EP0217126A1 - Galvanic hard chromium layer - Google Patents

Galvanic hard chromium layer Download PDF

Info

Publication number
EP0217126A1
EP0217126A1 EP86111775A EP86111775A EP0217126A1 EP 0217126 A1 EP0217126 A1 EP 0217126A1 EP 86111775 A EP86111775 A EP 86111775A EP 86111775 A EP86111775 A EP 86111775A EP 0217126 A1 EP0217126 A1 EP 0217126A1
Authority
EP
European Patent Office
Prior art keywords
cracks
chrome layer
hard chrome
solid particles
layer according
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
EP86111775A
Other languages
German (de)
French (fr)
Other versions
EP0217126B1 (en
Inventor
Rudolf Linde
Ulrich Dipl.-Ing. Buran
Hans-Jochem Dr. Neuhäuser
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.)
Goetze GmbH
Original Assignee
Goetze GmbH
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 Goetze GmbH filed Critical Goetze GmbH
Publication of EP0217126A1 publication Critical patent/EP0217126A1/en
Application granted granted Critical
Publication of EP0217126B1 publication Critical patent/EP0217126B1/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 hard chrome layer with a crack network extending through the entire layer thickness and its production method.
  • Electroplated hard chrome layers have above all a high hardness and associated high wear resistance, a strong surface smoothness and associated low coefficient of friction and low adhesive power as well as a good resistance to aggressive chemical, corrosive, erosive and oxidative stress at possibly higher temperatures.
  • the treads of machine parts such as the tread of piston rings or cylinders in internal combustion engines, are coated with hard chrome layers in order to achieve special wear resistance.
  • Pressing tools and molds for the production of plastic molded articles are provided with chrome layers to achieve a particular smoothness and wear resistance
  • valve parts are especially protected by chrome layers in chemical plants.
  • Hard chrome layers are also not very elastic and brittle. Especially in the case of shock loads and strong vibrations, breaks can occur in the layers, which then lead to the layers flaking off.
  • the present invention is therefore based on the object of providing a hard chrome layer with improved physical and technological properties in which, above all, the disadvantages indicated are eliminated.
  • the aim is to find a galvanic process which can be used as universally as possible and with which layers of this type can be produced simply and cost-effectively.
  • this object is achieved by a hard chrome layer, in the cracks of which solid particles are embedded.
  • the gap width of the cracks should preferably be more than 0.5 ⁇ m, but in particular more than 1 ⁇ m, so that solid particles can be deposited at all, and the preferred thickness of the hard chrome layer is between 10 ⁇ m and 1,000 ⁇ m.
  • the invention is so created with a hard chrome layer, in the crack network solid particles are embedded, which improve the properties of the hard chrome layer in the desired manner, in particular in the case of a high crack density, in accordance with their properties, such as in the case of a galvanic dispersion layer.
  • the substances used in the production of galvanic dispersion layers are suitable as solid particles, individually or in combination, but they must not dissolve in the microcracking chromic acid baths, their grain size must be below the gap width of the chromium cracks, i.e. preferably between about 0.5 and 15 ⁇ m and the thickness of the chrome layer should be several times larger than the grain size of the particles.
  • Solid particles made of aluminum oxide, boron carbide, boron nitride, chromium carbide, silicon dioxide, titanium carbide, diamond and / or tungsten carbide can be used as solid particles to improve wear resistance. Such chromium layers containing solids are then particularly suitable for the tread coating of piston rings or cylinder liners in internal combustion engines.
  • the solid lubricant particles used consist of hexagonal boron nitride, graphite and / or polymer particles, especially polyvinyl chloride and / or polytetrafluoroethylene, and to improve ductility or reduce brittleness, ductile metals or metal alloys made of tin can be found in the cracks. Titanium or bronze can be stored. The tendency of chrome to adhesive wear can also be reduced by embedded molybdenum particles.
  • the color of the chrome layers according to the invention can be influenced by organic dyes or colored metal salts embedded in the cracks. It was also found that filling the cracks with solid particles increased the corrosion resistance of the layers.
  • the cracks were preferably filled with polyvinyl chloride particles, and the polyvinyl chloride was then melted into the cracks, so that the cracks were sealed and protected against corrosive attacks.
  • solid particles of one or more types of substance can be used in combination to fill the cracks, so that several physical properties are improved at the same time.
  • the cracks need not be completely filled with the solid particles.
  • cracks in the chrome layer zones directly on the substrate can be filled with a corrosion-preventing substance, while the cracks in the outer chrome layer zones are filled with wear particles or sliding substances or are even particle-free, so that corrosion-protected layers with good wear and sliding properties are created.
  • Just the outermost zones can additionally be filled with a substance that promotes enema, such as elemental tin or iron oxide.
  • chromium plating baths which are known per se and are known per se, such as preferably acidic chromic acid baths, with solid particles dispersed therein.
  • the workpiece to be chrome plated is first connected cathodically, so that a micro-cracked chrome layer forms, then the workpiece is switched anodically, so that the micro cracks widen to the desired gap width and the cracks fill with the solid particles and then again occurs a cathodic circuit so that the solid particles are encapsulated and sealed by closing the cracks.
  • This periodic current reversal can, if necessary, be repeated several times, the person skilled in the art being able to vary the chromium plating parameters in accordance with the application in such a way that the desired crack width, crack density and crack filling are produced with different solid particle fillings, if necessary.
  • Hard chrome layers are thus created by the invention, the physical and technological properties of which are significantly improved by solid particles embedded in the cracks.
  • the chrome layers can above all, as shown, an improved wear behavior, better sliding properties, better running-in behavior, better fire protection, better Have security against breakage and chipping and better corrosion behavior individually or in combination.
  • all known chromic acid-insoluble solid particles can be used to fill the cracks.
  • the method according to the invention for producing the chromium layers is relatively simple to carry out and allows the person skilled in the art to produce the desired properties universally by varying the chromium plating parameters and adapted to the application.
  • the invention is illustrated by the exemplary embodiments and the micrographs.
  • the chrome plating takes place for a total of about 5 hours at 55 ° C. with the formation of a chrome layer with a total thickness of 0.2 mm.
  • a test rod (diameter 12 mm) 5 cm long and 5 cm wide is first used for 30 minutes 65 A / dm * chrome-plated and then the anodic etching of the layer is carried out by anodically switching the test rod for 30 sec with a current density of 150 A / dm t .
  • This periodic chrome plating takes place in a total of 10 stages, the chrome plating and etching taking place under the same process parameters.
  • the three micrographs show scanning electron micrographs of the hard chrome layers according to the invention according to the exemplary embodiment.
  • the cracks extending through the chrome layer in the manner of a cobweb can be seen in FIG.
  • the silicon carbide particles embedded in the cracks can be recognized as bright particles.
  • the cross section of Figure 2 shows the cross sections of the cracks, which extend approximately at right angles to the surface.
  • the cracks are closed by the periodic reversal of the current during chrome plating by chrome layers formed over it, so that the embedded bright silicon dioxide particles are encapsulated in the cracks.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Abstract

