EP2340318B1 - Copper-tin alloy, composite material and use thereof - Google Patents

Copper-tin alloy, composite material and use thereof Download PDF

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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
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Prior art keywords
weight
tin
copper
alloy
composite material
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German (de)
French (fr)
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EP2340318A1 (en
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Michael KÖHLER
Andreas Heide
Ralf Hojda
Udo Riepe
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Sundwiger Messingwerk GmbH and Co KG
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Sundwiger Messingwerk GmbH and Co KG
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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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Description

Die Erfindung betrifft eine Kupfer-Zinn-Legierung, einen Verbundwerkstoff mit einer solchen Kupfer-Zinn-Legierung sowie eine Verwendung der Kupfer-Zinn-Legierung und des Verbundwerkstoffs. Die Kupfer-Zinn-Legierung und der diese umfassende Verbundwerkstoff eignet sich insbesondere für Verbindungselemente in der Elektrotechnik und in der Elektronik. Die Erfindung beschäftigt sich insbesondere mit dem Problem der Recyclingfähigkeit.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.

Generell werden heute Kupferlegierungen auf Basis Cu-Zn, Cu-Sn und Cu-Fe in großem Umfang für Verbindungselemente in der Elektrotechnik und in der Elektronik eingesetzt. Insbesondere werden solche Kupferlegierungen für Stanzgitter und Steckverbinder verwendet. Wichtige Kriterien für die Werkstoffauswahl sind dabei Elastizitätsmodul, Streckgrenze, Relaxationsverhalten und Biegbarkeit. Neben einer ausreichenden mechanischen Festigkeit stellen die elektrische Leitfähigkeit und die Korrosionsbeständigkeit wichtige Kriterien für die sichere Funktion der Bauteile über die Lebensdauer des Gesamtsystems dar. Oftmals kommt es dabei zu einer Überschneidung von Eigenschaftsanforderungen, die sich im Grundsatz gegeneinander ausschließen, wie beispielsweise die Kombination einer guten Leitfähigkeit mit hoher Korrosionsbeständigkeit. Verbessern Legierungselemente im Kupfer, wie Nickel und Chrom, einerseits die Korrosionsbeständigkeit, so verringern sie andererseits die Leitfähigkeit erheblich.In general, copper alloys based on Cu-Zn, Cu-Sn and Cu-Fe are widely used today for connecting elements in electrical engineering and in electronics. In particular, such 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. In addition to a sufficient mechanical strength, 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. On the one hand, 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.

Zunehmend an Bedeutung gewinnt auch das Thema Schweißbarkeit, insbesondere das Laserschweißen, mit anderen metallischen Werkstoffen. Vor dem Hintergrund der exorbitanten Metallpreissteigerungen in den letzten Jahren wird gerade auch das Thema der Recyclingfähigkeit der verwendeten Legierungen immer wichtiger.The topic of weldability, in particular laser welding, with other metallic materials is also gaining in importance. Against the background of the exorbitant increases in metal prices in recent years, the issue of the recyclability of the alloys used is becoming increasingly important.

Cu-Zn bzw. Messinglegierungen sind mischkristall-verfestigende Werkstoffe. Es sind binäre Legierungen, die in der Regel zwischen 5 und 40 Gew.-% an Zink enthalten. Mit steigendem Zinkgehalt nehmen Zugfestigkeit und Härte zu. Die Dehnung erreicht bei 30 Gew.-% Zink einen Höchstwert. Höhere Festigkeits- und Härtewerte sind nur durch Kaltumformung zu erzielen.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.

