EP0195995A1 - Process for the electrodeposition of composite tin-graphite or tin-lead graphite layers, and baths used therefor - Google Patents

Process for the electrodeposition of composite tin-graphite or tin-lead graphite layers, and baths used therefor Download PDF

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Publication number
EP0195995A1
EP0195995A1 EP86103563A EP86103563A EP0195995A1 EP 0195995 A1 EP0195995 A1 EP 0195995A1 EP 86103563 A EP86103563 A EP 86103563A EP 86103563 A EP86103563 A EP 86103563A EP 0195995 A1 EP0195995 A1 EP 0195995A1
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Prior art keywords
tin
graphite
lead
bath according
acid
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German (de)
French (fr)
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EP0195995B1 (en
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Georg Behringer
Klaus Otto
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Siemens AG
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Siemens 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
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials

Definitions

  • the invention relates to a method for producing tin-graphite or tin-lead-graphite layers, in which at least the tin layer is electrodeposited.
  • the invention also relates to a bath for the galvanic deposition of such dispersion coatings from an aqueous solution of tin (II) and optionally lead (II) salts.
  • Tin layers can be applied by hot-dip tinning or also by means of galvanic baths. From DE-OS 24 13 402 slidable tin layers for electrical sliding contacts on plug-in elements are known, in which the tin or lead layers, in particular galvanically applied, in the ball polishing process with the addition of substances conducive to sliding, such as graphite powder, in the border area the surface is incorporated and solidified at the same time cold.
  • the graphite is therefore only mechanically incorporated into the interface to a depth of about 0.5 ⁇ m, for which a separate operation is required.
  • the shape of the parts to be treated is important, with an optimal distribution over all Interfaces of the contact cannot be reached.
  • the object of the invention is to provide an improved method for applying layers to tin-graphite or. Tin / lead-graphite base and the associated agents.
  • the object is achieved in that the tin-graphite or tin / lead-graphite layer is galvanically produced as a dispersion coating in a single operation, with a plating bath on a strongly acidic basis in which graphite powder is dispersed by means of an acid-resistant wetting agent , and working at temperatures ⁇ 35 ° G.
  • the tin-graphite coating is advantageously electroplated at current densities of 1 to 15 A / dm 2 .
  • a bath for the electrodeposition of tin-graphite dispersion coatings from an aqueous solution of tin-II and optionally lead-II salts is used in which the solution has a pH ⁇ 2 and contains an acid-resistant wetting agent
  • the wetting agent is advantageously an organic substance which has little or no tendency to foam.
  • Such wetting agents can be one or more of the substances from the group consisting of phenol and dibutylaniline, gelatin and cresol, cresol sulfonic acid and 2-methylpentyl sulfate, dibutyl sodium naphthalene sulfonate or sodium lauryl sulfate and be sodium xantogenate.
  • the graphite powder dispersed in the wetting agent preferably has a grain size distribution ⁇ 1 to 5 ⁇ m, i.e. 70% of the graphite particles are smaller than 1 ⁇ .
  • suitable wetting agents were found which are able to disperse the fine graphite grains and at the same time to incorporate them into the galvanically deposited tin or. Adequate guarantees of tin / lead layers.
  • the galvanic baths mixed with the specified wetting agents are preferably used at room temperature or at temperatures ⁇ 35 ° C
  • the invention allows galvanically deposited tin and tin / lead layers, which can also have a low antimony content, which increases the hardness of the coating to considerably improve the abrasion resistance.
  • the necessary plug-in force is reduced in spite of high contact pressure. It could be demonstrated in detail that the galvanically produced dispersion coatings made of tin-graphite or. Tin / Bfei graphite the abrasion resistance by 10 to 25 times compared to the previously known tin or. Tin / lead layers is increased
  • the deposited tin layer contained 1.6% by weight of graphite.
  • the abrasion resistance increased 10 times.
  • the deposited layer contained 2% by weight of graphite.
  • the abrasion resistance increased 18 times.
  • the deposited tin layer contained 1.8% by weight of C.
  • the abrasion resistance compared to a pure tin layer was increased twice.
  • the deposited tin / lead layer (90/10) contained 1.8% by weight of graphite and 1% by weight of antimony.
  • the abrasion resistance compared to pure tin / lead layers has been increased 25 times
  • the deposited tin / lead layer (60/40) contained 1% by weight of graphite and 1% by weight of antimony.
  • the abrasion resistance increases 10 times compared to a pure tin-lead layer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacturing Of Electrical Connectors (AREA)