Bei Hartchromschichten mit verbesserten physikalischen Eigenschaften sind in das Rißnetzwerk vor allem zur Erhöhung der Verschleißfestigkeit des Gleitverhaltens, der Duktilität und der Korrosionsfestigkeit Feststoffpartikel aus vor allem Hartstoffen, Festschmierstoffen, duktilen Metallen oder deren Legierungen und/oder aufgeschmolzenen Polymeren eingelagert. Das Verchromen erfolgt dabei in mikrorißbildenden Verchromungselektrolyten mit den darin dispergierten Feststoffpartikeln unter ein- oder mehrfacher Stromumkehr, so daß bei anodischer Schaltung des Werkstücks das Mikrorißnetzwerk der Chromschicht sich aufweitet und Feststoffpartikel sich einlagern. Bevorzugte Anwendungsgebiete sind Laufflächenbeschichtungen von Kolbenringen oder Zylinderlaufbüchsen für Verbrennungskraftmaschinen.In the case of hard chrome layers with improved physical properties, solid particles made primarily of hard materials, solid lubricants, ductile metals or their alloys and / or melted polymers are embedded in the crack network, above all to increase the wear resistance of the sliding behavior, the ductility and the corrosion resistance. The chrome plating takes place in microcracking chromium plating electrolytes with the solid particles dispersed therein with one or multiple current reversal, so that when the workpiece is anodically switched, the microcrack network of the chrome layer expands and solid particles become embedded. Preferred areas of application are tread coatings on piston rings or cylinder liners for internal combustion engines.

Description

Die Erfindung betrifft eine galvanische Hartchromschicht mit einem durch die gesamte Schichtdicke sich erstreckenden Rißnetzwerk und ihr Herstellungsverfahren.The invention relates to a galvanic hard chrome layer with a crack network extending through the entire layer thickness and its production method.

Galvanisch abgeschiedene Hartchromschichten besitzen vor allem eine hohe Härte und damit verbunden eine hohe Verschleißfestigkeit, eine starke Oberflächenglätte und damit verbunden einen geringen Reibungskoeffizienten und eine geringe Klebefähigkeit sowie eine gute Widerstandsfähigkeit gegenüber aggresiv-chemischer, korrosiver, erosiver und oxydativer Beanspruchung bei gegebenenfalls höheren Temperaturen. Deshalb werden zur Erzielung einer besonderen Verschleißfestigkeit die Laufflächen von Maschinenteilen, wie beispielsweise in Verbrennungsmaschinen die Laufflächen von Kolbenringen oder Zylindern, mit Hartchromschichten überzogen, es werden zur Erzielung einer besonderen Glätte und Verschleißfestigkeit Preßwerkzeuge und Preßformen für die Herstellung von Kunststofformartikeln mit Chromschichten versehen oder es werden zur besseren Haltbarkeit Armaturenteile vor allem in Chemieanlagen durch Chromschichten besonders geschützt.Electroplated hard chrome layers have above all a high hardness and associated high wear resistance, a strong surface smoothness and associated low coefficient of friction and low adhesive power as well as a good resistance to aggressive chemical, corrosive, erosive and oxidative stress at possibly higher temperatures. For this reason, the treads of machine parts, such as the tread of piston rings or cylinders in internal combustion engines, are coated with hard chrome layers in order to achieve special wear resistance.Pressing tools and molds for the production of plastic molded articles are provided with chrome layers to achieve a particular smoothness and wear resistance For better durability, valve parts are especially protected by chrome layers in chemical plants.

Bei der galvanischen Chromabscheidung treten in den Chromschichten relativ hohe Zugspannungen auf, die bei Erreichen einer bestimmten Schichtdicke durch Überschreiten der Dehnfähigkeit des nur schwach elastischen Chroms zu Mikrorißbildungen fuhren, die im geätzten Oberflächenschliffbild in der Form eines spinnwebeartiken Netzwerkes feiner Linien und Sprünge in Erscheinung treten. Solche Mikrorißnetze erleichtern bei ölgeschmierten Verschleißschutzschichten als Ölnuten oder oder Ölnäpfchen die Benetzbarkeit der Chromschichten mit Öl und damit die Ausbildung des für die Schmierung erforderlichen Ölfilms, so daß in diesem Fall während oder nach der Verchromung durch Auswahl geeigneter Verchromungsparameter, durch periodische Stromumkehr, durch thermische Nachbehandlung oder durch Ätzverfahren das Chromrißnetzwerk unter Bildung einer porösen Chromschicht aufgeweitet wird. Vor allem korrosionsschützendere Chromschichten sollen jedoch möglichst frei von Rissen sein und man wählt dann ein Verchromungsverfahren, bei dem die Chromschichten allenfalls ein Mikrorißnetzwerk aufweisen.In the electroplated chrome deposition, relatively high tensile stresses occur in the chrome layers, which, when a certain layer thickness is reached, lead to microcracking in the etched surfaces by exceeding the elasticity of the only weakly elastic chrome micrograph in the form of a spider web-like network of fine lines and cracks. In the case of oil-lubricated wear protection layers as oil grooves or or oil wells, such micro-crack nets facilitate the wettability of the chrome layers with oil and thus the formation of the oil film required for the lubrication, so that in this case during or after the chrome plating by selection of suitable chrome plating parameters, by periodic current reversal, by thermal aftertreatment or the chrome crack network is expanded by etching to form a porous chrome layer. Above all, however, corrosion-protecting chrome layers should be as free from cracks as possible, and a chrome plating process is then chosen in which the chrome layers have at most a micro-crack network.

Hartchromschichten sind darüberhinaus wenig elastisch und spröde. Vor allem bei Stoßbelastungen und stärkeren Erschütterungen können Brüche in den Schichten entstehen, die dann zum Abplatzen der Schichten führen.Hard chrome layers are also not very elastic and brittle. Especially in the case of shock loads and strong vibrations, breaks can occur in the layers, which then lead to the layers flaking off.

