EP0218645B1 - Galvanisches bad zum gemeinsamen abscheiden von metall und einem dauerschmierenden feststoffschmiermittel - Google Patents

Galvanisches bad zum gemeinsamen abscheiden von metall und einem dauerschmierenden feststoffschmiermittel 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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EP
European Patent Office
Prior art keywords
galvanic bath
solid lubricant
bath according
galvanic
cationic
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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
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EP86902298A
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German (de)
English (en)
French (fr)
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EP0218645A1 (de
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

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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)
  • Paints Or Removers (AREA)
  • Electroplating Methods And Accessories (AREA)
EP86902298A 1985-04-22 1986-04-18 Galvanisches bad zum gemeinsamen abscheiden von metall und einem dauerschmierenden feststoffschmiermittel Expired - Lifetime EP0218645B1 (de)

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 (de) 1987-04-22
EP0218645B1 true EP0218645B1 (de) 1991-09-11

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EP86902298A Expired - Lifetime EP0218645B1 (de) 1985-04-22 1986-04-18 Galvanisches bad zum gemeinsamen abscheiden von metall und einem dauerschmierenden feststoffschmiermittel

Country Status (6)

Country Link
US (1) US4728398A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (1) EP0218645B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS62502552A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CH (1) CH667108A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE3681392D1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1986006419A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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US5160590A (en) * 1989-09-06 1992-11-03 Kawasaki Steel Corp. Electrolytic processing method for electrolytically processing metal surface
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
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
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
CN101946029B (zh) * 2007-12-11 2012-12-19 恩索恩公司 包含纳米颗粒的金属基复合涂层的电解沉积
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
KR20180078227A (ko) * 2015-11-06 2018-07-09 가부시끼가이샤 제이씨유 니켈도금용 첨가제 및 이것을 함유하는 새틴 니켈도금욕
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
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JPS5618080B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1973-08-14 1981-04-25
CH623851A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1975-10-04 1981-06-30 Akzo Nv
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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 (de) * 1984-07-16 1989-02-01 BBC Brown Boveri AG Verfahren zum Aufbringen einer schutzoxydbildende Elemente enthaltenden Korrosionsschutzschicht auf den Grundkörper einer Gasturbinenschaufel und Korrosionssschutzschicht auf dem Grundkörper einer Gasturbinenschaufel

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2010091924A1 (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
CH667108A5 (de) 1988-09-15
JPH0428797B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1992-05-15
US4728398A (en) 1988-03-01
EP0218645A1 (de) 1987-04-22
JPS62502552A (ja) 1987-10-01
WO1986006419A1 (en) 1986-11-06
DE3681392D1 (de) 1991-10-17

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