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 PDFInfo
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- 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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- EP
- European Patent Office
- Prior art keywords
- tin
- graphite
- lead
- bath according
- acid
- 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.)
- Granted
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- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 43
- 239000010439 graphite Substances 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 6
- 238000004070 electrodeposition Methods 0.000 title claims description 5
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 title description 2
- 239000002131 composite material Substances 0.000 title 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000080 wetting agent Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000007747 plating Methods 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- JHFUZSMOUCNESD-UHFFFAOYSA-N 2-methylpentyl hydrogen sulfate Chemical compound CCCC(C)COS(O)(=O)=O JHFUZSMOUCNESD-UHFFFAOYSA-N 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- FZPXKEPZZOEPGX-UHFFFAOYSA-N n,n-dibutylaniline Chemical compound CCCCN(CCCC)C1=CC=CC=C1 FZPXKEPZZOEPGX-UHFFFAOYSA-N 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 2
- AUJJPYKPIQVRDH-UHFFFAOYSA-N antimony potassium Chemical compound [K].[Sb] AUJJPYKPIQVRDH-UHFFFAOYSA-N 0.000 claims 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 2
- 239000004327 boric acid Substances 0.000 claims 2
- 229940095064 tartrate Drugs 0.000 claims 2
- -1 tin fluoroborate Chemical compound 0.000 claims 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical group [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims 2
- KQWBJUXAIXBZTC-UHFFFAOYSA-J 2-methylprop-2-enoate;tin(4+) Chemical compound [Sn+4].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O KQWBJUXAIXBZTC-UHFFFAOYSA-J 0.000 claims 1
- 239000003929 acidic solution Substances 0.000 claims 1
- 150000001462 antimony Chemical class 0.000 claims 1
- LLABTCPIBSAMGS-UHFFFAOYSA-L lead(2+);methanesulfonate Chemical compound [Pb+2].CS([O-])(=O)=O.CS([O-])(=O)=O LLABTCPIBSAMGS-UHFFFAOYSA-L 0.000 claims 1
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 claims 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 claims 1
- 238000009713 electroplating Methods 0.000 abstract description 3
- 239000002659 electrodeposit Substances 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 23
- 238000005299 abrasion Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005405 multipole Effects 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- 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)
- Manufacturing Of Electrical Connectors (AREA)
- Electroplating Methods And Accessories (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
- 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
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.
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.
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.
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
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)
sind.5. Bath according to claim 4, characterized in that the wetting agent one or more of the substances from the group
are.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3511621 | 1985-03-29 | ||
| DE3511621 | 1985-03-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0195995A1 true EP0195995A1 (en) | 1986-10-01 |
| EP0195995B1 EP0195995B1 (en) | 1989-09-27 |
Family
ID=6266826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86103563A Expired EP0195995B1 (en) | 1985-03-29 | 1986-03-17 | Process for the electrodeposition of composite tin-graphite or tin-lead graphite layers, and baths used therefor |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4652349A (en) |
| EP (1) | EP0195995B1 (en) |
| JP (1) | JPS61227196A (en) |
| DE (1) | DE3665886D1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2348210A (en) * | 1999-03-26 | 2000-09-27 | Miba Gleitlager Ag | Electrodeposited alloy layer used as an overlay of a plain bearing |
| 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 |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19654953A1 (en) * | 1996-06-01 | 1998-03-26 | Glyco Metall Werke | Layer material used for sliding element |
| EP1369504A1 (en) * | 2002-06-05 | 2003-12-10 | Hille & Müller | Metal strip for the manufacture of components for electrical connectors |
| DE10261303B3 (en) * | 2002-12-27 | 2004-06-24 | Wieland-Werke Ag | Electrically conducting composite material used in automotive applications as electrical contact components, such as connectors or connections, comprises a metal strip and a contact layer containing carbon powder and a further additive |
