EP0087132B1 - Method for the manufacture of strips coated with noble metal as semiproducts for electrical contacts - Google Patents

Method for the manufacture of strips coated with noble metal as semiproducts for electrical contacts Download PDF

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Publication number
EP0087132B1
EP0087132B1 EP83101533A EP83101533A EP0087132B1 EP 0087132 B1 EP0087132 B1 EP 0087132B1 EP 83101533 A EP83101533 A EP 83101533A EP 83101533 A EP83101533 A EP 83101533A EP 0087132 B1 EP0087132 B1 EP 0087132B1
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EP
European Patent Office
Prior art keywords
process according
noble metal
strip
intermediate layer
heat treatment
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
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EP83101533A
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German (de)
French (fr)
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EP0087132A1 (en
Inventor
Hans-Jürgen Prof. Dr. Dipl.-Ing. Gevatter
Bernhard Dipl.-Ing. Müller
Hans-Joachim Dr. Dipl.-Chem. Neese
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Doduco Solutions GmbH
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Doduco GmbH and Co KG Dr Eugen Duerrwaechter
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Publication of EP0087132A1 publication Critical patent/EP0087132A1/en
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • H01H11/041Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • H01H11/041Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion
    • H01H2011/046Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion by plating
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S205/00Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/917Treatment of workpiece between coating steps