Für Steckverbinder in Form von Federbändern, beispielsweise aus einer CuZn 30- oder aus einer CuZn 37-Legierung, wird üblicherweise eine Vickershärte von Hv = 150 verlangt. Zusätzlich muss die Einhaltung eines auf die Blechdicke s normierten Mindestbiegeradius r/s = 1 für eine 90°-Abkantung gegeben sein. Der Nachteil der Cu-Zn-Legierungen liegt allerdings in der relativ schlechten Schweißbarkeit, denn das Legierungselement Zink weist einen relativ hohen Dampfdruck auf. Reines Zink siedet bei 1,013 bar bereits bei 907°C. Ferner weisen Cu-Zn-Legierungen einen geringen Elastizitätsmodul von ca. 110 KN/mm2 (SI-Einheit: GPa) auf. Darüber hinaus lassen sich aus Korrosionsschutzgründen verzinnte Messingbänder aufgrund des eingetragenen Zinns nicht gut recyceln. Auch das Relaxationsverhalten von Cu-Zn-Legierungen ist ausgeprägt, die Einsatztemperatur damit begrenzt.For connectors in the form of spring bands, for example, a CuZn 30 or a CuZn 37 alloy, a Vickers hardness of Hv = 150 is usually required. In addition, compliance with a minimum bending radius r / s = 1 normalized to the sheet thickness s for a 90 ° rebate must be ensured. The disadvantage of the Cu-Zn alloys, however, 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. Furthermore, Cu-Zn alloys have a low elastic modulus of about 110 KN / mm 2 (SI unit: GPa). In addition, 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-Legierungen, also Zinnbronzen, gehören zu den ältesten technisch verwertbaren Kupferlegierungen. Den Cu-Sn-Legierungen wird üblicherweise etwas Phosphor zugegeben, weshalb diese Legierungen auch als Phosphorbronzen bezeichnet werden. Die Eigenschaften dieser Legierungen werden vorrangig vom Zinngehalt bestimmt, der in der Regel zwischen 4 und 8 Gew.-% liegt. Der Elastizitätsmodul von Phosphorbronzen beträgt je nach Sn-Gehalt zwischen 115 und 120 kN/mm2 (SI-Einheit: GPa). Die Biegbarkeit von Zinnbronzen ist hervorragend. Steigende Sn-Gehalte verbessern für einen gegebenen Temperzustand das Biegbarkeitsverhalten. Federbänder aus Phosphorbronze können ohne Probleme bis auf ein Härteniveau einer Vickershärte von Hv = 200 verfestigt werden und weisen noch eine Biegbarkeit von r/s = 1 bei einer Abkantung von 90° auf. Die Laserschweißbarkeit von Zinn- bzw. Phosphorbronzen ist gegeben, denn diese Legierungen weisen keine leicht flüchtigen Elemente (insbesondere Zink) und keine störenden zweiten Phasen auf. Das Relaxationsverhalten von Zinn- bzw. Phosphorbronzen ist besser als das von Messinglegierungen, wenngleich es nicht an das Niveau von aushärtbaren Kupferwerkstoffen heranreicht.Cu-Sn alloys, ie tin bronzes, are among the oldest technically usable copper alloys. 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 .-%. Depending on the Sn content, 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. Phosphor bronze bronze tapes can be readily consolidated to a hardness level of Vickers hardness of Hv = 200 and still have a bendability of r / s = 1 with a 90 ° fold. 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-Legierungen werden in Form von Bändern für Stanzteile und Steckverbinder eingesetzt, wenn eine gute bis sehr gute Federeigenschaft, eine gute elektrische und thermische Belastbarkeit, eine geringe Spannungsrelaxation, eine gute Biegbarkeit, gute Schweißbarkeit und Lötbarkeit gefordert werden. Auch in verzinnter Form lassen sich Phosphorbronzen gut recyceln. Zinn ist bereits in der Legierung als solcher enthalten.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.

