EP0218645B1 - Galvanic bath for the simultaneous deposition of metals and a permanent solid lubricant - Google Patents

Galvanic bath for the simultaneous deposition of metals and a permanent solid lubricant Download PDF

Info

Publication number
EP0218645B1
EP0218645B1 EP86902298A EP86902298A EP0218645B1 EP 0218645 B1 EP0218645 B1 EP 0218645B1 EP 86902298 A EP86902298 A EP 86902298A EP 86902298 A EP86902298 A EP 86902298A EP 0218645 B1 EP0218645 B1 EP 0218645B1
Authority
EP
European Patent Office
Prior art keywords
galvanic bath
solid lubricant
bath according
galvanic
cationic
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 - Lifetime
Application number
EP86902298A
Other languages
German (de)
French (fr)
Other versions
EP0218645A1 (en
Inventor
Jean-François Paulet
Jean-Claude Puippe
Heinz Steup
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Werner Fluehmann AG
Original Assignee
Werner Fluehmann AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Werner Fluehmann AG filed Critical Werner Fluehmann AG
Publication of EP0218645A1 publication Critical patent/EP0218645A1/en
Application granted granted Critical
Publication of EP0218645B1 publication Critical patent/EP0218645B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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 galvanic bath with conventional electrodepositing metals and solid lubricant particles and a water-soluble, surface-active agent, which has cationic properties at the pH of the particular galvanic bath used, for the joint deposition of metal and a permanently lubricating solid lubricant.
  • a galvanic bath of this type is known from DE-AS 21 64 050.
  • Compounds which have fluorine-carbon bonds in the molecule - perfluorinated compounds - are proposed as a surface-active agent having cationic properties.
  • Several patents are known in connection with the deposition of nickel-polytetrafluoroethylene dispersion layers (e.g. CH-PS 623 851, GB-PS 1 366 823, US-PS 3 677 907), in which perfluorinated compounds are also used as cationic surfactants.
  • the named baths have the disadvantage that the perfluorinated compounds can only be used in a narrow concentration range and are not very effective.
  • the product concentrations must be adhered to very precisely, which makes bathing difficult.
  • the deposited products often show pores, burns and undesirable surface roughness. Because of their increased brittleness, such layers tend to flake, which means that such galvanic coatings are used Metal coatings is limited.
  • the inventors have therefore set themselves the task of providing a galvanic bath of the type mentioned at the outset which does not, or at least in part, does not have the disadvantages mentioned.
  • the galvanic bath is a water-soluble, cationic surfactant of the type contains, wherein A1-A9 H or an alkyl radical with a low C number, R1-R9 H, OH or an alkyl radical with a low C number, X is a halogen or SO4 and n is the valence of X.
  • A1-A7 CH3 and A9, A9 and R1-R9 H are: Connections have also been found to be particularly advantageous proven. These compounds differ from the previous ones only in that R2 contains a CH3 group instead of H. In the latter two types of compounds, the bromides and chlorides have proven to be particularly advantageous as halides.
  • Baths according to the invention have an advantageous effect, in which, in addition to the cationic surface-active compounds containing the invention, phosphorus acid and / or hypophosphorous acid and / or at least one of their salts are additionally added. This makes it possible to achieve even phosphor storage in addition to uniform solid lubricant particle separation in the metal matrix.
  • the surface of the dispersion layer obtained is practically non-porous.
  • the permanently lubricating solid lubricants are preferably polyfluorocarbon resins - in particular polytetrafluoroethylene -, graphite, graphite fluoride and molybdenum disulfide.
  • its average particle size should not exceed 10 ⁇ m. The best results were achieved with particle sizes of 3-6 ⁇ m. With this particle size, the dispersion layers also gave the best friction values.
  • layers which were produced from baths according to the invention showed advantageous mechanical properties.
  • the elongation was far above the usual value of about 0.3% and the internal stresses far below 150 N / mm2.
  • the lubrication properties and wear resistance were consistently of high quality and reproducible in all cases when using polytetrafluoroethylene, graphite, graphite fluoride and molybdenum disulfide as permanent lubricant galvanic baths for the same purpose could not always be determined according to the prior art.
  • the structures of the coatings showed no defects.
  • the installation rate of the dispersion layer was constant over the entire time - but sometimes only after a short start-up phase.
  • Examples 5 and 6 general electroplating baths such as sulfamate or sulfate baths were used.
  • a cationic surfactant either (Diisobutylcresoxyethoxyethyldimethylbenzylammoniumchloridmonohydrat), sold commercially as Hyamin 10-X and so listed in the examples for brevity, or (Diisobutylphenoxyethoxyethyldimethylbenzylammoniumchloridmonohydrat), sold commercially as Hyamin 1622 and so used in the examples for brevity.
  • the polytetrafluoroethylene dispersion used contained 60% solids; the particle size was between 0.2 and 3 ⁇ m. This dispersion was slowly added to the electrolyte with vigorous stirring. Hyamin 10-X was separately dissolved in warm water and added to the electrolyte. At an operating temperature of 50 ° C and a current density of 4A / dm2, the following polytetrafluoroethylene (hereinafter referred to as PTFE) installation rates were obtained depending on the hyamine content when applying the dispersion layers to an aluminum sheet:
  • PTFE polytetrafluoroethylene
  • FIG. 1 shows a micrograph of such a dispersion layer transversely to the layer plane in incident light.
  • the light dots represent the nickel particles and the dark dots the PTFE particles. It can be seen that the rate of incorporation of the solid lubricant was constant over the entire deposition period.
  • Example 2 In a manner analogous to that in Example 1, a dispersion layer whose metal matrix consisted of 65% Ni and 35% Co was deposited at a temperature of 50 ° C. and a current density of 5A / dm2. The installation rate on MoS2 was 14% by volume.
  • the basic components of the bath correspond to the bath from Example 3.
  • the graphite fluoride used had a fluorine / graphite ratio of 0.9, a density of 2.6 and a specific surface area of 200-340 m 2 / g.
  • the tribological measurements were carried out according to the pin-disk method under the following conditions: hardened steel ball with a diameter of 5 mm; 50 revolutions / minute; Load 4 N; Temperature 20 ° C; rel. Humidity approx. 50%; Running time 24 hours.
  • a galvanic bath was produced as in Example 2, but to which an additional 100 ml / l of 30% by weight phosphorous acid was added, and this as the only one Solid lubricant contained 30 g / l graphite fluoride CF X (average particle size 6 microns).
  • the pH of the bath was 2.5
  • a dispersion layer was deposited in a manner analogous to that in Example 1 at a temperature of 50 ° C. and a current density of 5A / dm2, the matrix of which also contained phosphorus in addition to nickel and cobalt.
  • Example 5 In a manner analogous to that in Example 5, a bath of the composition of Example 2 was prepared, but to which, instead of phosphorous acid, an additional 35 g / l sodium hypophosphite was added and which contained 30 g / l molybdenum disulphide MoS2 (particle size 4-6 ⁇ m) as the sole solid lubricant.
  • the pH of the bath was 3.
  • Example 5 The conditions for depositing the dispersion layer were identical to those of Example 1. As in Example 5, a dense cobalt-nickel-phosphorus matrix was obtained in the amorphous state, in which the MoS2 particles were installed in an evenly distributed manner.