Definitions

  • the starting point of the invention is a method with the features specified in the preamble of claim 1.
  • a base metal e.g. B. from copper, brass, bronze, nickel silver or from other suitable for supporting electrical contacts metal materials
  • a noble metal or with a noble metal alloy mostly with fine gold or with a high-quality gold alloy.
  • the coating is carried out selectively, namely only on one side of the belt or only in the form of strips or spots on the carrier belt.
  • the strips that carry the precious metal layer contain a lot of copper. Under the influence of heat - also in switching operation - copper tends to migrate through precious metal coatings, in particular through those made of gold or silver or their alloys, to the surface of the precious metal coating and form copper oxide there, which increases the contact resistance. Conversely, the precious metals also tend to diffuse into the carrier. In order to avoid this, it is known for contact bimetals to provide a diffusion barrier between the noble metal layer and the carrier. Most of the time, the diffusion barrier consists of a thin nickel intermediate layer, but other materials for such an intermediate layer have also been investigated, e.g. B. chrome and cobalt. Such a diffusion-inhibiting intermediate layer can completely cover the carrier tape, but at least selectively covers it. in those places where the precious metal layer is applied. The intermediate layer can be applied galvanically.
  • the galvanically deposited coatings in particular the diffusion-inhibiting intermediate layers, are, however, relatively brittle. Their lack of ductility means that they tend to tear or even peel off the carrier during the required punching and bending processes.
  • the abrasion resistance of the electroplated noble metal layer is lower than the abrasion resistance of those noble metal layers which were welded to a base metal base by cold or hot roll cladding.
  • the plated-on coating is sufficiently ductile and abrasion-resistant, but because of the high degrees of deformation during rolling, it is subject to considerable fluctuations in its thickness and possibly also in its width and position on the carrier strip. These fluctuations must be taken into account in the dimensioning of the precious metal layer and its thickness and width must therefore be selected to be relatively large, namely significantly larger than would be necessary with a galvanically applied precious metal layer. Roll-clad bimetallic strips therefore require a higher use of precious metals than galvanically coated bimetallic strips.
  • the invention has for its object to provide a particularly economical process for the production of contact bimetallic strips, the use of which gives firmly adhering, ductile and abrasion-resistant precious metal coatings with high constancy of the layer thickness and width.
  • the use of both a heat treatment and a rolling process ensures that the diffusion-inhibiting intermediate layer and the noble metal layer become so ductile that punching and bending processes, which are usually required for producing finished contact parts from the strip, do not impair the quality of the coating.
  • the precious metal layer is solidified and shows less wear in switching operation than a similarly composed, deposited precious metal layer which has not been post-treated by heat treatment and rolling. It is also observed that the adhesive strength of the noble metal layer on the intermediate layer and the intermediate layer on the carrier tape is significantly improved.
  • the method according to the invention combines the advantages of roll cladding (well-adhering and ductile coatings) with the advantages of applying the coating by electrodeposition or deposition from the gas phase when producing contact bimetallic strips se, in particular by vapor deposition (high dimensional accuracy, uniform layer thicknesses, most economical use of precious metals: it is possible to increase the thickness of the precious metal coating in the finished semi-finished product considerably less than 1 wm, e.g. only 0.1 jl.m or 0.2 ⁇ m thick hold!, producibility of practically any support pattern on belts of any length).
  • the advantageous effects of the method according to the invention are particularly evident in the production of strips with gold or gold alloy overlays over an intermediate layer of nickel.
  • the process according to the invention is carried out in such a way that after the deposits have been deposited, they are first subjected to a heat treatment and then cold-formed by rolling.
  • the degree of deformation caused by rolling depends on the composition and structure of the noble metal layer and the type of intermediate layer, as well as on the desired solidification of the noble metal layer, the intermediate layer and the carrier material.
  • the degree of deformation (indicated as the decrease in thickness of the strip based on its thickness before the start of the deformation) should be between 10% and 50%, preferably between 20% and 40%. This degree of deformation can u. U. achieve by a one-step rolling process, but should preferably be achieved by a three- or four-step rolling process, preferably without intermediate annealing.
  • the treatment temperatures and the treatment duration are not selected independently of one another, but are coordinated with one another in such a way that the desired increase in ductility occurs within a reasonable period of time (approx. 5 minutes to 15 minutes).
  • the upper limit of the temperature is set so that the temperature influence in the surrounding medium does not adversely affect the carrier tape or the noble metal coating.
  • the treatment temperatures are between 400 ° C and 750 ° C, preferably between 550 ° C and 650 ° C.
  • the deposited intermediate layer is preferably made together with the noble metal coating by the action of heat and a cold rolling process. post-treated. However, it is also possible to subject the intermediate layer to a heat treatment and possibly also a rolling process before the noble metal coating is applied (claims 6 to 8). If the carrier material permits this, the intermediate layer (in particular nickel) can be exposed to a higher temperature than the noble metal coating during the separate heat treatment and therefore achieve a higher degree of ductility than if it were only subjected to a heat treatment together with the noble metal coating.
  • the process according to the invention can also advantageously be applied, in a corresponding application, to the production of strips selectively coated with precious metal, in which the diffusion-inhibiting intermediate layer, in particular made of nickel, has already been applied to the strip by cold or hot roll plating and only the precious metal layer is deposited got to.
  • the process brings about strengthening and an increase in ductility, combined with an improvement in the adhesive and abrasion resistance of the precious metal layer and a considerable saving in precious metal.
  • a particular advantage of the invention is that it can also be used to produce precious metal coatings from alloys that are difficult or impossible to separate from a galvanic alloy bath; this applies in particular to low-carat gold alloys.
  • the constituents of the alloy are deposited in layers one above the other and in the course of the subsequent heat treatment the metals deposited in layers are allowed to diffuse into one another to form the alloy.
  • a 3 mm wide, longitudinally extending strip of nickel is first electrodeposited onto a 0.55 mm thick carrier tape made of bronze CuSn6 in a layer thickness of 3 fJ.m. Then a 3 mm wide fine gold strip with a layer thickness of 2 ⁇ m is electroplated on the nickel strips.
  • the strip is then subjected to a heat treatment and in the process about 5 minutes. long annealed at a temperature of about 600 ° C. After the heat treatment, the strip is cold-rolled in four pass passes to a final thickness of 0.4 mm, the fourth pass pass causing the strip to have the smallest decrease in thickness.
  • a 4 mm wide strip-shaped nickel layer with a thickness of 5 ⁇ m is first electroplated on one side.
  • the nickel-plated strip is then subjected to a heat treatment and for a period of about 5 minutes. annealed at a temperature of approx. 650 ° C.
  • the strip is then cold rolled in 3 pass passes to a thickness of 0.55 mm.
  • a 3 ⁇ m thick layer of Au80Ag20 alloy in the form of a 3 mm is now made from an alloy bath on the tape prepared in this way wide strip deposited on the nickel layer.
  • the strip is then subjected to a heat treatment and for a period of about 8 minutes. annealed at a temperature of approx. 630 ° C.
  • the strip is then cold rolled down to a final thickness of 0.4 mm as in the first example.
  • a 3 "" m thick nickel layer in the form of a 3 mm wide strip is electrodeposited onto a 0.4 mm thick carrier tape made of nickel silver CuNi12Zn24.
  • a precious metal plating from 70% by weight of gold, 25% by weight of silver and 5% by weight of copper, the corresponding amounts of gold, silver and copper are galvanically layered one above the other in the form of 2 mm wide strips deposited, in the layer sequence starting with silver on the nickel layer followed by gold, copper, silver, gold, copper and again gold at the top.
  • This sandwich-like precious metal layer is subjected to a subsequent annealing treatment in which the strip is held for about 8 minutes. is subjected to a temperature of about 630 ° C, homogenized to form an Au-Ag-Cu alloy by diffusion of the alloy components into one another.
  • the strip is then cold rolled down to 3 mm in a final pass of 0.3 mm.
  • a nickel-plated carrier tape To produce a nickel-plated carrier tape, one starts from a narrow, elongated, 30 mm thick plate made of silver bronze CuAg2, into which a 0.5 mm deep groove is milled. A 0.5 mm thick nickel strip is inserted into the groove and then the plate is formed into a 0.55 mm thick band by hot roll cladding. According to each of Examples 1 to 4, this strip can be provided with a precious metal coating and further processed.
  • An 8 ⁇ m thick fine gold layer is electrodeposited onto the silver insert on a 0.7 mm thick strip of SE copper with a 3 mm wide and 225 ⁇ m thick insert plating made of silver.
  • the tape is then 5 min. annealed for a long time at a temperature of approx. 560 ° C and then rolled in three or four pass passes cold and without intermediate annealing by 30% (reduction in thickness based on the initial thickness of the strip) to the final dimension.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacture Of Switches (AREA)
  • Contacts (AREA)

Description

Ausgangspunkt der Erfindung ist ein Verfahren mit den im Oberbegriff des Patentanspruch 1 angegebenen Merkmalen.The starting point of the invention is a method with the features specified in the preamble of claim 1.