Zu den niedrig legierten Kupferwerkstoffen gehören die Cu-Fe-Legierungen. Durch geringe Zusätze an Eisen und Phosphor kann die Werkstoffeigenschaft des reinen Kupfers, z.B. die Festigkeit, das Entfestigungs- oder Relaxationsverhalten, verbessert werden. Weit verbreitet für Stanzgitter in der Automobiltechnik ist insbesondere eine CuFe2P-Legierung in der Temperstufe FH. Der Werkstoff weist in dieser Temperstufe eine Zugfestigkeit von Rm = 420 bis 500 N/mm2 (SI-Einheit: MPa) auf. Die Vickershärte liegt bei Hv = 130 bis 150. Die scharfkantige Biegbarkeit ist noch gegeben. Zu den Vorzügen der CuFe2P-Legierung gehört, dass der Elastizitätsmodul etwa 125 KN/mm2 (GPa) beträgt und somit das Material gute Federeigenschaften besitzt. Die elektrische Leitfähigkeit liegt zwischen 60% und 70% IACS (International Annealed Copper Standard: 100% IACS entsprechen etwa 58 MS/m). Eine Verzinnung des Werkstoffs aus Korrosionsschutzgründen ist gut möglich.The low-alloyed copper materials include the Cu-Fe alloys. By small additions of iron and phosphorus, 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 material has a tensile strength of Rm = 420 to 500 N / mm 2 (SI unit: MPa) in this heat treatment stage. The Vickers hardness is Hv = 130 to 150. The sharp-edged bendability is still present. Among the advantages of the CuFe2P alloy is that 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.

Zu den Nachteilen der CuFe2P-Legierung zählt, dass diese keinen homogenen Werkstoff bildet, sondern Fe2P-Ausscheidungen aufweist. Insbesondere hierdurch wird ein Laserschweißen erschwert. Trifft der Laserstrahl beim Punktschweißen auf gröbere Fe2P-Ausscheidungen, so kann er abgelenkt werden, wodurch das Durchschweißergebnis unbefriedigend wird. Ein weiterer Nachteil liegt in der schlechten Recyclingfähigkeit von verzinnten Schrotten der CuFe2P-Legierung. Die elektrische Leitfähigkeit einer CuFe2P-Legierung wird beim Aufschmelzen durch ein in Lösung gehendes Zinn von etwa 1 Gew.-% um 25% erniedrigt. Die verzinnten Stanzschrotte, die beim Herstellen von Stanzgittern üblicherweise 50% bis 70% des eingesetzten Materials ausmachen, können nicht in den Schmelzprozess direkt zurückgeführt werden, sondern müssen aufwändig verhüttet und elektrochemisch getrennt werden. Die Rückführung in den Werkstoffkreislauf erfolgt demnach als Kathode. Dieser Vorgang ist sehr energieintensiv und damit gegenüber dem direkten Einschmelzen der Schrotte sehr teuer.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.

Aus Fig. 1 wird für eine CuFe2P-Legierung der geschilderte Einfluss eines Zinnanteils auf die elektrische Leitfähigkeit ersichtlich. Die elektrische Leitfähigkeit fällt bereits ab Gehalten oberhalb von 0,3 Gew.-% Zinn drastisch ab. Wird beispielsweise ein 0,4 mm dickes Band aus einer CuFe2P-Legierung aus Korrosionsschutzgründen beidseitig mit etwa 3 µm Zinn beschichtet, so würde beim direkten Recycling auf Basis dieser Schrotte eine mit rund 1,5 Gew.-% Zinn verunreinigte CuFe2P-Legierung entstehen. Neben drastischen Einbußen bei der elektrischen Leitfähigkeit hat dieser Zinn-Anteil auch eine starke negative Auswirkung auf das Verfestigungsverhalten.Out 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 μm 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.

Aus der JP 2007 039 735 A sind CuNiP-Legierungen bekannt, die optional Sn, Zn und Fe umfassen können.From the JP 2007 039 735 A CuNiP alloys are known, which may optionally include Sn, Zn and Fe.

Aufgabe der Erfindung ist es, eine Legierung und einen Verbundwerkstoff anzugeben, welcher in seinen physikalischen und technologischen Eigenschaften möglichst dem einer CuFe2P-Legierung entspricht, möglichst gut laserschweißbar ist und gut recycelt werden kann. Eine weitere Aufgabe besteht darin, eine Verwendung für eine solche Legierung und einen solchen Verbundwerkstoff anzugeben.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.

