EP0218645A1 - 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.

Info

Publication number
EP0218645A1
EP0218645A1 EP86902298A EP86902298A EP0218645A1 EP 0218645 A1 EP0218645 A1 EP 0218645A1 EP 86902298 A EP86902298 A EP 86902298A EP 86902298 A EP86902298 A EP 86902298A EP 0218645 A1 EP0218645 A1 EP 0218645A1
Authority
EP
European Patent Office
Prior art keywords
solid lubricant
galvanic bath
galvanic
bath according
graphite
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
Application number
EP86902298A
Other languages
German (de)
English (en)
Other versions
EP0218645B1 (fr
Inventor
Jean-Francois 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.)
Fluehmann AG Werner
Original Assignee
Fluehmann AG Werner
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 Fluehmann AG Werner filed Critical Fluehmann AG Werner
Publication of EP0218645A1 publication Critical patent/EP0218645A1/fr
Application granted granted Critical
Publication of EP0218645B1 publication Critical patent/EP0218645B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 of conventional composition with 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 mutual 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 which has cationic properties.
  • Several patents are known in connection with the deposition of nickel-polytetrafluoroethylene dispersion layers (e.g. CH-PS 623 851, G3-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. Furthermore, 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. Due to increased brittleness, layers of this type tend to flake off, as a result of which such galvanic layers 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
  • A- 1 -A 9 H or an alkyl radical with a low C number R 1 -R 9 H, OH or an alkyl radical with a low C number
  • X is a halogen or SO 4 and n is the valence of X.
  • 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.
  • phosphorus acid and / or hypophosphorous acid and / or at least one of their salts are additionally added. This makes it possible to achieve uniform phosphor storage in addition to the 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.
  • 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 - in some cases, however, only after a short start-up phase.
  • a galvanic bath was made from:
  • 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 / dm 2 , the following polytetrafluoroethylene (hereinafter referred to as PTFE) installation rates were obtained, depending on the hyamine content, when the dispersion layers were applied to an aluminum sheet: Hyamine content PTFE installation rate
  • the installation rate of PTFE could be increased to over 50% by volume, e.g. at:
  • Hyamin 10-X concentration 25 mg / g PTFE
  • Figure 1 shows a micrograph of such a dispersion layer transverse 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
  • a galvanic bath was made from:
  • Example 2 In a manner analogous to that in Example 1, a dispersion layer was deposited at a temperature of 50 ° C. and a current density of 5A / dm 2 , the metal matrix of which consisted of 65% Ni and 35% Co. The installation rate on MoS 2 was 14% by volume.
  • a galvanic bath was made from:
  • a galvanic bath was made from:
  • 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.
  • a dispersion layer was produced at a temperature of 50 ° C and a current density of 8A / dm 2 .
  • a micrograph - under the same conditions as the image from FIG. 1 - is shown in FIG. 2.
  • the graphite fluoride dark particles
  • the installation rate of solid lubricant was 11% by volume of the layer.
  • the layer had the following properties:
  • 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 with an additional 100 ml / l of 30% by weight
  • Phosphorous acid was added as the only one Solid lubricant 30 g / l graphite fluoride CF x (average particle size 6 microns) contained.
  • the pH of the bath was 2.5
  • a dispersion layer was deposited at a temperature of 50 ° C. and a current density of 5A / dm 2 , 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 disulfide MoS 2 (particle size 4-6 ⁇ m) as the sole solid lubricant .
  • the pH of the bath was 3.
  • the conditions for depositing the dispersion layer were identical to those of example 1.
  • a dense cobalt-nickel-phosphorus matrix was obtained in the amorphous state as in Example 5, in which the MoS 2 particles were incorporated in an evenly distributed manner.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Paints Or Removers (AREA)

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.
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 true EP0218645A1 (fr) 1987-04-22
EP0218645B1 EP0218645B1 (fr) 1991-09-11

Family

ID=4216979

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86902298A Expired - Lifetime EP0218645B1 (fr) 1985-04-22 1986-04-18 Bain galvanique pour le depot simultane de metaux et d'un lubrifiant solide permanent

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)

Cited By (1)

* Cited by examiner, † Cited by third party
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

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US5160590A (en) * 1989-09-06 1992-11-03 Kawasaki Steel Corp. Electrolytic processing method for electrolytically processing metal surface
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
US20060040126A1 (en) * 2004-08-18 2006-02-23 Richardson Rick A Electrolytic alloys with co-deposited particulate matter
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
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
US20180327922A1 (en) * 2015-11-06 2018-11-15 Jcu Corporation Nickel-plating additive and satin nickel-plating bath containing same
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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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 (fr) * 1973-07-23 1975-03-28
JPS5618080B2 (fr) * 1973-08-14 1981-04-25
CH623851A5 (fr) * 1975-10-04 1981-06-30 Akzo Nv
NL7604399A (nl) * 1976-04-26 1977-10-28 Akzo Nv Werkwijze voor het aanbrengen van een kunststof bevattende deklagen.
JPS54112785A (en) * 1978-02-24 1979-09-03 Asahi Glass Co Ltd Electrode and manufacture thereof
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FR2443497A1 (fr) * 1978-12-06 1980-07-04 Oreal Nouveaux agents de surface cationiques, procede pour les preparer et leur emploi
FR2470595A2 (fr) * 1979-12-04 1981-06-12 Oreal Nouveaux agents de surface cationiques, procede pour les preparer et leur emploi
EP0168868B1 (fr) * 1984-07-16 1989-02-01 BBC Brown Boveri AG Procédé pour appliquer une couche protectrice résistant à la corrosion avec des éléments formant des oxydes proctecteurs sur la base d'une aube de turbine à gaz et couche protectrice résistant à la corrosion

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Cited By (1)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
JPS62502552A (ja) 1987-10-01
DE3681392D1 (de) 1991-10-17
CH667108A5 (de) 1988-09-15
JPH0428797B2 (fr) 1992-05-15
US4728398A (en) 1988-03-01
EP0218645B1 (fr) 1991-09-11
WO1986006419A1 (fr) 1986-11-06

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