EP0849373A1 - Strip shaped composite material, process and apparatus for making it - Google Patents

Strip shaped composite material, process and apparatus for making it Download PDF

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Publication number
EP0849373A1
EP0849373A1 EP97121506A EP97121506A EP0849373A1 EP 0849373 A1 EP0849373 A1 EP 0849373A1 EP 97121506 A EP97121506 A EP 97121506A EP 97121506 A EP97121506 A EP 97121506A EP 0849373 A1 EP0849373 A1 EP 0849373A1
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EP
European Patent Office
Prior art keywords
oil
tract
composite material
tin
alloy
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Granted
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EP97121506A
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German (de)
French (fr)
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EP0849373B1 (en
Inventor
Isabell Dipl.-Ing. Dr.Rer.Nat. Buresch
Hermann Sturm
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Wieland Werke AG
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Wieland Werke AG
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/08—Tin or alloys based thereon
    • 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
    • Y10S428/9335—Product by special process
    • Y10S428/939—Molten or fused coating
    • 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
    • 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 band-shaped composite material according to the preamble of claim 1.
  • a targeted adjustment of the thickness of the intermetallic Phase (IMP) is carried out on subsequent hot-tinned strips Heat treatment in hood, pull-through or suspension belt furnaces at temperatures between 150 to 180 ° C and Glow times z. B. in hood ovens of over 16 h. With galvanic tinned strips undergo additional reflow treatment with IR radiation or hot air to by melting the Tin better solderability and / or better adhesive strength of the tin on the base material. In In both cases, however, the surface is slightly oxidized or not protected against further oxidation, so that a permanent low contact resistance even under mechanical Load is not guaranteed.
  • the invention is therefore based on the object, a band-shaped Composite material of the type mentioned with an oxide-free surface indicate the good wear and corrosion resistance having.
  • the incorporation of carbon in the Sn layer leads to Improvement of friction behavior, d. H. for connectors to reduce the insertion and pulling force, for improvement corrosion resistance, especially resistance to Fretting corrosion and thus ensuring a constant Contact resistance during the life of for example connectors.
  • the oil can, for example by ultrasonic treatment in acetone, do not remove.
  • the bond states can be different. There are however no oxidic bond structures of the main elements in front.
  • the base material is preferably made of copper or one Copper alloy, made of iron or an iron alloy Nickel or a nickel alloy, made of zinc or one Zinc alloy.
  • a method for producing the composite material according to the invention is characterized in that the tinned Base material with a residence time of 1 to 130 min a hot oil bath is drawn, which is an oil on paraffin and / or Ester and / or fatty acid base, both natural as well as synthetic origin with common additives, contains and its temperature T above the melting point the respective tinning.
  • the hot oil bath contains preferably a paraffin oil or paraffin-based solvent raffinates and is free of chlorine or PCB.
  • the temperature lies above the melting point of the respective tinning: with pure tin therefore preferably 240 ° C, with SnPb 200 ° C, at SnAg0.5Sb1 250 ° C.
  • the dwell time is preferably 2 up to 4 min.
  • the intermetallic phase depends on the layer thickness and temperature / time treatment to 10 to 100% of the total tin layer thickness set.
  • the Sn surface then shows a high-gloss surface, which is corrosion-resistant, in particular, however, is resistant to fretting corrosion.
  • the static Contact resistance changes due to the oil treatment Not. This reduces the frictional forces by 20 to 75%.
  • the composite material in a cold oil bath on paraffin and / or Ester and / or fatty acid base both natural as well as synthetic origin with common additives a temperature of 5 to 50 ° C, in particular 10 to 30 ° C, to deter. This quenching the C content in the Sn layer continues to increase.
  • the dwell time of the composite material in the cold oil bath is preferably 2 to 10 min.
  • a device for carrying out this variant of the invention is characterized by the features of claims 10 to 14.
  • oil is on paraffin and / or Ester and / or fatty acid base, both natural as well as synthetic origin with common additives, directly after tinning the base material to the still hot tin coating sprayed on.
  • the oil is here not too “tied” to the tin plating compared to the untreated tinning are positive influences, especially with regard to fretting corrosion, measurable.
  • the oil bath temperature must be above the melting point of the respective tinning. If the belt 1 is brought up to temperature inductively and then moves into the oil bath 2, there is a risk of dewetting and the "dog bone effect".
  • a smoke extraction 9 is integrated in the highest point of the hot oil tract 3.
  • the strip 1 After deflection by a roller 11 for quenching without air supply, the strip 1 runs through a thermal lock 10 into a cooled oil bath 4 with a temperature of 5 to 50 ° C., preferably 10 to 30 ° C.
  • a temperature of 5 to 50 ° C. preferably 10 to 30 ° C.
  • the excess oil is wiped off with blow-off nozzles 12 or squeezing rollers and the strip 1 is wound up after passing through a deflection roller 13 (reel 14, not shown).
  • the hot oil 2 is circulated with an integrated heating area.
  • the cold oil 4 is circulated with an integrated recooling device.
  • the sequence 15 is only for maintenance.
  • a CuSn6 bronze tape measuring 0.63 mm x 80 mm was hot-tinned with pure tin (layer thickness ⁇ 1.8 mm) and then oil-treated in a bath from a commercially available, paraffin-based solvent raffinate (the respective treatment parameters are in column I of the table below listed).
  • Table II of the table shows the layer thickness on the front (VS) and back (RS) of the tape.
  • layer thickness refers to this case, the total thickness of the free Sn layer and the intermetallic phase (IMP), while the coulometrically measured layer thickness only affects the free Sn layer. The difference is the thickness of the IMP.
  • the table shows that oil treatment at 195 ° C compared to the initial state slight improvement in the training of the IMP and the tendency to fretting corrosion is achieved, but only by the oil treatment according to the invention at 250 ° C. Significant reduction in hiring times the IMP achieved (a free Sn layer is according to Column II no longer detectable).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Coating With Molten Metal (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)
  • Chemically Coating (AREA)
  • Gasket Seals (AREA)