Abstract

To avoid the bad guidance of a galvanic and unfavorable physical properties during the simultaneous depositions of metals and a permanent solid lubricant from galvanic bathes of conventional composition containing solid lubricant particles and a perfluorinated cationic surface agent, the bath contains the compound of formula (I) instead of the perfluorinated compound, wherein A1-A9 is H or an alkyl rest with a lower C number, R1-R9 is H, OH or a lower alkyl rest, X is halogen or SO4 and n is the valence of X. As solid lubricant, polytetrafluoroethylen, graphite, graphite fluoride or molybdenum sulphide may preferably be used.

Description

Die Erfindung betrifft ein galvanisches Bad mit üblichen galvanisch abscheidenden Metallen sowie Feststoffschmiermittelteilchen und einem wasserlöslichen, grenzflächenaktiven Mittel, welches bei dem pH-Wert des besonderen, angewandten galvanischen Bades kationische Eigenschaften aufweist, zum gemeinsamen Abscheiden von Metall und einem dauerschmierenden Feststoffschmiermittel.The invention relates to a galvanic bath with conventional electrodepositing metals and solid lubricant particles and a water-soluble, surface-active agent, which has cationic properties at the pH of the particular galvanic bath used, for the joint deposition of metal and a permanently lubricating solid lubricant.

Ein galvanisches Bad dieser Art ist aus der DE-AS 21 64 050 bekannt. Als kationische Eigenschaften aufweisendes, grenzflächenaktives Mittel werden Verbindungen, die Fluor-Kohlenstoff-Bindungen im Molekül besitzen - perfluorierte Verbindungen -, vorgeschlagen. Im Zusammenhang mit der Abscheidung von Nickel-Polytetrafluorethylen-Dispersionsschichten sind mehrere Patente bekannt (z.B. CH-PS 623 851, GB-PS 1 366 823, US-PS 3 677 907), bei denen ebenfalls als Kationentenside perfluorierte Verbindungen eingesetzt werden.A galvanic bath of this type is known from DE-AS 21 64 050. Compounds which have fluorine-carbon bonds in the molecule - perfluorinated compounds - are proposed as a surface-active agent having cationic properties. Several patents are known in connection with the deposition of nickel-polytetrafluoroethylene dispersion layers (e.g. CH-PS 623 851, GB-PS 1 366 823, US-PS 3 677 907), in which perfluorinated compounds are also used as cationic surfactants.

Die benannten Bäder haben den Nachteil, dass die perfluorierten Verbindungen nur in einem engen Konzentrationsbereich einsetzbar und wenig wirksam sind. Ferner müssen die Produktekonzentrationen sehr genau eingehalten werden, was die Bäderführung schwierig gestaltet. Desweiteren zeigen die abgeschiedenen Produkte häufig Poren, Anbrennungen und unerwünschte Oberflächenrauhigkeiten. Aufgrund erhöhter Sprödigkeit neigen derartige Schichten vielfach zu Abplatzungen, wodurch die Anwendung solcher galvanischen Metallüberzüge begrenzt ist.The named baths have the disadvantage that the perfluorinated compounds can only be used in a narrow concentration range and are not very effective. In addition, the product concentrations must be adhered to very precisely, which makes bathing difficult. Furthermore, the deposited products often show pores, burns and undesirable surface roughness. Because of their increased brittleness, such layers tend to flake, which means that such galvanic coatings are used Metal coatings is limited.

Die Erfinder haben sich daher die Aufgabe gestellt, ein galvanisches Bad der eingangs genannten Art bereitzustellen, das die erwähnten Nachteile nicht oder wenigstens zum Teil nicht aufweist.The inventors have therefore set themselves the task of providing a galvanic bath of the type mentioned at the outset which does not, or at least in part, does not have the disadvantages mentioned.

