EP1288321B1 - Material for a metal strip - Google Patents

Material for a metal strip Download PDF

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Publication number
EP1288321B1
EP1288321B1 EP02017970A EP02017970A EP1288321B1 EP 1288321 B1 EP1288321 B1 EP 1288321B1 EP 02017970 A EP02017970 A EP 02017970A EP 02017970 A EP02017970 A EP 02017970A EP 1288321 B1 EP1288321 B1 EP 1288321B1
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EP
European Patent Office
Prior art keywords
material according
tin
silver
less
ratio
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
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EP02017970A
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German (de)
French (fr)
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EP1288321A1 (en
Inventor
Udo Adler
Jürgen Dr. Gebhard
Heinrich Klenen
Thomas Helmenkamp
Robert Leffers
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KME Special Products GmbH and Co KG
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KM Europa Metal AG
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Priority to DK02017970T priority Critical patent/DK1288321T3/en
Publication of EP1288321A1 publication Critical patent/EP1288321A1/en
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Publication of EP1288321B1 publication Critical patent/EP1288321B1/en
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Classifications

    • 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
    • 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
    • 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
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9265—Special properties
    • Y10S428/929—Electrical contact feature
    • 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.]
    • 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
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component

Definitions

  • the invention relates to a material for a metal strip for the production of electrical contact components.
  • Plug-in contact connections are widely used in electrotechnical applications. This basically means a mechanical arrangement of plug and Plug sleeve for opening and closing an electrically conductive connection. Plug contact connections come in a wide variety of applications used, for example in the automotive electrical, telecommunications or the industrial plant electronics.
  • a common manufacturing method of such plug contact elements is blankslosestanzen a copper or a copper alloy strip and this for Plug contact element to process further.
  • Copper has a high electrical conductivity.
  • the copper or copper alloy strips are tinned in advance. tin is particularly suitable as a coating material because of its good corrosion resistance for copper. The order of the coating in the technical standard counts Hot-dip process.
  • tin alloys for surface coating of the base material in particular also tin-silver alloys, because these are among the very good contact materials.
  • DE 36 28 783 C2 discloses an electrical connector made of a copper alloy, the 0.3 to 2 wt .-% magnesium and 0.001 to 0.1 wt .-% phosphorus having.
  • the electrical connectors are characterized by their strength, their electrical conductivity and stress relaxation properties at elevated Temperatures off. They show satisfactory performance properties, even when They are made in a compact size and complicated shape.
  • the prior art also includes a copper alloy by DE 43 38 769 A1 for the manufacture of electrical connectors with a composition of essentially 0.5 to 3% by weight nickel, 0.1 to 0.9% tin, 0.08 to 0.8% by weight Silicon, 0.1 to 3 wt% zinc, 0.007 to 0.25 wt% iron, 0.001 to 0.2 wt% Phosphorus and 0.001 to 0.2% magnesium with the main constituent copper as Rest including the unavoidable impurities.
  • EP 1 158 618 A2 includes an electrically conductive metal strip for production of electrical contact components, in particular of connectors, with a base material of a copper alloy to the prior art.
  • the basic material has a melting technically applied metallic coating a tin-silver alloy, wherein between the base material and the Be layering an intermetallic phase is formed.
  • the base material - in% by weight is made of nickel (Ni) 1.0% to 4.0%, silicon (Si) 0.08% to 1.0 %, Tin (Sn) 0.02% to 1.0%, zinc (Zn) 0.01% to 2.0%, zirconium (Zr) 0.005% up to 0.2%, silver (Ag) 0.02% to 0.5%, balance copper including melting Impurities.
  • the coating consists of a tin-silver alloy with a silver content between 1% by weight and 3.8% by weight.
  • EP 1 157 820 A1 counts an electrically conductive metal strip for manufacturing of electrical contact components, in particular of connectors, with a base material made of copper or a copper alloy to the prior art.
  • the base material has a melting technically applied metallic coating made of a tin-silver alloy, wherein between the base material and the coating is formed an intermetallic phase.
  • the coating consists of a tin-silver alloy with a silver content between 1% by weight and 3.8% by weight.
  • the known metal bands or the connectors thereof have in the Proven practice.
  • the technical and qualitative requirements are increasing the contact components in terms of mechanical and electrical properties. This is especially true when using the contact components under difficult or aggressive environmental conditions, such as for connectors in the Automotive electrical and here especially in the engine electronics. Under such difficult Operating conditions can be particularly demanding with regard to temperature resistance, Relaxation resistance, corrosion resistance and adhesion of the Coating occur where the known contact components reach their limit bump. It may then come to peeling (exfoliation) of the surface coating.