Abstract

In a composite strip of metal or metal alloy, preferably copper, iron, nickel, zinc or their alloys, with an electroplated or hot dip coated pure tin or tin alloy layer and an intermetallic phase formed between the two, 1-50 at.%, preferably 6-30 at.%, carbon is incorporated in the tin coating outer surface region of up to 2 mu m thickness. Also claimed are: (i) the production of the above composite strip, in which a tinned metal strip is pulled, with a dwell time of 1-130 minutes, preferably 2-4 minutes, through a hot oil bath at above the tinned layer m. pt. or is sprayed with oil immediately after tinning, the oil being a natural or synthetic paraffin, ester and/or fatty acid based oil with usual additives; and (ii) an apparatus for carrying out the above process, comprising an unwinding reel (6), a hot oil passageway (3), a thermal lock chamber (10), a cold oil passageway (5) and a winding reel (14).

Description

Die Erfindung betrifft ein bandförmiges Verbundmaterial nach dem Oberbegriff des Anspruchs 1.The invention relates to a band-shaped composite material according to the preamble of claim 1.

Eine gezielte Einstellung der Dicke der intermetallischen Phase (IMP) erfolgt bei feuerverzinnten Bändern durch nachträgliche Wärmebehandlung in Hauben-, Durchzieh- oder Schwebebandöfen bei Temperaturen zwischen 150 bis 180 °C und Glühzeiten z. B. in Haubenöfen von über 16 h. Bei galvanisch verzinnten Bändern erfolgt eine zusätzliche Reflowbehandlung mit IR-Strahlung oder Heißluft, um durch Umschmelzen des Zinns eine bessere Lötbarkeit und/oder eine bessere Haftfestigkeit des Zinns auf dem Grundmaterial zu erreichen. In beiden Fällen wird jedoch die Oberfläche leicht oxidiert bzw. nicht vor weiterer Oxidation geschützt, so daß ein dauerhaft niedriger Kontaktwiderstand auch unter mechanischer Belastung nicht gewährleistet ist.A targeted adjustment of the thickness of the intermetallic Phase (IMP) is carried out on subsequent hot-tinned strips Heat treatment in hood, pull-through or suspension belt furnaces at temperatures between 150 to 180 ° C and Glow times z. B. in hood ovens of over 16 h. With galvanic tinned strips undergo additional reflow treatment with IR radiation or hot air to by melting the Tin better solderability and / or better adhesive strength of the tin on the base material. In In both cases, however, the surface is slightly oxidized or not protected against further oxidation, so that a permanent low contact resistance even under mechanical Load is not guaranteed.

