EP2340318B1 - Kupfer-zinn-legierung, verbundwerkstoff und verwendung - Google Patents

Kupfer-zinn-legierung, verbundwerkstoff und verwendung Download PDF

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Publication number
EP2340318B1
EP2340318B1 EP09744964.9A EP09744964A EP2340318B1 EP 2340318 B1 EP2340318 B1 EP 2340318B1 EP 09744964 A EP09744964 A EP 09744964A EP 2340318 B1 EP2340318 B1 EP 2340318B1
Authority
EP
European Patent Office
Prior art keywords
weight
tin
copper
alloy
composite material
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.)
Active
Application number
EP09744964.9A
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German (de)
English (en)
French (fr)
Other versions
EP2340318A1 (de
Inventor
Michael KÖHLER
Andreas Heide
Ralf Hojda
Udo Riepe
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.)
Sundwiger Messingwerk GmbH and Co KG
Original Assignee
Sundwiger Messingwerk GmbH and Co KG
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Publication of EP2340318A1 publication Critical patent/EP2340318A1/de
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Publication of EP2340318B1 publication Critical patent/EP2340318B1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12389—All metal or with adjacent metals having variation in thickness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12715—Next to Group IB metal-base component

Definitions

  • the invention relates to a copper-tin alloy, a composite material with such a copper-tin alloy and a use of the copper-tin alloy and the composite material.
  • the copper-tin alloy and the comprehensive composite material is particularly suitable for fasteners in electrical engineering and electronics.
  • the invention is particularly concerned with the problem of recyclability.
  • copper alloys based on Cu-Zn, Cu-Sn and Cu-Fe are widely used today for connecting elements in electrical engineering and in electronics.
  • copper alloys are used for lead frames and connectors.
  • Important criteria for the selection of materials are modulus of elasticity, yield strength, relaxation behavior and bendability.
  • the electrical conductivity and corrosion resistance are important criteria for the safe function of the components over the life of the entire system. Often there is an overlap of property requirements, which in principle preclude each other, such as the combination of a good Conductivity with high corrosion resistance.
  • alloying elements in copper, such as nickel and chromium on the one hand improve the corrosion resistance, on the other hand, they considerably reduce the conductivity.
  • Cu-Zn or brass alloys are solid solution hardening materials. They are binary alloys, which usually contain between 5 and 40 wt .-% of zinc. With increasing zinc content, tensile strength and hardness increase. The elongation reaches a maximum at 30% by weight of zinc. Higher strength and hardness values can only be achieved by cold forming.
  • the disadvantage of the Cu-Zn alloys lies in the relatively poor weldability, because the alloying element zinc has a relatively high vapor pressure. Pure zinc already boils at 1.013 bar at 907 ° C.
  • Cu-Zn alloys have a low elastic modulus of about 110 KN / mm 2 (SI unit: GPa).
  • tinned brass bands can not be recycled well due to the tin included for corrosion protection reasons.
  • the relaxation behavior of Cu-Zn alloys is also pronounced, limiting the operating temperature.
  • Cu-Sn alloys ie tin bronzes
  • the Cu-Sn alloys are usually added some phosphorus, which is why these alloys are also referred to as phosphorus bronzes.
  • the properties of these alloys are determined primarily by the tin content, which is usually between 4 and 8 wt .-%.
  • the modulus of elasticity of phosphorus bronzes is between 115 and 120 kN / mm 2 (SI unit: GPa).
  • the bendability of tin bronzes is excellent. Rising Sn levels improve the flexibility for a given temper.
  • the laser weldability of tin or phosphorus bronzes is given, because these alloys have no volatile elements (especially zinc) and no disturbing second phases.
  • the relaxation behavior of tin or phosphorus bronzes is better than that of brass alloys, although it does not reach the level of hardenable copper materials.
  • Cu-Sn alloys are used in the form of tapes for stampings and connectors, if a good to very good spring characteristic, a good electrical and thermal resilience, low stress relaxation, good bendability, good weldability and solderability are required. Even in tinned form, phosphorus bronzes are easy to recycle. Tin is already included in the alloy as such.
  • the low-alloyed copper materials include the Cu-Fe alloys.
  • the material properties of pure copper such as the strength, the softening or relaxation behavior can be improved.
  • Widely used for stamped grids in automotive engineering is in particular a CuFe2P alloy in the heat setting FH.
  • the sharp-edged bendability is still present.
  • the modulus of elasticity is about 125 KN / mm 2 (GPa), and thus the material has good spring properties.
  • the electrical conductivity is between 60% and 70% IACS (I nternational Annealed C opper S tandard: 100% IACS correspond approximately to 58 MS / m). A tinning of the material for corrosion protection reasons is well possible.
  • One of the disadvantages of the CuFe2P alloy is that it does not form a homogeneous material but has Fe2P precipitates. In particular, this makes laser welding difficult. If the laser beam encounters coarser Fe2P precipitates during spot welding, it can be deflected, making the penetration result unsatisfactory.
  • Another disadvantage is the poor recyclability of tin-plated scrap of CuFe2P alloy.
  • the electrical conductivity of a CuFe2P alloy is reduced by 25% upon reflow by a dissolving tin of about 1% by weight.
  • the tinned punching scrap which usually make up 50% to 70% of the material used in the manufacture of stamped laths, can not be returned directly to the melting process, but rather must be smelted and electrochemically separated. The return to the material cycle is therefore as a cathode. This process is very energy intensive and thus very expensive compared to the direct melting of the scraps.