Es ist bekannt, Bänder aus einem unedlen Trägermetall, z. B. aus Kupfer, Messing, Bronze, Neusilber oder aus anderen für Träger von elektrischen Kontakten geeigneten Metallwerkstoffen, auf galvanischem Wege mit einem Edelmetall oder mit einer Edelmetallegierung, zumeist mit Feingold oder mit einer hochkarätigen Goldlegierung zu beschichten. Die Beschichtung erfolgt aus Gründen der Edelmetalleinsparung selektiv, nämlich flächendeckend nur auf einer Seite des Bandes oder nur in Form von Streifen oder Flecken (Spots) auf dem Trägerband.It is known to strip from a base metal, e.g. B. from copper, brass, bronze, nickel silver or from other suitable for supporting electrical contacts metal materials, to be galvanically coated with a noble metal or with a noble metal alloy, mostly with fine gold or with a high-quality gold alloy. For reasons of precious metal savings, the coating is carried out selectively, namely only on one side of the belt or only in the form of strips or spots on the carrier belt.

Es ist auch bekannt, vorgestanzte Bänder galvanisch zu beschichten ; es handelt sich dabei um Bänder, bei denen Bereiche, welche bei der nachfolgenden Formung zu einzelnen Kontaktteilen ohnehin fortfallen würden, zu einem Teil schon vor der galvanischen Beschichtung durch Stanzen entfernt wurden ; auf den durch Stanzen entfernten Bereichen kann sich kein Edelmetall mehr niederschlagen, stattdessen aber u. U. an den durch Stanzen erzeugten Schnittflächen, wodurch sich die Qualität der Edelmetallauflage insbesondere hinsichtlich seiner Haftfestigkeit verbessern läßt.It is also known to galvanically coat pre-punched strips; these are tapes in which areas which would otherwise be eliminated in the subsequent shaping into individual contact parts were in part removed by stamping before the galvanic coating; Precious metal can no longer deposit on the areas removed by stamping, but instead u. U. on the cut surfaces produced by stamping, whereby the quality of the precious metal layer can be improved, in particular with regard to its adhesive strength.

In der Regel sind die Bänder, welche die Edelmetallauflage tragen, stark kupferhaltig. Unter Wärmeeinwirkung - also auch im Schaltbetrieb - neigt Kupfer dazu, durch Edelmetallauflagen, insbesondere durch solche aus Gold oder Silber oder deren Legierungen hindurch bis zur Oberfläche der Edelmetallauflage zu wandern und dort Kupferoxid zu bilden, welches den Kontaktübergangswiderstand erhöht. Umgekehrt neigen auch die Edelmetalle dazu, in den Träger hinein zu diffundieren. Um dies zu vermeiden, ist es bei Kontaktbimetallen bekannt, zwischen der Edelmetallauflage und dem Träger eine Diffusionsbarriere vorzusehen. Meistens besteht die Diffusionsbarriere aus einer dünnen Nickelzwischenschicht, doch sind auch schon andere Materialien für eine solche Zwischenschicht untersucht worden, z. B. Chrom und Kobalt. Eine solche diffusionshemmende Zwischenschicht kann das Trägerband vollständig bedecken, bedeckt es aber wenigstens selektiv. an jenen Stellen, an denen die Edelmetallauflage aufgebracht wird. Die Zwischenschicht kann galvanisch aufgetragen werden.As a rule, the strips that carry the precious metal layer contain a lot of copper. Under the influence of heat - also in switching operation - copper tends to migrate through precious metal coatings, in particular through those made of gold or silver or their alloys, to the surface of the precious metal coating and form copper oxide there, which increases the contact resistance. Conversely, the precious metals also tend to diffuse into the carrier. In order to avoid this, it is known for contact bimetals to provide a diffusion barrier between the noble metal layer and the carrier. Most of the time, the diffusion barrier consists of a thin nickel intermediate layer, but other materials for such an intermediate layer have also been investigated, e.g. B. chrome and cobalt. Such a diffusion-inhibiting intermediate layer can completely cover the carrier tape, but at least selectively covers it. in those places where the precious metal layer is applied. The intermediate layer can be applied galvanically.

