in which the mean grain size of the formed continuous recrystallization is 1 ⁇ m or less, and its crystal grain boundary is mainly composed of curved portions and is round.
  • a transmission electron microscope photograph of comparative example No. 6 is shown in Fig. 3, in which the grain size is nearly linear.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Conductive Materials (AREA)

Claims (7)

  1. Cuivre et alliage de cuivre comprenant :
    une structure ayant des grains cristallins fins avec une taille de grain de 1 µm ou moins composée de limites de grains cristallins principalement formées de parties courbes après un laminage à froid final, la structure étant obtenue par recristallisation dynamique continue causée par le laminage à froid final, et
    un allongement de 2% ou plus dans un test de traction.
  2. Cuivre et alliage de cuivre comprenant
    une structure ayant des grains cristallins fins avec une taille de grain de 1 µm ou moins après un laminage à froid final avec une réduction η, dans laquelle η est exprimée par la formule suivante et satisfait η ≥ 3 ; et
    un allongement de 2% ou plus dans un test de traction. η = ln ( T 0 / T 1 )
    Figure imgb0007
    T0 : épaisseur de plaque avant laminage, T1 : épaisseur de plaque après laminage.
  3. Procédé de fabrication pour du cuivre et un alliage de cuivre, le procédé comprenant :
    un laminage à froid final avec une réduction η, dans lequel η est exprimée par la formule suivante et satisfait η ≥ 3,
    obtenant de ce fait une structure ayant des grains cristallins fins avec une taille de grain de 1 µm ou moins après le laminage à froid final, et
    un allongement de 2% ou plus dans un test de traction. η = ln ( T 0 / T 1 )
    Figure imgb0008
    T0 : épaisseur de plaque avant laminage, T1 : épaisseur de plaque après laminage.
  4. Procédé de fabrication pour du cuivre et un alliage de cuivre selon la revendication 3 dans lequel le cuivre et l'alliage de cuivre indiqués dans la revendication 1 ou 2 sont traités par un recuit qui réduit les contraintes, et l'allongement par un test de traction est amélioré à 6% ou plus.
  5. Cuivre et alliage de cuivre fabriqués selon le procédé de fabrication de la revendication 3 ou 4.
  6. Procédé de fabrication pour du cuivre et un alliage de cuivre selon la revendication 3 ou 4 dans lequel l'alliage de cuivre est un alliage Cu-Ni-Si ou Cu-Cr-Zr.
  7. Cuivre et alliage de cuivre selon la revendication 5 dans lesquels l'alliage de cuivre est un alliage Cu-Ni-Si ou Cu-Cr-Zr.
EP02006886A 2001-03-27 2002-03-26 Cuivre et alliage de cuivre et procédé de fabrication Expired - Lifetime EP1245690B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001091179 2001-03-27
JP2001091179 2001-03-27

Publications (2)

Publication Number Publication Date
EP1245690A1 EP1245690A1 (fr) 2002-10-02
EP1245690B1 true EP1245690B1 (fr) 2006-10-11

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EP02006886A Expired - Lifetime EP1245690B1 (fr) 2001-03-27 2002-03-26 Cuivre et alliage de cuivre et procédé de fabrication

Country Status (5)

Country Link
US (2) US20020189729A1 (fr)
EP (1) EP1245690B1 (fr)
KR (1) KR100513943B1 (fr)
CN (1) CN1223690C (fr)
DE (1) DE60215240T2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4087307B2 (ja) * 2003-07-09 2008-05-21 日鉱金属株式会社 延性に優れた高力高導電性銅合金
JP4809602B2 (ja) * 2004-05-27 2011-11-09 古河電気工業株式会社 銅合金
JP5306591B2 (ja) * 2005-12-07 2013-10-02 古河電気工業株式会社 配線用電線導体、配線用電線、及びそれらの製造方法
JP5355865B2 (ja) 2006-06-01 2013-11-27 古河電気工業株式会社 銅合金線材の製造方法および銅合金線材
US8876990B2 (en) * 2009-08-20 2014-11-04 Massachusetts Institute Of Technology Thermo-mechanical process to enhance the quality of grain boundary networks
CN104087768B (zh) * 2014-06-25 2017-02-15 盐城市鑫洋电热材料有限公司 一种改善镍铬铁电热合金性能的方法
CN105291891A (zh) * 2015-11-25 2016-02-03 北京力鑫科技有限公司 一种强化型吊弦的制作方法及电气化铁路接触网
JP6617313B2 (ja) * 2017-08-03 2019-12-11 Ｊｘ金属株式会社 フレキシブルプリント基板用銅箔、それを用いた銅張積層体、フレキシブルプリント基板、及び電子機器
CN109338314A (zh) * 2018-12-04 2019-02-15 有研亿金新材料有限公司 一种超细晶铜锰合金靶材的加工方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08960B2 (ja) * 1989-03-15 1996-01-10 日本碍子株式会社 ベリリウム銅合金の熱間成形方法及び熱間成形製品
JPH09256084A (ja) * 1996-03-19 1997-09-30 Hitachi Cable Ltd 耐屈曲性銅合金線
JP3510469B2 (ja) * 1998-01-30 2004-03-29 古河電気工業株式会社 導電性ばね用銅合金及びその製造方法
JP2000038628A (ja) * 1998-07-22 2000-02-08 Furukawa Electric Co Ltd:The 半導体リードフレーム用銅合金
JP3856582B2 (ja) * 1998-11-17 2006-12-13 日鉱金属株式会社 フレキシブルプリント回路基板用圧延銅箔およびその製造方法
JP2000256766A (ja) * 1999-03-05 2000-09-19 Sanyo Special Steel Co Ltd ＣｕＮｉＦｅ合金の熱間加工方法
JP4345075B2 (ja) * 1999-03-26 2009-10-14 Ｄｏｗａホールディングス株式会社 ワイアーボンディング性およびダイボンディング性に優れた銅及び銅基合金とその製造方法
US6251199B1 (en) * 1999-05-04 2001-06-26 Olin Corporation Copper alloy having improved resistance to cracking due to localized stress

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Publication number Publication date
DE60215240T2 (de) 2007-05-03
KR100513943B1 (ko) 2005-09-09
DE60215240D1 (de) 2006-11-23
CN1386873A (zh) 2002-12-25
US20080277032A1 (en) 2008-11-13
EP1245690A1 (fr) 2002-10-02
CN1223690C (zh) 2005-10-19
US20020189729A1 (en) 2002-12-19
KR20020076139A (ko) 2002-10-09

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