Der Erfindung liegt daher die Aufgabe zugrunde, ein bandförmiges Verbundmaterial der genannten Art mit oxidfreier Oberfläche anzugeben, das gute Verschleiß- und Korrosionsbeständigkeit aufweist.The invention is therefore based on the object, a band-shaped Composite material of the type mentioned with an oxide-free surface indicate the good wear and corrosion resistance having.

Die Aufgabe wird überraschenderweise dadurch gelöst, daß in einem äußeren Randabschnitt der Zinn-Beschichtung bis zu einer Dicke D von etwa 2 µm 1 bis 50 At.-% Kohlenstoff (C), vorzugsweise 6 bis 30 At.-% C, eingelagert sind (At.-% = Atomgewicht-%). The object is surprisingly achieved in that an outer edge portion of the tin coating up to a thickness D of about 2 µm 1 to 50 at% carbon (C), preferably 6 to 30 at% C, are embedded (at% = Atomic weight%).

Das Einbauen von Kohlenstoff in die Sn-Schicht führt zur Verbesserung des Reibverhaltens, d. h. bei Steckverbindern zur Verminderung der Steck- und Ziehkraft, zur Verbesserung der Korrosionsbeständigkeit, insbes. der Beständigkeit gegen Fretting Corrosion und damit Gewährleistung eines konstanten Kontaktübergangswiderstandes während der Lebensdauer von beispielsweise Steckverbindern. Das Öl läßt sich, beispielsweise durch Ultraschallbehandlung in Aceton, nicht entfernen. Die Bindungszustände können verschieden sein. Es liegen jedoch keine oxidischen Bindungsstrukturen der Hauptelemente vor.The incorporation of carbon in the Sn layer leads to Improvement of friction behavior, d. H. for connectors to reduce the insertion and pulling force, for improvement corrosion resistance, especially resistance to Fretting corrosion and thus ensuring a constant Contact resistance during the life of for example connectors. The oil can, for example by ultrasonic treatment in acetone, do not remove. The bond states can be different. There are however no oxidic bond structures of the main elements in front.

Das Grundmaterial besteht vorzugsweise aus Kupfer oder einer Kupfer-Legierung, aus Eisen oder einer Eisen-Legierung, aus Nickel oder einer Nickel-Legierung, aus Zink oder einer Zink-Legierung.The base material is preferably made of copper or one Copper alloy, made of iron or an iron alloy Nickel or a nickel alloy, made of zinc or one Zinc alloy.

Ein Verfahren zur Herstellung des erfindungsgemäßen Verbundmaterials ist dadurch gekennzeichnet, daß das verzinnte Grundmaterial bei einer Verweildauer von 1 bis 130 min durch ein heißes Ölbad gezogen wird, welches ein Öl auf Paraffin- und/oder Ester- und/oder Fettsäurebasis, sowohl natürlichen als auch synthetischen Ursprungs mit üblichen Additiven, enthält und dessen Temperatur T oberhalb des Schmelzpunkts der jeweiligen Verzinnung liegt. Das heiße Ölbad enthält vorzugsweise ein Paraffinöl oder paraffin-basische Solvent-Raffinate und ist frei von Chlor oder PCB. Die Temperatur liegt oberhalb des Schmelzpunktes der jeweiligen Verzinnung: bei Rein-Zinn also vorzugsweise 240 °C, bei SnPb 200 °C, bei SnAg0,5Sb1 250 °C. Die Verweildauer beträgt vorzugsweise 2 bis 4 min.A method for producing the composite material according to the invention is characterized in that the tinned Base material with a residence time of 1 to 130 min a hot oil bath is drawn, which is an oil on paraffin and / or Ester and / or fatty acid base, both natural as well as synthetic origin with common additives, contains and its temperature T above the melting point the respective tinning. The hot oil bath contains preferably a paraffin oil or paraffin-based solvent raffinates and is free of chlorine or PCB. The temperature lies above the melting point of the respective tinning: with pure tin therefore preferably 240 ° C, with SnPb 200 ° C, at SnAg0.5Sb1 250 ° C. The dwell time is preferably 2 up to 4 min.