  • the invention is - based on the prior art - the task in economically advantageous a material for a metal strip for the production of to provide electrical contact components, which good electrical and mechanical Properties with an improvement in adhesion between base material and coating combined.
  • the material consists of a copper alloy with nickel shares between 0.5 and 3.5 wt .-%, silicon contents of 0.08 to 1.0 wt .-%, tin content of 0.1 to 1.0 wt .-%, zinc contents of 0.1 to 1.0 wt .-%, zirconium shares between 0.005 to 0.2 wt .-%, silver content between 0.02 to 0.5 wt .-% and indium between 0.1 and 5 wt .-%.
  • the tin content in the material itself decreases its conductivity, but increases this strength and toughness.
  • the decrease in conductivity is due to the Addition of silver compensated.
  • the main purpose of the silver share is to as matrix component under the influence of temperature on diffusion processes with the Coating material to participate in a metal strip and the expected diffusion-controlled Influence phase formation of intermetallic compounds.
  • the silver content is therefore between 0.02 wt .-% and 0.5 wt .-%.
  • the zirconium with a proportion between 0.005 and 0.2 wt .-% increases the corrosion and temperature resistance and improves the thermoformability.
  • Indium between 0.1 Although wt .-% and 5 wt .-% lowers the melting point, but improves Overall resistance to external conditions.
  • the Soldering properties positively influenced.
  • the material preferably contains a silver content of less than 0.15% by weight. (Claim 2).
  • a manganese content of less than 0.5 wt .-% promotes temperature resistance (Claim 3).
  • Magnesium with a proportion of less than 0.2 wt .-% (claim 4) improved the strength and the stress relaxation property at elevated temperature of Alloy with only slight impairment of electrical conductivity, the based on the main component copper. Magnesium dissolves in the copper matrix.
  • the ratio of silver to zinc is greater than 0.1 (Claim 7).
  • a further advantageous feature is achieved according to claim 8, if the ratio of magnesium and zirconium is greater than 0.1 tin.
  • the exfoliating behavior of the material is according to the features of the patent claim 9 significantly improved when the ratio (nickel + silicon) to (tin + zinc + Silver + magnesium) is greater than 1.5, but smaller than 4.
  • the metal strip using the material described above according to Claim 10 is initially characterized by its good electrical and me chanical properties, in particular by its good conductivity and relaxation resistance with good formability and peel resistance of the coating. A stable contact resistance is ensured.
  • the metal band has a high temperature resistance with low contact resistance on. It is abrasion and abrasion resistant with higher hardness, yet it is well deformable and good solderable. The insertion and removal forces are low with improved friction corrosion resistance.
  • the metal strip is economically advantageous because during its production Copper scrap can be used with tin components. In the material cycle becomes a achieved balanced tin balance. This can be a consistent quality of be ensured under scrap insert produced metal strips.
  • tinned Scrap and Neumetall can be tinned depending on the thickness of the tin plating
  • a base material can be obtained as a cast product with a tin content from 0.02 to 1% by weight. Process advantages are cast products with a tin content between 0.25 and 0.5% by weight.
  • the intermetallic phase between the base material and the coating is fine-grained and even. This results in a good formability, in particular Bendability, higher shear strengths and low moduli of elasticity as well a high creep resistance of the metal strip.
  • the alloy components zinc and silver influence the diffusion behavior in the intermetallic phase between the base material and the according to claim 11 made of tin-silver coating.
  • the inevitably through Diffusion of copper in the tin layer resulting copper-tin phases are in their expression over temperature and time in the sense of a slowing down and disability the formation specifically affects the so-called epsilon phase.
  • epsilon phase By a much better strength between the base material and coating guaranteed. This will be peel-off, in particular the Peeling (exfoliation) of the coating, even with unfavorable and difficult Operating conditions of the metal strip or the connector produced therefrom moved to higher temperatures and longer times.
  • the main reason for a possible age-related failure of the coating just at temperatures above 150 ° C is a disproportionately fast conversion of the so-called ⁇ -phase (Cu 6 Sn 5 ) in the ⁇ -phase (Cu 3 Sn) in training, starting from the Phase boundary between base material and coating due to high diffusion rates.
  • the invention now recognizes the fact that the presence of the ⁇ -phase alone does not necessarily lead to detachment processes at the boundary between the base material and the coating, not even in the case of a stress state of a connector caused by the forming process. If the expression of the ⁇ phase is prevented or hindered, this has a positive effect on the intermetallic phase and long-term stability of the coating.
  • Zinc and silver as well as the nickel present in the material are in their invention shares in the diffusion process and their participation in the formation of the intermetallic phase specifically by enrichment in the phase boundary to suppress the rapid conversion of the ⁇ -phase to ⁇ -phase or significantly slow down with the success of a homogeneous highly adhesive Composite between base material and coating.