| JP4783954B2 (en) * | 2004-06-21 | 2011-09-28 | Ｄｏｗａメタルテック株式会社 | Composite plating material and method for producing the same |
| JP4813785B2 (en) * | 2004-09-29 | 2011-11-09 | Ｄｏｗａメタルテック株式会社 | Tin plating material |
| JP4749746B2 (en) * | 2005-03-24 | 2011-08-17 | Ｄｏｗａメタルテック株式会社 | Tin plating material and method for producing the same |
| JP4704132B2 (en) * | 2005-07-04 | 2011-06-15 | Ｄｏｗａメタルテック株式会社 | Composite plating material and method for producing the same |
| JP4855032B2 (en) * | 2005-09-29 | 2012-01-18 | Ｄｏｗａメタルテック株式会社 | Composite plating material and method for producing the same |
| JP2011017066A (en) * | 2009-07-10 | 2011-01-27 | Kyushu Nogeden:Kk | Tin plated film and tin-plating bath for forming the same |
| BR112016011396B1 (en) | 2013-11-19 | 2021-12-14 | Aqua Metals Inc | DEVICES AND METHOD FOR RECYCLING WITHOUT FUSER OF LEAD ACID BATTERIES. |
| CN107923057B (en) * | 2015-05-13 | 2020-07-14 | 艾库伊金属有限公司 | Electrodeposited lead compositions, methods of production and uses |
| RS61647B1 (en) | 2015-05-13 | 2021-04-29 | Aqua Metals Inc | Systems and methods for recovery of lead from lead acid batteries |
| EP3294929B1 (en) | 2015-05-13 | 2021-04-14 | Aqua Metals Inc. | Closed loop systems and methods for recycling lead acid batteries |
| US10316420B2 (en) | 2015-12-02 | 2019-06-11 | Aqua Metals Inc. | Systems and methods for continuous alkaline lead acid battery recycling |
| EP4457388A1 (en) * | 2021-12-30 | 2024-11-06 | Dr.Ing. Max Schlötter GmbH & Co. KG | Dispersion electrolyte for graphite-containing layers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489523A (en) * | 1944-02-09 | 1949-11-29 | Gen Motors Corp | Electrodeposition of tin or lead-tin alloys |
| GB1224166A (en) * | 1967-12-21 | 1971-03-03 | Bristol Aerojet Ltd | Improvements in and relating to electrodeposition of composite materials |
| GB1265472A (en) * | 1967-11-29 | 1972-03-01 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1435559A (en) * | 1965-06-02 | 1966-04-15 | Bath suitable for the manufacture of tin coatings | |
| GB1236954A (en) * | 1968-04-26 | 1971-06-23 | Bristol Aerojet Ltd | Improvements in and relating to electrodeposited composite coatings |
| GB1375541A (en) * | 1970-07-29 | 1974-11-27 | ||
| DE2413402A1 (en) * | 1974-03-20 | 1975-10-02 | Friedrich Heck | Sliding contact - is provided with a sintered tin coating contg crystalline graphite |
| DE2543082C3 (en) * | 1975-09-26 | 1979-06-28 | Siemens Ag, 1000 Berlin Und 8000 Muenchen | Cyanidic silver electrolyte and process for the electrodeposition of silver-graphite dispersion coatings and its application |
| DE2634128C2 (en) * | 1976-07-29 | 1985-01-17 | Siemens AG, 1000 Berlin und 8000 München | Bath and process for the electrodeposition of nickel-graphite dispersion coatings |
-
1986
- 1986-03-17 EP EP86103563A patent/EP0195995B1/en not_active Expired
- 1986-03-17 DE DE8686103563T patent/DE3665886D1/en not_active Expired
- 1986-03-24 US US06/842,980 patent/US4652349A/en not_active Expired - Fee Related
- 1986-03-26 JP JP61068277A patent/JPS61227196A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489523A (en) * | 1944-02-09 | 1949-11-29 | Gen Motors Corp | Electrodeposition of tin or lead-tin alloys |
| GB1265472A (en) * | 1967-11-29 | 1972-03-01 | ||
| GB1224166A (en) * | 1967-12-21 | 1971-03-03 | Bristol Aerojet Ltd | Improvements in and relating to electrodeposition of composite materials |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2348210A (en) * | 1999-03-26 | 2000-09-27 | Miba Gleitlager Ag | Electrodeposited alloy layer used as an overlay of a plain bearing |
| GB2348210B (en) * | 1999-03-26 | 2004-01-21 | Miba Gleitlager Ag | Electrodeposited alloy layer, in particular an overlay of a plain bearing |
| 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 |
| CN103080381A (en) * | 2010-09-09 | 2013-05-01 | 联邦-莫古尔威斯巴登股份有限公司 | Layered composite material for sliding elements, method for producing same and use thereof |
| CN103080381B (en) * | 2010-09-09 | 2015-08-19 | 联邦-莫古尔威斯巴登股份有限公司 | For the composite stratified material of sliding members, for the production of this matrix material method with and uses thereof |
| WO2016127992A1 (en) * | 2015-02-13 | 2016-08-18 | Schaeffler Technologies AG & Co. KG | Coating for a bearing, bearing, and method |
Also Published As
| Publication number | Publication date |
|---|---|
| US4652349A (en) | 1987-03-24 |
| JPS61227196A (en) | 1986-10-09 |
| EP0195995B1 (en) | 1989-09-27 |
| DE3665886D1 (en) | 1989-11-02 |
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