  • Fig. 1 For a CuFe2P alloy, the influence of a percentage of tin on the electrical conductivity is shown. The electrical conductivity drops drastically even from levels above 0.3 wt .-% tin. For example, a 0.4 mm thick band of a CuFe2P alloy for corrosion protection reasons Coated with about 3 ⁇ m tin on both sides, a CuFe2P alloy contaminated with about 1.5% by weight tin would result from direct recycling based on this scrap. In addition to drastic losses in the electrical conductivity, this tin content also has a strong negative effect on the solidification behavior.
  • CuNiP alloys are known, which may optionally include Sn, Zn and Fe.
  • the object of the invention is to provide an alloy and a composite material which corresponds as far as possible in its physical and technological properties of a CuFe2P alloy, as well as possible laser weldable and can be recycled well. Another object is to provide a use for such an alloy and composite material.
  • the above object is achieved by a copper-tin alloy having the composition according to claim 1.
  • the copper-tin alloy comprises 0.2 to 0.8 wt .-% tin (Sn), 0.3 to 0.5 wt .-% nickel (Ni) and / or cobalt (Co), 0 to 0 , 05 wt .-% zinc (Zn), 0 to 0.02 wt .-% iron (Fe), 0.008 to 0.05 wt .-% phosphorus (P) and the balance copper (Cu).
  • the invention is based on the idea of specifying an alternative to the CuFe2P alloy, new alloy, which has comparable properties, but can be easily recycled even in tinned state.
  • Pure Cu-Sn alloys such as a CuSn0.15 alloy, undoubtedly have the potential to be used as such an alternative. Coated with tin, the scrap of such an alloy can be fed directly to the recycling cycle.
  • the mechanical and technological properties correspond to those of a CuFe2P alloy relatively well. Significant weaknesses, however, occur in the softening behavior and the relaxation resistance.
  • the table shows that Cu-Sn alloys can meet the specified requirements in terms of technological and physical properties.
  • an alloy layer is formed between the base material and the tin coating.
  • the Cu-Sn alloy according to the invention exhibits a property profile which is comparable to the CuFe 2 P alloy in the area of the softening behavior and the relaxation.
  • the Cu-Sn alloy according to the invention is further distinguished in a special way by the direct traceability of tin-plated scrap from the individual stages of the value-added chain.
  • the tin-coated scrap can be returned directly to the smelting process, so that the recycling costs are significantly lower than smelting.
  • the smelting costs for example, can quickly reach the level of manufacturing costs with a scrap content of 70% and put into question the economic efficiency.
  • the stated copper-tin alloy contains a proportion of Sn between 0.3 and 0.7% by weight, in particular between 0.4 and 0.6% by weight the invention, the proportion of Ni and / or Co in the copper-tin alloy is between 0.3 and 0.5 wt .-%.
  • the strength can be improved.
  • the copper-tin alloy has 0.3 to 0.7 wt% Sn, 0.3 to 0.5 wt% Ni and / or Co, 0 to 0.04 wt%. Zn, 0 to 0.015 wt .-% Fe, 0.08 to 0.03 wt .-% P, and the balance Cu on.
  • the copper-tin alloy is further improved when it contains 0.4 to 0.6% by weight Sn, 0.3 to 0.5% by weight Ni and / or Co, 0 to 0.03% by weight. % Zn, 0 to 0.01 wt .-% Fe, 0.008 to 0.015 wt .-% P, and the remainder comprises Cu.
  • a further advantageous precise adjustment of the properties of the copper-tin alloy can be carried out if there is a total of impurities and other admixtures of not more than 0.3% by weight.
  • a copper-tin alloy containing 0.38 wt% Sn, 0.30 wt% Ni and / or Co, 0.003 wt% Zn, 0.008 wt%. % Fe, 0.014 wt .-% P, and the remainder comprises Cu.
  • the copper-tin alloy according to the invention is very good laser weldable, since no volatile elements are contained and the alloy is free of a second phase. In particular, the alloy does not exhibit NiP precipitates.
  • the alloy is ideal for a good laser weldable composite material, which can be used in particular for stamped grid.
  • stamped grids are used today, for example in automotive technology for ABS and ESP systems.
  • a base material of the aforementioned copper-tin alloy is provided with a tin layer or covered, which can be made in particular by the method of hot tinning.
  • the composite material is characterized by a high relaxation resistance up to temperatures of 100 ° C.
  • the specified copper-tin alloy with a composition according to the claims directed thereto.
  • the outer coating or tin cover ensures high corrosion resistance.
  • the thickness of the tin layer is preferably between 1 and 3 ⁇ m.
  • a transition layer is formed between the base material and the tin layer.
  • the tin layer is preferably applied in such a way that the transition layer comprises an intermetallic phase of Cu, Ni and / or Co and Sn.
  • the formation of the transition layer is in particular designed such that it has a thickness between 0.1 and 1 micron.
  • the alloy of the core transitions through the transition layer into a layer of pure tin. Via the formed transition or alloy layer, a good connection of the tin layer is achieved.
  • the overall result is a five-layer structure.
  • On one core of the specified copper-tin alloy as the base material sits on both sides of a layer of an intermetallic phase consisting of CuNiCoSn with a thickness between 0.1 and 1.0 microns.
  • the composite material is finally covered for corrosion protection reasons with a layer of free or pure tin, which has a thickness of 1.0 to 3.0 microns.
  • the layer composite material has a total thickness of 0.2 to 1 mm, preferably up to 2 mm, particularly preferably up to 3 mm.
  • the electrical conductivity of the specified composite material corresponds to that of the previously used comparison material CuFe2P. Thermal conductivity and other technological values of the composite are also fully comparable.
  • Both the copper-tin alloy according to the invention and the tinned composite material are outstandingly suitable for tapes, films, profiled strips, stampings or connectors, in particular for applications in electrical engineering or electronics.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Non-Insulated Conductors (AREA)
  • Contacts (AREA)
EP09744964.9A 2008-10-31 2009-10-27 Kupfer-zinn-legierung, verbundwerkstoff und verwendung Active EP2340318B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008054183 2008-10-31
PCT/EP2009/007669 WO2010049118A1 (de) 2008-10-31 2009-10-27 Kupfer-zinn-legierung, verbundwerkstoff und verwendung