Nach dem galvanischen Beschichten werden aus den beschichteten Bändern durch Stanz- und Biegevorgänge einzelne Kontaktteile hergestellt. Die galvanisch abgeschiedenen Überzüge, insbesondere die diffusionshemmenden Zwischenschichten, sind jedoch relativ spröde. Ihre mangelnde Duktilität hat zur Folge, daß sie bei den erforderlichen Stanz- und Biegevorgängen dazu neigen, zu reißen oder gar vom Träger abzublättern. Außerdem ist die Abriebfestigkeit der galvanisch aufgebrachten Edelmetallschicht geringer als die Abriebfestigkeit von solchen Edelmetallschichten, welche durch Kalt- oder Warmwalzplattieren mit einem Träger aus Unedelmetall verschweißt wurden. Bei auf solche Weise erzeugten Kontaktbimetallbändern ist die aufplattierte Beschichtung zwar hinreichend duktil und abriebfest, wegen der hohen Verformungsgrade beim Walzen unterliegt sie jedoch beträchtlichen Schwankungen ihrer Dicke und ggfs. auch ihrer Breite und Lage auf dem Trägerband. Diese Schwankungen müssen bei der Bemessung der Edelmetallauflage berücksichtigt und dessen Dicke und Breite deshalb verhältnismäßig groß gewählt werden, und zwar deutlich größer als dies bei einer galvanisch aufgebrachten Edelmetallschicht nötig wäre. Walzplattierte Kontaktbimetallbänder erfordern also einen höheren Edelmetalleinsatz als galvanisch beschichtete Kontaktbimetallbänder.After the galvanic coating, individual contact parts are produced from the coated strips by punching and bending processes. The galvanically deposited coatings, in particular the diffusion-inhibiting intermediate layers, are, however, relatively brittle. Their lack of ductility means that they tend to tear or even peel off the carrier during the required punching and bending processes. In addition, the abrasion resistance of the electroplated noble metal layer is lower than the abrasion resistance of those noble metal layers which were welded to a base metal base by cold or hot roll cladding. In the case of contact bimetallic strips produced in this way, the plated-on coating is sufficiently ductile and abrasion-resistant, but because of the high degrees of deformation during rolling, it is subject to considerable fluctuations in its thickness and possibly also in its width and position on the carrier strip. These fluctuations must be taken into account in the dimensioning of the precious metal layer and its thickness and width must therefore be selected to be relatively large, namely significantly larger than would be necessary with a galvanically applied precious metal layer. Roll-clad bimetallic strips therefore require a higher use of precious metals than galvanically coated bimetallic strips.

Aus der AT-B-78 310 ist bereits ein Verfahren zum Herstellen von galvanisch mit Gold überzogenen Bändern bekannt, bei dem der Goldüberzug bei einer Temperatur von 750 °C bis 800 °C einer Wärmebehandlung unter gleichzeitiger Druckanwendung, z. B. durch Walzen, unterzogen wird, um die Haftung und Duktilität zu verbessern.From AT-B-78 310 a method for the production of electroplated bands is already known, in which the gold plating at a temperature of 750 ° C to 800 ° C a heat treatment with simultaneous application of pressure, for. B. by rolling, to improve adhesion and ductility.

Der Erfindung liegt die Aufgabe zugrunde, ein besonders wirtschaftliches Verfahren zur Herstellung von Kontaktbimetallbändern anzugeben, bei dessen Anwendung man fest haftende, duktile und abriebfeste Edelmetallauflagen mit hoher Konstanz der Schichtdicke und Auflagenbreite erhält.The invention has for its object to provide a particularly economical process for the production of contact bimetallic strips, the use of which gives firmly adhering, ductile and abrasion-resistant precious metal coatings with high constancy of the layer thickness and width.

Das erfindungsgemäße Verfahren ist Gegenstand des Patentanspruchs 1. Vorteilhafte Weiterbildungen der Erfindung sind Gegenstand der Unteransprüche.The method according to the invention is the subject of claim 1. Advantageous further developments of the invention are the subject of the subclaims.

Durch die Anwendung sowohl einer Wärmebehandlung als auch eines Walzvorgangs wird erreicht, daß die diffusionshemmende Zwischenschicht und die Edelmetallauflage so duktil werden, daß Stanz- und Biegevorgänge, welche zur Herstellung von fertigen Kontaktteilen aus dem Band üblicherweise erforderlich sind, die Güte der Beschichtung nicht beeinträchtigen. Zugleich wird die Edelmetallauflage verfestigt und weist im Schaltbetrieb weniger Verschleiß auf als eine gleich zusammengesetzte, abgeschiedene Edelmetallschicht, welche nicht durch Wärmebehandlung und Walzen nachbehandelt wurde. Ferner wird beobachtet, daß die Haftfestigkeit der Edelmetallauflage auf der Zwischenschicht sowie der Zwischenschicht auf dem Trägerband deutlich verbessert ist.The use of both a heat treatment and a rolling process ensures that the diffusion-inhibiting intermediate layer and the noble metal layer become so ductile that punching and bending processes, which are usually required for producing finished contact parts from the strip, do not impair the quality of the coating. At the same time, the precious metal layer is solidified and shows less wear in switching operation than a similarly composed, deposited precious metal layer which has not been post-treated by heat treatment and rolling. It is also observed that the adhesive strength of the noble metal layer on the intermediate layer and the intermediate layer on the carrier tape is significantly improved.