Zur Verbesserung der physikalischen Eigenschaften galvanisch abgeschiedener Metallschichten ist es bekannt, in das Matrixmetall fein dispergierte Feststoffteilchen einzulagern, indem man die Metallabscheidung aus einem galvanischen Bad mit darin fein dispergierten Feststoffteilchen vornimmt. So besitzen Nickeldispersionsschichten mit eingelagerten Hartstoffteilchen aus vor allem Siliziumkarbid ein verbessertes Verschleißverhalten und Nickeldispersionsschichten mit eingelagerten Festschmierstoffteilchen besitzen einen geringeren Reibungskoeffizienten. Während die Herstellung galvanischer Nickeldispersionsschichten relativ unproblematisch ist, können Chromdispersionsschichten nicht so ohne weiteres hergestellt werden und galvanische Chromdispersionsschichten mit entsprechend verbesserten Eigenschaften sind in der Praxis nicht im Einsatz. Offensichtlich wegen der stärkeren Wasserstoffentwicklung am Chrom während der Galvanisierung werden dispergierte Feststoffteilchen am Abscheiden in der Chromschicht verhindert. Deshalb müssen Hartchromschichten mit darin fein dispergierten Feststoffteilchen relativ aufwendig durch bevorzugt Plasmaspritzverfahren hergestellt werden.To improve the physical properties of electrodeposited metal layers, it is known to incorporate finely dispersed solid particles into the matrix metal by performing the metal deposition from an electroplating bath with solid particles finely dispersed therein. For example, nickel dispersion layers with embedded hard material particles made of silicon carbide in particular have improved wear behavior and nickel dispersion layers with embedded solid lubricant particles have a lower coefficient of friction. While the production of galvanic nickel dispersion layers is relatively unproblematic, chromium dispersion layers cannot be easily produced and galvanic chromium dispersion layers with correspondingly improved properties are not used in practice. Obviously due to the increased hydrogen development on the chromium during the galvanization, dispersed solid particles are prevented from being deposited in the chromium layer. Hard chrome layers with finely dispersed solid particles must therefore be produced relatively expensively by preferably plasma spraying processes.

Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, eine Hartchromschicht mit verbesserten physikalischen und technologischen Eigenschaften zu schaffen, in denen vor allem die aufgezeigten Nachteile beseitigt sind. Gleichzeitig soll ein möglichst universell anwendbares galvanisches Verfahren gefunden werden, mit dem sich derartige Schichten einfach und kostensparend herstellen lassen.The present invention is therefore based on the object of providing a hard chrome layer with improved physical and technological properties in which, above all, the disadvantages indicated are eliminated. At the same time, the aim is to find a galvanic process which can be used as universally as possible and with which layers of this type can be produced simply and cost-effectively.

Erfindungsgemäß wird diese Aufgabe durch eine Hartchromschicht gelöst, in deren Risse Feststoffpartikel eingelagert sind. Bevorzugt soll dabei die Spaltbreite der Risse über 0,5 um, insbesondere aber über 1 um liegen, damit sich überhaupt Feststoffpartikel einlagern können, und die bevorzugte Dicke der Hartchromschicht liegt zwischen 10 um und 1.000 um. Durch die Erfindung ist somit eine Hartchromschicht geschaffen, in dessen Rißnetzwerk Feststoffteilchen eingelagert sind, die insbesondere bei einer hohen Rißdichte entsprechend ihren Eigenschaften, wie bei einer galvanischen Dispersionsschicht, die Eigenschaften der Hartchromschicht in der gewünschten Weise verbessern.According to the invention, this object is achieved by a hard chrome layer, in the cracks of which solid particles are embedded. The gap width of the cracks should preferably be more than 0.5 μm, but in particular more than 1 μm, so that solid particles can be deposited at all, and the preferred thickness of the hard chrome layer is between 10 μm and 1,000 μm. The invention is so created with a hard chrome layer, in the crack network solid particles are embedded, which improve the properties of the hard chrome layer in the desired manner, in particular in the case of a high crack density, in accordance with their properties, such as in the case of a galvanic dispersion layer.

Als Feststoffteilchen kommen dementsprechend die bei der Herstellung von galvanischen Dispersionsschichten verwendeten Substanzen einzeln oder in Kombination in Frage, allerdings dürfen sie sich nicht in den mikrorißbildenden Chromsäurebädern auflösen, ihre Korngröße muß unterhalb der Spaltbreite der Chromrisse, also bevorzugt etwa zwischen 0,5 und 15 um liegen und die Dicke der Chromschicht sollte um ein Mehrfaches größer sein als die Korngröße der Teilchen.Accordingly, the substances used in the production of galvanic dispersion layers are suitable as solid particles, individually or in combination, but they must not dissolve in the microcracking chromic acid baths, their grain size must be below the gap width of the chromium cracks, i.e. preferably between about 0.5 and 15 μm and the thickness of the chrome layer should be several times larger than the grain size of the particles.

Als Feststoffteilchen zur Verbesserung der Verschleißfestigkeit kommen dabei Hartstoffteilchen aus vor allem Aluminiumoxid, Borkarbid, Bornitrid, Chromkarbid, Siliziumdioxid, Titankarbid, Diamant und/oder Wolframkarbid in Frage. Solche Festkörper enthaltenden Chromschichten sind dann vor allem zur Laufflächenbeschichtung von Kolbenringen oder Zylinderlaufbüchsen in Verbrennungskraftmaschinen geeignet. Die verwendeten Festschmierstoffteilchen bestehen aus hexagonalem Bornitrid, Graphit und/oder Polymerteilchen aus vor allem Polyvinylchlorid und/oder Polytetrafluorethylen und zur Verbesserung der Duktilität beziehungsweise Verringerung der Sprödigkeit können in die Risse duktile Metalle oder Metallegierungen aus Zinn, Titan oder Bronze eingelagert sein. Ebenso kann die Neigung von Chrom zu adhäsivem Verschleiß durch eingelagerte Molybdänteilchen verringert werden.Solid particles made of aluminum oxide, boron carbide, boron nitride, chromium carbide, silicon dioxide, titanium carbide, diamond and / or tungsten carbide can be used as solid particles to improve wear resistance. Such chromium layers containing solids are then particularly suitable for the tread coating of piston rings or cylinder liners in internal combustion engines. The solid lubricant particles used consist of hexagonal boron nitride, graphite and / or polymer particles, especially polyvinyl chloride and / or polytetrafluoroethylene, and to improve ductility or reduce brittleness, ductile metals or metal alloys made of tin can be found in the cracks. Titanium or bronze can be stored. The tendency of chrome to adhesive wear can also be reduced by embedded molybdenum particles.

Gefunden wurde aber auch, daß die Farbe der erfindungsgemäßen Chromschichten mit in den Rissen eingelagerten organischen Farbstoffen oder gefärbten Metallsalzen beeinflußt werden kann. Gefunden wurde ferner, daß durch die Ausfüllung der Risse mit Feststoffteilchen die Korrosionsfestigkeit der Schichten erhöht wurde. Bevorzugt wurden die Risse dazu mit Polyvinylchloridteilchen gefüllt, und das Polyvinylchlorid wurde anschließend in den Rissen aufgeschmolzen, so daß die Risse damit versiegelt und gegenüber korrosiven Angriffen geschützt sind.However, it was also found that the color of the chrome layers according to the invention can be influenced by organic dyes or colored metal salts embedded in the cracks. It was also found that filling the cracks with solid particles increased the corrosion resistance of the layers. For this purpose, the cracks were preferably filled with polyvinyl chloride particles, and the polyvinyl chloride was then melted into the cracks, so that the cracks were sealed and protected against corrosive attacks.