Abstract

Zur Herstellung von Zinn-Graphit- bzw. Zinn/Blei-Schichten ist es bekannt, eine Zinn- bzw. Zinn/Blei-Schicht galvanisch abzuscheiden und Graphit in die Grenzfläche mechanisch einzubringen. Gemäß der Erfindung wird in einem einzigen Arbeitsgang die Zinn-Graphit- bzw. Zinn/Blei-Graphit-Schicht galvanisch erzeugt, wobei mit einem Galvanisierbad auf stark saurer Basis, in dem Graphitpulver mittels eines säurebeständigen Netzmittels dispergiert ist, und bei Temperaturen <= 35 °C gearbeitet wird. Beim zugehörigen galvanischen Bad hat die Lösung einen pH-Wert <= 2 und enthält ein säurebeständiges Netzmittel für Graphit.For the production of tin-graphite or tin / lead layers, it is known to electrodeposit a tin or tin / lead layer and mechanically introduce graphite into the interface. According to the invention, the tin-graphite or tin / lead-graphite layer is generated galvanically in a single operation, with a plating bath on a strongly acidic basis, in which graphite powder is dispersed by means of an acid-resistant wetting agent, and at temperatures <= 35 ° C is worked. In the associated electroplating bath, the solution has a pH <= 2 and contains an acid-resistant wetting agent for graphite.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von Zinn-Graphit-oder ZinnlBlei-Graphit-Schichten, bei dem wenigstens die Zinn-Schicht galvanisch abgeschieden wird. Daneben bezieht sich die Erfindung auch auf ein Bad zum galvanischen Abscheiden derartiger Dispersionsüberzüge aus einer wässrigen Lösung von Zinn-II-und gegebenenfalls Blei-II-Salzen.The invention relates to a method for producing tin-graphite or tin-lead-graphite layers, in which at least the tin layer is electrodeposited. In addition, the invention also relates to a bath for the galvanic deposition of such dispersion coatings from an aqueous solution of tin (II) and optionally lead (II) salts.

Für den Einsatz von mehrpoligen Steckkontaktleisten werden bisher vorwiegend edelmetallüberzogene Kontaktstifte bzw. -messer und Kontaktbuchsen verwendet, die ausschließlich galvanisch aufgebracht werden. Es ist bekannt zur Standzeitverfängerungen dabei Graphiteinlagerungen in die Edetmetallüberzüge vorzusehen: Beispielsweise aus der DE-PS 25 43 082 ist ein cyanidischer Silberefektrolyt und ein Verfahren zur galvanischen Abscheidung von Silber-Graphit-Dispersionsüberzügen und seine Anwendung für Kontakte bekannt, bei denen der Graphit als Festschmierstoff dientTo date, the use of multipole plug contact strips has predominantly been made of noble-metal-coated contact pins or knives and contact sockets, which are applied exclusively by electroplating. It is known to extend graphite deposits in the noble metal coatings in order to extend the service life: for example from DE-PS 25 43 082 a cyanide silver electrolyte and a method for the electrodeposition of silver-graphite dispersion coatings and its use for contacts are known in which the graphite is a solid lubricant serves

