EP1738000B1 - Production of a structured hard chromium layer and production of a coating - Google Patents

Production of a structured hard chromium layer and production of a coating Download PDF

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Publication number
EP1738000B1
EP1738000B1 EP05700700.7A EP05700700A EP1738000B1 EP 1738000 B1 EP1738000 B1 EP 1738000B1 EP 05700700 A EP05700700 A EP 05700700A EP 1738000 B1 EP1738000 B1 EP 1738000B1
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EP
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Prior art keywords
layer
structured
chromium layer
workpiece
structured hard
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EP05700700.7A
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German (de)
French (fr)
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EP1738000A2 (en
Inventor
Rudolf Linde
Stefan Dürdoth
Wolfgang Stuckert
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Federal Mogul Burscheid GmbH
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Federal Mogul Burscheid GmbH
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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the invention relates to a method for producing a structured hard chrome layer on a workpiece, a method for producing a coating with a structured hard chrome layer, structured hard chrome layers and coatings obtainable thereby, and an electrolyte for carrying out the method.
  • Electrochemically produced hard chrome coatings are not only used for decorative finishing of surfaces. Rather, hard chrome layers are also applied as functional coatings on conductive and non-conductive workpieces, for example, to exercise a protective function or to influence the surface properties low. Typical applications are therefore protective coatings of hard chrome to reduce corrosion, wear or friction, and structured hard chrome layers on printing rollers to facilitate the wetting with printing inks or on stamping, embossing and thermoforming tools to optimize manufacturing processes in the industry.
  • EP 0 196 053 A2 and DE 34 02 554 A1 describe in each case processes for the electrodeposition of hard chromium on metallic surfaces from an aqueous, chromic acid, sulfuric acid or sulfate and a sulfonic acid-containing electrolyte, wherein working with cathodic current efficiencies ⁇ 20%. Due to the composition of the electrolyte, the risk of disruptive etching of the surface to be coated should be excluded. However, no structures are created in the hard chrome layer.
  • GB 2 153 387 A1 describes a method for depositing hard chrome on workpieces of metal alloys from an aqueous electrolyte wherein the electrolyte contains chromic acid and sulfuric acid and an organic compound is added in the form of a saturated aliphatic sulfonic acid having a maximum of two carbon atoms and a maximum of six sulfonic acid groups their salts or halogen derivatives and the process is carried out with a concentration of more than 0.5 g / l of the organic substance, at a bath temperature of 20 ° - 70 ° C and a current density of 15 - 100 A / dm second
  • An electrochemical process for producing structured hard chrome layers is known, for example, from US Pat DE 44 32 512 A1 known.
  • the structure of the hard chrome layer is made possible by the addition of salts, such as salts of the elements selenium or tellurium, to the electrolyte.
  • the layers produced have a spherical structure with spherical shapes of a size between less than 1 micron and several microns. This results in a often non-uniform spherical structure of the hard chrome layer, which is not suitable for all applications.
  • the object of the invention is therefore to provide a method for producing a structured hard chrome layer, with which the disadvantages of the prior art are overcome.
  • structured hard chrome layers are produced, which are of cup-shaped and / or labyrinth-like and / or columnar design. This is achieved by a specific influencing of the cathode film forming during the electrochemical deposition, which will be explained below.
  • the electrolytes used in galvanic processes contain salts which dissociate into anions and cations in the aqueous medium.
  • a hydration shell forms around the dissociated ions.
  • hydrated metal ions of the electrolyte migrate to the workpiece to be coated, which is connected as a cathode.
  • cathode film In the boundary region between the electrolyte and cathode directly on the surface of the cathode is the so-called cathode film.
  • a hydrated metal ion enters this phase boundary, it picks up electrons from the cathode and thereby aligns in the diffusion zone.
  • Helmholtz double layer Under this diffusion zone and directly on the cathode surface is formed an electrochemical double layer, the "Helmholtz double layer". This consists of an electrically charged zone at the electrolyte-cathode interface and is about a few atomic or molecular layers thick. Their formation involves ions, electrons or directed dipole molecules. Since the "Helmholtz double layer" is positively charged on one side and negatively charged on the other side, it behaves on the cathode like a plate capacitor with a very small plate spacing.
  • the metal ion In order for the metal ion to get onto the workpiece surface and be incorporated into a growth site on the surface of the workpiece, it must overcome the cathode film.
  • This process can be influenced by a suitable choice of deposition conditions, such as chemical composition of the electrolyte, temperature, hydrodynamics and electric current.
  • the deposition conditions for the electrolyte are selected so that the transmissivity of the cathode film for the metal ion is as uniform as possible.
  • chromium When the element chromium is to be deposited from an aqueous electrolyte on a workpiece, it is in strongly acidic solution as a negatively charged hydrodichromate complex.