Im Sinne der Erfindung können dabei Feststoffteilchen einer Stoffart oder merherer Stoffarten in Kombination zur Füllung der Risse verwendet sein, so daß gleichzeitig mehrere physikalische Eigenschaften verbessert sind. Ebenso brauchen die Risse nicht vollständig mit den Feststoffteilchen ausgefüllt sein. Im Sinne der Erfindung ist es darüberhinaus auch möglich, die Risse in den einzelnen Schichtlagen mit verschiedenen Festschmierstoffarten zu füllen. So können Risse der Chromschichtzonen unmittelbar am Substrat ,mit einer korrosionsverhindernden Substanz gefüllt sein, während die Risse der äußeren Chromschichtzonen mit Verschleißpartikeln oder Gleitsubstanzen gefüllt sind beziehungsweise sogar partikelfrei sind, so daß korrosionsgeschützte Schichten mit gleichzeitigen guten Verschleiß- und Gleiteigenschaften entstehen. Ebenso können die äußersten Zonen zusätzlich mit einer den Einlauf fördernden Substanz, wie elementarem Zinn oder Eisenoxid, gefüllt sein.For the purposes of the invention, solid particles of one or more types of substance can be used in combination to fill the cracks, so that several physical properties are improved at the same time. Likewise, the cracks need not be completely filled with the solid particles. In the sense of the invention, it is also possible to fill the cracks in the individual layer layers with different types of solid lubricants. For example, cracks in the chrome layer zones directly on the substrate can be filled with a corrosion-preventing substance, while the cracks in the outer chrome layer zones are filled with wear particles or sliding substances or are even particle-free, so that corrosion-protected layers with good wear and sliding properties are created. Just the outermost zones can additionally be filled with a substance that promotes enema, such as elemental tin or iron oxide.

Zur Herstellung der erfindungsgemäßen Chromschichten werden an und für sich bekannte mikrorißbildende Verchromungsbäder, wie bevorzugt saure Chromsäurebäder, mit darin dispergierten Feststoffteilchen verwendet. Während des Verchromens wird dann das zu verchromende Werkstück zunächst kathodisch geschaltet, so daß sich eine mikrorissige Chromschicht bildet, danach wird das Werkstück anodisch geschaltet, so daß sich die Mikrorisse auf die gewünschte Spaltbreite aufweiten und die Risse sich mit den Feststoffpartikeln füllen und anschließend erfolgt wiederum eine kathodische Schaltung, so daß die Feststoffteilchen durch Schließung der Risse eingekapselt und eingeschlossen werden. Diese periodische Stromumkehr kann gegebenenfalls mehrfach wiederholt werden, wobei der Fachmann die Verchromungsparameter entsprechend dem Anwendungsfall so variieren kann, daß die gewünschte Rißbreite, Rißdichte und Rißfüllung mit gegebenenfalls unterschiedlichen Feststoffpartikelfüllungen entstehen.In order to produce the chromium layers according to the invention, chromium plating baths which are known per se and are known per se, such as preferably acidic chromic acid baths, with solid particles dispersed therein. During the chrome plating, the workpiece to be chrome plated is first connected cathodically, so that a micro-cracked chrome layer forms, then the workpiece is switched anodically, so that the micro cracks widen to the desired gap width and the cracks fill with the solid particles and then again occurs a cathodic circuit so that the solid particles are encapsulated and sealed by closing the cracks. This periodic current reversal can, if necessary, be repeated several times, the person skilled in the art being able to vary the chromium plating parameters in accordance with the application in such a way that the desired crack width, crack density and crack filling are produced with different solid particle fillings, if necessary.

Durch die Erfindung sind somit Hartchromschichten geschaffen, deren physikalische und technologische Eigenschaften durch in die Risse eingelagerte Feststoffpartikel wesentlich verbessert sind. Die Chromschichten können dabei vor allem, wie aufgezeigt, ein verbessertes Verschleißverhalten, bessere Gleiteigenschaften, besseres Einlaufverhalten, bessere Brandspursicherheit, bessere Sicherheit vor Brüchen und Abplatzen und ein besseres Korrosionsverhalten einzeln oder in Kombination besitzen. Im Sinne der Erfindung können alle bekannten chromsäureunlöslichen Feststoffpartikel zur Füllung der Risse verwendet werden.Hard chrome layers are thus created by the invention, the physical and technological properties of which are significantly improved by solid particles embedded in the cracks. The chrome layers can above all, as shown, an improved wear behavior, better sliding properties, better running-in behavior, better fire protection, better Have security against breakage and chipping and better corrosion behavior individually or in combination. For the purposes of the invention, all known chromic acid-insoluble solid particles can be used to fill the cracks.

Das erfindungsgemäße Verfahren zur Herstellung der Chromschichten ist relativ einfach durchzuführen und erlaubt es dem Fachmann, universell durch Variation der Verchromungsparameter die gewünschten und auf den Anwendungsfall abgestimmten Eigenschaften zu erzeugen.The method according to the invention for producing the chromium layers is relatively simple to carry out and allows the person skilled in the art to produce the desired properties universally by varying the chromium plating parameters and adapted to the application.

Die Erfindung wird durch die Ausführungsbeispiele und die Schliffbilder näher erläutert.The invention is illustrated by the exemplary embodiments and the micrographs.

Ausgegangen wird von einem mikrorißbildenden Verchromungselektrolyten mit

  • 250 g/1 Chromsäure und
  • 2,5 g/1 Schwefelsäure,
  • in dem durch Rühren 50 g/1 Feststoffteilchen mit einer Korngröße zwischen 0,5 und 5 um dispergiert und während des Verchromens in Schwebe gehalten wird.
The starting point is a micro-cracking chromium plating electrolyte
  • 250 g / 1 chromic acid and
  • 2.5 g / 1 sulfuric acid,
  • in which 50 g / 1 of solid particles with a particle size between 0.5 and 5 µm are dispersed by stirring and kept in suspension during the chrome plating.

Das Verchromen erfolgt insgesamt während ca. 5 Stunden bei 55°C unter Bildung einer Chromschicht von insgesamt 0,2 mm Dicke.The chrome plating takes place for a total of about 5 hours at 55 ° C. with the formation of a chrome layer with a total thickness of 0.2 mm.

Zum Verchromen wird ein Teststab (Durchmesser 12 mm) von 5 cm Länge und 5 cm Breite zunächst 30 Minuten bei 65 A/dm* kathodisch verchromt und anschließend erfolgt das anodische Ätzen der Schicht durch anodische Schaltung des Teststabes für 30 sec mit einer Stromdichte von 150 A/dmt. Dieses periodische Verchromen erfolgt in insgesamt 10 Stufen, wobei das Verchromen und Ätzen unter den gleichen Verfahrensparametern erfolgt.For chrome plating, a test rod (diameter 12 mm) 5 cm long and 5 cm wide is first used for 30 minutes 65 A / dm * chrome-plated and then the anodic etching of the layer is carried out by anodically switching the test rod for 30 sec with a current density of 150 A / dm t . This periodic chrome plating takes place in a total of 10 stages, the chrome plating and etching taking place under the same process parameters.