Die gestellte Aufgabe wird erfindungsgemäss dadurch gelöst, dass das galvanische Bad ein wasserlössliches, kationisches grenzflächenaktives Mittel vom Typ

Figure imgb0001

enthält, wobei A₁-A₉ H oder ein Alkylrest mit niedriger C-Zahl, R₁-R₉ H, OH oder ein Alkylrest mit niedriger C-Zahl, X ein Halogen oder SO₄ und n die Wertigkeit von X ist.The object is achieved according to the invention in that the galvanic bath is a water-soluble, cationic surfactant of the type
Figure imgb0001
contains, wherein A₁-A₉ H or an alkyl radical with a low C number, R₁-R₉ H, OH or an alkyl radical with a low C number, X is a halogen or SO₄ and n is the valence of X.

Als vorteilhaft haben sich Mittel erwiesen, bei welchen A₁-A₇ CH₃ und A₈, A₉ sowie R₁-R₉ H sind:

Figure imgb0002

Als besonders vorteilhaft haben sich auch Verbindungen
Figure imgb0003
erwiesen. Diese Verbindungen unterscheiden sich gegenüber den vorigen nur dadurch, dass R₂ eine CH₃-Gruppe statt H enthält. Bei den beiden letztgenannten Verbindungstypen haben sich als Halogenide besonders die Bromide und Chloride vorteilhaft bewährt.Agents have proven to be advantageous in which A₁-A₇ CH₃ and A₉, A₉ and R₁-R₉ H are:
Figure imgb0002
Connections have also been found to be particularly advantageous
Figure imgb0003
proven. These compounds differ from the previous ones only in that R₂ contains a CH₃ group instead of H. In the latter two types of compounds, the bromides and chlorides have proven to be particularly advantageous as halides.

Es sollte noch erwähnt werden, dass es praktisch keinen Unterschied macht, ob als kationische grenzflächenaktive Mittel die bisher genannten Verbindungen oder deren Monohydrate für die erfindungsgemässen Bäder eingesetzt werden.It should also be mentioned that it makes practically no difference whether the compounds mentioned above or their monohydrates are used as cationic surfactants for the baths according to the invention.

An die Grundzusammensetzung der Galvanisierbäder werden keine besonderen Anforderungen gestellt. Es können übliche, die gewünschten Metalle enthaltenen Galvanisierbäder verwendet werden, z.B. ein Sulfamat- oder Watts-Bad.No special requirements are placed on the basic composition of the electroplating baths. Common plating baths containing the desired metals can be used, e.g. a sulfamate or watts bath.

Vorteilhafte Wirkung haben erfindungsgemässe Bäder, bei denen neben den erfindungsgemäss enthaltenden kationischen grenzflächenaktiven Verbindungen zusätzlich Phoshorige Säure und/oder Hypophosphorige Säure und /oder mindestens eines deren Salze zugesetzt werden. Es ist dadurch möglich, in der Metallmatrix neben der gleichmässigen Feststoffschmiermittelpartikelabscheidung auch eine gleichmässige Phosphoreinlagerung zu erzielen. Die Oberfläche der erhaltenen Dispersionsschicht ist praktisch porenfrei. So können in besonders vorteilhafter Weise bei Nickel und Kobalt enthaltenden galvanischen Bädern, denen neben den erfindungsgemässen kationischen grenzflächenaktiven Verbindungen zusätzlich Phosphorige Säure und/oder Hypophosphorsäure und/oder deren Salz(e) zugesetzt werden, Kobalt-Nickel-Phosphorschichten, in denen Feststoffschmiermittelteilchen eingelagert sind, hergestellt werden.Baths according to the invention have an advantageous effect, in which, in addition to the cationic surface-active compounds containing the invention, phosphorus acid and / or hypophosphorous acid and / or at least one of their salts are additionally added. This makes it possible to achieve even phosphor storage in addition to uniform solid lubricant particle separation in the metal matrix. The surface of the dispersion layer obtained is practically non-porous. So can In a particularly advantageous manner in the case of electroplating baths containing nickel and cobalt, to which, in addition to the cationic surface-active compounds according to the invention, phosphorous acid and / or hypophosphoric acid and / or their salt (s) are additionally added, cobalt-nickel-phosphor layers in which solid lubricant particles are incorporated are produced will.

Als dauerschmierende Feststoffschmiermittel kommen vorzugsweise Polyfluorcarbonharze - insbesondere Polytetrafluorethylen -, Graphit, Graphitfluorid und Molybdändisulfid in Frage. Um eine ausreichende Einbaurate an Feststoffschmiermittel zu erreichen, sollte dessen mittlere Teilchengrösse 10 µm nicht überschreiten. Die besten Resultate wurden bei Teilchengrössen von 3-6 µm erreicht. Bei dieser Teilchengrösse ergaben die Dispersionsschichten auch die besten Reibungswerte.The permanently lubricating solid lubricants are preferably polyfluorocarbon resins - in particular polytetrafluoroethylene -, graphite, graphite fluoride and molybdenum disulfide. In order to achieve an adequate installation rate of solid lubricant, its average particle size should not exceed 10 µm. The best results were achieved with particle sizes of 3-6 µm. With this particle size, the dispersion layers also gave the best friction values.

Bei erfindungsgemässen Bädern, bei denen insbesondere die Chloride als grenzflächenaktive Mittel eingesetzt wurden, konnten praktisch keine der vorgenannten Nachteil mehr beobachtet werden.In the baths according to the invention, in which in particular the chlorides were used as surface-active agents, practically none of the aforementioned disadvantages could be observed.