Hinsichtlich der Legierung wird die vorgenannte Aufgabe durch eine Kupfer-Zinn-Legierung mit der Zusammensetzung gemäß Anspruch 1 gelöst. Demnach umfasst die Kupfer-Zinn-Legierung 0,2 bis 0,8 Gew.-% Zinn (Sn), 0,3 bis 0,5 Gew.-% Nickel (Ni) und/oder Kobalt (Co), 0 bis 0,05 Gew.-% Zink (Zn), 0 bis 0,02 Gew.-% Eisen (Fe), 0,008 bis 0,05 Gew.-% Phosphor(P) sowie als Rest Kupfer (Cu).With regard to the alloy, the above object is achieved by a copper-tin alloy having the composition according to claim 1. Accordingly, 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).

Die Erfindung geht dabei von der Überlegung aus, eine zur CuFe2P-Legierung alternative, neue Legierung anzugeben, die vergleichbare Eigenschaften aufweist, sich jedoch auch im verzinnten Zustand problemlos recyceln lässt. Reine Cu-Sn-Legierungen, wie beispielsweise eine CuSn0,15-Legierung haben zweifellos das Potenzial, als eine solche Alternative herangezogen werden zu können. Beschichtet mit Zinn können die Schrotte einer solchen Legierung dem Wertstoffkreislauf direkt zugeführt werden. Die mechanischen und technologischen Eigenschaften entsprechen dabei denen einer CuFe2P-Legierung relativ gut. Deutliche Schwächen treten allerdings beim Erweichungsverhalten und der Relaxationsbeständigkeit auf.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.

Umfangreiche Untersuchungen haben nun ergeben, dass eine Kupfer-Zinn-Legierung mit einer gezielten Abstimmung der Legierungselemente Zinn, Nickel und/oder Kobalt sowie Phosphor sowohl zu einer CuFe2P-Legierung vergleichbare mechanische und technologische Eigenschaften als auch das für die jeweilige Weiterverarbeitung und Endanwendung erforderliche Eigenschaftsprofil im Bereich des Erweichungsverhaltens und der Relaxation, d.h. dem Kriechen des Bauteils unter Spannung bei erhöhter Temperatur, erreicht. Dabei ist entweder Nickel oder Kobalt mit dem angegebenen Anteil enthalten. Bevorzugt ist hierbei ein Teil des Nickels durch Kobalt ersetzt, wobei dann die Summe beider Legierungselemente gemeinsam den angegebenen Anteil ergibt.Extensive investigations have now shown that a copper-tin alloy with a specific coordination of the alloying elements tin, nickel and / or cobalt and phosphorus both to a CuFe2P alloy comparable mechanical and technological properties as that for the respective Further processing and end use required property profile in the area of the softening behavior and the relaxation, ie the creep of the component under tension at elevated temperature achieved. In this case, either nickel or cobalt is included with the specified proportion. In this case, part of the nickel is preferably replaced by cobalt, in which case the sum of the two alloying elements together gives the stated proportion.

Ein Vergleich der technologischen und physikalischen Eigenschaften einer Cu-Sn-Legierung mit einer CuFe2P-Legierung ergibt folgendes Bild: CuFe2P CuSnNiCoP Zugfestigkeit Rm [MPa] 450 438 - 440 Fließgrenze 0,2 % Rp 0,2 [MPa] 420 405 - 430 Bruchdehnung A50 [%] 9 4-5 Elastizitätsmodul [GPa] 123 126 Elektr. Leitfähigkeit [%IACS] 63 55 - 70 Thermische Leitfähigkeit [W/mK] 260 250 Mindestbiegeradius [r/s, 90°] 1 1 Wärmeausdehnungskoeffizient [Rt-100 °C] 17,7 x 10-6 17,7 x 10-6 Vickershärte [Hv] 145 130-134 Erweichungstemperatur [°C(1h)] 350 350 A comparison of the technological and physical properties of a Cu-Sn alloy with a CuFe2P alloy gives the following picture: CuFe2P CuSnNiCoP Tensile strength Rm [MPa] 450 438-440 Yield point 0.2% R p 0.2 [MPa] 420 405 - 430 Elongation at break A50 [%] 9 4-5 Young's modulus [GPa] 123 126 Conductivity [% IACS] 63 55 - 70 Thermal conductivity [W / mK] 260 250 Minimum bending radius [r / s, 90 °] 1 1 Thermal expansion coefficient [Rt-100 ° C] 17.7 x 10 -6 17.7 x 10 -6 Vickers hardness [Hv] 145 130-134 Softening temperature [° C (1h)] 350 350