In Testversuchen wurden zur Herstellung von

  • a) Verschleißschichten Siliziumkarbidteilchen verwendet
  • b) Gleitschichten mit verbessertem Einlaufverhalten wurden mit hexagonalen Bornitridpartikeln hergestellt.
  • c) Zur Herstellung von Schichten mit verbessertem Korrosionsverhalten wurden Polyvinylchloridteilchen eingesetzt, wobei das Polymer in der fertigen Schicht über 10 Minuten bei 80°C zum Aufschmelzen erhitzt wurde.
  • d) Zur Herstellung von gelben Schichten wurden Bleichromatpartikel verwendet.
In test trials, the production of
  • a) Wear layers of silicon carbide particles used
  • b) Sliding layers with improved run-in behavior were produced with hexagonal boron nitride particles.
  • c) Polyvinyl chloride particles were used to produce layers with improved corrosion behavior, the polymer in the finished layer being heated to melt at 80 ° C. for 10 minutes.
  • d) Lead chromate particles were used to produce yellow layers.

In den hergestellten Teststäbchen wurden entsprechend verbesserte technologische und physikalische Eigenschaften festgestellt.Improved technological and physical properties were found in the test strips produced.

Die drei Schliffbilder zeigen rasterelektronenmikroskopische Aufnahmen der erfindungsgemäßen Hartchromschichten nach dem Ausführungsbeispiel.The three micrographs show scanning electron micrographs of the hard chrome layers according to the invention according to the exemplary embodiment.

  • Figur 1 ist dabei ein Oberflächenschliffbild in tausendfacher Vergrößerung,FIG. 1 is a surface micrograph in a thousand times magnification,
  • Figur 2 ein Querschliffbild in tausendfacher Vergrößerung,FIG. 2 shows a cross section in a magnification of a thousand times,
  • Figur 3 ein Schrägschliffbild in viertausendfacher Vergrößerung.Figure 3 is an oblique section in four thousand times magnification.

In Figur 1 sind die spinnwebenartig durch die Chromschicht sich erstreckenden Risse zu erkennen. Als helle Teilchen sind die in den Rissen eingelagerten Siliziumkarbidteilchen zu erkennen.The cracks extending through the chrome layer in the manner of a cobweb can be seen in FIG. The silicon carbide particles embedded in the cracks can be recognized as bright particles.

Das Querschliffbild der Figur 2 zeigt die Querschnitte der Risse, die sich etwa rechtwinklig zur Oberfläche erstrecken. Die Risse sind durch die periodische Stromumkehr während des Verchromens durch darüber gebildete Chromschichten verschlossen, so daß die eingelagerten hellen Siliziumdioxidteilchen in den Rissen eingekapselt sind.The cross section of Figure 2 shows the cross sections of the cracks, which extend approximately at right angles to the surface. The cracks are closed by the periodic reversal of the current during chrome plating by chrome layers formed over it, so that the embedded bright silicon dioxide particles are encapsulated in the cracks.

Im Schrägschliffbild der Figur 3 ist bei viertausendfacher Vergrößerung zu erkennen, wie die Siliziumkarbidpartikel in den Rissen durch nachträglich abgeschiedenes Chrom teilweise umhüllt und verankert sind.In the oblique section of FIG. 3, at a magnification of four thousand times, it can be seen how the silicon carbide particles in the cracks are partially covered and anchored by subsequently deposited chromium.

Claims (17)

1. Galvanische Hartchromschicht mit einem durch die gesamte Schichtdicke sich erstreckenden Rißnetzwerk, dadurch gekennzeichnet, daß in die Risse Feststoffpartikel eingelagert sind.1. Galvanic hard chrome layer with a crack network extending through the entire layer thickness, characterized in that solid particles are embedded in the cracks. 2. Hartchromschicht nach Anspruch 1, dadurch gekennzeichnet, daß die Dicke der Hartchromschicht zwischen 0,01 und 1,0 mm beträgt.2. Hard chrome layer according to claim 1, characterized in that the thickness of the hard chrome layer is between 0.01 and 1.0 mm. 3. Hartchromschicht nach einen der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die Spaltbreite der Risse größer als 0,001 mm ist.3. Hard chrome layer according to one of claims 1 or 2, characterized in that the gap width of the cracks is greater than 0.001 mm. 4. Hartchromschicht nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Korngröße der eingelagerten Feststoffpartikel zwischen 0,0005 und 0,015 mm beträgt.4. Hard chrome layer according to one of claims 1 to 3, characterized in that the grain size of the embedded solid particles is between 0.0005 and 0.015 mm. 5. Hartchromschicht nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß zur Erhöhung der Verschleißfestigkeit in die Risse als Feststoffpartikel Hartstoffpartikel eingelagert sind.5. hard chrome layer according to at least one of claims 1 to 4, characterized in that hard particles are embedded as solid particles to increase the wear resistance in the cracks. 6. Hartchromschicht nach Anspruch 5, dadurch gekennzeichnet, daß die Hartstoffpartikel aus Wolframkarbid, Chromkarbid, Aluminiumoxid, Siliziumkarbid, Siliziumnitrid, Borkarbid und/oder Diamant bestehen.6. hard chrome layer according to claim 5, characterized in that the hard material particles consist of tungsten carbide, chromium carbide, aluminum oxide, silicon carbide, silicon nitride, boron carbide and / or diamond. 7. Hartchromschicht nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß zur Erhöhung der Gleiteigenschaften in die Risse als Feststoffpartikel Festschmierstoffpartikel eingelagert sind.7. hard chrome layer according to at least one of claims 1 to 4, characterized in that solid lubricant particles are incorporated as solid particles to increase the sliding properties in the cracks. 8. Hartchromschicht nach Anspruch 7, dadurch gekennzeichnet, daß die Festschmierstoffpartikel aus Graphit, hexagonalem Bornitrid und/oder Polytetrafluorethylen bestehen.8. hard chrome layer according to claim 7, characterized in that the solid lubricant particles consist of graphite, hexagonal boron nitride and / or polytetrafluoroethylene. 9. Hartchromschicht nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß zur Erhöhung der Duktilität in die Risse als Feststoffpartikel duktile Metalle und/oder Metallegierungen eingelagert sind.9. hard chrome layer according to at least one of claims 1 to 4, characterized in that ductile metals and / or metal alloys are incorporated as solid particles to increase the ductility in the cracks. 10. Hartchromschicht nach Anspruch 9, dadurch gekennzeichnet, daß die duktilen Metalle und/oder Metalllegierungen aus Titan, Zinn und/oder Bronze bestehen.10. Hard chrome layer according to claim 9, characterized in that the ductile metals and / or metal alloys consist of titanium, tin and / or bronze. 11. Hartchromschicht nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß zur Erhöhung der Korrosionsfestigkeit in die Risse als Feststoffpartikel thermoplastische Polymere eingelagert sind, und daß die Thermoplasten nach der Einlagerung in die Risse aufgeschmolzen sind.11. Hard chrome layer according to at least one of claims 1 to 4, characterized in that to increase the corrosion resistance, thermoplastic polymers are embedded in the cracks as solid particles, and that the thermoplastics are melted after being stored in the cracks. 12. Hartchromschicht nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß in die Risse als Feststoffpartikel organische und/oder anorganische Farbstoffe eingelagert sind.12. Hard chrome layer according to at least one of claims 1 to 4, characterized in that organic and / or inorganic dyes are embedded in the cracks as solid particles. 13. Hartchromschicht nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß in die Risse als Feststoffpartikel Gemische aus mindestens zwei Komponenten von Hartstoffpartikeln, Festschmierstoffpartikeln, Metallen, Metallegierungen, organischen Thermoplasten und/oder organischen und anorganischen Farbstoffen eingelagert sind.13. Hard chrome layer according to at least one of claims 1 to 4, characterized in that mixtures of at least two components of hard material particles, solid lubricant particles, metals, metal alloys, organic thermoplastics and / or organic and inorganic dyes are embedded in the cracks as solid particles. 14. Hartchromschicht nach mindestens einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß die Chromschicht aus mehreren Chromschichtlagen besteht, in deren Risse unterschiedliche Feststoffe oder Feststoffgemische eingelagert sind.14. hard chrome layer according to at least one of claims 1 to 13, characterized in that the chrome layer consists of several layers of chrome layers, in the cracks of which different solids or solid mixtures are embedded. 15. Hartchromschicht nach mindestens einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß die Risse der einzelnen Chromschichtlagen unterschiedlich stark mit Feststoffpartikel gefüllt sind.15. hard chrome layer according to at least one of claims 1 to 14, characterized in that the cracks of the individual chrome layer layers are filled to different extents with solid particles. 16. Verfahren zur Herstellung der Hartchromschichten nach mindestens einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß die Verchromung mit einem mikrorißbildenden Verchromungselektrolyten erfolgt, in dem die Feststoffpartikel durch Rühren und/oder Lufteinblasen in Schwebe gehalten sind, und daß während der Verchromung das zu verchromende Werkstück ein- oder mehrfach anodisch geschaltet wird.16. A method for producing the hard chrome layers according to at least one of claims 1 to 15, characterized in that the chrome plating is carried out with a micro-cracking chromium plating electrolyte in which the solid particles are stirred and / or air blowing are kept in suspension and that during the chrome plating the workpiece to be chromed is switched one or more times anodically. 17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß die Zeit der kathodischen Schaltung des Werkstückes um ein Vielfaches größer ist als die Zeit der anodischen Schaltung des Werkstückes.17. The method according to claim 16, characterized in that the time of the cathodic circuit of the workpiece is many times greater than the time of the anodic circuit of the workpiece.
EP86111775A 1985-09-03 1986-08-26 Galvanic hard chromium layer Expired - Lifetime EP0217126B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853531410 DE3531410A1 (en) 1985-09-03 1985-09-03 GALVANIC HARD CHROME LAYER
DE3531410 1985-09-03