Darüber hinaus zeigten Schichten, die aus erfindungsgemässen Bädern hergestellt wurden, vorteilhafte mechanische Eigenschaften. So lag die Dehnung weit über dem üblichen Wert von etwa 0.3 % und die Innenspannungen weit unter 150 N/mm². Die Schmiereigenschaften sowie die Verschleissfestigkeit waren beim Einsatz von Polytetrafluorethylen, Graphit, Graphitfluorid und Molybdendisulfid als dauerschmierende Feststoffschmiermittel durchwegs von hoher Qualität und in jedem Fall reproduzierbar, was bei den galvanischen Bädern für den gleichen Zweck nach dem Stand der Technik nicht immer festgestellt werden konnte. Die Strukturen der Beschichtungen zeigten keine Fehlstellen. Die Einbaurate der Dispersionsschicht war über die gesamte Zeit konstant - teilweise jedoch erst nach einer kurzen Anlaufphase - .In addition, layers which were produced from baths according to the invention showed advantageous mechanical properties. The elongation was far above the usual value of about 0.3% and the internal stresses far below 150 N / mm². The lubrication properties and wear resistance were consistently of high quality and reproducible in all cases when using polytetrafluoroethylene, graphite, graphite fluoride and molybdenum disulfide as permanent lubricant galvanic baths for the same purpose could not always be determined according to the prior art. The structures of the coatings showed no defects. The installation rate of the dispersion layer was constant over the entire time - but sometimes only after a short start-up phase.

Weitere Vorteile, Merkmale und Einzelheiten der Erfindung ergeben sich aus den folgenden ausgewählten, besonders gute Ergebnisse liefernden Beispielen. Dabei wurde bis auf die Beispiele 5 und 6 von allgemeinen Galvanisierbädern wie z.B. Sulfamat- oder Sulfatbädern ausgegangen. Als kationisches grenzflächenaktives Mittel wurde entweder

Figure imgb0004

(Diisobutylcresoxyethoxyethyldimethylbenzylammoniumchloridmonohydrat), im Handel vertrieben als Hyamin 10-X und so in den Beispielen der Kürze wegen aufgzführt, oder
Figure imgb0005
(Diisobutylphenoxyethoxyethyldimethylbenzylammoniumchloridmonohydrat), im Handel vertrieben als Hyamin 1622 und so in den Beispielen der Kürze wegen aufgeführt, verwendet.Further advantages, features and details of the invention emerge from the following selected examples which provide particularly good results. With the exception of Examples 5 and 6, general electroplating baths such as sulfamate or sulfate baths were used. As a cationic surfactant, either
Figure imgb0004
(Diisobutylcresoxyethoxyethyldimethylbenzylammoniumchloridmonohydrat), sold commercially as Hyamin 10-X and so listed in the examples for brevity, or
Figure imgb0005
(Diisobutylphenoxyethoxyethyldimethylbenzylammoniumchloridmonohydrat), sold commercially as Hyamin 1622 and so used in the examples for brevity.

Beispiel 1example 1

Es wurde ein galvanisches Bad hergestellt aus:

Nickelsulfamat Ni(NH₂SO₃)₂
300 g/l
Nickelchlorid NiCl₂.6H₂O
18 g/l
Borsäure H₃BO₃
25 g/l
nichtionisches Netzmittel
3 ml/l
kationisches grenzflächenaktives Mittel:   Hyamin 10-X
Feststoffschmiermittel:
   Polytetrafluorethylen (PTFE)
20 g/l
pH-Wert:
4
A galvanic bath was made from:
Nickel sulfamate Ni (NH₂SO₃) ₂
300 g / l
Nickel chloride NiCl₂.6H₂O
18 g / l
Boric acid H₃BO₃
25 g / l
non-ionic wetting agent
3 ml / l
cationic surfactant: Hyamin 10-X
Solid lubricant:
Polytetrafluoroethylene (PTFE)
20 g / l
PH value:
4th

Die verwendete Polytetrafluorethylen-Dispersion enthielt 60 % Feststoffanteil; die Partikelgrösse lag zwischen 0.2 und 3 µm. Diese Dispersion wurde langsam unter starker Rührung dem Elektrolyt zugesetzt. Hyamin 10-X wurde separat in warmem Wasser gelöst und dem Elektrolyt zudosiert. Bei einer Arbeitstemperatur von 50°C und einer Stromdichte von 4A/dm² wurden je nach Hyamin-Gehalt bei dem Aufbringen der Dispersionsschichten auf ein Aluminiumblech folgende Polytetrafluorethylen (nachfolgend als PTFE bezeichnet)-Einbauraten erhalten:

Figure imgb0006
The polytetrafluoroethylene dispersion used contained 60% solids; the particle size was between 0.2 and 3 µm. This dispersion was slowly added to the electrolyte with vigorous stirring. Hyamin 10-X was separately dissolved in warm water and added to the electrolyte. At an operating temperature of 50 ° C and a current density of 4A / dm², the following polytetrafluoroethylene (hereinafter referred to as PTFE) installation rates were obtained depending on the hyamine content when applying the dispersion layers to an aluminum sheet:
Figure imgb0006

Durch Erhöhung der PTFE-Konzentration und der Stromdichte konnte die Einbaurate an PTFE auf über 50 Vol.-% erhöht werden, z.B. bei:

PTFE-Konzentration:
50 g/l
Hyamin 10-X-Konzentration:
25 mg/g PTFE
Stromdichte:
10 A/dm²
Einbaurate:
51.3 %
By increasing the PTFE concentration and the current density, the installation rate of PTFE could be increased to over 50% by volume, for example with:
PTFE concentration:
50 g / l
Hyamin 10-X concentration:
25 mg / g PTFE
Current density:
10 A / dm²
Installation rate:
51.3%

Figur 1 zeigt eine mikroskopische Aufnahme einer derartigen Dispersionsschicht quer zur Schichtebene im Auflicht. Die hellen Punkte stellen die Nickelpartikel und die dunklen Punkte die PTFE-Partikel dar. Man sieht, dass die Einbaurate des Feststoffschmiermittels über den ganzen Abscheidungszeitraum konstant war.FIG. 1 shows a micrograph of such a dispersion layer transversely to the layer plane in incident light. The light dots represent the nickel particles and the dark dots the PTFE particles. It can be seen that the rate of incorporation of the solid lubricant was constant over the entire deposition period.