Publications (2)

Publication Number Publication Date
EP2340318A1 EP2340318A1 (de) 2011-07-06
EP2340318B1 true EP2340318B1 (de) 2017-02-15

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EP09744964.9A Active EP2340318B1 (de) 2008-10-31 2009-10-27 Kupfer-zinn-legierung, verbundwerkstoff und verwendung

Country Status (9)

Country Link
US (1) US20110206941A1 (ru)
EP (1) EP2340318B1 (ru)
JP (1) JP2012506952A (ru)
KR (1) KR20110079638A (ru)
CN (1) CN102177265B (ru)
BR (1) BRPI0921441A2 (ru)
ES (1) ES2623604T3 (ru)
RU (1) RU2482204C2 (ru)
WO (1) WO2010049118A1 (ru)

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WO2012067903A2 (en) * 2010-11-17 2012-05-24 Luvata Appleton Llc Alkaline collector anode
CN102176809A (zh) * 2011-01-14 2011-09-07 中国科学院上海技术物理研究所 一种用于印制电路板上的贴片电阻与电容的调试器
CN102703748B (zh) * 2012-07-06 2013-10-16 山东大学 一种纳米多孔铜锡合金的制备方法
RU2502817C1 (ru) * 2012-12-18 2013-12-27 Юлия Алексеевна Щепочкина Сплав на основе меди
JP5773015B2 (ja) 2013-05-24 2015-09-02 三菱マテリアル株式会社 銅合金線
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
RU2587110C9 (ru) * 2014-09-22 2016-08-10 Дмитрий Андреевич Михайлов МЕДНЫЙ СПЛАВ, ЛЕГИРОВАННЫЙ ТЕЛЛУРОМ ТелО, ДЛЯ КОЛЛЕКТОРОВ ЭЛЕКТРИЧЕСКИХ МАШИН
CN107034381B (zh) * 2017-04-26 2019-03-19 江西理工大学 一种Cu-Ni-Co-Sn-P铜合金及其制备方法
RU2709909C1 (ru) * 2018-11-26 2019-12-23 Федеральное государственное автономное образовательное учреждение высшего образования "Белгородский государственный национальный исследовательский университет" (НИУ "БелГУ") Низколегированный медный сплав
CN116411202A (zh) * 2021-12-29 2023-07-11 无锡市蓝格林金属材料科技有限公司 一种铜锡合金线材及其制备方法

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Also Published As

Publication number Publication date
JP2012506952A (ja) 2012-03-22
CN102177265A (zh) 2011-09-07
WO2010049118A1 (de) 2010-05-06
ES2623604T3 (es) 2017-07-11
RU2482204C2 (ru) 2013-05-20
EP2340318A1 (de) 2011-07-06
CN102177265B (zh) 2014-07-09
KR20110079638A (ko) 2011-07-07
US20110206941A1 (en) 2011-08-25
BRPI0921441A2 (pt) 2016-01-05
RU2011121810A (ru) 2012-12-10

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