Publications (2)

Publication Number Publication Date
EP0217126A1 true EP0217126A1 (en) 1987-04-08
EP0217126B1 EP0217126B1 (en) 1990-07-04

Family

ID=6280017

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86111775A Expired - Lifetime EP0217126B1 (en) 1985-09-03 1986-08-26 Galvanic hard chromium layer

Country Status (7)

Country Link
US (1) US4846940A (en)
EP (1) EP0217126B1 (en)
JP (1) JP2602499B2 (en)
BR (1) BR8604205A (en)
DE (2) DE3531410A1 (en)
ES (1) ES2001645A6 (en)
HK (1) HK115395A (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0668375A1 (en) * 1994-02-18 1995-08-23 INDUSTRIALE S.r.l. Process for forming composite galvanic coatings of hard chromium with a disperse phase, and wear-resistant coating formed thereby
EP0709496A1 (en) 1994-10-28 1996-05-01 Perfect Circle Europe Process for electroplating a chromium layer containing solid particles and bath used in this process
DE19745811A1 (en) * 1997-10-16 1999-04-22 Federal Mogul Burscheid Gmbh Galvanic hard chrome layer
EP0924319A2 (en) * 1997-11-28 1999-06-23 Federal-Mogul Burscheid GmbH Process for manufacturing a piston oil scraping ring
US6503642B1 (en) 1999-07-08 2003-01-07 Federal Mogul Burscheid Gmbh Hard-chrome plated layer
DE102007037778A1 (en) 2007-08-10 2009-02-12 Mahle International Gmbh Hard chrome layer, coated substrate and tribological system
DE102007038188A1 (en) 2007-08-13 2009-02-19 Federal-Mogul Burscheid Gmbh Coated machine element e.g. piston ring with a surface useful in internal combustion engine, comprises a structured hard chrome layer, a physical vapor deposition- or a chemical vapor deposition layer, and a chromium-solid particle layer
DE102008017270B3 (en) * 2008-04-04 2009-06-04 Federal-Mogul Burscheid Gmbh Structured chromium solid particle layer and method for its production and coated machine element
US8110087B2 (en) 2004-04-21 2012-02-07 Federal-Mogul Burscheid Gmbh Production of a structured hard chromium layer and production of a coating
US8277953B2 (en) 2002-11-29 2012-10-02 Federal-Mogul Burscheid Gmbh Production of structured hard chrome layers
DE102011084052A1 (en) 2011-10-05 2013-04-11 Federal-Mogul Burscheid Gmbh Coated piston ring for use in combustion engine such as reciprocating piston engine, has base body whose outer circumferential surface and flank surface form outer edge, which exhibits ridge or ablation having specific range width
DE102011084051A1 (en) 2011-10-05 2013-04-11 Federal-Mogul Burscheid Gmbh Coated piston ring for use in internal combustion engine, has metallic base unit with outer peripheral surface and flank surfaces that are provided partly with electrochemically deposited metallic wear protection layer
DE102012204156A1 (en) 2012-03-16 2013-09-19 Federal-Mogul Burscheid Gmbh Piston ring with chrome solid particle wear protection layer and corrosion resistant flank surface
CN103403229A (en) * 2010-12-27 2013-11-20 日本活塞环株式会社 Composite chromium plating film, and sliding member equipped with the film
WO2015049562A1 (en) * 2013-10-03 2015-04-09 Bräcker Ag Spinning or twisting ring
EP3754050A1 (en) * 2019-06-20 2020-12-23 Hamilton Sundstrand Corporation Wear-resistant coating
DE102020105003A1 (en) 2020-02-26 2021-08-26 Federal-Mogul Burscheid Gmbh Piston ring with hard chrome layer and improved run-in behavior
DE102021125366A1 (en) 2021-09-30 2023-03-30 Federal-Mogul Burscheid Gmbh Wear protection layer for piston rings