Seit einiger Zeit ist man bemüht; für die oben angegebenen Kontakte die Edefmetallschichten durch Zinn-bzw. Zin/Blei-Schichten zu ersetzen. Zinn-Schichten können durch Feuerverzinnung oder ebenfalls mittels galvanischer Bäder aufgebracht werden. Aus der DE-OS 24 13 402 sind gleitfähige Zinn-Schichten für elektrische Gleitkontakte an Steckelementen bekannt, bei denen die insbesondere galvanisch aufgebrachten Zinn-oder auch Zinn/Blei-Schichten im Kugelpolierverfahren unter Zugabe von die Gleitung förderlichen Stoffen, wie Graphitpuder, im Grenzbereich der Oberfläche inkorperiert und gleichzeitig kalt verfestigt werden.For some time now, efforts have been made; for the contacts specified above, the edefmetall layers by tin or. Replace zinc / lead layers. Tin layers can be applied by hot-dip tinning or also by means of galvanic baths. From DE-OS 24 13 402 slidable tin layers for electrical sliding contacts on plug-in elements are known, in which the tin or lead layers, in particular galvanically applied, in the ball polishing process with the addition of substances conducive to sliding, such as graphite powder, in the border area the surface is incorporated and solidified at the same time cold.

Beim Stand der Technik erfolgt der Einbau des Graphits in die Zinnschicht also nur mechanisch in die Grenzfläche bis zu etwa 0,5 um Tiefe, wozu ein separater Arbeitsgang erforderlich ist Dabei ist die Form der zu behandelnden Teile von Bedeutung, wobei eine optimale Verteilung auf allen Grenzflächen des Kontaktes nicht erreicht werden kann.In the prior art, the graphite is therefore only mechanically incorporated into the interface to a depth of about 0.5 μm, for which a separate operation is required. The shape of the parts to be treated is important, with an optimal distribution over all Interfaces of the contact cannot be reached.

Aufgabe der Erfindung ist es demgegenüber, ein verbessertes Verfahren zum Aufbringen von Schichten auf Zinn-Graphit-bzw. Zinn/Blei-Graphit-Basis und die zugehörigen Mittel anzugeben.In contrast, the object of the invention is to provide an improved method for applying layers to tin-graphite or. Tin / lead-graphite base and the associated agents.

Gemäß der Erfindung ist die Aufgabe dadurch gelöst daß die Zinn-Graphit-oder Zinn/Blei-Graphit-Schicht als Dispersionsüberzug in einem einzigen Arbeitsgang galvanisch erzeugt wird, wobei mit einem Galvanisierbad auf stark saurer Basis, in dem Graphitpulver mittels eines säurebeständigen Netzmittes dispergiert ist, und bei Temperaturen ≦ 35 °G gearbeitet wird. Dabei erfolgt die galvanische Abscheidung des Zinn-Graphit-Überzuges vorteilhafterweise bei Stromdichten von 1 bis 15 A/dm2.According to the invention, the object is achieved in that the tin-graphite or tin / lead-graphite layer is galvanically produced as a dispersion coating in a single operation, with a plating bath on a strongly acidic basis in which graphite powder is dispersed by means of an acid-resistant wetting agent , and working at temperatures ≦ 35 ° G. The tin-graphite coating is advantageously electroplated at current densities of 1 to 15 A / dm 2 .