Das erfindungsgemäße Verfahren vereinigt beim Herstellen von Kontaktbimetallbändern die Vorteile des Walzplattierens (gut haftende und duktile Auflagen) mit den Vorteilen des Aufbringens der Beschichtung durch galvanische Abscheidung oder Abscheidung aus der Gasphase, insbesondere durch Aufdampfen (hohe Maßgenauigkeit, gleichmäßige Schichtdicken, sparsamster Edelmetalleinsatz : es ist möglich, die Dicke der Edelmetallauflage im fertigen Halbzeug erheblich kleiner als 1 wm, z. B. nur 0,1 jl.m oder 0,2 µm dick zu halten !, Herstellbarkeit praktisch beliebiger Auflagemuster auf beliebig langen Bändern). Die vorteilhaften Wirkungen des erfindungsgemäßen Verfahrens zeigen sich insbesondere bei der Herstellung von Bändern mit Auflagen aus Gold oder Goldlegierungen über einer Zwischenschicht aus Nickel.The method according to the invention combines the advantages of roll cladding (well-adhering and ductile coatings) with the advantages of applying the coating by electrodeposition or deposition from the gas phase when producing contact bimetallic strips se, in particular by vapor deposition (high dimensional accuracy, uniform layer thicknesses, most economical use of precious metals: it is possible to increase the thickness of the precious metal coating in the finished semi-finished product considerably less than 1 wm, e.g. only 0.1 jl.m or 0.2 µm thick hold!, producibility of practically any support pattern on belts of any length). The advantageous effects of the method according to the invention are particularly evident in the production of strips with gold or gold alloy overlays over an intermediate layer of nickel.

Das erfindungsgemäße Verfahren wird so durchgeführt, daß nach dem Abscheiden der Auflagen diese zunächst einer Wärmebehandlung unterzogen und anschließend durch Walzen kalt verformt werden.The process according to the invention is carried out in such a way that after the deposits have been deposited, they are first subjected to a heat treatment and then cold-formed by rolling.

Der Verformungsgrad durch das Walzen hängt von der Zusammensetzung und vom Aufbau der Edelmetallauflage und der Art der Zwischenschicht sowie von der angestrebten Verfestigung der Edelmetallauflage, der Zwischenschicht und des Trägermaterials ab. Der Verformungsgrad (angegeben als Dickenabnahme des Bandes bezogen auf seine Dicke vor Beginn der Verformung) soll zwischen 10 % und 50 %, vorzugsweise zwischen 20 % und 40 % liegen. Dieser Verformungsgrad läßt sich u. U. durch einen einstufigen Walzvorgang erreichen, soll aber bevorzugt durch einen drei- oder vierstufigen Walzvorgang, am besten ohne Zwischenglühungen, erreicht werden.The degree of deformation caused by rolling depends on the composition and structure of the noble metal layer and the type of intermediate layer, as well as on the desired solidification of the noble metal layer, the intermediate layer and the carrier material. The degree of deformation (indicated as the decrease in thickness of the strip based on its thickness before the start of the deformation) should be between 10% and 50%, preferably between 20% and 40%. This degree of deformation can u. U. achieve by a one-step rolling process, but should preferably be achieved by a three- or four-step rolling process, preferably without intermediate annealing.

Beim Vorgang der Wärmebehandlung werden die Behandlungstemperaturen und die Behandlungsdauer nicht unabhängig voneinander gewählt, sondern so aufeinander abgestimmt, daß binnen einer angemessenen Zeitspanne (ca. 5 min. bis 15 min.) die angestrebte Duktilitätssteigerung eintritt. Je höher die Temperatur gewählt wird, desto kürzer kann die Behandlungsdauer sein. Die Obergrenze der Temperatur wird so festgelegt, daß die Temperatur einwirkung in dem umgebenden Medium weder das Trägerband noch die Edelmetallauflage nachteilig verändert.In the heat treatment process, the treatment temperatures and the treatment duration are not selected independently of one another, but are coordinated with one another in such a way that the desired increase in ductility occurs within a reasonable period of time (approx. 5 minutes to 15 minutes). The higher the temperature, the shorter the treatment time. The upper limit of the temperature is set so that the temperature influence in the surrounding medium does not adversely affect the carrier tape or the noble metal coating.

Bei Verwendung der gebräuchlichsten Edelmetallauflagen (Feingold, Goldlegierungen, Silber, Palladiumlegierungen) liegen die Behandlungstemperaturen zwischen 400 °C und 750 °C, vorzugsweise zwischen 550 °C und 650 °C.When using the most common precious metal coatings (fine gold, gold alloys, silver, palladium alloys), the treatment temperatures are between 400 ° C and 750 ° C, preferably between 550 ° C and 650 ° C.