  • chromium has the oxidation state 6, although small amounts of chromium (III) compounds may be included.
  • an electrolyte with a chromium (VI) compound in an amount corresponding to 50 to 300 g / l, preferably 50 to 150 g / l, chromic anhydride, 0.5 to 10 g / l sulfuric acid and 5 g / 1 to 15 g / l of aliphatic sulfonic acid having 1 to 6 carbon atoms to form a cathode film having a very dense barrier layer.
  • the barrier layer will strike, resulting in the formation of a layer of chromium of uneven thickness on the workpiece, operating at a cathodic current efficiency of 12% or less.
  • the cathodic current efficiency of 12% or less ensures the formation of the structured hard chrome layer in the method according to the invention, since structuring of the hard chrome layer is not obtained with a higher current efficiency.
  • the structured hard chrome layers produced by the method according to the invention are more uniform than the structured hard chrome layers of the prior art because of the cup-shaped and / or labyrinth-like and / or columnar structure.
  • Structured hard chrome layers obtainable by the process according to the invention are best suited for coating piston rings, in particular those of internal combustion engines.
  • layers produced according to the invention also have outstanding tribological properties, such as good sliding properties and wear and scuffing resistance, in particular in the case of insufficient lubrication.
  • the hard chrome layers obtained according to the invention can be used for many decorative and functional applications.
  • the surface topography of the hard chrome layers produced according to the invention makes it possible, for example, for a high absorption capacity for light and heat radiation when using solar collectors. Furthermore, the special structure of the hard chrome layers according to the invention allows a better absorption capacity for liquids. Also, gas cushions can be well constructed on the textured surface.
  • component (a) ie the Cr (VI) compound, CrO 3 is preferably used, since it is particularly suitable for the electrodeposition.
  • component (c) i.
  • aliphatic sulfonic acid methanesulfonic acid, ethanesulfonic acid, methanedisulfonic acid, or ethanedisulfonic acid are preferably used, which has proven to be particularly favorable for the formation of the advantageous decorative and functional properties of the hard chromium layer produced.
  • the electrolyte may in one embodiment be substantially free of fluorides.
  • the latter often complicate the formation of the structured hard chrome layer. Therefore, only as many fluorides in the electrolyte are tolerable that do not affect the deposition of the structured hard chrome layer. It has proven to be favorable if not more than 0.1 g / l fluorides are present in the electrolyte.
  • conventional catalysts for the separation of chromium such as SO 4 2- and / or Cl - , may be present in the electrolyte in conventional amounts.
  • structured hard chrome layers are deposited on workpieces by the method described above.
  • the term "workpiece” means metallic or non-metallic objects which are to be provided with a structured hard chrome layer.
  • a non-metallic article it is coated with a thin metal film prior to application of the patterned hard chromium layer to render it electrically conductive.
  • the structured hard chrome layer on the workpiece In order to deposit the structured hard chrome layer on the workpiece, the latter is connected as a cathode and immersed in the electrolyte. Then a DC current is applied to the workpiece, e.g. a pulsating direct current with a frequency up to 1000 Hz, applied. During the deposition of the chromium, the temperature is maintained at 45 ° C to 95 ° C, preferably 55 ° C. The longer the deposition is carried out, the greater the layer thickness of the hard chrome layer.
  • a DC current e.g. a pulsating direct current with a frequency up to 1000 Hz
  • the method according to the invention can be used with a current density of 20 A / dm 2 to 200 A / dm 2 .
  • This range of current density leads to the deposition of particularly favorable structured hard chrome layers. The higher the current density is chosen, the denser the protruding areas of the surface of the hard chrome layer according to the invention.
  • a second layer is deposited before and / or after the deposition of the structured hard chromium layer.
  • several layers can be applied to the workpiece, for example a metal layer of a conventional electrolyte on the structured hard chromium layer according to the invention.
  • the two layers may be made of different materials, and when a conventional metal layer is applied to the patterned hard chrome layer, improved anchoring of the conventional metal layer is enabled.
  • a conventional hard chromium layer or a structured hard chromium layer according to the invention can be deposited in each case with inclusions, wherein the inclusions can consist of aluminum oxide, diamond and / or boron nitride of the hexagonal type. In the electrolyte used for these materials are suspended. The deposits lead to a further improvement of the tribological properties.
  • a hard chromium layer according to the invention is applied electrolytically to a conventional hard chrome layer of uniform layer thickness.
  • the invention also relates to a method for producing a coating, wherein chromium is deposited on a workpiece to form a structured hard chrome layer, and to the structured hard chrome layer is applied a composition containing epoxy resin, a solid lubricant, a hard material or mixtures thereof.
  • the structured hard chrome layer may be a structured hard chrome layer produced according to the invention.