Die intermetallische Phase (IMP) wird je nach Schichtdicke und Temperatur/Zeitbehandlung auf 10 bis 100 % der Gesamtzinnschichtdicke eingestellt. Die Sn-Oberfläche zeigt dann eine hochglänzende Oberfläche, welche korrosionsbeständig, insbes. jedoch reibkorrosionsbeständig ist. Der statische Kontaktwiderstand verändert sich durch die Ölbehandlung nicht. Die Reibkräfte verringern sich dadurch um 20 bis 75 %.The intermetallic phase (IMP) depends on the layer thickness and temperature / time treatment to 10 to 100% of the total tin layer thickness set. The Sn surface then shows a high-gloss surface, which is corrosion-resistant, in particular, however, is resistant to fretting corrosion. The static Contact resistance changes due to the oil treatment Not. This reduces the frictional forces by 20 to 75%.

Weiterhin empfiehlt es sich, unmittelbar nach der Ölbehandlung das Verbundmaterial in einem kalten Ölbad auf Paraffin- und/oder Ester- und/oder Fettsäurebasis, sowohl natürlichen als auch synthetischen Ursprungs mit üblichen Additiven, bei einer Temperatur von 5 bis 50 °C, insbes. von 10 bis 30 °C, abzuschrecken. Durch dieses Abschrecken wird der C-Gehalt in der Sn-Schicht weiterhin erhöht. Die Verweildauer des Verbundmaterials im kalten Ölbad beträgt vorzugsweise 2 bis 10 min.Furthermore, it is recommended to immediately after the oil treatment the composite material in a cold oil bath on paraffin and / or Ester and / or fatty acid base, both natural as well as synthetic origin with common additives a temperature of 5 to 50 ° C, in particular 10 to 30 ° C, to deter. This quenching the C content in the Sn layer continues to increase. The dwell time of the composite material in the cold oil bath is preferably 2 to 10 min.

Eine Vorrichtung zur Durchführung dieser Erfindungsvariante ist durch die Merkmale der Ansprüche 10 bis 14 gekennzeichnet.A device for carrying out this variant of the invention is characterized by the features of claims 10 to 14.

Nach einer weiteren Erfindungsvariante wird Öl auf Paraffin- und/oder Ester- und/oder Fettsäurebasis, sowohl natürlichen als auch synthetischen Ursprungs mit üblichen Additiven, direkt nach der Verzinnung des Grundmaterials auf die noch heiße Zinn-Beschichtung aufgesprüht. Das Öl wird hierbei nicht zu fest an die Verzinnung "gebunden", gegenüber der unbehandelten Verzinnung sind jedoch positive Einflüsse, insbes. bezüglich der Reibkorrosion, meßbar.According to a further variant of the invention, oil is on paraffin and / or Ester and / or fatty acid base, both natural as well as synthetic origin with common additives, directly after tinning the base material to the still hot tin coating sprayed on. The oil is here not too "tied" to the tin plating compared to the untreated tinning are positive influences, especially with regard to fretting corrosion, measurable.

Die Erfindung wird anhand des folgenden Ausführungsbeispiels näher erläutert:The invention is based on the following embodiment explained in more detail:

Die Fig. zeigt schematisch den Verfahrensablauf zur Wärmebehandlung verzinnter Bänder 1 in heißem Öl 2 eines Heißöltraktes 3 mit anschließendem Abschrecken in kaltem Öl 4 eines Kaltöltraktes 5, wobei das Band 1 kalt von einem nicht näher dargestellten Abhaspel 6 über Umlenkrollen 7 und eine Schleuse 8 in das auf 190 bis 270 °C heiße Ölbad 2 eingeführt wird. Die Ölbadtemperatur muß dabei über dem Schmelzpunkt der jeweiligen Verzinnung liegen. Wenn das Band 1 induktiv auf Temperatur gebracht wird und dann in das Ölbad 2 einfährt, besteht die Gefahr der Bildung von Entnetzungen und des "Hundeknocheneffektes".
Eine Rauchabsaugung 9 ist im höchsten Punkt des Heißöltraktes 3 integriert.
Durch eine thermische Schleuse 10 läuft das Band 1 nach Umlenkung durch eine Rolle 11 zum Abschrecken ohne Luftzufuhr in ein gekühltes Ölbad 4 mit einer Temperatur von 5 bis 50 °C, vorzugsweise 10 bis 30 °C. Beim Austauchen aus dem Ölbad 4 wird das überschüssige Öl mit Abblasdüsen 12 oder Abquetschrollen abgestreift und das Band 1 nach Passieren einer Umlenkrolle 13 aufgehaspelt (nicht näher dargestellte Aufhaspel 14). Das heiße Öl 2 wird im Kreislauf mit integriertem Heizbereich gefahren. Das kalte Öl 4 wird im Kreislauf mit integrierter Rückkühleinrichtung gefahren. Der Ablauf 15 dient nur der Wartung.The figure schematically shows the process sequence for the heat treatment of tinned strips 1 in hot oil 2 of a hot oil tract 3 with subsequent quenching in cold oil 4 of a cold oil tract 5, the strip 1 cold from a reel 6, not shown, via deflection rollers 7 and a lock 8 in the oil bath 2, which is heated to 190 to 270 ° C., is introduced. The oil bath temperature must be above the melting point of the respective tinning. If the belt 1 is brought up to temperature inductively and then moves into the oil bath 2, there is a risk of dewetting and the "dog bone effect".
A smoke extraction 9 is integrated in the highest point of the hot oil tract 3.
After deflection by a roller 11 for quenching without air supply, the strip 1 runs through a thermal lock 10 into a cooled oil bath 4 with a temperature of 5 to 50 ° C., preferably 10 to 30 ° C. When emerging from the oil bath 4, the excess oil is wiped off with blow-off nozzles 12 or squeezing rollers and the strip 1 is wound up after passing through a deflection roller 13 (reel 14, not shown). The hot oil 2 is circulated with an integrated heating area. The cold oil 4 is circulated with an integrated recooling device. The sequence 15 is only for maintenance.

Zahlenbeispiel: Numerical example :

Ein CuSn6-Bronzeband der Abmessung 0,63 mm x 80 mm wurde mit Reinzinn feuerverzinnt (Schichtdicke ≈ 1,8 mm) und anschließend in einem Bad aus einem handelsüblichen, paraffinbasischem Solvent-Raffinat ölbehandelt (die jeweiligen Behandlungsparameter sind in Spalte I der nachfolgenden Tabelle aufgeführt). I II III IV Behandlung (A 1.) = Abschrecken) Schichtdicke RFA [µm] Coul C-Gehalt in At.-% 0 → 2 µm Tiefe Fretting Corrosion [mΩ / Zyklen] (VS/RS) (VS/RS) Ausgangszustand 1,5/1,7 1,1/1,5 0,7 % → 0 % 1000 / 1250 195 °C/1 min 1,5/1,7 0,8/1,3 6 % → 0,8 % 1000 / 2080 195 °C/4 min A 1.) 1,5/1,8 0,8/0,7 1 % → 0,6 % 1000 / 1850 250 °C/4 min 1,4/1,8 n.n.2.)/0,2 10 % → 0,1 % 3,8 / 5000 250 °C/4 min A 1.) 1,4/1,8 n.n.2.)/n.n2.) 25,8 % → 0,1 % 2,6 / 5000 n.n.2.) = nicht nachweisbar A CuSn6 bronze tape measuring 0.63 mm x 80 mm was hot-tinned with pure tin (layer thickness ≈ 1.8 mm) and then oil-treated in a bath from a commercially available, paraffin-based solvent raffinate (the respective treatment parameters are in column I of the table below listed). I. II III IV Treatment (A1 ) = quenching) Layer thickness RFA [µm] coul C content in At .-% 0 → 2 µm depth Fretting corrosion [mΩ / cycles] (VS / RS) (VS / RS) Initial state 1.5 / 1.7 1.1 / 1.5 0.7% → 0% 1000/1250 195 ° C / 1 min 1.5 / 1.7 0.8 / 1.3 6% → 0.8% 1000/2080 195 ° C / 4 min A 1.) 1.5 / 1.8 0.8 / 0.7 1% → 0.6% 1000/1850 250 ° C / 4 min 1.4 / 1.8 nn 2.) / 0.2 10% → 0.1% 3.8 / 5000 250 ° C / 4 min A 1.) 1.4 / 1.8 nn 2.) / nn 2.) 25.8% → 0.1% 2.6 / 5000 nn 2.) = undetectable

