EP0218645B1 - Bain galvanique pour le depot simultane de metaux et d'un lubrifiant solide permanent - Google Patents

Bain galvanique pour le depot simultane de metaux et d'un lubrifiant solide permanent Download PDF

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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
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Prior art keywords
galvanic bath
solid lubricant
bath according
galvanic
cationic
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Expired - Lifetime
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EP86902298A
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German (de)
English (en)
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EP0218645A1 (fr
Inventor
Jean-François Paulet
Jean-Claude Puippe
Heinz Steup
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Werner Fluehmann AG
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Werner Fluehmann 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

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  • 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

On évite le mauvais déroulement d'un bain galvanique et des propriétés physiques défavorables lors du dépôt simultané de métaux et d'un lubrifiant solide permanent à partir de bains galvaniques de composition habituelle renfermant des particules de lubrifiant solide et un agent de surface cationique perfluoré lorsque le bain renferme le composé de formule (I) au lieu du composé perfluoré, où A1-A9 représente H ou un reste alkyle avec un nombre d'atomes de carbone inférieur, R1-R9 représente H, OH ou un reste alkyle inférieur représente, X est halogène ou SO4 et n représente la valence de X. Comme lubrifiant solide, on peut utiliser de préférence le polytétrafluoroéthylène, le graphite, le fluorure de graphite ou le sulfure de molybdène.

Claims (11)

1. Bain galvanique comportant des métaux usuels susceptibles d'être déposés par voie galvanique ainsi que des particules de lubrifiant solide et un agent tensio-actif hydrosoluble qui présente des propriétés cationiques à la valeur de pH du bain galvanique, en vue du dépôt simultané de métal et d'un lubrifiant solide à effet de lubrification permanent,
caractérisé en ce que
l'agent tensio-actif cationique hydrosoluble est une combinaison du type
Figure imgb0014
 dans laquelle A₁-A₉ représente H ou un groupement alkyle à bas nombre d'atomes de carbones, R₁-R₉ représente H, OH ou un groupement alkyle à bas nombre d'atomes de carbones, X représente un halogène ou SO₄ et n représente la valence de X.
2. Bain galvanique selon la revendication 1, caractérisé en ce que l'agent tensio-actif cationique hydrosoluble est une combinaison du type
Figure imgb0015
3. Bain galvanique selon la revendication 1, caractérisé en ce que l'agent tensio-actif cationique hydrosoluble est une combinaison du type
Figure imgb0016
4. Bain galvanique selon l'une des revendications 1 à 3, caractérisé en ce que X représente Br.
5. Bain galvanique selon l'une des revendications 1 à 3, caractérisé en ce que X représente Cl.
6. Bain galvanique selon l'une des revendications 1 à 5, caractérisé en ce que le lubrifiant solide est du polytétrafluoroéthylène, du graphite, du fluorure de graphite ou du sulfure de molybdène.
7. Bain galvanique selon la revendication 6, caractérisé en ce que la dimension des particules du lubrifiant solide est de 3 à 6 µm.
8. Bain galvanique selon l'une des revendications 1 à 7, caractérisé en ce que le bain contient en outre de l'acide phosphoreux et/ou au moins un des sels de celui-ci.
9. Bain galvanique selon l'une des revendications 1 à 8, caractérisé en ce que le bain contient en outre de l'acide hypophosphoreux et/ou au moins un des sels de celui-ci.
10. Bain galvanique selon l'une des revendications 1 à 9, caractérisé en ce que les métaux usuels susceptibles d'être déposés par voie galvanique contenus dans le bain comprennent le cobalt et le nickel.
11. Utilisation d'un bain galvanique selon les revendications 8 et 10 ou 9 et 10 contenant du cobalt et du nickel pour la préparation de couches de cobalt-nickel-phosphore comportant des particules de lubrifiant solide incorporées.
EP86902298A 1985-04-22 1986-04-18 Bain galvanique pour le depot simultane de metaux et d'un lubrifiant solide permanent Expired - Lifetime EP0218645B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1718/85 1985-04-22
CH1718/85A CH667108A5 (de) 1985-04-22 1985-04-22 Galvanisches bad zum gemeinsamen abscheiden von metall und einem dauerschmierenden feststoffschmiermittel.

Publications (2)

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

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Country Status (6)

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

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WO2010091924A1 (fr) * 2009-02-13 2010-08-19 Paul Hettich Gmbh & Co. Kg Procédé de fabrication d'une ferrure, d'une grille latérale ou d'une grille de cuisson pour applications à hautes températures, ainsi que pièce métallique

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JPH049499A (ja) * 1990-04-26 1992-01-14 Nkk Corp 優れた剥離性および高い硬度を有するめつき金属板
JPH049498A (ja) * 1990-04-26 1992-01-14 Nkk Corp 優れた剥離性および高い硬度を有するニツケル‐燐合金めつき金属板およびその製造方法
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
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DE102007002111A1 (de) 2007-01-15 2008-07-17 Futurecarbon Gmbh Beschichtungsbad zum Beschichten eines Bauteils, beschichtetes Bauteil sowie Verfahren zu dessen Herstellung
WO2009076430A1 (fr) * 2007-12-11 2009-06-18 Enthone Inc. Dépôt électrolytique de revêtements composites à base de métal comprenant des nanoparticules
US8226807B2 (en) * 2007-12-11 2012-07-24 Enthone Inc. Composite coatings for whisker reduction
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US20160010214A1 (en) 2014-07-10 2016-01-14 Macdermid Acumen, Inc. Composite Electroless Nickel Plating
JPWO2017077655A1 (ja) * 2015-11-06 2018-08-16 株式会社Ｊｃｕ ニッケルめっき用添加剤およびこれを含有するサテンニッケルめっき浴
DE102016100245A1 (de) * 2016-01-08 2017-07-13 Staku Anlagenbau Gmbh Selbstschmierende elektrolytisch abgeschiedene Phosphatierungsbeschichtung
CN112853416A (zh) * 2020-12-31 2021-05-28 暨南大学 兼具自润滑和耐磨功能的复合镀层及其制备方法与镀液

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Publication number Priority date Publication date Assignee Title
WO2010091924A1 (fr) * 2009-02-13 2010-08-19 Paul Hettich Gmbh & Co. Kg Procédé de fabrication d'une ferrure, d'une grille latérale ou d'une grille de cuisson pour applications à hautes températures, ainsi que pièce métallique
DE102009008931A1 (de) * 2009-02-13 2010-08-19 Paul Hettich Gmbh & Co. Kg Verfahren zur Herstellung eines Beschlages, eines Seitengitters oder eines Gargutträgers für Hochtemperaturanwendungen und metallisches Bauteil

Also Published As

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

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