  • the epoxy resin serves as a binder to hold the solid lubricant and / or the hard material in the recesses of the patterned hard chrome layer.
  • As a solid lubricant in particular MoS 2 boron nitride, preferably the hexagonal type of boron nitride, or Teflon, or a mixture of two or more of these substances is suitable.
  • hard materials are microscale diamond, alumina, Si 3 N 4 , B 4 C, SiC or a mixture of two or more of these substances.
  • This coating construction not only improves the general wear properties, but also provides excellent runflat properties when MoS 2 is used of the workpiece in case of insufficient lubrication.
  • boron nitride is included in the composition, there is an excellent self-lubrication of the coating so that it can be dispensed depending on the application on the use of other lubricants. If a mixture of two or more of said solid lubricants is used in the composition which is applied to the structured hard chrome layer, the favorable tribological properties mentioned above add up.
  • the invention further comprises a structured hard chrome layer as obtainable by one of the above methods.
  • the invention relates to a coating obtainable by the above process for producing a coating.
  • the electrolyte which may preferably contain the Cr (VI) compound in an amount corresponding to 50 to 150 g / l of chromic anhydride, serves in particular for the electrodeposition of the structured hard chrome layers described in greater detail above on workpieces.
  • FIGS. 1 to 10 show photographs of the hard chrome layers of Examples 1 to 4.
  • the product to be coated is immersed in the electrolyte after a standard pretreatment. At 55 ° C., chromium is deposited on the product part for 30 minutes at a current density of 40 A / dm 2 .
  • the resulting article has a conventional glossy and uniform chrome layer, as in Fig. 1 shown.
  • an electrolyte according to the invention which contains: chromic anhydride CrO 3 200 g / l sulfuric acid H 2 SO 4 3 g / l methane CH 3 SO 3 H (70% pure) 9 ml / l.
  • chromic anhydride CrO 3 200 g / l sulfuric acid H 2 SO 4 3 g / l methane CH 3 SO 3 H 70% pure
  • structured hard chrome layers according to the invention are deposited on workpieces.
  • the current densities are varied as follows: Fig. 2 : 30 A / dm 2 ; Fig. 3 : 40 A / dm 2 ; Fig.
  • Conventional hard chrome layers with deposits of aluminum oxide and structured hard chrome layers according to the invention are alternately deposited on a product part.
  • an electrolyte is used which chromic anhydride CrO 3 100 g / l sulfuric acid H 2 SO 4 3.5 g / l methane CH 3 SO 3 H (70% pure) 6 ml / l contains.
  • the structured hard chrome layers are deposited at a temperature of 60 ° C., a cathodic current efficiency of 10% and a current density of 80 A / dm 2 for 30 minutes. In total, six layers are applied alternately with and without deposits.
  • Fig. 7 and 8th show a typical cross-section of these graded structured chromium layers in different magnifications.
  • the corrosion protection is ensured by the conventional hard chrome layers, while the favorable tribological properties result from the structured hard chrome layers according to the invention.
  • diamond or hexagonal boron nitride can also be incorporated.
  • the resulting graded structured hard chrome layers can be further treated as described in Example 4 to aid the self-lubricating properties of the surface.
  • a patterned hard chrome layer according to the invention produced on a workpiece according to Example 2 the structural valleys or depressions of the surface are filled with a mixture of epoxy resin and boron nitride of the hexagonal type.
  • the photographs of Fig. 9 and 10 illustrate the filling of the recesses of the hard chrome layer.
  • the resulting coating has excellent self-lubricating properties.
  • the additional use of other lubricants can be dispensed with.
  • a workpiece covered with a patterned hard chrome layer prepared according to Example 2 is treated with a mixture of epoxy resin and MoS 2 so that the recesses of the chromium layer are filled with the mixture.
  • the epoxy resin serves as a binder to fix the MoS 2 in the depressions and in part also on the elevations. This results in good wear properties, as well as excellent emergency running properties when a lack of lubrication of the workpiece occurs.
  • an improved corrosion behavior is given.
  • the wells of a patterned hard chrome layer produced on a product part according to Example 2 are filled with a mixture of epoxy resin and microscale diamond, ie diamond granules with a size in the micron range.
  • a mixture of epoxy resin and microscale diamond, ie diamond granules with a size in the micron range are filled with a mixture of epoxy resin and microscale diamond, ie diamond granules with a size in the micron range.
  • a workpiece produced according to Example 5 is additionally treated with a mixture of Example 6.
  • the resulting coating has greatly improved tribological properties, as compared to Examples 5 and 6, e.g. excellent self-lubrication, as well as compared to the untreated structured hard chrome layer more favorable corrosion behavior.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Herstellung einer strukturierten Hartchromschicht auf einem Werkstück, ein Verfahren zur Herstellung einer Beschichtung mit einer strukturierten Hartchromschicht, dadurch erhältliche strukturierte Hartchromschichten und Beschichtungen sowie einen Elektrolyten zur Durchführung der Verfahren.The invention relates to a method for producing a structured hard chrome layer on a workpiece, a method for producing a coating with a structured hard chrome layer, structured hard chrome layers and coatings obtainable thereby, and an electrolyte for carrying out the method.

