EP0859065B1 - Copper base alloys and terminals using the same - Google Patents

Copper base alloys and terminals using the same Download PDF

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Publication number
EP0859065B1
EP0859065B1 EP98102539A EP98102539A EP0859065B1 EP 0859065 B1 EP0859065 B1 EP 0859065B1 EP 98102539 A EP98102539 A EP 98102539A EP 98102539 A EP98102539 A EP 98102539A EP 0859065 B1 EP0859065 B1 EP 0859065B1
Authority
EP
European Patent Office
Prior art keywords
alloy
copper base
terminals
spring
terminal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98102539A
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German (de)
English (en)
French (fr)
Other versions
EP0859065A1 (en
Inventor
Yoshiake Hana
Akira Sugawara
Takayoshi Endo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dowa Holdings Co Ltd
Yazaki Corp
Original Assignee
Yazaki Corp
Dowa Mining Co Ltd
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Publication date
Application filed by Yazaki Corp, Dowa Mining Co Ltd filed Critical Yazaki Corp
Publication of EP0859065A1 publication Critical patent/EP0859065A1/en
Application granted granted Critical
Publication of EP0859065B1 publication Critical patent/EP0859065B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Definitions

  • This invention relates to copper base alloys for use in connector terminals in automobiles and other applications, as well as connector terminals that are made of those copper base alloys.
  • phospher bronze has high strength but its electrical conductivity (hereunder simply referred to as "conductivity”) is also low (to take C52100 as an example, its conductivity is ca. 12% IACS); in addition, it has problems with anti-stress relaxation characteristics, and from an economic viewpoint (high price).
  • Cu-Sn-Fe-P alloys have been developed with a view to solving those problems of brass and phospher bronze. For example, Cu-2.0Sn-0.1Fe-0.03P has a conductivity of 35 % IACS and is superior in strength; however, its anti-stress relaxation characteristics has not been completely satisfactory in view of its use as an alloy for terminals.
  • US 5 322 575 A describes a copper base alloy having the features set out in the preamble of claim 1.
  • a further problem is that the terminals manufactured from the aforementioned copper base alloys reflect the characteristics of those alloys in a straightforward manner.
  • the terminals using brass, phosphor bronze or Cu-Sn-Fe-P alloys do not satisfy the requirements for high conductivity and good anti-stress relaxation characteristics simultaneously, so they will generate heat by themselves, potentially causing various problems including oxidation, plate separation, stress relaxation, circuit voltage drop, and the softening or deformation of the housing.
  • the present inventors conducted repeated test and research efforts on Cu-Ni-Sn-P alloys, as well as Cu-Ni-Sn-P-Zn alloys and found that characteristics satisfactory in terms of tensile strength, conductivity, anti-stress relaxation characteristics, anti-migration characteristics, as well as bending workability could be attained by selecting appropriate compositions for those alloys, and causing uniform precipitation of fine precipitate of Ni-P compound in the size of no larger than 100 nm being uniformly dispersed in the alloy. It was also found that terminals with a built-in spring that was produced from those copper base alloys or terminals that were entirely made of those copper base alloys including a spring as an integral part possessed superior characteristics.
  • the present invention provides a copper base alloy for use in terminals that consists essentially, on a weight basis, of 0.5-3.0 % Ni, 0.5-2.0 % Sn, 0.010-0.20 % P, and optionally 0.01-2.0 % Zn, the balance being Cu and incidental impurities, said alloy having fine precipitates of Ni-P compound uniformly dispersed in the alloy, the crystal grain size of said alloy being 50 ⁇ m or less, the ratio of Ni to P (Ni/P) being in the range of 10-50, characterized in that the size of said fine precipitates of Ni-P compound uniformly dispersed in the alloy is no larger than 100 nm.
  • Nickel (Ni) dissolves in the Cu matrix to provide improved strength, elasticity, heat resistance, anti-stress relaxation, anti-migration and anti-stress corrosion cracking characteristics. Further, Ni forms a compound with P, which disperses and precipitates to provide higher conductivity. If the Ni content is less than 0.5%, the desired effects will not be achieved; if the Ni content exceeds 3.0%, its effects will be saturated and its economy will be impaired. Therefore, the Ni content is specified to range from 0.5 to 3.0 wt%.
  • Tin (Sn) also dissolves in the Cu matrix to provide improved strength, elasticity and corrosion resistance. If the Sn content is less than0.5%, the desired effects will not be achieved with respect to the strength and elasticity,; if the Sn content exceeds 2.0%, its effects will be saturated. Therefore, the Sn content is specified to range from 0.5 to 2.0 wt%.
  • Phosphorus (P) not only works as a deoxidizer of the melt but also forms a compound with Ni, which disperses and precipitates to improve not only conductivity but also strength, elasticity, and anti-stress relaxation characteristics. If the P content is less than 0.005%, the desired effects will not be achieved; if the P content exceeds 0.20%, the conductivity, workability and adhesive quality of soldering or plating after the heat treatment thereof will be severely impaired even in the copresence of Ni, as well as anti-migration characteristics will be decreased. Therefore, the P content is specified to range from 0.010 to 0.2 wt%, preferably from 0.02 to 0.15 wt%.
  • the ratio of weight percentages of Ni to P should preferably be limited within a specified range; preferably in the range of from 10 to 50; more preferably in the range of from 15 to 30. If the size of precipitated Ni-P compound exceeds 100 nm, contribution of the precipitate to the improvement in strength, elasticity and anti-stress relaxation characteristics and the bending workability will be impaired.
  • the life of a metal mold for pressing which comprises a punch made of a hard alloy and a die made of a tool steel, often decreases if the alloy structure contains a large amount of Ni-P precipitate whose size exceeds 100 nm. Therefore, the size of Ni-P precipitate is specified to be 100 nm or less, more preferably 70 nm or less.