Zur Ausführung des erfindungsgemäßen Verfahrens wird ein Bad zum galvanischen Abscheiden von Zinn-Graphit-Dispersionsüberzügen aus einer wässrigen Lösung von Zinn-II-und gegebenenfalls Blei-Il-Salzen verwendet bei der die Lösung einen pH-Wert ≦ 2 hat und ein säurebeständiges Netzmittel enthält Vorteilhafterweise ist das Netzmittel eine organische Substanz, die nicht oder nur wenig zur Schaumbildung neigt Solche Netzmittel können eine oder mehrere der Substanzen aus der Gruppe Phenol und Dibutylanilin, Gelatine und Kresol, Kresol-Sulfonsäure und 2-Methyl-Pentylsulfat, Dibutyl-Natriumnapthalinsulfonat oder Natriumlaurylsulfat und Natriumxantogenat sein. Dabei hat das im Netzmittel dispergierte Graphitpulver vorzugsweise eine Komgrößenverteilung < 1 bis 5 um, d.h. 70 % der Graphitteilchen sind kleiner als 1µ.To carry out the method according to the invention, a bath for the electrodeposition of tin-graphite dispersion coatings from an aqueous solution of tin-II and optionally lead-II salts is used in which the solution has a pH ≦ 2 and contains an acid-resistant wetting agent The wetting agent is advantageously an organic substance which has little or no tendency to foam. Such wetting agents can be one or more of the substances from the group consisting of phenol and dibutylaniline, gelatin and cresol, cresol sulfonic acid and 2-methylpentyl sulfate, dibutyl sodium naphthalene sulfonate or sodium lauryl sulfate and be sodium xantogenate. The graphite powder dispersed in the wetting agent preferably has a grain size distribution <1 to 5 µm, i.e. 70% of the graphite particles are smaller than 1µ.

Im Rahmen der Erfindung wurden geeignete Netzmittel gefunden, die in der Lage sind, die feinen Graphitkömer zu dispergieren und gleichzeitig deren Einbau in die galvanisch abgeschiedenen Zinn-bzw. Zinn/Blei-Schichten in hinreichendem Maße zu garantieren. Die mit den angegebenen Netzmitteln versetzten galvanischen Bäder werden vorzugsweise bei Raumtemperatur oder bei Temperaiuren ≦ 35 °C eingesetztIn the context of the invention, suitable wetting agents were found which are able to disperse the fine graphite grains and at the same time to incorporate them into the galvanically deposited tin or. Adequate guarantees of tin / lead layers. The galvanic baths mixed with the specified wetting agents are preferably used at room temperature or at temperatures ≦ 35 ° C

Aus der DE-PS 26 34 128 war zwar bereits ein Bad und ein Verfahren zum galvanischen Abscheiden von Nickel-Graphit-Dispersionsüberzügen aus einer wässrigen Lösung von Nickelsulfamat bekannt, das auf saurer Basis arbeitet und ein für saure Nickelbäder geeignetes Netzmittel enthält Allerdings liegen bei Nickel andere Voraussetzungen wie beim Zinn vor. Bislang wurde davon ausgegangen, daß Schichten auf Zinn-Graphit-Basis galvanisch nicht herstellbar sind.From DE-PS 26 34 128 a bath and a method for the electrodeposition of nickel-graphite dispersion coatings from an aqueous solution of nickel sulfamate was already known, which works on an acidic basis and contains a wetting agent suitable for acidic nickel baths. However, there are nickel other requirements as for tin. So far it has been assumed that layers based on tin-graphite cannot be produced galvanically.

Aufgrund der Erfindung läßt sich bei galvanisch abgeschiedene Zinn-und Zinn/Blei-Schichten, die auch einen geringen Antimongehalt aufweisen können, welcher die Härte des Überzuges erhöht die Abriebbeständigkeit erheblich verbessern. Dabei wird die notwendige Steckkraft trotz hohen Kontaktdruckes vermindert Es konnte im einzelnen nachgewiesen werden, daß bei den galvanisch hergestellten Dispersionsüberzügen aus Zinn-Graphit-bzw. Zinn/Bfei-Graphit die Abriebbeständigkeit um das 10 bis 25-fache gegenüber den bisher bekannten Zinn-bzw. Zinn/Blei-Schichten erhöht istThe invention allows galvanically deposited tin and tin / lead layers, which can also have a low antimony content, which increases the hardness of the coating to considerably improve the abrasion resistance. The necessary plug-in force is reduced in spite of high contact pressure. It could be demonstrated in detail that the galvanically produced dispersion coatings made of tin-graphite or. Tin / Bfei graphite the abrasion resistance by 10 to 25 times compared to the previously known tin or. Tin / lead layers is increased

Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus der nachfolgenden Beschreibung von Ausführungsbeispielen:

  • Bei den einzelnen Beispielen werden die metallischen Kontakte zunächst einer in der Galvanotechnik üblichen Vorbehandlung unterzogen und anschließend in einem der Elektrolyten der nachfolgend angegebenen Zusammensetzung mit einem Zinn-Graphit-bzw. Zinn/Blei-Graphit-Dispersionsüberzug beschichtet
Further details and advantages of the invention result from the following description of exemplary embodiments:
  • In the individual examples, the metallic contacts are first subjected to a pretreatment that is customary in electroplating technology and then in one of the electrolytes of the composition specified below with a tin-graphite or. Tin / lead-graphite dispersion coating coated

Beispiel 1example 1

Figure imgb0001
Figure imgb0001

Die abgeschiedene Zinnschicht enthielt 1,6 Gew.-% Graphit. Die Abriebbeständigkeit stieg um das 10-fache.The deposited tin layer contained 1.6% by weight of graphite. The abrasion resistance increased 10 times.

Beispiel IIExample II

Figure imgb0002
Figure imgb0002

Die abgeschiedene Schicht enthielt 2 Gew.-% Graphit. Die Abriebbeständigkeit stieg um das 18-fache.The deposited layer contained 2% by weight of graphite. The abrasion resistance increased 18 times.

Beispiel IIIExample III

Figure imgb0003
Figure imgb0003

Die abgeschiedene Zinnschicht enthielt 1,8 Gew.-% C. Die Abriebbeständigkeit gegenüber einer reinen Zinnschicht wurde um das 2-fache erhöht.The deposited tin layer contained 1.8% by weight of C. The abrasion resistance compared to a pure tin layer was increased twice.

BEISPIEL IVEXAMPLE IV

Figure imgb0004
Figure imgb0004

Die abgeschiedene Zinn/Blei-Schicht (90/10) enthielt 1,8 Gew.-% Graphit und 1 Gew.-% Antimon. Die Abriebbeständigkeit gegenüber reinen Zinn/Blei-Schichten ist um das 25-fache gesteigertThe deposited tin / lead layer (90/10) contained 1.8% by weight of graphite and 1% by weight of antimony. The abrasion resistance compared to pure tin / lead layers has been increased 25 times

Beispiel VExample V

Figure imgb0005
Figure imgb0005

Die abgeschiedene Zinn/Blei-Schicht(60/40) enthielt 1 Gew.-% Graphit und 1 Gew.% Antimon. Die Abriebbeständigkeit steigt um das 10-fache gegenüber einer reinen ZinnBlei-SchichtThe deposited tin / lead layer (60/40) contained 1% by weight of graphite and 1% by weight of antimony. The abrasion resistance increases 10 times compared to a pure tin-lead layer

Claims (15)