Beispiel 2Example 2

Es wurde ein galvanisches Bad hergestellt aus:

Nickelsulfamat Ni(NH₂SO₃)₂
600 g/l
Kobaltchlorid CoCl₂.6H₂O
30 g/l
Borsäure H₃BO₃
40 g/l
nichtionisches Netzmittel
3 ml/l
kationisches grenzflächenaktives Mittel:
   Hyamin 1622
30 mg/g PTFE
Feststoffschmiermittel:
   Molybdändisulfid MoS₂
   (Teilchengrösse 4-6 µm)
20 g/l
pH-Wert
4
A galvanic bath was made from:
Nickel sulfamate Ni (NH₂SO₃) ₂
600 g / l
Cobalt chloride CoCl₂.6H₂O
30 g / l
Boric acid H₃BO₃
40 g / l
non-ionic wetting agent
3 ml / l
cationic surfactant:
Hyamin 1622
30 mg / g PTFE
Solid lubricant:
Molybdenum disulfide MoS₂
(Particle size 4-6 µm)
20 g / l
PH value
4th

In analoger Weise wie in Beispiel 1 wurde bei einer Temperatur von 50°C und einer Stromdichte von 5A/dm² eine Dispersionsschicht abgeschieden, deren Metallmatrix aus 65 % Ni und 35% Co bestand. Die Einbaurate am MoS₂ betrug 14 Vol-%.In a manner analogous to that in Example 1, a dispersion layer whose metal matrix consisted of 65% Ni and 35% Co was deposited at a temperature of 50 ° C. and a current density of 5A / dm². The installation rate on MoS₂ was 14% by volume.

Beispiel 3Example 3

Es wurde ein galvanisches Bad hergestellt aus:

Kobaltsulfat CoSO₄.7H₂O
252 g/l
Kobaltchlorid CoCl₂.6H₂O
15 g/l
Borsäure
25 g/l
nichtionisches Netzmittel
3 ml/l
kationisches grenzflächenaktives Mittel:
   Hyamin 10-X
0-25 mg/g Graphit
Feststoffschmiermittel:
Graphit (mittlere Teilchengrösse 3 µm)   25 g/l
pH-Wert:
4
A galvanic bath was made from:
Cobalt sulfate CoSO₄.7H₂O
252 g / l
Cobalt chloride CoCl₂.6H₂O
15 g / l
Boric acid
25 g / l
non-ionic wetting agent
3 ml / l
cationic surfactant:
Hyamin 10-X
0-25 mg / g graphite
Solid lubricant:
Graphite (average particle size 3 µm) 25 g / l
PH value:
4th

In analoger Weise wie in Beispiel 1 wurden bei einer Temperatur von 50°C und einer Stromdichte von 4A/dm² Dispersionsschichten bei verschiedenen Konzentrationen des kationischen grenzflächenaktiven Mittels hergestellt. Folgende Resultate wurden erhalten:

Figure imgb0007
In a manner analogous to that in Example 1, dispersion layers were prepared at a temperature of 50 ° C. and a current density of 4A / dm 2 at different concentrations of the cationic surfactant. The following results were obtained:
Figure imgb0007

Beispiel 4Example 4

Es wurde ein galvanisches Bad hergestellt aus:

Kobaltsulfat CoSO₄.7H₂O
252 g/l
Kobaltchlorid CoCl₂.6H₂O
15 g/l
Borsäure HBO₃
25 g/l
nichtionisches Netzmittel
3 ml/l
kationisches grenzflächenaktives Mittel:
   Hyamin 10-X
25 mg/g CFX
Feststoffschmiermittel:
   Graphitfluorid CFX
30 g/l
   (mittlere Teilchengrösse 6 µm)
pH-Wert:
4
A galvanic bath was made from:
Cobalt sulfate CoSO₄.7H₂O
252 g / l
Cobalt chloride CoCl₂.6H₂O
15 g / l
Boric acid HBO₃
25 g / l
non-ionic wetting agent
3 ml / l
cationic surfactant:
Hyamin 10-X
25 mg / g CF X
Solid lubricant:
Graphite fluoride CF X
30 g / l
(average particle size 6 µm)
PH value:
4th

Das Bad entspricht in seinen Basiskomponenten dem Bad aus Beispiel 3. Das verwendete Graphitfluorid hatte ein Fluor/Graphit-Verhältniss von 0.9, eine Dichte von 2.6 und eine spezifische Oberfläche von 200-340 m²/g.The basic components of the bath correspond to the bath from Example 3. The graphite fluoride used had a fluorine / graphite ratio of 0.9, a density of 2.6 and a specific surface area of 200-340 m 2 / g.