  • zinc (Zn) which can be added as an auxiliary component, has the ability to further improve the adhesive quality of a plating layer to the surface of a copper base alloy, when heat treated after plating.
  • Zn content is up to 0.01%, the above-mentioned effects will not be achieved; if the Zn content exceeds 2.0%, its effects will be saturated. Therefore, the Zn content within the range of 0.01 - 2.0 wt% is preferred.
  • insertion force and extraction force herein used for connector terminals represent, respectively, the “force required to insert a male terminal into a female terminal” and the “force required to break the male terminal away from the female terminal”.
  • the insertion force should preferably be small and the extraction force should preferably be large. If the insertion force is unduly large, the male terminal cannot be readily inserted into the female terminal. This causes a particular problem with circuits of high packing density because routine assembling operations cannot be accomplished efficiently if the number of terminals to be connected increases. On the other hand, if the extraction force is too weak, separation occurs due to the vibration or an oxide film will easily form and the contact resistance is too unstable to insure satisfactory electrical reliability for connectors.
  • the initial insertion/extraction force of the terminal is desirably from 1.5N to 30N and, to this end, the terminal material to be used must have a tensile strength of at least 500 N/mm 2 , a spring limit of at least 400 N/mm 2 and, from a view point of good moldability of terminals, a value of R/t of 2 or less.
  • the crystal grain size is 50 ⁇ m or less, more preferably 25 ⁇ m or less.
  • the initial resistance at low voltage and low current is desirably small, preferably not more than 3 m ⁇ .
  • the value of contact electric resistance is dependent primarily on how much the contact load on the coupling will decrease due to heat cycles. However, the stress relaxation caused by spontaneous heat generation from the material as well as the stress relaxation caused by the effects of temperature in the automobile's engine room or around the exhaust system will also reduce the contact load, which eventually leads to a higher contact electric resistance.
  • the terminal material itself must not undergo stress relaxation greater than 10% upon standing at 150°C for 1,000 hours, and it is also required to have a tensile strength of at least 500 N/mm 2 , a spring limit of at least 400 N/mm 2 , an electric conductivity of at least 30 % IACS and a stress relaxation after working into a spring of no more than 20%.
  • the bending axis was set to be parallel to the rolling direction.
  • stress relaxation(%) ⁇ (L 1 -L 2 )/(L 1 -L 0 ))X100
  • the migration test was conducted in the following way: A plate as shown in Fig. 1 (1: ABS resin; 2: opening) made of ABS resin (2 mm(t) X 16 mm(w) X 72 mm(1)) and having in the central area thereof a circular opening was sandwiched by a pair of test pieces (each 0.2 mm(t) X 5 mm(w) X 80 mm(1)) and the resulting assembly was joined together by winding around it at both upper and lower portions with separate pieces of Teflon tape. Then, the fixed assembly was held in a testing vessel filled with tap water as shown in Fig. 2 (3: Teflon tape; 4: test piece; 5: tap water; 6: testing vessel; 7: ammeter; 8: DC power source). The migration characteristics of each test piece was evaluated by measuring maximum leakage current after 8 hours' application of 14 V DC voltage.
  • Alloys having the compositions shown in Table 4 were melted in a high-frequency melting furnace and hot-rolled at 850°C to a thickness of 5.0 mm.
  • the surface of each slab was scalped to a thickness of 4.8 mm and by subsequent repetition of cold-rolling operations and heat treatments, sheets having a thickness of 0.2 mm with a final reduction ratio of 67% were obtained.
  • conditions of heat treatments (age-precipitation) were varied in order to vary the sizes of precipitates and the crystal grain diameters thereof.
  • precipitates an average diameter of the largest 10 precipitate particles determined by transmission electron microscopy, wherein the specimen being observed at three phases at the magnification of 50,000X, was shown as the size of the precipitate. Crystal grain diameters were evaluated according to JIS H 0501.
  • all the alloy sample Nos. 27 - 34 prepared in accordance with the present invention had a tensile strength of no less than 500 N/mm 2 , a spring limit of no less than 400 N/mm 2 and a conductivity of no less than 30% IACS, and their bending workability was also satisfactory.
  • these samples had superior stress relaxation characteristics of no less than 10% as well as superior anti-migration characteristics.
  • the copper base alloy of the present invention for use in terminals is superior in tensile strength, spring limit, electric conductivity, anti-stress relaxation characteristics, anti-migration characteristics and bending workability.
  • a terminal which is constructed by the alloy of the present invention and which has a spring in it is superior in the resistance at low voltage and low current as well as stress relaxation characteristics, and therefore the alloy has a remarkable advantage from a view point of industry.
  • a copper base alloy for use in a terminal which has an electric conductivity of as high as at least 30% IACS and also has both high tensile strength and high spring limit as well as superior stress relaxation characteristics of not higher than 10%.
  • a terminal which has contained in its structure a spring made of the alloy of the present invention or a terminal wholly made of the alloy of the present invention inclusive of its spring, the terminal having proper initial properties inclusive of a proper insertion power in the range of 1.5 - 30 N, a proper resistance at low voltage and low current of no more than 3 ml and a proper stress relaxation characteristics of no more than 20%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Conductive Materials (AREA)
EP98102539A 1997-02-18 1998-02-13 Copper base alloys and terminals using the same Expired - Lifetime EP0859065B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP72594/97 1997-02-18
JP7259497 1997-02-18
JP9072594A JPH10226835A (ja) 1997-02-18 1997-02-18 端子用銅基合金とそれを用いた端子