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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)
  • Contacts (AREA)
  • Laminated Bodies (AREA)
  • Package Frames And Binding Bands (AREA)
  • Clamps And Clips (AREA)
  • Adornments (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Material comprises 0.5-3.5 wt.% nickel, 0.08-1.0 wt.% silicon, 0.1-1.0 wt.% tin, 0.1-1.0 wt.% zinc, 0.005-0.2 wt.% zirconium, 0.02-0.5 wt.% silver and balance of copper including melting-induced impurities. Preferably the material contains less than 0.15 wt.% silver, less than 0.5 wt.% manganese, less than 0.2 wt.% magnesium and 0.1-5 wt.% indium.

Description

Die Erfindung betrifft einen Werkstoff für ein Metallband zur Fertigung von elektrischen Kontaktbauteilen.The invention relates to a material for a metal strip for the production of electrical contact components.

Steckkontaktverbindungen sind in elektrotechnischen Anwendungen weit verbreitet. Man versteht hierunter grundsätzlich eine mechanische Anordnung aus Stecker und Steckerhülse zum Öffnen und Schließen einer elektrisch leitenden Verbindung. Steckkontaktverbindungen kommen in unterschiedlichsten Anwendungsbereichen zum Einsatz, beispielsweise in der Kraftfahrzeugelektrik, der Nachrichtentechnik oder der Industrieanlagenelektronik.Plug-in contact connections are widely used in electrotechnical applications. This basically means a mechanical arrangement of plug and Plug sleeve for opening and closing an electrically conductive connection. Plug contact connections come in a wide variety of applications used, for example in the automotive electrical, telecommunications or the industrial plant electronics.

Ein übliches Fertigungsverfahren derartiger Steckkontaktelemente ist, Rohlinge aus einem Kupfer- bzw. einem Kupferlegierungsband auszustanzen und diese zum Steckkontaktelement weiter zu verarbeiten. Kupfer hat eine hohe elektrische Leitfähigkeit. Zum Schutz gegen Korrosion und Verschleiß sowie zur Erhöhung der Oberflächenhärte werden die Kupfer- bzw. Kupferlegierungsbänder vorab verzinnt. Zinn eignet sich wegen seiner guten Korrosionsbeständigkeit besonders als Überzugsmaterial für Kupfer. Zum technischen Standard zählt der Auftrag der Beschichtung im Schmelztauchverfahren.A common manufacturing method of such plug contact elements is blanks auszustanzen a copper or a copper alloy strip and this for Plug contact element to process further. Copper has a high electrical conductivity. To protect against corrosion and wear as well as to increase the surface hardness The copper or copper alloy strips are tinned in advance. tin is particularly suitable as a coating material because of its good corrosion resistance for copper. The order of the coating in the technical standard counts Hot-dip process.

In diesem Zusammenhang sind unterschiedlichste Zinnlegierungen zur Oberftächenbeschichtung des Basiswerkstoffs bekannt, insbesondere auch Zinn-Silber-Legierungen, da diese zu den sehr guten Kontaktwerkstoffen zählen. In this context, a wide variety of tin alloys for surface coating of the base material, in particular also tin-silver alloys, because these are among the very good contact materials.

Durch die europäische Patentschrift 0 443 291 B1 ist es bekannt, bei einem elektrischen Steckverbinderpaar den Basiswerkstoff eines Steckerelements mit Reinzinn oder einer Zinn-Blei-Legierung zu beschichten, während das andere Steckerelement eine auf schmelzflüssigem Wege aufgebrachte härtere Oberflächenbeschichtung aus einer Legierung aufweist, die bis zu 10 Gew.-% Silber enthält. Neben Silber werden noch eine Reihe weiterer Legierungsmetalle vorgeschlagen. Dieser Ansatz ist richtungsweisend für die Herstellung qualitativ hochwertiger Steckverbinder mit gleichbleibend niedrigem Kontaktwiderstand und möglichst geringen Steck- und Ziehkräften.By European Patent 0 443 291 B1 it is known in an electric Connector pair the base material of a plug element with pure tin or a tin-lead alloy while the other plug element a harder surface coating applied by molten metal an alloy containing up to 10% by weight of silver. Beyond silver nor a number of other alloying metals proposed. This approach is trend-setting for producing high quality connectors with consistent low contact resistance and the lowest possible insertion and removal forces.

Die DE 36 28 783 C2 offenbart ein elektrisches Verbindungsstück aus einer Kupferlegierung, die 0,3 bis 2 Gew.-% Magnesium sowie 0,001 bis 0,1 Gew.-% Phosphor aufweist. Die elektrischen Verbindungsstücke zeichnen sich durch ihre Festigkeit, ihre elektrische Leitfähigkeit und Spannungsrelaxationseigenschaften bei erhöhten Temperaturen aus. Sie zeigen befriedigende Gebrauchseigenschaften, selbst wenn sie in kompakter Größe und komplizierter Form hergestellt sind.DE 36 28 783 C2 discloses an electrical connector made of a copper alloy, the 0.3 to 2 wt .-% magnesium and 0.001 to 0.1 wt .-% phosphorus having. The electrical connectors are characterized by their strength, their electrical conductivity and stress relaxation properties at elevated Temperatures off. They show satisfactory performance properties, even when They are made in a compact size and complicated shape.