1. Verfahren zur Herstellung von Zinn-Graphit oder Zinn/Blei-Graphit-Schichten, bei dem wenigstens die Zinn- Schicht galvanisch abgeschieden wird, dadurch gekennzeichnet, daß die Zinn-Graphit oder Zinn/Blei-Graphit-Schicht als Dispersionsüberzug in einem einzigen Arbeitsgang galvanisch erzeugt wird, wobei mit einem Galvanisierbad auf stark saurer Basis, in dem Graphitpulver mittels eines säurebeständigen Netzmittels dispergiert ist, und bei Temperaturen ≦ 35 °C gearbeitet wird.1. A method for producing tin-graphite or tin / lead-graphite layers, in which at least the tin layer is electrodeposited, characterized in that the tin-graphite or tin / lead-graphite layer as a dispersion coating in a single Working is generated galvanically, with a plating bath on a strongly acidic basis, in which graphite powder is dispersed by means of an acid-resistant wetting agent, and working at temperatures ≦ 35 ° C. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die galvanische Abscheidung des Zinn-Graphit-oder Zinn/Blei-Graphit-Überzuges bei Stromdichten von 1 bis 15 A/dm2 erfolgt.2. The method according to claim 1, characterized in that the galvanic deposition of the tin-graphite or tin / lead-graphite coating takes place at current densities of 1 to 15 A / dm 2 . 3. Bad zum galvanischen Abscheiden von Zinn-Graphit-Dispersionsüberzügen aus einer wässrigen Lösung von Zinn-II-und gegebenenfalls Blei-II-Salzen, dadurch gekennzeichnet, daß die Lösung einen pH-Wert ≦ 2 hat und ein säurebeständiges Netzmittel für Graphit enthält.3. Bath for the electrodeposition of tin-graphite dispersion coatings from an aqueous solution of tin-II and optionally lead-II salts, characterized in that the solution has a pH ≦ 2 and contains an acid-resistant wetting agent for graphite. 4. Bad nach Anspruch 3, dadurch gekennzeichnet, daß das Netzmittel eine organische Substanz ist, die nicht oder nur wenig zur Schaumbildung neigt. 4th Bath according to claim 3, characterized in that the wetting agent is an organic substance which has little or no tendency to foam. 5. Bad nach Anspruch 4, dadurch gekennzeichnet, daß das Netzmittel eine oder mehrere der Substanzen aus der Gruppe Phenol und Dibutylanilin, Gelatine und Kresol, Kresol-Sulfonsäure und 2-Methyl-Pentylsulfat, Dibutyl-Natriumnaphtalinsulfonat oder Natriumlaurylsulfat und Natriumxantogenat
sind.5. Bath according to claim 4, characterized in that the wetting agent one or more of the substances from the group Phenol and dibutylaniline, Gelatin and cresol, Cresol sulfonic acid and 2-methyl-pentyl sulfate, Dibutyl sodium naphthalene sulfonate or Sodium lauryl sulfate and sodium xantogenate
are. 6. Bad nach Anspruch 3, dadurch gekennzeichnet, daß das Graphitpulver eine Korngrößenverteilung < 1 -5 um hat.6. Bath according to claim 3, characterized in that the graphite powder has a grain size distribution < 1 -5 µm. 7. Bad nach Anspruch 3, dadurch gekennzeichnet, daß das Zinn-II-Salz Zinnsulfat Zinnfluorborat, Zinnmethansulfonat oder Zinnmethacrylsulfonat ist. 7 . Bath according to claim 3, characterized in that the tin-II salt is tin sulfate, tin fluoroborate, tin methane sulfonate or tin methacrylate sulfonate. 8. Bad nach Anspruch 3, dadurch gekennzeichnet, daß das Blei-II-Salz Bleimethacrylsulfonat oder Bleimethansulfonat ist.8. Bath according to claim 3, characterized in that the lead II salt is lead methacrylic sulfonate or lead methane sulfonate. 9. Bad nach Anspruch 3, dadurch gekennzeichnet, daß zusätzlich ein Antimonsalz, beispielsweise Kalium-Antimon-III-Oxidtartrat vorhanden ist.9. Bath according to claim 3, characterized in that an antimony salt, for example potassium antimony III oxide tartrate, is additionally present. 