Publications (2)

Publication Number Publication Date
EP0859065A1 EP0859065A1 (en) 1998-08-19
EP0859065B1 true EP0859065B1 (en) 2004-05-12

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP98102539A Expired - Lifetime EP0859065B1 (en) 1997-02-18 1998-02-13 Copper base alloys and terminals using the same

Country Status (4)

Country Link
EP (1) EP0859065B1 (ko)
JP (1) JPH10226835A (ko)
KR (1) KR100357501B1 (ko)
DE (1) DE69823713T2 (ko)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6471792B1 (en) 1998-11-16 2002-10-29 Olin Corporation Stress relaxation resistant brass
JP3908588B2 (ja) * 2001-06-06 2007-04-25 マブチモーター株式会社 小型モータの回転子及びその製造方法
JP4984108B2 (ja) * 2005-09-30 2012-07-25 Ｄｏｗａメタルテック株式会社 プレス打抜き性の良いＣｕ−Ｎｉ−Ｓｎ−Ｐ系銅合金およびその製造法
JP4680765B2 (ja) 2005-12-22 2011-05-11 株式会社神戸製鋼所 耐応力緩和特性に優れた銅合金
JP5243744B2 (ja) * 2007-08-01 2013-07-24 Ｄｏｗａメタルテック株式会社 コネクタ端子
KR101227315B1 (ko) * 2007-08-07 2013-01-28 가부시키가이샤 고베 세이코쇼 구리 합금판
JP5466879B2 (ja) 2009-05-19 2014-04-09 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
CN107739880A (zh) * 2009-07-10 2018-02-27 鲁瓦塔富兰克林股份有限公司 用于热交换器管的铜合金
JP5436391B2 (ja) * 2010-10-22 2014-03-05 Ｄｏｗａメタルテック株式会社 皮膜および電気電子部品
JP6113674B2 (ja) * 2014-02-13 2017-04-12 株式会社神戸製鋼所 耐熱性に優れる表面被覆層付き銅合金板条
CN107208191B (zh) 2015-04-24 2020-03-13 古河电气工业株式会社 铜合金材料及其制造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS596346A (ja) * 1982-07-05 1984-01-13 Furukawa Electric Co Ltd:The 半導体機器のリ−ド材用銅合金
JPH01316432A (ja) * 1988-06-16 1989-12-21 Dowa Mining Co Ltd ハンダ耐候性にすぐれた導電材料用銅合金
JPH036341A (ja) * 1989-06-02 1991-01-11 Dowa Mining Co Ltd 高強度高導電性銅基合金
JP2844120B2 (ja) * 1990-10-17 1999-01-06 同和鉱業株式会社 コネクタ用銅基合金の製造法
US5322575A (en) * 1991-01-17 1994-06-21 Dowa Mining Co., Ltd. Process for production of copper base alloys and terminals using the same
US5387293A (en) * 1991-01-17 1995-02-07 Dowa Mining Co., Ltd. Copper base alloys and terminals using the same
JPH07331363A (ja) * 1994-06-01 1995-12-19 Nikko Kinzoku Kk 高力高導電性銅合金

Also Published As

Publication number Publication date
KR19980071423A (ko) 1998-10-26
KR100357501B1 (ko) 2002-12-18
EP0859065A1 (en) 1998-08-19
JPH10226835A (ja) 1998-08-25
DE69823713T2 (de) 2005-04-28
DE69823713D1 (de) 2004-06-17

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