Zum Stand der Technik zählt durch die DE 43 38 769 A1 auch eine Kupferlegierung zur Herstellung von elektrischen Steckverbindern mit einer Zusammensetzung von im wesentlichen 0,5 bis 3 Gew.-% Nickel, 0,1 bis 0,9-% Zinn, 0,08 bis 0,8 Gew.-% Silizium, 0,1 bis 3 Gew.-% Zink, 0,007 bis 0,25 Gew.-% Eisen, 0,001 bis 0,2 Gew.-% Phosphor sowie 0,001 bis 0,2 % Magnesium mit dem Hauptbestandteil Kupfer als Rest einschließlich der unvermeidbaren Verunreinigungen.The prior art also includes a copper alloy by DE 43 38 769 A1 for the manufacture of electrical connectors with a composition of essentially 0.5 to 3% by weight nickel, 0.1 to 0.9% tin, 0.08 to 0.8% by weight Silicon, 0.1 to 3 wt% zinc, 0.007 to 0.25 wt% iron, 0.001 to 0.2 wt% Phosphorus and 0.001 to 0.2% magnesium with the main constituent copper as Rest including the unavoidable impurities.

Im Umfang der EP 1 158 618 A2 zählt ein elektrisch leitfähiges Metallband zur Fertigung von elektrischen Kontaktbauteilen, insbesondere von Steckverbindern, mit einem Basiswerkstoff aus einer Kupferlegierung zum Stand der Technik. Der Basis-Werkstoff weist eine schmelztechnisch aufgebrachte metallische Beschichtung aus einer Zinn-Silber-Legierung auf, wobei zwischen dem Basiswerkstoff und der Be schichtung eine intermetallische Phase ausgebildet ist. Der Basiswerkstoff - in Gew.-% ausgedrückt - besteht aus Nickel (Ni) 1,0 % bis 4,0 %, Silizium (Si) 0,08 % bis 1,0 %, Zinn (Sn) 0,02 % bis 1,0 %, Zink (Zn) 0,01 % bis 2,0 %, Zirkonium (Zr) 0,005 % bis 0,2 %, Silber (Ag) 0,02 % bis 0,5 %, Rest Kupfer einschließlich erschmelzungsbedingter Verunreinigungen. Die Beschichtung besteht aus einer Zinn-Silber-Legierung mit einem Silberanteil zwischen 1 Gew.% und 3,8 Gew.-%.The scope of EP 1 158 618 A2 includes an electrically conductive metal strip for production of electrical contact components, in particular of connectors, with a base material of a copper alloy to the prior art. The basic material has a melting technically applied metallic coating a tin-silver alloy, wherein between the base material and the Be layering an intermetallic phase is formed. The base material - in% by weight is made of nickel (Ni) 1.0% to 4.0%, silicon (Si) 0.08% to 1.0 %, Tin (Sn) 0.02% to 1.0%, zinc (Zn) 0.01% to 2.0%, zirconium (Zr) 0.005% up to 0.2%, silver (Ag) 0.02% to 0.5%, balance copper including melting Impurities. The coating consists of a tin-silver alloy with a silver content between 1% by weight and 3.8% by weight.

Auch durch die EP 1 157 820 A1 zählt ein elektrisch leitfähiges Metallband zur Fertigung von elektrischen Kontaktbauteilen, insbesondere von Steckverbindern, mit einem Basiswerkstoff aus Kupfer bzw. einer Kupferlegierung zum Stand der Technik. Der Basiswerkstoff weist eine schmelztechnisch aufgebrachte metallische Beschichtung aus einer Zinn-Silber-Legierung auf, wobei zwischen dem Basiswerkstoff und der Beschichtung eine intermetallische Phase ausgebildet ist. Die Beschichtung besteht aus einer Zinn-Silber-Legierung mit einem Silberanteil zwischen 1 Gew.-% und 3,8 Gew.-%.Also, by EP 1 157 820 A1 counts an electrically conductive metal strip for manufacturing of electrical contact components, in particular of connectors, with a base material made of copper or a copper alloy to the prior art. The base material has a melting technically applied metallic coating made of a tin-silver alloy, wherein between the base material and the coating is formed an intermetallic phase. The coating consists of a tin-silver alloy with a silver content between 1% by weight and 3.8% by weight.