Aus der Tabelle wird ersichtlich, dass Cu-Sn-Legierungen die angegebenen Anforderungen hinsichtlich der technologischen und physikalischen Eigenschaften erfüllen können.The table shows that Cu-Sn alloys can meet the specified requirements in terms of technological and physical properties.

Bei dem Einsatz der erfindungsgemäßen Cu-Sn-Legierung in verzinnter Form bildet sich eine Legierungsschicht zwischen dem Grundwerkstoff und der Zinnauflage aus. Eine Anpassung der Fertigungsanlagen ist bei der Umstellung auf den neuen Werkstoff nicht erforderlich.When using the Cu-Sn alloy according to the invention in tinned form, an alloy layer is formed between the base material and the tin coating. An adaptation of the production facilities is not required when converting to the new material.

Die erfindungsgemäße Cu-Sn-Legierung zeigt darüber hinaus im Bereich des Erweichungsverhaltens und der Relaxation ein zur CuFe2P-Legierung vergleichbares Eigenschaftsprofil.In addition, 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.

Die erfindungsgemäße Cu-Sn-Legierung zeichnet sich weiter in besonderer Weise durch die direkte Rückführbarkeit verzinnter Schrotte aus den einzelnen Stufen der Wertschöpfungskette aus. Die verzinnten Schrotte können direkt in den Schmelzprozess zurückgeführt werden, so dass die Recyclingkosten gegenüber einer Verhüttung deutlich geringer ausfallen. Die Verhüttungskosten können beispielsweise bei einem Schrottanteil von 70 % schnell die Höhe der Fabrikationskosten erreichen und die Wirtschaftlichkeit in Frage stellen. Aus diesem Grund ändert auch eine Betrachtung der Metallwerte zwischen einer Kuper-EisenLegierung wie der CuFe2P- Legierung und der hier angegebenen Cu-Sn-Legierung nichts daran, dass die angegebene Legierung sowohl unter ökonomischen als auch ökologischen Gesichtspunkten (der zusätzliche Einsatz von Strom und Säure zur elektrolytischen Aufbereitung der Schrotte können entfallen) eine sinnvolle Alternative zu verzinnten Kupfer-Eisen-Legierungen darstellt.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. For this reason, even a consideration of the metal values between a copper-iron alloy such as the CuFe2P alloy and the Cu-Sn alloy given here does not change the fact that the stated alloy is economical and ecological (the additional use of electricity and acid for the electrolytic treatment of the scrap can be omitted) represents a reasonable alternative to tinned copper-iron alloys.

Hinsichtlich der geforderten Eigenschaften ist es vorteilhaft, wenn die angegebene Kupfer-Zinn-Legierung einen Anteil an Sn zwischen 0,3 und 0,7 Gew.-%, insbesondere zwischen 0,4 und 0,6 Gew.-%, enthält: Entsprechend der Erfindung liegt der Anteil an Ni und / oder Co in der Kupfer-Zinn-Legierung zwischen 0,3 und 0,5 Gew.-%.With regard to the required properties, it is advantageous if 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 .-%.

Durch einen bevorzugten Anteil an Phosphor zwischen 0,008 und 0,03 Gew.-%, insbesondere zwischen 0,008 und 0,015 Gew.-%, kann die Festigkeit verbessert werden.By a preferred amount of phosphorus between 0.008 and 0.03 wt .-%, in particular between 0.008 and 0.015 wt .-%, the strength can be improved.

In einer bevorzugten Legierungszusammensetzung weist die Kupfer-Zinn-Legierung 0,3 bis 0,7 Gew.-% Sn, 0,3 bis 0,5 Gew.-% Ni und/oder Co, 0 bis 0,04 Gew.-% Zn, 0 bis 0,015 Gew.-% Fe, 0,08 bis 0,03 Gew.-% P, sowie als Rest Cu auf.In a preferred alloy composition, 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.