In Spalte II der Tabelle ist jeweils die Schichtdicke auf der Vorderseite (VS) und Rückseite (RS) des Bandes eingetragen. Die mittels Röntgen-Fluoreszenz-Analyse (RFA) gemessene Schichtdicke betrifft dabei die Gesamtdicke der freien Sn-Schicht und der intermetallischen Phase (IMP), während die coulometrisch gemessene Schichtdicke nur die freie Sn-Schicht betrifft. Die Differenz ergibt also die Dicke der IMP.Column II of the table shows the layer thickness on the front (VS) and back (RS) of the tape. As measured by R öntgen- F luoreszenz- A nalysis (RFA) layer thickness refers to this case, the total thickness of the free Sn layer and the intermetallic phase (IMP), while the coulometrically measured layer thickness only affects the free Sn layer. The difference is the thickness of the IMP.

In Spalte III der Tabelle ist der mittels Auger-Elektronen-Spektroskopie (AES) und "secondary-ion-mass-spectroscopy" (sims) gemessene C-Gehalt eingetragen.In column III of the table, as measured by A E uger- lektronen- spectroscopy (AES), and "s econdary- on- i m s ASA pectroscopy" (SIMS) C content is registered.

In Spalte IV der Tabelle ist die Neigung zu Fretting Corrosion eingetragen, gemessen nach der sogenannten "rider-on-flat"-Methode (Kontaktwiderstand in mΩ nach n Zyklen bei 1 N Kontaktkraft und 25 µm Amplitude). Dabei wird entweder die Anzahl der Zyklen angegeben, nach der ein Kontaktwiderstand von 1000 mΩ erreicht ist, oder - falls 1000 mΩ nicht erreicht werden - wird die Messung nach 5000 Zyklen abgebrochen. Column IV of the table shows the tendency to fretting corrosion registered, measured according to the so-called "rider-on-flat" method (Contact resistance in mΩ after n cycles at 1 N Contact force and 25 µm amplitude). Either the Number of cycles specified after which a contact resistance of 1000 mΩ is reached, or - if 1000 mΩ is not reached the measurement is stopped after 5000 cycles.

Anhand der Tabelle ist festzustellen, daß durch eine Ölbehandlung bei 195 °C gegenüber dem Ausgangszustand zwar eine leichte Verbesserung hinsichtlich der Ausbildung der IMP und der Neigung zu Fretting Corrosion erzielt wird, aber erst durch die erfindungsgemäße Ölbehandlung bei 250 °C wird eine wesentliche Verkürzung der bisher üblichen Zeiten zur Einstellung der IMP erzielt (eine freie Sn-Schicht ist gemäß Spalte II nicht mehr nachweisbar).The table shows that oil treatment at 195 ° C compared to the initial state slight improvement in the training of the IMP and the tendency to fretting corrosion is achieved, but only by the oil treatment according to the invention at 250 ° C. Significant reduction in hiring times the IMP achieved (a free Sn layer is according to Column II no longer detectable).

Gleichzeitig geht mit zunehmendem Kohlenstoffgehalt die Neigung zur Fretting Corrosion beträchtlich zurück.At the same time, the tendency goes with increasing carbon content for fretting corrosion.