Die bekannten Metallbänder bzw. die Steckverbinder hieraus haben sich in der Praxis bewährt. Jedoch steigen zunehmend die technischen und qualitativen Anforderungen der Kontaktbauteile hinsichtlich der mechanischen und elektrischen Eigenschaften. Dies gilt insbesondere beim Einsatz der Kontaktbauteile unter schwierigen oder aggressiven Umgebungsbedingungen, beispielsweise für Steckverbinder in der Kraftfahrzeugelektrik und hier vor allem in der Motorelektronik. Unter solch schwierigen Einsatzbedingungen können Anforderungen vor allem hinsichtlich Temperaturbeständigkeit, Relaxationsbeständigkeit, Korrosionsfestigkeit und Haftfestigkeit der Beschichtung auftreten, bei denen die bekannten Kontaktbauteile an ihre Grenze stoßen. Es kann dann zum Abblättern (Peeling) der Oberflächenbeschichtung kommen. The known metal bands or the connectors thereof have in the Proven practice. However, the technical and qualitative requirements are increasing the contact components in terms of mechanical and electrical properties. This is especially true when using the contact components under difficult or aggressive environmental conditions, such as for connectors in the Automotive electrical and here especially in the engine electronics. Under such difficult Operating conditions can be particularly demanding with regard to temperature resistance, Relaxation resistance, corrosion resistance and adhesion of the Coating occur where the known contact components reach their limit bump. It may then come to peeling (exfoliation) of the surface coating.

Der Erfindung liegt - ausgehend vom Stand der Technik - die Aufgabe zugrunde, in ökonomisch vorteilhafter Weise einen Werkstoff für ein Metallband zur Fertigung von elektrischen Kontaktbauteilen zu schaffen, welcher gute elektrische und mechanische Eigenschaften mit einer Verbesserung der Haftung zwischen Basiswerkstoff und Beschichtung vereinigt.The invention is - based on the prior art - the task in economically advantageous a material for a metal strip for the production of to provide electrical contact components, which good electrical and mechanical Properties with an improvement in adhesion between base material and coating combined.

Die Lösung dieser Aufgabe besteht nach der Erfindung in den Merkmalen des Patentanspruchs 1.The solution of this problem consists according to the invention in the features of the claim 1.

Danach besteht der Werkstoff aus einer Kupferlegierung mit Nickelanteilen zwischen 0,5 und 3,5 Gew.-%, Siliziumanteilen von 0,08 bis 1,0 Gew.-%, Zinnanteilen von 0,1 bis 1,0 Gew.-%, Zinkanteilen von 0,1 bis 1,0 Gew.-%, Zirkoniumanteilen zwischen 0,005 bis 0,2 Gew.-%, Silberanteilen zwischen 0,02 bis 0,5 Gew.-%und Indiumanteilen zwischen 0,1 und 5 Gew.-%.Thereafter, the material consists of a copper alloy with nickel shares between 0.5 and 3.5 wt .-%, silicon contents of 0.08 to 1.0 wt .-%, tin content of 0.1 to 1.0 wt .-%, zinc contents of 0.1 to 1.0 wt .-%, zirconium shares between 0.005 to 0.2 wt .-%, silver content between 0.02 to 0.5 wt .-% and indium between 0.1 and 5 wt .-%.

Durch den Zinnanteil im Werkstoff sinkt an sich dessen Leitfähigkeit, jedoch steigt hierdurch die Festigkeit und Zähigkeit. Die Abnahme der Leitfähigkeit wird durch die Zulegierung von Silber kompensiert. Der Hauptzweck des Silberanteils besteht darin, als Matrixkomponente unter Temperatureinfluss an Diffusionsvorgängen mit dem Beschichtungswerkstoff eines Metallbands teilzunehmen und die zu erwartende diffusionsgesteuerte Phasenbildung intermetallischer Verbindungen zu beeinflussen. Der Silberanteil liegt daher zwischen 0,02 Gew.-% und 0,5 Gew.-%. Das Zirkonium mit einem Anteil zwischen 0,005 und 0,2 Gew.-% steigert die Korrosions- und Temperaturbeständigkeit und verbessert die Warmformbarkeit. Indium zwischen 0,1 Gew.-% und 5 Gew.-% erniedrigt zwar den Schmelzpunkt, verbessert jedoch insgesamt die Beständigkeit gegen äußere Bedingungen. Zusätzlich werden die Löteigenschaften positiv beeinflusst. Bevorzugt enthält der Werkstoff einen Silbergehalt von weniger als 0,15 Gew.-% (Patentanspruch 2).Due to the tin content in the material itself decreases its conductivity, but increases this strength and toughness. The decrease in conductivity is due to the Addition of silver compensated. The main purpose of the silver share is to as matrix component under the influence of temperature on diffusion processes with the Coating material to participate in a metal strip and the expected diffusion-controlled Influence phase formation of intermetallic compounds. The silver content is therefore between 0.02 wt .-% and 0.5 wt .-%. The zirconium with a proportion between 0.005 and 0.2 wt .-% increases the corrosion and temperature resistance and improves the thermoformability. Indium between 0.1 Although wt .-% and 5 wt .-% lowers the melting point, but improves Overall resistance to external conditions. In addition, the Soldering properties positively influenced. The material preferably contains a silver content of less than 0.15% by weight. (Claim 2).