Die abgeschiedene Zwischenschicht wird vorzugsweise gemeinsam mit der Edelmetallauflage durch Wärmeeinwirkung und einen Kaltwalzvor-. gang nachbehandelt. Es ist jedoch auch möglich, die Zwischenschicht bereits vor dem Aufbringen der Edelmetallauflage einer Wärmebehandlung und ggfs. auch einem Walzvorgang zu unterziehen (Ansprüche 6 bis 8). Sofern das Trägermaterial dies zuläßt, kann die Zwischenschicht (insbesondere Nickel) bei der gesonderten Wärmebehandlung einer höheren Temperatur ausgesetzt werden als die Edelmetallauflage und daher ein höheres Maß an Duktilität erreichen, als wenn sie nur gemeinsam mit der Edelmetallauflage einer Wärmebehandlung unterzogen würde.The deposited intermediate layer is preferably made together with the noble metal coating by the action of heat and a cold rolling process. post-treated. However, it is also possible to subject the intermediate layer to a heat treatment and possibly also a rolling process before the noble metal coating is applied (claims 6 to 8). If the carrier material permits this, the intermediate layer (in particular nickel) can be exposed to a higher temperature than the noble metal coating during the separate heat treatment and therefore achieve a higher degree of ductility than if it were only subjected to a heat treatment together with the noble metal coating.

Das erfindungsgemäße Verfahren läßt sich mit Vorteil in entsprechender Anwendung auch übertragen auf die Herstellung von selektiv mit Edelmetall beschichteten Bändern, bei welchen die diffusionshemmende Zwischenschicht, insbesondere aus Nickel, bereits durch Kalt- oder Warmwalzplattieren auf das Band aufgebracht wurde und nur noch die Edelmetallauflage abgeschieden werden muß. In diesen Fällen bringt das Verfahren noch eine Verfestigung und Duktilitätssteigerung, verbunden mit einer Verbesserung der Haft- und Abriebfestigkeit der Edelmetallauflage sowie eine beträchtliche Einsparung an Edelmetall.The process according to the invention can also advantageously be applied, in a corresponding application, to the production of strips selectively coated with precious metal, in which the diffusion-inhibiting intermediate layer, in particular made of nickel, has already been applied to the strip by cold or hot roll plating and only the precious metal layer is deposited got to. In these cases, the process brings about strengthening and an increase in ductility, combined with an improvement in the adhesive and abrasion resistance of the precious metal layer and a considerable saving in precious metal.

Ein besonderer Vorteil der Erfindung liegt darin, daß mit ihrer Hilfe auch Edelmetallauflagen aus Legierungen hergestellt werden können, die sich aus einem galvanischen Legierungsbad nicht oder nur schwierig abscheiden lassen ; dies gilt insbesondere für niederkarätige Goldlegierungen. Gemäß einer Weiterbildung der Erfindung werden die Bestandteile der Legierung schichtweise übereinander abgeschieden und im Verlauf der nachfolgenden Wärmebehandlung läßt man die schichtweise abgeschiedenen Metalle zur Legierungsbildung ineinander eindiffundieren. Um die zur Legierungsbildung erforderliche Zeitspanne kurz zu halten, kann es von Vorteil sein, die Bestandteile der zu bildenden Legierung nicht in nur je einer Schicht, sondern in mehreren Schichten abzuscheiden, welche mit Schichten der anderen Legierungsbestandteile abwechseln. Auf diese Weise werdend die Diffusionswege verkürzt.A particular advantage of the invention is that it can also be used to produce precious metal coatings from alloys that are difficult or impossible to separate from a galvanic alloy bath; this applies in particular to low-carat gold alloys. According to a development of the invention, the constituents of the alloy are deposited in layers one above the other and in the course of the subsequent heat treatment the metals deposited in layers are allowed to diffuse into one another to form the alloy. In order to keep the time required for alloy formation short, it can be advantageous not to separate the constituents of the alloy to be formed in only one layer, but in several layers, which alternate with layers of the other alloy constituents. In this way the diffusion paths are shortened.

Nachfolgend werden noch einige Ausführungsbeispiele des erfindungsgemäßen Verfahrens angegeben.Some exemplary embodiments of the method according to the invention are given below.

1. Auf ein 0,55 mm dickes Trägerband aus der Bronze CuSn6 wird zunächst ein 3 mm breiter, in Längsrichtung verlaufender Streifen aus Nickel in einer Schichtdicke von 3 fJ.m galvanisch abgeschieden. Anschließend wird auf den Nickelstreifen ein ebenfalls 3 mm breiter Streifen aus Feingold mit einer Schichtdicke von 2 µm galvanisch abgeschieden. Anschließend wird das Band einer Wärmebehandlung unterzogen und dabei ca. 5 min. lang bei einer Temperatur von ca. 600 °C geglühlt. Nach der Wärmebehandlung wird das Band in vier Walzstichen auf eine Enddicke von 0,4 mm kalt herabgewalzt, wobei der vierte Walzstich die geringste Dickenabnahme des Bandes bewirkt.1. A 3 mm wide, longitudinally extending strip of nickel is first electrodeposited onto a 0.55 mm thick carrier tape made of bronze CuSn6 in a layer thickness of 3 fJ.m. Then a 3 mm wide fine gold strip with a layer thickness of 2 µm is electroplated on the nickel strips. The strip is then subjected to a heat treatment and in the process about 5 minutes. long annealed at a temperature of about 600 ° C. After the heat treatment, the strip is cold-rolled in four pass passes to a final thickness of 0.4 mm, the fourth pass pass causing the strip to have the smallest decrease in thickness.