Analog wie in den vorhergehenden Beispielen wurde bei einer Temperatur von 50°C und einer Stromdichte von 8A/dm² eine Dispersionsschicht hergestellt. Eine mikroskopische Aufnahme - unter den gleichen Bedingungen wie die Aufnahme aus Figur 1 - zeigt Figur 2. Das Graphitfluorid (dunkle Partikel) ist nach einer kurzen Zeit, in der nur eine Metallabscheidung erfolgt, in der Schicht gleichmässig verteilt. Die Einbaurate an Feststoffschmiermittel betrug 11 Vol.-% der Schicht. Die Schicht hatte folgende Eigenschaften:

interne (Zug-)Spannung :
80 N/mm²
Dehnung :
1.5 %
Mikrohärte :
300 Hv
Reibungskoeffizient :
0.14
As in the previous examples, a dispersion layer was produced at a temperature of 50 ° C. and a current density of 8A / dm². A microscopic picture - under the same conditions as the picture from FIG. 1 - is shown in FIG. 2. The graphite fluoride (dark particles) is evenly distributed in the layer after a short time in which only metal deposition takes place. The installation rate of solid lubricant was 11% by volume of the layer. The layer had the following properties:
internal (tensile) tension:
80 N / mm²
Strain :
1.5%
Micro hardness:
300 Hv
Friction coefficient:
0.14

Die tribologischen Messungen wurden nach der Pin-Disk-Methode unter folgenden Bedingungen durchgeführt: Gehärtete Stahlkugel mit Durchmesser 5 mm; 50 Umdrehungen/Minute; Belastung 4 N; Temperatur 20°C; rel. Feuchtigkeit ca. 50 %; Laufzeit 24 Stunden.The tribological measurements were carried out according to the pin-disk method under the following conditions: hardened steel ball with a diameter of 5 mm; 50 revolutions / minute; Load 4 N; Temperature 20 ° C; rel. Humidity approx. 50%; Running time 24 hours.

Beispiel 5Example 5

Es wurde ein galvanisches Bad wie in Beispiel 2 hergestellt, dem jedoch noch zusätzlich 100 ml/l 30 Gew.-%-ige Phosphorige Säure zugesetzt wurde und das als alleiniges Feststoffschmiermittel 30 g/l Graphitfluorid CFX (mittlere Teilchengrösse 6 µm) enthielt. Der pH-Wert des Bades betrug 2.5A galvanic bath was produced as in Example 2, but to which an additional 100 ml / l of 30% by weight phosphorous acid was added, and this as the only one Solid lubricant contained 30 g / l graphite fluoride CF X (average particle size 6 microns). The pH of the bath was 2.5

Wiederum wurde in analoger Weise wie in Beispiel 1 bei einer Temperatur von 50°C und einer Stromdichte von 5A/dm² eine Dispersionsschicht abgeschieden, deren Matrix neben Nickel und Kobalt noch Phosphor enthielt. Die abgeschiedenen Nickel-Kobalt-Phosphor-Schicht, in der die CFX-Teilchen gleichmässig verteilt vorlagen, war amorph.Again, a dispersion layer was deposited in a manner analogous to that in Example 1 at a temperature of 50 ° C. and a current density of 5A / dm², the matrix of which also contained phosphorus in addition to nickel and cobalt. The deposited nickel-cobalt-phosphor layer, in which the CF X particles were evenly distributed, was amorphous.

Beispiel 6Example 6

In analoger Weise wie in Beispiel 5 wurde ein Bad der Zusammensetzung von Beispiel 2 hergestellt, dem jedoch statt Phosphoriger Säure zusätzlich 35 g/l Natriumhypophosphit zugesetzt wurde und das als alleiniges Feststoffschmiermittel 30 g/l Molybdändisulfid MoS₂ (Teilchengrösse 4-6 µm) enthielt. Der pH-Wert des Bades Betrug 3.In a manner analogous to that in Example 5, a bath of the composition of Example 2 was prepared, but to which, instead of phosphorous acid, an additional 35 g / l sodium hypophosphite was added and which contained 30 g / l molybdenum disulphide MoS₂ (particle size 4-6 µm) as the sole solid lubricant. The pH of the bath was 3.

Die Bedingungen zur Abscheidung der Dispersionsschicht waren mit denen von Beispiel 1 identisch. Es wurde wie in Beispiel 5 eine dichte Kobalt-Nickel-Phosphor-Matrix im amorphen Zustand erhalten, in der die MoS₂-Teilchen gleichmässig verteilt eingebaut waren.The conditions for depositing the dispersion layer were identical to those of Example 1. As in Example 5, a dense cobalt-nickel-phosphorus matrix was obtained in the amorphous state, in which the MoS₂ particles were installed in an evenly distributed manner.

Die Durchführung weiterer Versuche bezogen sich auf die gemeinsame Anwendung von Phosphoriger Säure, Hypophosphoriger Säure, Phosphit(en), und/oder Hypophosphit(en) unter Anwendung von Nickel und Kobalt enthaltenden Bädern. Es wurden darüber hinaus auch die verschiedenen Feststoffschmiermittel im Gemisch zu den Bädern zugegeben. Dabei zeigte sich, dass in keinem der Versuche weder die Einbaurate der Feststoffschmiermittelgemische negativ beeinflusst wurde noch die gemeinsame Verwendung der vorgenannten Zusätze von nachteiligem Einfluss auf die Dispersionsschicht war. Das Gegenteil war eher der Fall, denn bei einigen Versuchen wurden mit Bädern, die sowohl Phosphorige Säure als auch Hypophosphit(e) und/oder Phosphit(e) und/oder Hypophosphorige Säure enthielten, glättere Dispersionsschichtoberflächen erzielt als bei Anwesenheit einer der genannten Verbindungen allein.The implementation of further experiments related to the joint use of phosphorous acid, hypophosphorous acid, phosphite (s), and / or hypophosphite (s) under Use of baths containing nickel and cobalt. The various solid lubricants were also added to the baths in a mixture. It was found that in none of the tests was the fitting rate of the solid lubricant mixtures negatively influenced, nor was the joint use of the additives mentioned adversely affecting the dispersion layer. The opposite was more the case, because in some experiments baths containing both phosphorous acid and hypophosphite (s) and / or phosphite (s) and / or hypophosphorous acid achieved smoother dispersion layer surfaces than in the presence of one of the compounds mentioned .