Ein Mangananteil von weniger als 0,5 Gew.-% fördert die Temperaturbeständigkeit (Patentanspruch 3).A manganese content of less than 0.5 wt .-% promotes temperature resistance (Claim 3).

Magnesium mit einem Anteil von kleiner 0,2 Gew.-% (Patentanspruch 4) verbessert die Festigkeit und die Spannungsrelaxationseigenschaft bei erhöhter Temperatur der Legierung bei nur geringfügiger Beeinträchtigung der elektrischen Leitfähigkeit, die auf dem Hauptbestandteil Kupfer beruht. Magnesium löst sich in der Kupfermatrix.Magnesium with a proportion of less than 0.2 wt .-% (claim 4) improved the strength and the stress relaxation property at elevated temperature of Alloy with only slight impairment of electrical conductivity, the based on the main component copper. Magnesium dissolves in the copper matrix.

Wenn entsprechend Patentanspruch 5 Zinn und Zink in einem Verhältnis von etwa 1:1 im Werkstoff enthalten sind, wird der Leitfähigkeitsverlust verringert und die Beschichtbarkeit erhöht. Ferner wird eine maximale Härtesteigerung bei guter Dehnung im ausgehärteten Zustand erzielt.If according to claim 5 tin and zinc in a ratio of about 1: 1 contained in the material, the conductivity loss is reduced and the coatability elevated. Furthermore, a maximum hardness increase with good elongation achieved in the cured state.

Das in Patentanspruch 6 angegebene Verhältnis Zinn zu Silber von etwa 1:4 führt zu Vorteilen bei dem Recycling von mit Zinn beschichteten Metallbändern.The specified in claim 6 tin to silver ratio of about 1: 4 leads to Advantages of recycling tin-coated metal strips.

Des Weiteren ist es von Vorteil, wenn das Verhältnis Silber zu Zink größer 0,1 ist (Patentanspruch 7).Furthermore, it is advantageous if the ratio of silver to zinc is greater than 0.1 (Claim 7).

Eine weitere vorteilhafte Eigenschaft wird entsprechend Patentanspruch 8 erzielt, wenn das Verhältnis Magnesium und Zirkonium größer 0,1 Zinn bemessen ist.A further advantageous feature is achieved according to claim 8, if the ratio of magnesium and zirconium is greater than 0.1 tin.

Das Peelingverhalten des Werkstoffs wird gemäß den Merkmalen des Patentanspruchs 9 deutlich verbessert, wenn das Verhältnis (Nickel + Silizium) zu (Zinn + Zink + Silber + Magnesium) größer 1,5, jedoch kleiner 4 bemessen ist.The exfoliating behavior of the material is according to the features of the patent claim 9 significantly improved when the ratio (nickel + silicon) to (tin + zinc + Silver + magnesium) is greater than 1.5, but smaller than 4.

Das Metallband unter Verwendung des vorstehend beschriebenen Werkstoffs gemäß Patentanspruch 10 zeichnet sich zunächst durch seine guten elektrischen und me chanischen Eigenschaften aus, insbesondere durch seine gute Leitfähigkeit und Relaxationsbeständigkeit bei guter Umformbarkeit sowie Ablösebeständigkeit der Beschichtung. Ein stabiler Kontaktübergangswiderstand ist sichergestellt. Das Metallband weist eine hohe Temperaturbeständigkeit mit niedrigem Übergangswiderstand auf. Es ist abrieb- und durchriebfest bei höherer Härte, dennoch ist es gut verformbar und gut lötbar. Die Steck- und Ziehkräfte sind niedrig bei verbesserter Reibkorrosionsbeständigkeit.The metal strip using the material described above according to Claim 10 is initially characterized by its good electrical and me chanical properties, in particular by its good conductivity and relaxation resistance with good formability and peel resistance of the coating. A stable contact resistance is ensured. The metal band has a high temperature resistance with low contact resistance on. It is abrasion and abrasion resistant with higher hardness, yet it is well deformable and good solderable. The insertion and removal forces are low with improved friction corrosion resistance.

Darüber hinaus ist das Metallband ökonomisch vorteilhaft, da bei dessen Herstellung Kupferschrott mit Zinnanteilen eingesetzt werden kann. Im Stoffkreislauf wird eine ausgeglichene Zinnbilanz erreicht. Hierdurch kann eine gleichbleibende Qualität der unter Schrotteinsatz hergestellten Metallbänder sichergestellt werden. Durch eine Abstimmung des Einsatzes von blankem Schrott (CuNiSi-Werkstoff), verzinntem Schrott und Neumetall (Kupfer) kann je nach Stärke der Zinnauflage des verzinnten Schrotts ein Basiswerkstoff als Gießprodukt gewonnen werden mit einem Zinngehalt von 0,02 bis 1 Gew.-%. Verfahrensvorteilhaft sind Gießprodukte mit einem Zinngehalt zwischen 0,25 und 0,5 Gew.-%.In addition, the metal strip is economically advantageous because during its production Copper scrap can be used with tin components. In the material cycle becomes a achieved balanced tin balance. This can be a consistent quality of be ensured under scrap insert produced metal strips. By a Tuning of the use of bare scrap (CuNiSi material), tinned Scrap and Neumetall (copper) can be tinned depending on the thickness of the tin plating Scrap a base material can be obtained as a cast product with a tin content from 0.02 to 1% by weight. Process advantages are cast products with a tin content between 0.25 and 0.5% by weight.