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63168074U (en) * 1987-04-20 1988-11-01
GB9103481D0 (en) * 1991-02-20 1991-04-10 T & N Technology Ltd Bearings
US5770323A (en) * 1991-02-20 1998-06-23 T & N Technology Limited Bearings
US5453293A (en) * 1991-07-17 1995-09-26 Beane; Alan F. Methods of manufacturing coated particles having desired values of intrinsic properties and methods of applying the coated particles to objects
US5614320A (en) * 1991-07-17 1997-03-25 Beane; Alan F. Particles having engineered properties
US5490445A (en) * 1994-03-14 1996-02-13 Ford Motor Company Ultra low device volume piston system
DE19529843A1 (en) * 1995-08-12 1997-02-13 Marco Santini Galvanic chrome plating process
DE69711722T2 (en) * 1996-11-11 2002-08-08 Teikoku Piston Ring Co Ltd Galvanic composite chrome coating and thus coated sliding part
DE69704752T3 (en) * 1996-11-11 2005-08-04 Teikoku Piston Ring Co., Ltd. Galvanic composite chromium coating and coated sliding part
US6039860A (en) * 1998-11-09 2000-03-21 Mcdonnell Douglas Corporation Method for chromium plating titanium alloy
DE69930191T2 (en) * 1998-12-03 2006-08-03 Yamaha Hatsudoki K.K., Iwata Coated brake disc and method of making same
SE514700C2 (en) 1999-03-19 2001-04-02 Daros Holding Ab Electrolytic coating of a substrate with a ceramic chrome layer, ceramic chrome layer and piston ring
US20020197504A1 (en) * 1999-12-27 2002-12-26 Hiroyuki Takamura Sliding member
AT408351B (en) * 2000-05-17 2001-11-26 Miba Gleitlager Ag METHOD FOR GALVANICALLY DEPOSITING A DISPERSION LAYER ON A SURFACE OF A WORKPIECE
JP4059621B2 (en) * 2000-09-29 2008-03-12 日本ピストンリング株式会社 Chromium plating sliding member and manufacturing method thereof
DE10121593A1 (en) 2001-05-03 2002-11-07 Duralloy Ag Haerkingen Process for coating workpieces with a bearing metal
JP4068879B2 (en) * 2001-08-21 2008-03-26 株式会社神戸製鋼所 Metal parts with excellent antibacterial and / or algal resistance
BRPI0507291A2 (en) 2004-01-30 2009-01-13 Riken Kk composite chrome plating film and sliding component with it and its production method
CN100359048C (en) * 2004-12-27 2008-01-02 西安建筑科技大学 Conductor roll restoring method
DE102005023627B4 (en) * 2005-05-21 2010-05-06 Federal-Mogul Burscheid Gmbh Steel Kolbe ring
US7383807B2 (en) * 2005-05-23 2008-06-10 Federal-Mogul World Wide, Inc. Coated power cylinder components for diesel engines
JP4757778B2 (en) * 2006-11-10 2011-08-24 電気化学工業株式会社 Silicon nitride powder, production method and use thereof
DE102008036996B4 (en) * 2008-08-07 2010-09-02 Federal-Mogul Burscheid Gmbh Sliding and / or counter ring of a drive seal
JP6569178B2 (en) * 2015-10-08 2019-09-04 地方独立行政法人大阪産業技術研究所 Article having composite hard coating and method for producing the same
US9945481B2 (en) 2016-07-07 2018-04-17 Federal-Mogul Llc Polymer coating in cracked piston ring coating
DE102017221606A1 (en) 2017-11-30 2019-06-06 Federal-Mogul Burscheid Gmbh piston ring
US10864567B2 (en) 2018-04-17 2020-12-15 Government Of The United States As Represented By The Secretary Of The Army Systems and methods for electroprocessing a gun barrel using a moving electrode

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1070343A (en) * 1965-01-27 1967-06-01 British Iron Steel Research Improvements in or relating to the formation of metal coatings by electro-deposition
US3356467A (en) * 1964-12-28 1967-12-05 Udylite Corp Article coated with a coelectrodeposit of nickel and plastic particles, an overlayerthereon, and method of making said article
DE2146908A1 (en) * 1970-09-21 1972-03-23 Toyota Motor Co Ltd Process for the simultaneous electrolytic deposition of a fluorine-containing resin and a metal on the surface of an object
US3844910A (en) * 1972-07-25 1974-10-29 Kempten Elektroschmelz Gmbh Process for the production of metal coatings

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE652909A (en) * 1963-12-18 1964-12-31
GB1220331A (en) * 1967-04-27 1971-01-27 Bristol Aerojet Ltd Improvements in and relating to the electro-deposition of composite coatings
US3762882A (en) * 1971-06-23 1973-10-02 Di Coat Corp Wear resistant diamond coating and method of application
JPS5315011B2 (en) * 1972-06-03 1978-05-22
JPS533446B2 (en) * 1973-11-01 1978-02-07

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356467A (en) * 1964-12-28 1967-12-05 Udylite Corp Article coated with a coelectrodeposit of nickel and plastic particles, an overlayerthereon, and method of making said article
GB1070343A (en) * 1965-01-27 1967-06-01 British Iron Steel Research Improvements in or relating to the formation of metal coatings by electro-deposition
DE2146908A1 (en) * 1970-09-21 1972-03-23 Toyota Motor Co Ltd Process for the simultaneous electrolytic deposition of a fluorine-containing resin and a metal on the surface of an object
US3844910A (en) * 1972-07-25 1974-10-29 Kempten Elektroschmelz Gmbh Process for the production of metal coatings