Elektrochemisch erzeugte Hartchromschichten dienen nicht nur zur dekorativen Veredelung von Oberflächen. Vielmehr werden Hartchromschichten auch als funktionelle Beschichtungen auf leitende und nicht leitende Werkstücke aufgebracht, beispielsweise um eine Schutzfunktion auszuüben oder die Oberflächeneigenschaften günstig zu beeinflussen. Typische Anwendungen sind daher Schutzschichten aus Hartchrom zur Verminderung von Korrosion, Verschleiß oder Reibung, sowie strukturierte Hartchromschichten auf Druckwalzen zur Erleichterung der Benetzung mit Druckfarben oder auf Stanz-, Präge- und Tiefziehwerkzeugen zur Optimierung von Fertigungsprozessen in der Industrie.Electrochemically produced hard chrome coatings are not only used for decorative finishing of surfaces. Rather, hard chrome layers are also applied as functional coatings on conductive and non-conductive workpieces, for example, to exercise a protective function or to influence the surface properties low. Typical applications are therefore protective coatings of hard chrome to reduce corrosion, wear or friction, and structured hard chrome layers on printing rollers to facilitate the wetting with printing inks or on stamping, embossing and thermoforming tools to optimize manufacturing processes in the industry.

EP 0 196 053 A2 und DE 34 02 554 A1 beschreiben jeweils Verfahren zur galvanischen Abscheidung von Hartchrom auf metallischen Oberflächen aus einem wässrigen, Chromsäure, Schwefelsäure bzw. Sulfat und eine Sulfonsäure enthaltenden Elektrolyten, wobei mit kathodischen Stromausbeuten ≥ 20 % gearbeitet wird. Durch die Zusammensetzung des Elektrolyten soll die Gefahr einer störenden Ätzung der zu beschichtenden Oberfläche ausgeschlossen werden. In der Hartchromschicht werden jedoch keine Strukturen erzeugt. EP 0 196 053 A2 and DE 34 02 554 A1 describe in each case processes for the electrodeposition of hard chromium on metallic surfaces from an aqueous, chromic acid, sulfuric acid or sulfate and a sulfonic acid-containing electrolyte, wherein working with cathodic current efficiencies ≥ 20%. Due to the composition of the electrolyte, the risk of disruptive etching of the surface to be coated should be excluded. However, no structures are created in the hard chrome layer.