Die intermetallische Phase zwischen dem Basiswerkstoff und der Beschichtung ist feinkörnig und gleichmäßig. Hieraus resultieren eine gute Umformbarkeit, insbesondere Biegbarkeit, höhere Scherfestigkeiten und geringe Elastizitätsmodule sowie eine hohe Kriechbeständigkeit des Metallbands.The intermetallic phase between the base material and the coating is fine-grained and even. This results in a good formability, in particular Bendability, higher shear strengths and low moduli of elasticity as well a high creep resistance of the metal strip.

Die Legierungsbestandteile Zink und Silber beeinflussen das Diffusionsverhalten in der intermetallischen Phase zwischen dem Basiswerkstoff und der gemäß Patentanspruch 11 vorgenommenen Beschichtung aus Zinn-Silber. Die zwangsläufig durch Diffusion von Kupfer in die Zinnschicht entstehenden Kupfer-Zinn-Phasen werden in ihrer Ausprägung über Temperatur und Zeit im Sinne einer Verlangsamung und Behinderung der Bildung speziell der sogenannten Epsilon-Phase beeinflusst. Hier durch wird eine wesentlich bessere Festigkeit zwischen Basiswerkstoff und Beschichtung gewährleistet. Damit werden Ablöseerscheinungen, insbesondere das Abblättern (Peeling) der Beschichtung, auch bei ungünstigen und schwierigen Einsatzbedingungen des Metallbands bzw. der hieraus hergestellten Steckverbinder zu größeren Temperaturen und längeren Zeiten verschoben.The alloy components zinc and silver influence the diffusion behavior in the intermetallic phase between the base material and the according to claim 11 made of tin-silver coating. The inevitably through Diffusion of copper in the tin layer resulting copper-tin phases are in their expression over temperature and time in the sense of a slowing down and disability the formation specifically affects the so-called epsilon phase. Here By a much better strength between the base material and coating guaranteed. This will be peel-off, in particular the Peeling (exfoliation) of the coating, even with unfavorable and difficult Operating conditions of the metal strip or the connector produced therefrom moved to higher temperatures and longer times.

Wesentliche Ursache für ein mögliches alterungsbedingtes Versagen der Beschichtung gerade bei Temperaturen über 150°C ist eine überproportional schnelle Umwandlung der sogenannten η-Phase (Cu6Sn5) in die ε-Phase (Cu3Sn) hinein bei der Ausbildung, ausgehend von der Phasengrenze zwischen Basiswerkstoff und Beschichtung aufgrund hoher Diffusionsgeschwindigkeiten. Die Erfindung macht sich nunmehr die Erkenntnis zu eigen, dass das Vorhandensein der ε-Phase allein nicht notwendigerweise zu Ablösevorgängen an der Grenze zwischen Basiswerkstoff und Beschichtung führt, auch nicht bei einem durch den Umformvorgang hervorgerufenen Spannungszustand eines Steckverbinders. Wird die Ausprägung der ε-Phase unterbunden oder behindert, wirkt sich dies positiv auf die intermetallische Phase und Langzeitbeständigkeit der Beschichtung aus.The main reason for a possible age-related failure of the coating just at temperatures above 150 ° C is a disproportionately fast conversion of the so-called η-phase (Cu 6 Sn 5 ) in the ε-phase (Cu 3 Sn) in training, starting from the Phase boundary between base material and coating due to high diffusion rates. The invention now recognizes the fact that the presence of the ε-phase alone does not necessarily lead to detachment processes at the boundary between the base material and the coating, not even in the case of a stress state of a connector caused by the forming process. If the expression of the ε phase is prevented or hindered, this has a positive effect on the intermetallic phase and long-term stability of the coating.

Zink und Silber sowie das im Werkstoff vorliegende Nickel sind in ihren erfindungsgemäß vorgesehenen Anteilen geeignet, beim Diffusionsvorgang und ihrer Teilnahme an der Bildung der intermetallischen Phase speziell durch Anreicherung in der Phasengrenze die schnelle Umwandlung von der η-Phase zur ε-Phase zu unterdrücken bzw. wesentlich zu verlangsamen mit dem Erfolg eines homogenen hochhaftenden Verbunds zwischen Basiswerkstoff und Beschichtung.Zinc and silver as well as the nickel present in the material are in their invention shares in the diffusion process and their participation in the formation of the intermetallic phase specifically by enrichment in the phase boundary to suppress the rapid conversion of the η-phase to ε-phase or significantly slow down with the success of a homogeneous highly adhesive Composite between base material and coating.