10. Bad nach Anspruch 3, dadurch gekennzeichnet, daß die saure Lösung Schwefelsäure, Borflußsäure, Methansulfonsäure oder Methacrylsulfonsäure enthält.10. Bath according to claim 3, characterized in that the acidic solution contains sulfuric acid, borofluoric acid, methanesulfonic acid or methacrylic sulfonic acid. 11. Galvanisches Bad nach Anspruch 3, dadurch gekennzeichnet, daß es Zinnsulfat entsprechend 26 g Sn/l, 140 g/l Schwefelsäure, 5 g/l Phenol, 1 g/l Dibutylanilin und 100 g/l Graphit enthält.11. Galvanic bath according to claim 3, characterized in that it contains tin sulfate corresponding to 26 g Sn / l, 140 g / l sulfuric acid, 5 g / l phenol, 1 g / l dibutylaniline and 100 g / l graphite. 12. Bad nach Anspruch 3, dadurch gekennzeichnet, daß es Zinnfluorborat entsprechend 66 g Sn/l, 120 g/I Borflußsäure, 20 g/l Borsäure, 4 g/l Gelatine, 6 g/l Kresol, und 100 g/l Graphit enthält.12. Bath according to claim 3, characterized in that it contains tin fluoroborate corresponding to 66 g Sn / l, 120 g / l boric acid, 20 g / l boric acid, 4 g / l gelatin, 6 g / l cresol, and 100 g / l graphite contains. 13. Bad nach Anspruch 3, dadurch gekennzeichnet, daß es Zinn-II-Methansulfonat entsprechend 70 g Sn/l, 300 g/l Methansulfonsäure, 6 g/l Kresol-Sulfonsäure, 8 g/l 2-Methyl-Pentylsulfat, und 100 g/I Graphit enthält.13. Bath according to claim 3, characterized in that it is tin II methanesulfonate corresponding to 70 g Sn / l, 300 g / l methanesulfonic acid, 6 g / l cresol sulfonic acid, 8 g / l 2-methyl-pentyl sulfate, and 100 g / I contains graphite. 14. Bad nach Anspruch 3, dadurch gekennzeichnet, daß es Zinn-II-Methacrylsulfonat entsprechend 70 g Sn/l, Blei-II-Methacrylsulfonat entsprechend 6 g Pb/l, 110 g/l Methacrylsulfonsäure, 3 g/l Kalium-Antimon-III-Oxidtartrat, 0,5- g/l Dibutyl-Natriumnaphtalinsulfonat und 100 g/l Graphit enthält.14. Bath according to claim 3, characterized in that it is tin-II-methacrylic sulfonate corresponding to 70 g Sn / l, lead-II-methacrylic sulfonate corresponding to 6 g Pb / l, 110 g / l methacrylic sulfonic acid, 3 g / l potassium antimony III-oxide tartrate, 0.5 g / l dibutyl sodium naphthalene sulfonate and 100 g / l graphite contains. 15. Galvanisches Bad nach Anspruch 3, dadurch gekennzeichnet, daß es Zinn-II-Methansulfonat entsprechend 9 g Sn/l, Blei-II-Methansulfonat entsprechend 4,5 g Pb/l, 250 g/l Methansulfonsäure, 0,5 g/l Natriumlaurylsulfat, 0,1 g/l Natriumxanthogenat und 60 g/l Graphit enthält.15. Galvanic bath according to claim 3, characterized in that it contains tin II methanesulfonate corresponding to 9 g Sn / l, lead II methanesulfonate corresponding to 4.5 g Pb / l, 250 g / l methanesulfonic acid, 0.5 g / l sodium lauryl sulfate, 0.1 g / l sodium xanthate and 60 g / l graphite.
EP86103563A 1985-03-29 1986-03-17 Process for the electrodeposition of composite tin-graphite or tin-lead graphite layers, and baths used therefor Expired EP0195995B1 (en)

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WO2012031792A1 (en) * 2010-09-09 2012-03-15 Federal-Mogul Wiesbaden Gmbh Layered composite material for sliding elements, method for producing same and use thereof
WO2016127992A1 (en) * 2015-02-13 2016-08-18 Schaeffler Technologies AG & Co. KG Coating for a bearing, bearing, and method

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US4652349A (en) 1987-03-24
EP0195995B1 (en) 1989-09-27
JPS61227196A (en) 1986-10-09

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