Ein weiteres elektrochemisches Verfahren zur Abscheidung von Hartchromschichten auf Werkstücken ist aus US 5 196 108 bekannt. Der dabei verwendete Elektrolyt enthält ein Molybdänanion, so dass mit einer hohen kathodischen Stromausbeute gearbeitet werden kann. Eine Strukturierung der Hartchromschicht ist nicht Ziel dieses Verfahrens.Another electrochemical process for the deposition of hard chrome layers on workpieces is out US 5,196,108 known. The electrolyte used contains a Molybdänanion, so that you can work with a high cathodic current efficiency. A structuring of the hard chrome layer is not the aim of this method.

In der GB 2 153 387 A1 wird ein Verfahren zur Abscheidung von Hartchrom auf Werkstücken aus Metalllegierungen aus einem wässrigen Elektrolyt beschrieben, wobei der Elektrolyt Chromsäure und Schwefelsäure enthält und eine organische Verbindung hinzugefügt wird, in Form einer gesättigten aliphatischen Sulfonsäure mit einem Maximum von zwei Kohlenstoffatomen und einem Maximum von sechs Sulfonsäuregruppen oder deren Salze oder Halogenderivate und das Verfahren mit einer Konzentration von mehr als 0,5 g/l der organischen Substanz durchgeführt wird, bei einer Badtemperatur von 20° - 70° C und einer Stromdichte von 15 - 100 A/dm2.In the GB 2 153 387 A1 describes a method for depositing hard chrome on workpieces of metal alloys from an aqueous electrolyte wherein the electrolyte contains chromic acid and sulfuric acid and an organic compound is added in the form of a saturated aliphatic sulfonic acid having a maximum of two carbon atoms and a maximum of six sulfonic acid groups their salts or halogen derivatives and the process is carried out with a concentration of more than 0.5 g / l of the organic substance, at a bath temperature of 20 ° - 70 ° C and a current density of 15 - 100 A / dm second

Ein elektrochemisches Verfahren zur Erzeugung strukturierter Hartchromschichten ist beispielsweise aus der DE 44 32 512 A1 bekannt. Dabei wird die Struktur der Hartchromschicht durch Zugabe von Salzen, wie Salzen der Elemente Selen oder Tellur, zum Elektrolyten ermöglicht. Die erzeugten Schichten besitzen allerdings eine kugelige Struktur mit Kugelformen einer Größe zwischen weniger als 1 µm und mehreren µm. Dadurch resultiert ein oft nicht gleichmäßiger sphärischer Aufbau der Hartchromschicht, der sich nicht für alle Anwendungen eignet.An electrochemical process for producing structured hard chrome layers is known, for example, from US Pat DE 44 32 512 A1 known. The structure of the hard chrome layer is made possible by the addition of salts, such as salts of the elements selenium or tellurium, to the electrolyte. However, the layers produced have a spherical structure with spherical shapes of a size between less than 1 micron and several microns. This results in a often non-uniform spherical structure of the hard chrome layer, which is not suitable for all applications.