Weiter verbessert wird die Kupfer-Zinn-Legierung, wenn sie 0,4 bis 0,6 Gew.-% Sn, 0,3 bis 0,5 Gew.-% Ni und/oder Co, 0 bis 0,03 Gew.-% Zn, 0 bis 0,01 Gew.-% Fe, 0,008 bis 0,015 Gew.-% P, sowie als Rest Cu umfasst.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.

Eine weitere vorteilhafte präzise Einstellung der Eigenschaften der Kupfer-Zinn-Legierung kann vorgenommen werden, wenn eine Summe aus Verunreinigungen und sonstigen Beimengungen von maximal 0,3 Gew.-% vorliegt.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.

Als ein konkretes Ausführungsbeispiel mit hervorragenden Eigenschaften wird eine Kupfer-Zinn-Legierung genannt, die 0,38 Gew.-% Sn, 0,30 Gew.-% Ni und/oder Co, 0,003 Gew.-% Zn, 0,008 Gew.-% Fe, 0,014 Gew.-% P, sowie als Rest Cu umfasst.As a concrete embodiment having excellent properties, mention is made of 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.

Die erfindungsgemäße Kupfer-Zinn-Legierung ist sehr gut laserschweißbar, da keine leicht flüchtigen Elemente enthalten sind und die Legierung frei von einer zweiten Phase ist. Insbesondere weist die Legierung keine NiP-Ausscheidungen aus.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.

Die Legierung eignet sich hervorragend für einen gut laserschweißbaren Verbundwerkstoff, der insbesondere für Stanzgitter verwendet werden kann. Solche Stanzgitter werden heute beispielsweise in der Automobiltechnik für ABS- und ESP-Systeme eingesetzt. Dazu wird ein Grundwerkstoff aus der vorgenannten Kupfer-Zinn-Legierung mit einer Zinnschicht versehen bzw. abgedeckt, was insbesondere durch das Verfahren der Feuerverzinnung vorgenommen werden kann. Insofern befindet sich auf dem Grundwerkstoff aus der angegebenen Kupfer-Zinn-Legierung eine Schicht aus reinem oder freiem Zinn. Der Verbundwerkstoff zeichnet sich durch eine hohe Relaxationsbeständigkeit bis zu Temperaturen von 100 °C aus. Erweist im Inneren als Kern die angegebene Kupfer-Zinn-Legierung mit einer Zusammensetzung entsprechend der darauf gerichteten Ansprüche auf. Durch die äußere Beschichtung bzw. Abdeckung aus Zinn ist eine hohe Korrosionsbeständigkeit gewährleistet. Bevorzugt beträgt die Dicke der Zinnschicht zwischen 1 und 3 µm.The alloy is ideal for a good laser weldable composite material, which can be used in particular for stamped grid. Such stamped grids are used today, for example in automotive technology for ABS and ESP systems. For this purpose, 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. In this respect, there is a layer of pure or free tin on the base material of the specified copper-tin alloy. The composite material is characterized by a high relaxation resistance up to temperatures of 100 ° C. Inside, as the core, 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 μm.

Beim Verzinnen der erfindungsgemäßen Kupfer-Zinn-Legierung kommt es zur Bildung einer Übergangsschicht zwischen dem Grundwerkstoff und der Zinnschicht. Bevorzugt wird die Zinnschicht derart aufgebracht, dass die Übergangsschicht eine intermetallische Phase aus Cu, Ni und / oder Co sowie Sn umfasst. Die Ausbildung der Übergangsschicht wird insbesondere derart gestaltet, dass diese eine Dicke zwischen 0,1 und 1 µm aufweist. Insofern umfasst der Verbundwerkstoff im Inneren oder als Kern die angegebene Kupfer-Zinn-Legierung mit den entsprechenden Anteilen an Nickel und / oder Kobalt sowie Phosphor. Die Legierung des Kerns geht über die Übergangsschicht in eine Schicht aus reinem Zinn über. Über die ausgebildete Übergangs- bzw. Legierungsschicht wird eine gute Anbindung der Zinnschicht erzielt.When tinning the copper-tin alloy according to the invention, 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. In this respect, the composite material in the interior or core of the specified copper-tin alloy with the corresponding proportions of nickel and / or cobalt and phosphorus. 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.