Claims (11)

1. Galvanic bath comprising usual metals capable of being galvanically deposited as well as solid lubricant particles and a hydrosoluble surfactant having cationic properties at the pH value of the galvanic bath, for the simultaneous deposition of metal and a lubricant solid having a permanent lubricating effect,
characterized in that
the cationic hydrosoluble surfactant is a compound of the type
Figure imgb0011
 in which A₁-A₉ represents H or an alkyl group having a low number of carbon atoms, R₁-R₉ represents H, OH or an alkyl group having a low number of carbon atoms, X represents a halogen or SO₄ and n represents the valence of X.
2. Galvanic bath according to claim 1, characterized in that the cationic hydrosoluble surfactant is a compound of the type
Figure imgb0012
3. Galvanic bath according to claim 1, characterized in that the cationic hydrosoluble surfactant is a compound of the type
Figure imgb0013
4. Galvanic bath according to one of claims 1 to 3, characterized in that X represents Br.
5. Galvanic bath according to one of claims 1 to 3, characterized in that X represents Cl.
6. Galvanic bath according to one of claims 1 to 5, characterized in that the solid lubricant is polytetrafluoroethylene, graphite, graphite fluoride or molybdenum sulfide.
7. Galvanic bath according to claim 6, characterized in that the particle dimension of the solid lubricant is of 3 to 6 µm.
8. Galvanic bath according to one of claims 1 to 7, characterized in that the bath further includes phosphorous acid and/or at least one of its salts.
9. Galvanic bath according to one of claims 1 to 7, characterized in that the bath further includes hypophosphorous acid and/or at least one of its salts.
10. Galvanic bath according to one of claims 1 to 9, characterized in that the usual metals capable of being galvanically deposited contained in the bath include cobalt and nickel.
11. Use of a galvanic bath according to claims 8 and 10 or 9 and 10 containing cobalt and nickel, for preparing cobalt-nickel-phosphor layers including solid lubricant particles incorporated therein.
EP86902298A 1985-04-22 1986-04-18 Galvanic bath for the simultaneous deposition of metals and a permanent solid lubricant Expired - Lifetime EP0218645B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1718/85A CH667108A5 (en) 1985-04-22 1985-04-22 GALVANIC BATHROOM FOR THE COMBINED DEPOSITION OF METAL AND A PERMANENTLY LUBRICATING SOLID LUBRICANT.
CH1718/85 1985-04-22

Publications (2)

Publication Number Publication Date
EP0218645A1 EP0218645A1 (en) 1987-04-22
EP0218645B1 true EP0218645B1 (en) 1991-09-11

Family

ID=4216979

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86902298A Expired - Lifetime EP0218645B1 (en) 1985-04-22 1986-04-18 Galvanic bath for the simultaneous deposition of metals and a permanent solid lubricant

Country Status (6)

Country Link
US (1) US4728398A (en)
EP (1) EP0218645B1 (en)
JP (1) JPS62502552A (en)
CH (1) CH667108A5 (en)
DE (1) DE3681392D1 (en)
WO (1) WO1986006419A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009008931A1 (en) * 2009-02-13 2010-08-19 Paul Hettich Gmbh & Co. Kg Method for producing a fitting, a side grille or a product carrier for high temperature applications and metallic component

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5160590A (en) * 1989-09-06 1992-11-03 Kawasaki Steel Corp. Electrolytic processing method for electrolytically processing metal surface
JPH049498A (en) * 1990-04-26 1992-01-14 Nkk Corp Metallic plate plated with nickel-phosphorus alloy which has excellent peeling property and high hardness and production thereof
JPH049499A (en) * 1990-04-26 1992-01-14 Nkk Corp Plated metallic plate having superior exfoliation resistance and high hardness
US5931710A (en) * 1998-01-12 1999-08-03 Johnson, Sr.; Clyde Surface drive kit for marine craft
US6114040A (en) * 1998-09-09 2000-09-05 E. I. Du Pont De Nemours And Company Cathodic electrodeposited coatings having high lubricity
US6837923B2 (en) * 2003-05-07 2005-01-04 David Crotty Polytetrafluoroethylene dispersion for electroless nickel plating applications
US20060040126A1 (en) * 2004-08-18 2006-02-23 Richardson Rick A Electrolytic alloys with co-deposited particulate matter
DE102007002111A1 (en) 2007-01-15 2008-07-17 Futurecarbon Gmbh Plating bath for plating component has second liquid component in form of dispersion mixed with first one
ES2694027T3 (en) * 2007-12-11 2018-12-17 Macdermid Enthone Inc. Electrolytic deposition of metal-based composite coatings comprising nano-particles
US8226807B2 (en) * 2007-12-11 2012-07-24 Enthone Inc. Composite coatings for whisker reduction
US20110162751A1 (en) * 2009-12-23 2011-07-07 Exxonmobil Research And Engineering Company Protective Coatings for Petrochemical and Chemical Industry Equipment and Devices
US20160010214A1 (en) * 2014-07-10 2016-01-14 Macdermid Acumen, Inc. Composite Electroless Nickel Plating
CN108350589A (en) * 2015-11-06 2018-07-31 株式会社杰希优 Nickel plating additive and satin nickel plating bath containing it
DE102016100245A1 (en) * 2016-01-08 2017-07-13 Staku Anlagenbau Gmbh Self-lubricating electrodeposited phosphating coating
CN112853416A (en) * 2020-12-31 2021-05-28 暨南大学 Composite coating with self-lubricating and wear-resisting functions, preparation method thereof and plating solution