Claims (14)

Bandförmiges Verbundmaterial mit einem Grundmaterial aus Metall oder einer Metall-Legierung und mit einer galvanisch oder durch Schmelzverzinnen aufgebrachten Oberflächenbeschichtung aus Rein-Zinn oder einer Zinn-Legierung, wobei zwischen beiden Materialien eine intermetallische Phase (IMP) ausgebildet ist,
dadurch gekennzeichnet,
daß in einem äußeren Randabschnitt der Zinn-Beschichtung bis zu einer Dicke D von etwa 2 µm 1 bis 50 At.-% Kohlenstoff (C) eingelagert sind.Band-shaped composite material with a base material made of metal or a metal alloy and with a surface coating made of pure tin or a tin alloy applied by electroplating or by tin-plating, an intermetallic phase (IMP) being formed between the two materials,
characterized,
that 1 to 50 at% carbon (C) are embedded in an outer edge section of the tin coating up to a thickness D of about 2 µm. Verbundmaterial nach Anspruch 1, dadurch gekennzeichnet,
daß 6 bis 30 At.-% C eingelagert sind.Composite material according to claim 1, characterized in
that 6 to 30 at% C are stored. Verbundmaterial nach Anspruch 1 oder 2, dadurch gekennzeichnet,
daß das Grundmaterial aus Kupfer oder einer Kupfer-Legierung, aus Eisen oder einer Eisen-Legierung, aus Nickel oder einer Nickel-Legierung, aus Zink oder einer Zink-Legierung besteht.Composite material according to claim 1 or 2, characterized in
that the base material consists of copper or a copper alloy, iron or an iron alloy, nickel or a nickel alloy, zinc or a zinc alloy. Verfahren zur Herstellung des Verbundmaterials nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet,
daß das verzinnte Grundmaterial bei einer Verweildauer von 1 bis 130 min durch ein heißes Ölbad gezogen wird, welches ein Öl auf Paraffin- und/oder Ester- und/oder Fettsäurebasis, sowohl natürlichen als auch synthetischen Ursprungs mit üblichen Additiven, enthält und dessen Temperatur T oberhalb des Schmelzpunkts der jeweiligen Verzinnung liegt.Method for producing the composite material according to one or more of claims 1 to 3, characterized in that
that the tinned base material is drawn through a hot oil bath which contains an oil based on paraffin and / or ester and / or fatty acid, both of natural and synthetic origin with conventional additives, and its temperature T lies above the melting point of the respective tinning. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Verweildauer 2 bis 4 min beträgt.A method according to claim 4, characterized in that the residence time is 2 to 4 min. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet,
daß das Verbundmaterial unmittelbar nach der Ölbehandlung in einem kalten Ölbad auf Paraffin- und/oder Ester- und/oder Fettsäurebasis, sowohl natürlichen als auch synthetischen Ursprungs mit üblichen Additiven, bei einer Temperatur von 5 bis 50 °C abgeschreckt wird.A method according to claim 4 or 5, characterized in that
that the composite material is quenched immediately after the oil treatment in a cold oil bath based on paraffin and / or ester and / or fatty acid, both natural and synthetic, with conventional additives, at a temperature of 5 to 50 ° C. Verfahren nach Anspruch 6, dadurch gekennzeichnet,
daß bei einer Temperatur von 10 bis 30 °C abgeschreckt wird.A method according to claim 6, characterized in
that is quenched at a temperature of 10 to 30 ° C. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet,
daß die Verweildauer des Verbundmaterials im kalten Ölbad 2 bis 10 min beträgt.A method according to claim 6 or 7, characterized in
that the residence time of the composite material in the cold oil bath is 2 to 10 minutes. Verfahren zur Herstellung des Verbundprofils nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet,
daß Öl auf Paraffin- und/oder Ester- und/oder Fettsäurebasis, sowohl natürlichen als auch synthetischen Ursprungs mit üblichen Additiven, direkt nach der Verzinnung des Grundmaterials auf die noch heiße Zinn-Beschichtung aufgesprüht wird.Method for producing the composite profile according to one or more of claims 1 to 3, characterized in that
that oil based on paraffin and / or ester and / or fatty acid, both natural and synthetic, with conventional additives, is sprayed onto the still hot tin coating immediately after the tinning of the base material. Vorrichtung zur Durchführung des Verfahrens nach einem oder mehreren der Ansprüche 4 bis 8, dadurch gekennzeichnet,
daß sie einen Abhaspel (6), einen Heißöltrakt (3), eine thermische Schleuse (10), einen Kaltöltrakt (5) und einen Aufhaspel (14) aufweist.Device for carrying out the method according to one or more of claims 4 to 8, characterized in that
that it has a decoiler (6), a hot oil tract (3), a thermal lock (10), a cold oil tract (5) and a coiler (14). Vorrichtung nach Anspruch 10, dadurch gekennzeichnet,
daß dem Heißöltrakt (3) eine Schleuse (8) vorgeschaltet ist.Apparatus according to claim 10, characterized in
that the hot oil tract (3) is preceded by a lock (8). Vorrichtung nach Anspruch 10 oder 11, dadurch gekennzeichnet,
daß im Kaltöltrakt (5) eine Umlenkrolle (11) angeordnet ist.Device according to claim 10 or 11, characterized in that
that a deflection roller (11) is arranged in the cold oil tract (5). Vorrichtung nach einem oder mehreren der Ansprüche 10 bis 12, dadurch gekennzeichnet,
daß für den Heißöltrakt (3) und den Kaltöltrakt (5) jeweils getrennte Kreisläufe vorgesehen sind.Device according to one or more of claims 10 to 12, characterized in that
that separate circuits are provided for the hot oil tract (3) and the cold oil tract (5). Vorrichtung nach Anspruch 13, dadurch gekennzeichnet,
daß im Kreislauf für den Kaltöltrakt (5) eine Rückkühleinrichtung integriert ist.Device according to claim 13, characterized in
that a recooling device is integrated in the circuit for the cold oil tract (5).
EP97121506A 1996-12-19 1997-12-06 Strip shaped composite material and process for making it Expired - Lifetime EP0849373B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19652987A DE19652987C2 (en) 1996-12-19 1996-12-19 Band-shaped composite material and method and device for its production
DE19652987 1996-12-19