Betrachtet man einen dreidimensionalen Aufbau wie ein Stanzgitter aus dem Verbundwerkstoff, so ergibt sich insgesamt ein Fünf-Schichten-Aufbau. Auf einem Kern aus der angegebenen Kupfer-Zinn-Legierung als Grundwerkstoff sitzt beidseitig eine Schicht einer intermetallischen Phase, bestehend aus CuNiCoSn mit einer Dicke zwischen 0,1 und 1,0 µm. Der Verbundwerkstoff ist abschließend aus Korrosionsschutzgründen mit einer Schicht aus freiem bzw. reinem Zinn abgedeckt, die eine Dicke von 1,0 bis 3,0 µm aufweist. Der Schichtverbundwerkstoff weist insgesamt eine Gesamtdicke von 0,2 bis 1 mm, bevorzugt bis 2 mm, besonders bevorzugt bis 3 mm auf.Considering a three-dimensional structure like a stamped grid made of composite material, 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.

Die elektrische Leitfähigkeit des angegebenen Verbundwerkstoffs entspricht dem des bisher eingesetzten Vergleichswerkstoffs CuFe2P. Wärmeleitfähigkeit und weitere technologische Werte des Verbundwerkstoffes sind ebenfalls voll vergleichbar.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.

Sowohl die erfindungsgemäße Kupfer-Zinn-Legierung als auch der verzinnte Verbundwerkstoff ist hervorragend für Bänder, Folien, profilierte Bänder, Stanzteile oder Steckverbinder, insbesondere für Anwendungen in der Elektrotechnik oder der Elektronik, geeignet.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.

Claims (12)

  1. Copper-tin alloy, comprising:
    0.2 to 0.8% by weight Sn,
    0.3 to 0.5% by weight Ni and/or Co,
    0 to 0.05% by weight Zn,
    0 to 0.02% by weight Fe,
    0.008 to 0.05% by weight P,
    and also Cu as remainder.
  2. Copper-tin alloy according to Claim 1,
    having an Sn content of between 0.3 and 0.7% by weight, in particular of between 0.4 and 0.6% by weight.
  3. Copper-tin alloy according to either of the preceding claims,
    having a P content of between 0.008 and 0.03% by weight, in particular of between 0.008 and 0.015% by weight.
  4. Copper-tin alloy according to Claim 1, comprising:
    0.3 to 0.7% by weight Sn,
    0.3 to 0.5% by weight Ni and/or Co,
    0 to 0.04% by weight Zn,
    0 to 0.015% by weight Fe,
    0.008 to 0.03% by weight P,
    and also Cu as remainder.
  5. Copper-tin alloy according to Claim 4, comprising:
    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% by weight Fe,
    0.008 to 0.015% by weight P,
    and also Cu as remainder.
  6. Copper-tin alloy according to one of the preceding claims,
    in which the sum of impurities and other admixtures is at most 0.3% by weight.
  7. Composite material having a base material according to one of the preceding claims and a layer of tin applied thereto.
  8. Composite material according to Claim 7,
    wherein the layer of tin has a thickness of between between 1 and 3 µm.
  9. Composite material according to Claim 7 or 8, having a transition layer between the base material and the layer of tin, wherein the transition layer comprises an intermetallic phase of Cu, Ni and/or Co and also Sn.
  10. Composite material according to Claim 9,
    wherein the transition layer has a thickness of between 0.1 and 1 µm.
  11. Use of a copper-tin alloy according to one of Claims 1 to 6 for strips, wires, foils, profiled strips, stamped parts or plug-in connectors.
  12. Use of a composite material according to one of Claims 7 to 10 for strips, wires, foils, profiled strips, stamped parts or plug-in connectors.
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