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3677907A (en) * 1969-06-19 1972-07-18 Udylite Corp Codeposition of a metal and fluorocarbon resin particles
GB1366823A (en) * 1972-04-07 1974-09-11 Uemura Kogyo Kk Metal plating process
JPS5032071A (en) * 1973-07-23 1975-03-28
JPS5618080B2 (en) * 1973-08-14 1981-04-25
CH623851A5 (en) * 1975-10-04 1981-06-30 Akzo Nv
NL7604399A (en) * 1976-04-26 1977-10-28 Akzo Nv PROCEDURE FOR APPLYING A PLASTIC CONTAINING COATINGS.
JPS54112785A (en) * 1978-02-24 1979-09-03 Asahi Glass Co Ltd Electrode and manufacture thereof
US4222828A (en) * 1978-06-06 1980-09-16 Akzo N.V. Process for electro-codepositing inorganic particles and a metal on a surface
FR2443497A1 (en) * 1978-12-06 1980-07-04 Oreal NOVEL CATIONIC SURFACE AGENTS, PROCESS FOR THEIR PREPARATION AND THEIR USE
FR2470595A2 (en) * 1979-12-04 1981-06-12 Oreal Cationic surfactants for hair and skin compsns. - prepd. from alcohol(s) obtd. from lanolin, waxes or resin acids
EP0168868B1 (en) * 1984-07-16 1989-02-01 BBC Brown Boveri AG Process for the deposition of a corrosion-inhibiting layer, comprising protective oxide-forming elements at the base of a gas turbine blade, and a corrosion-inhibiting layer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009008931A1 (en) * 2009-02-13 2010-08-19 Paul Hettich Gmbh & Co. Kg Method for producing a fitting, a side grille or a product carrier for high temperature applications and metallic component
WO2010091924A1 (en) * 2009-02-13 2010-08-19 Paul Hettich Gmbh & Co. Kg Method for producing a fitting, a lateral screen or a refining product carrier for high temperature applications and metal component

Also Published As

Publication number Publication date
JPS62502552A (en) 1987-10-01
WO1986006419A1 (en) 1986-11-06
CH667108A5 (en) 1988-09-15
DE3681392D1 (en) 1991-10-17
JPH0428797B2 (en) 1992-05-15
US4728398A (en) 1988-03-01
EP0218645A1 (en) 1987-04-22

Similar Documents

Publication Publication Date Title
EP0218645B1 (en) Galvanic bath for the simultaneous deposition of metals and a permanent solid lubricant
DE3831954C2 (en) Process for co-deposition of fluorinated carbon and electroless nickel
EP2619348B1 (en) Layered composite material for sliding elements, method for producing same and use thereof
DE2643758C3 (en) Process for the cathodic deposition of metal coatings containing polyfluorocarbon resin particles
EP1114209B1 (en) Hard-chrome plated layer
EP1799881A2 (en) Non-galvanically applied nickel alloy
DE2712730A1 (en) METHOD OF APPLYING RESIN-CONTAINING COATINGS
DE10301135B4 (en) Object with a wear protection layer
DE2106918C3 (en) Process for the production of multi-layer bearing material
DE102009019601B3 (en) Layer composite material for sliding elements and for plain bearings, particularly crankshaft bearing, camshaft bearings or connecting rod bearings, comprises primary layer made from copper alloy or aluminum alloy
DE102004020385B4 (en) Method for producing plain bearing bushes
DE3724614A1 (en) ALUMINUM COMPOSITE OBJECT AND METHOD FOR THE PRODUCTION THEREOF
EP0122416B1 (en) Bath for the electrodeposition of composite coatings
DE2646881A1 (en) METHOD OF GALVANIZATION
DE3619386C2 (en)
DE3327346A1 (en) GALVANICALLY SEPARATE DISPERSION LAYER
DE2164050C3 (en) Electroplating bath of conventional composition for the joint deposition of metal and a permanently lubricating solid lubricant
DE1621792C3 (en) Object coated with metal and a fluorocarbon polymer
DE3100997C2 (en) Bath for the galvanic deposition of rhodium coatings
DE19622166A1 (en) Layer material used for sliding element
AT358352B (en) METHOD FOR DEPOSITING METAL COATINGS CONTAINING POLYFLUORCARBON RESIN PARTICLES
DE1496900A1 (en) Process for the deposition of bright nickel by electroplating
DE3139640A1 (en) "BATH AND METHOD FOR THE GALVANIC DEPOSITION OF BLACK NICKEL"
DE1020844B (en) Bath for the galvanic production of shiny and leveling nickel coatings
DE4119727A1 (en) Sliding member, for piston rings

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT

17P Request for examination filed

Effective date: 19870427

17Q First examination report despatched

Effective date: 19880229

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT

ITF It: translation for a ep patent filed

Owner name: ING. A. GIAMBROCONO & C. S.R.L.

REF Corresponds to:

Ref document number: 3681392

Country of ref document: DE

Date of ref document: 19911017

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920320

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19920408

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19920521

Year of fee payment: 7

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930418

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930418

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19931229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19940101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050418