Claims (11)

  1. Material for a metal strip for manufacturing electric contact components, which - expressed in percent by weight - has the following composition: Nickel (Ni) 0.5 to 3.5 % Silicon (Si) 0.08 to 1.0 % Tin (Sn) 0.1 to 1.0 % Zinc (Zn 0.1 to 1.0 % Zirconium (Zr) 0.005 to 0.2 % Silver (Ag) 0.02 to 0.5 % Indium (In) 0.1 to 5 %
    optionally manganese less than 0.5 % and magnesium less than 0.2 %, remainder copper including impurities caused by smelting.
  2. Material according to claim 1, containing silver (Ag) in a proportion of less than 0.15%.
  3. Material according to claim 1 or 2, containing manganese (Mn) in a proportion of less than 0.5 %.
  4. Material according to any one of claims 1 to 3, containing magnesium (Mg) in a proportion of less than 0.2 %.
  5. Material according to any one of claims 1 to 4, in which tin and zinc are contained in a ratio of about 1:1.
  6. Material according to any one of claims 1 to 5, in which tin and silver are contained in a ratio of about 1:4.
  7. Material according to any one of claims 1 to 6, having a ratio Ag to Zn greater than 0.1.
  8. Material according to any one of claims 4 to 7, having a ratio (Mg + Zr) to Sn greater than 0.1.
  9. Material according to any one of claims 4 to 8, in which the ratio (Ni + Si) to (Sn + Zn + Ag + Mg) is greater than 1.5, but less than 4.
  10. Use of a material according to any one of claims 1 to 9 for a coated, electrically conductive metal strip for manufacturing electric contact components, in particular parts of plug connectors which can be used in relatively high temperature areas of motor vehicle construction (engine compartment).
  11. Use of a material according to claim 10, for a metal strip coated with a tinsilver alloy.
EP02017970A 2001-08-21 2002-08-10 Material for a metal strip Expired - Lifetime EP1288321B1 (en)

Priority Applications (1)

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DE10139953A DE10139953A1 (en) 2001-08-21 2001-08-21 Material for a metal band

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EP1457743B1 (en) * 2003-03-12 2013-12-25 Behr France Rouffach SAS Electric heater,esp. for a vehicle
CN102146533B (en) * 2011-03-25 2012-11-14 富威科技（吴江）有限公司 Formula of copper nickel tin alloy strip and production process
ES2593624T3 (en) * 2012-10-10 2016-12-12 Kme Germany Gmbh & Co. Kg Material for electrical contact components
DE102018208116A1 (en) 2018-05-23 2019-11-28 Aurubis Stolberg Gmbh & Co. Kg Copper tape for making electrical contacts and method of making a copper tape and connectors
DE102020006059A1 (en) * 2020-10-05 2022-04-07 Wieland-Werke Aktiengesellschaft Electrically conductive material with coating

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JPS62227051A (en) 1986-03-28 1987-10-06 Mitsubishi Shindo Kk Terminal and connector made of cu alloy
DE4005836C2 (en) * 1990-02-23 1999-10-28 Stolberger Metallwerke Gmbh Electrical connector pair
JP2780584B2 (en) * 1992-11-13 1998-07-30 三菱伸銅株式会社 Cu alloy for electrical and electronic parts with excellent hot workability and punching workability
JP2898627B2 (en) * 1997-03-27 1999-06-02 日鉱金属株式会社 Copper alloy foil
US5893953A (en) * 1997-09-16 1999-04-13 Waterbury Rolling Mills, Inc. Copper alloy and process for obtaining same
JP3465876B2 (en) * 1999-01-27 2003-11-10 同和鉱業株式会社 Wear-resistant copper or copper-based alloy, method for producing the same, and electric component comprising the wear-resistant copper or copper-based alloy
DE10025106A1 (en) * 2000-05-20 2001-11-22 Stolberger Metallwerke Gmbh Electrically conductive metal tape and connectors from it
DE10025107A1 (en) * 2000-05-20 2001-11-22 Stolberger Metallwerke Gmbh Electrically conductive metal band and connector

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US6716541B2 (en) 2004-04-06
US20030044635A1 (en) 2003-03-06
ATE297475T1 (en) 2005-06-15
CN1407123A (en) 2003-04-02
DE10139953A1 (en) 2003-03-27
DE50203318D1 (en) 2005-07-14
EP1288321A1 (en) 2003-03-05
TWI315879B (en) 2009-10-11
KR100874396B1 (en) 2008-12-17
KR20030017327A (en) 2003-03-03
PT1288321E (en) 2005-08-31
ES2240619T3 (en) 2005-10-16
DK1288321T3 (en) 2005-10-03

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