Publications (2)

Publication Number Publication Date
EP0849373A1 true EP0849373A1 (en) 1998-06-24
EP0849373B1 EP0849373B1 (en) 2001-03-21

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ID=7815341

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EP97121506A Expired - Lifetime EP0849373B1 (en) 1996-12-19 1997-12-06 Strip shaped composite material and process for making it

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US (1) US6099977A (en)
EP (1) EP0849373B1 (en)
JP (1) JPH10195692A (en)
CN (1) CN1168844C (en)
DE (2) DE19652987C2 (en)
ES (1) ES2156330T3 (en)
MY (1) MY125545A (en)

Cited By (3)

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EP1411591A2 (en) 2002-10-19 2004-04-21 Robert Bosch Gmbh Electrical contact surfaces
EP1705267A1 (en) * 2005-03-24 2006-09-27 Dowa Mining Co., Ltd Tin-plated product and method for producing same
CN115181971A (en) * 2017-03-31 2022-10-14 Ｊｘ金属株式会社 Copper or copper alloy strip and reciprocating coil and method of making same

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EP1369504A1 (en) * 2002-06-05 2003-12-10 Hille & Müller Metal strip for the manufacture of components for electrical connectors
JP4739734B2 (en) * 2003-11-28 2011-08-03 ヴィーラント ウェルケ アクチーエン ゲゼルシャフト CONTINUOUS LAYER FOR PRODUCING COMPOSITE FOR ELECTRO-Mechanical Components, COMPOSITE MATERIAL AND METHOD OF USE
CN110724899A (en) * 2019-11-27 2020-01-24 云南电网有限责任公司电力科学研究院 Anti-corrosion method for electric power fitting
CN116377537B (en) * 2023-03-29 2023-11-14 扬州市景杨表面工程有限公司 Novel energy-saving electroplating process for new energy automobile graphite carbon sheet

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EP1411591A3 (en) * 2002-10-19 2004-08-25 Robert Bosch Gmbh Electrical contact surfaces
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CN115181971A (en) * 2017-03-31 2022-10-14 Ｊｘ金属株式会社 Copper or copper alloy strip and reciprocating coil and method of making same

Also Published As

Publication number Publication date
JPH10195692A (en) 1998-07-28
CN1195034A (en) 1998-10-07
DE19652987A1 (en) 1998-06-25
CN1168844C (en) 2004-09-29
DE59703183D1 (en) 2001-04-26
ES2156330T3 (en) 2001-06-16
US6099977A (en) 2000-08-08
EP0849373B1 (en) 2001-03-21
DE19652987C2 (en) 2000-10-05
MY125545A (en) 2006-08-30

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