2. Auf ein 0,7 mm dickes Trägerband aus Cu-Ni9Sn2 wird zunächst einseitig eine 4 mm breite streifenförmige Nickelschicht mit einer Dicke von 5 µm galvanisch abgeschieden. Anschließend wird das vernickelte Band einer Wärmebehandlung unterzogen und dabei für die Dauer von ca. 5 min. bei einer Temperatur von ca. 650 °C geglüht. Danach wird das Band in 3 Walzstichen kalt auf eine Dicke von 0,55 mm herabgewalzt.2. On a 0.7 mm thick carrier tape made of Cu-Ni9Sn2, a 4 mm wide strip-shaped nickel layer with a thickness of 5 µm is first electroplated on one side. The nickel-plated strip is then subjected to a heat treatment and for a period of about 5 minutes. annealed at a temperature of approx. 650 ° C. The strip is then cold rolled in 3 pass passes to a thickness of 0.55 mm.

Auf das derart vorbereitete Band wird nun aus einem Legierungsbad eine 3 µm dick Schicht aus der Legierung Au80Ag20 in Form eines 3 mm breiten Streifens auf die Nickelschicht abgeschieden. Anschließend wird das Band einer Wärmebehandlung unterzogen und dabei für die Dauer von ca. 8 min. bei einer Temperatur von ca. 630 °C geglüht. Danach wird das Band wie im 1. Beispiel kalt auf eine Enddicke von 0,4 mm herabgewalzt.A 3 µm thick layer of Au80Ag20 alloy in the form of a 3 mm is now made from an alloy bath on the tape prepared in this way wide strip deposited on the nickel layer. The strip is then subjected to a heat treatment and for a period of about 8 minutes. annealed at a temperature of approx. 630 ° C. The strip is then cold rolled down to a final thickness of 0.4 mm as in the first example.

3. Auf ein 0,4 mm dickes Trägerband aus Neusilber CuNi12Zn24 wird zunächst eine 3 ""m dicke Nickelschicht in Form eines 3 mm breiten Streifens galvanisch abgeschieden. Zur Erzeugung einer Edelmetallauflage aus 70 Gew.-% Gold, 25 Gew.-% Silber und 5 Gew.-% Kupfer werden über der Nickelschicht in Form von 2 mm breiten Streifen die entsprechenden Mengen an Gold, Silber und Kupfer in Schichten übereinander gesondert galvanisch abgeschieden, und zwar in der Schichtenfolge beginnend mit Silber auf der Nickelschicht gefolgt von Gold, Kupfer, Silber, Gold, Kupfer und zuoberst noch einmal Gold. Diese sandwichartige Edelmetallauflage wird durch eine nachfolgende Glühbehandlung, bei der das Band für die Dauer von etwa 8 min. einer Temperatur von ungefähr 630 °C ausgesetzt wird, unter Bildung einer Au-Ag-Cu-Legierung durch Diffusion der Legierungskomponenten ineinander homogenisiert. Anschließend wird das Band in 3 Walzstichen kalt auf eine Enddicke von 0,3 mm herabgewalzt.3. First, a 3 "" m thick nickel layer in the form of a 3 mm wide strip is electrodeposited onto a 0.4 mm thick carrier tape made of nickel silver CuNi12Zn24. To produce a precious metal plating from 70% by weight of gold, 25% by weight of silver and 5% by weight of copper, the corresponding amounts of gold, silver and copper are galvanically layered one above the other in the form of 2 mm wide strips deposited, in the layer sequence starting with silver on the nickel layer followed by gold, copper, silver, gold, copper and again gold at the top. This sandwich-like precious metal layer is subjected to a subsequent annealing treatment in which the strip is held for about 8 minutes. is subjected to a temperature of about 630 ° C, homogenized to form an Au-Ag-Cu alloy by diffusion of the alloy components into one another. The strip is then cold rolled down to 3 mm in a final pass of 0.3 mm.

4. Zur Herstellung eines vernickelten Trägerbandes geht man aus von einer schmalen, langgestreckten, 30 mm dicken Platte aus Silberbronze CuAg2, in welche eine 0,5 mm tiefe Nut eingefräst wird. In die Nut wird ein 0,5 mm dicker Nickelstreifen eingelegt und anschließend wird die Platte durch Warmwalzplattieren in ein 0,55 mm dickes Band umgeformt. Dieses Band kann nach einem jeden der Beispiele 1 bis 4 mit einer Edelmetallauflage versehen und weiterverarbeitet werden.4. To produce a nickel-plated carrier tape, one starts from a narrow, elongated, 30 mm thick plate made of silver bronze CuAg2, into which a 0.5 mm deep groove is milled. A 0.5 mm thick nickel strip is inserted into the groove and then the plate is formed into a 0.55 mm thick band by hot roll cladding. According to each of Examples 1 to 4, this strip can be provided with a precious metal coating and further processed.