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0668375A1 (en) * 1994-02-18 1995-08-23 INDUSTRIALE S.r.l. Process for forming composite galvanic coatings of hard chromium with a disperse phase, and wear-resistant coating formed thereby
EP0709496A1 (en) 1994-10-28 1996-05-01 Perfect Circle Europe Process for electroplating a chromium layer containing solid particles and bath used in this process
US5868917A (en) * 1994-10-28 1999-02-09 Floquet Monopole Process for the electrodeposition of a chromium coating containing solid inclusions and plating solution employed in this process
DE19745811C2 (en) * 1997-10-16 2002-06-13 Federal Mogul Burscheid Gmbh Electroplated hard chrome layer, use and method for the production thereof
DE19745811A1 (en) * 1997-10-16 1999-04-22 Federal Mogul Burscheid Gmbh Galvanic hard chrome layer
EP0924319A3 (en) * 1997-11-28 2006-05-10 Federal-Mogul Burscheid GmbH Process for manufacturing a piston oil scraping ring
US6199274B1 (en) 1997-11-28 2001-03-13 Federal-Mogul Burscheid Gmbh Method of making oil scraper piston rings
EP0924319A2 (en) * 1997-11-28 1999-06-23 Federal-Mogul Burscheid GmbH Process for manufacturing a piston oil scraping ring
US6503642B1 (en) 1999-07-08 2003-01-07 Federal Mogul Burscheid Gmbh Hard-chrome plated layer
US8277953B2 (en) 2002-11-29 2012-10-02 Federal-Mogul Burscheid Gmbh Production of structured hard chrome layers
US8110087B2 (en) 2004-04-21 2012-02-07 Federal-Mogul Burscheid Gmbh Production of a structured hard chromium layer and production of a coating
DE102007037778A1 (en) 2007-08-10 2009-02-12 Mahle International Gmbh Hard chrome layer, coated substrate and tribological system
WO2009021494A1 (en) 2007-08-10 2009-02-19 Mahle International Gmbh Hard chrome layer, coated substrate and tribological system
DE102007038188A1 (en) 2007-08-13 2009-02-19 Federal-Mogul Burscheid Gmbh Coated machine element e.g. piston ring with a surface useful in internal combustion engine, comprises a structured hard chrome layer, a physical vapor deposition- or a chemical vapor deposition layer, and a chromium-solid particle layer
DE102008017270B3 (en) * 2008-04-04 2009-06-04 Federal-Mogul Burscheid Gmbh Structured chromium solid particle layer and method for its production and coated machine element
US8337687B2 (en) 2008-04-04 2012-12-25 Federal-Mogul Burscheid Gmbh Structured chrome solid particle layer and method for the production thereof
CN103403229A (en) * 2010-12-27 2013-11-20 日本活塞环株式会社 Composite chromium plating film, and sliding member equipped with the film
CN103403229B (en) * 2010-12-27 2016-05-25 日本活塞环株式会社 Composite chrome plating overlay film and use the slide unit of this overlay film
DE102011084052A1 (en) 2011-10-05 2013-04-11 Federal-Mogul Burscheid Gmbh Coated piston ring for use in combustion engine such as reciprocating piston engine, has base body whose outer circumferential surface and flank surface form outer edge, which exhibits ridge or ablation having specific range width
DE102011084052B4 (en) 2011-10-05 2024-05-29 Federal-Mogul Burscheid Gmbh Coated piston ring with sharp oil scraper edge
DE102011084051A1 (en) 2011-10-05 2013-04-11 Federal-Mogul Burscheid Gmbh Coated piston ring for use in internal combustion engine, has metallic base unit with outer peripheral surface and flank surfaces that are provided partly with electrochemically deposited metallic wear protection layer
DE102011084051B4 (en) * 2011-10-05 2020-03-12 Federal-Mogul Burscheid Gmbh Coated piston ring with radially increasing layer thickness and process for its production
DE102012204156A1 (en) 2012-03-16 2013-09-19 Federal-Mogul Burscheid Gmbh Piston ring with chrome solid particle wear protection layer and corrosion resistant flank surface
US9404578B2 (en) 2012-03-16 2016-08-02 Federal-Mogul Burscheid Gmbh Piston ring with chromium solid particle wear-prevention layer and corrosion-resistant flank surface
WO2013135325A1 (en) 2012-03-16 2013-09-19 Federal-Mogul Burscheid Gmbh Piston ring with chromium solid particle wear-prevention layer and corrosion-resistant flank surface
WO2015049562A1 (en) * 2013-10-03 2015-04-09 Bräcker Ag Spinning or twisting ring
EP3754050A1 (en) * 2019-06-20 2020-12-23 Hamilton Sundstrand Corporation Wear-resistant coating
US11230777B2 (en) 2019-06-20 2022-01-25 Hamilton Sundstrand Corporation Wear-resistant coating
WO2021170460A1 (en) 2020-02-26 2021-09-02 Federal-Mogul Burscheid Gmbh Piston ring having a hard chromium layer and improved run-in behavior
DE102020105003A1 (en) 2020-02-26 2021-08-26 Federal-Mogul Burscheid Gmbh Piston ring with hard chrome layer and improved run-in behavior
DE102021125366A1 (en) 2021-09-30 2023-03-30 Federal-Mogul Burscheid Gmbh Wear protection layer for piston rings
WO2023052452A1 (en) 2021-09-30 2023-04-06 Federal-Mogul Burscheid Gmbh Piston ring having a wear protection layer containing particles, method for production and use

Also Published As

Publication number Publication date
JPS6256600A (en) 1987-03-12
BR8604205A (en) 1987-04-28
DE3672431D1 (en) 1990-08-09
US4846940A (en) 1989-07-11
DE3531410C2 (en) 1989-03-23
ES2001645A6 (en) 1988-06-01
DE3531410A1 (en) 1987-03-05
HK115395A (en) 1995-07-21
EP0217126B1 (en) 1990-07-04
JP2602499B2 (en) 1997-04-23

Similar Documents

Publication Publication Date Title
EP0217126B1 (en) Galvanic hard chromium layer
EP1114209B1 (en) Hard-chrome plated layer
CH624860A5 (en)
DE102012108057B4 (en) Method of manufacturing a last stage steam turbine blade
DE102004020385B4 (en) Method for producing plain bearing bushes
DE10301135B4 (en) Object with a wear protection layer
DE3038289A1 (en) METHOD FOR DEPOSITING METAL LAYERS ON THE WALLS OF CHILLERS
DE3220723C2 (en)
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
DE10159890B4 (en) Process for coating aluminum materials with functional layers of iron
EP1561843A2 (en) Process for the production of corrosion resistant and decorative coatings and coating systems for substrates of light-metal or light-metal alloys
EP2180088B1 (en) Method for electroplating hard chrome layers
EP1117856B1 (en) Method for coating workpieces
DE102014003114B3 (en) Process for coating a substrate, in which a wire-shaped spray material is melted in an arc and deposited as a layer on the substrate, as well as a wire arc sprayed layer
EP0909839B1 (en) Galvanic hard chromium layer
EP1997939B1 (en) Hydraulic cylinders and manufacturing method
DE102007028211A1 (en) Process for the preparation of a silver-structured coated sliding element and then available sliding element
DE112009000062B4 (en) Coated aluminum product
DE19508419C1 (en) Piston ring for internal combustion engines with a wear-resistant coating
DE19517065B4 (en) Casting mold for continuous casting
DE3741292C2 (en)
DE10212299A1 (en) Production of a component with a protective layer comprises applying a coating produced by a thermal spray process onto a galvanically deposited hard chromium layer and a cover layer functioning as an intermediate layer
DE112006000290T5 (en) An article with improved resistance to zinc erosion
DE102005022692A1 (en) Process for the preparation of coated surfaces and use thereof
DE3536525A1 (en) Metallic heat transfer surface for boiling liquids

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: 19870909

17Q First examination report despatched

Effective date: 19881213

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. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 3672431

Country of ref document: DE

Date of ref document: 19900809

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ET Fr: translation filed
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
ITTA It: last paid annual fee
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

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

Ref country code: GB

Payment date: 20000720

Year of fee payment: 15

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010826

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

Effective date: 20010826

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

Ref country code: FR

Payment date: 20050804

Year of fee payment: 20

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

Ref country code: IT

Payment date: 20050816

Year of fee payment: 20

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

Ref country code: DE

Payment date: 20050831

Year of fee payment: 20