5. Anstelle einer Zwischenschicht aus Nickel kann in den Beispielen 1 bis 4 auch eine solche aus Kobalt oder Chrom verwendet werden.5. Instead of an intermediate layer made of nickel, one made of cobalt or chromium can also be used in Examples 1 to 4.

6. Auf ein 0,7 mm dickes Band aus SE-Kupfer mit einer 3 mm breiten und 225 µm dicken, durch Walzplattieren hergestellten Einlageplattierung aus Silber wird galvanisch eine 8 µm dicke Feingoldschicht auf die Silbereinlage abgeschieden. Anschließend wird das Band 5 min. lang bei einer Temperatur von ca. 560 °C geglüht und danach in drei oder vier Walzstichen kalt und ohne Zwischenglühungen um 30 % (Dickenabnahme bezogen auf die Ausgangsdicke des Bandes) auf Endmaß herabgewalzt.6. An 8 µm thick fine gold layer is electrodeposited onto the silver insert on a 0.7 mm thick strip of SE copper with a 3 mm wide and 225 µm thick insert plating made of silver. The tape is then 5 min. annealed for a long time at a temperature of approx. 560 ° C and then rolled in three or four pass passes cold and without intermediate annealing by 30% (reduction in thickness based on the initial thickness of the strip) to the final dimension.

Claims (14)

1. A process of manufacturing base metal strip elements which are selectively coated with a noble metal or a noble metal alloy by electrodeposition or by deposition from a gas phase, for use as semifinished products for electric contacts, wherein the coated strip elements are heat-treated at temperatures between 400 and 750 °C for such a residence time that the applied layers and the base backing material are recrystallized, and the strip elements are subsequently subjected to a cold rolling operation in the course of which the coated strip is shaped to its final size with a thickness reduction between 10 and 50 % of its original thickness.
2. A process according to claim 1, characterized in that a diffusion-inhibiting intermediate layer is provided between the base metal strip and the layer of a noble metal or noble metal alloy.
3. A process according to claim 2, characterized in that the intermediate layer consists of nickel:
4. A process according to claim 2 or 3, characterized in that the intermediate layer is applied by roll cladding.
5. A process according to any of the preceding claims, characterized in that the heat treatment is effected at temperatures between 550 and 650 °C for a residence time between 5 minutes and 15 minutes.
6. A process according to any of the preceding claims, characterized in that the rolling operation is effected in three to four rolling passes without intermediate annealing.
7. A process according to any of the preceding claims, characterized in that the thickness of the strip is reduced by the rolling by between 20 and 40 %, preferably by about 30 %.
8. A process according to any of the preceding claims, characterized in that the heat treatment is jointly effected for the intermediate layer and for the noble metal coating.
9. A process according to any of claims 1 to 7, characterized in that the intermediate layer is subjected to a separate heat treatment before the noble metal coating is applied.
10. A process according to claim 9, characterized in that the intermediate layer is hot-rolled simultaneously with its separate heat treatment and in such a manner that the thickness of the strip provided with the intermediate layer is reduced by between 10 and 50% of its original thickness.
11. A process according to claim 10, characterized in that the thickness of the strip is reduced by about 30 %.
12. A process according to claim 10, characterized in that said separate heat treatment is succeeded by a cold rolling operation.
13. A process according to claim 9 or 10, characterized in that the intermediate layer consists of nickel or cobalt and the heat treatment is effected at temperatures between 550 and 650 °C before the noble metal covering is applied.
14. A process according to any of the preceding claims, characterized in that for the manufacture of a strip having a coating consisting of a noble metal alloy the components of which cannot be co-electrodeposite from a bath the different metals that noble metal alloy are successively electrodeposited and are then subjected to a joint heat treatment during which the deposited metals difuse into each other.
EP83101533A 1982-02-20 1983-02-18 Method for the manufacture of strips coated with noble metal as semiproducts for electrical contacts Expired EP0087132B1 (en)

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DE3206262 1982-02-20
DE3206262A DE3206262C2 (en) 1982-02-20 1982-02-20 Process for the production of galvanically selectively coated strips with noble metal as a semi-finished product for electrical contacts

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US5190601A (en) * 1989-12-07 1993-03-02 Sumitomo Electric Industries, Ltd. Surface structure of ceramics substrate and method of manufacturing the same
US5167794A (en) * 1990-04-16 1992-12-01 Mitsubishi Denki Kabushiki Kaisha Method for producing lead frame material
US5783317A (en) * 1996-03-27 1998-07-21 Brush Wellman Inc. Multilayer metal composite for microwave tubing and the like
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DE102014101882A1 (en) * 2014-02-14 2015-08-20 Heraeus Deutschland GmbH & Co. KG Process for producing a bondable coating on a carrier tape
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US4521257A (en) 1985-06-04
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DE3206262A1 (en) 1983-09-08
DE3206262C2 (en) 1986-02-13

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