Es wäre daher wünschenswert, strukturierte Hartchromschichten herzustellen, die einen gleichmäßigen Aufbau besitzen und hinsichtlich der tribologischen Eigenschaften des Werkstücks Verbesserungen bewirken, wie zum Beispiel verminderter Verschleiß und im Falle einer Mangelschmierung günstige Notlaufeigenschaften.It would therefore be desirable to produce structured hard chromium layers which have a uniform structure and bring about improvements in respect of the tribological properties of the workpiece, such as, for example, reduced wear and, in the case of insufficient lubrication, favorable runflat properties.

Aufgabe der Erfindung ist es somit, ein Verfahren zur Herstellung einer strukturierten Hartchromschicht bereitzustellen, mit denen die Nachteile des Stands der Technik überwunden werden.The object of the invention is therefore to provide a method for producing a structured hard chrome layer, with which the disadvantages of the prior art are overcome.

Erfindungsgemäß wird diese Aufgabe durch ein Verfahren zur Herstellung einer strukturierten Hartchromschicht mit näpfchenförmig und/oder labyrinthartig und/oder säulenförmig ausgebildeten Strukturen auf einem Werkstück, gelöst, wobei Chrom aus einem wässrigen Elektrolyt unter Verwendung von Gleichstrom bei einer Temperatur von 45° - 95° C auf ein Werkstück abgeschieden wird, wobei der Elektrolyt aus

  1. (a) Cr(VI)-Verbindung in einer Menge, die 50 bis 300 g/l Chromsäureanhydrid entspricht,
  2. (b) 0,5 g/l bis 10 g/l Schwefelsäure,
  3. (c) 5 g/l bis 15 g/l aliphatische Sulfonsäure mit 1 bis 6 Kohlenstoffatomen
und Wasser besteht, und mit einer kathodischen Stromausbeute von 12 % oder weniger gearbeitet wird.According to the invention, this object is achieved by a method for producing a structured hard chrome layer with cupped and / or labyrinthine and / or columnar structures on a workpiece, wherein chromium from an aqueous electrolyte using direct current at a temperature of 45 ° - 95 ° C. is deposited on a workpiece, the electrolyte from
  1. (a) Cr (VI) compound in an amount corresponding to 50 to 300 g / l of chromic anhydride,
  2. (b) 0.5 g / l to 10 g / l sulfuric acid,
  3. (c) 5 g / L to 15 g / L of aliphatic sulfonic acid having 1 to 6 carbon atoms
and water, and working with a cathodic current efficiency of 12% or less.

Mit dem erfindungsgemäßen Verfahren werden strukturierte Hartchromschichten hergestellt, die näpfchenförmig und/oder labyrinthartig und/oder säulenförmig ausgebildet sind. Dies wird durch eine gezielte Beeinflussung des sich bei der elektrochemischen Abscheidung bildenden Kathodenfilms erreicht, was im Folgenden erläutert wird.With the method according to the invention, structured hard chrome layers are produced, which are of cup-shaped and / or labyrinth-like and / or columnar design. This is achieved by a specific influencing of the cathode film forming during the electrochemical deposition, which will be explained below.

Die bei galvanischen Verfahren verwendeten Elektrolyte enthalten Salze, die im wässrigen Milieu in Anionen und Kationen dissoziieren. Dabei bildet sich eine Hydrathülle um die dissoziierten Ionen. Während einer elektrochemischen Abscheidung wandern hydratisierte Metallionen des Elektrolyten zum zu beschichtenden Werkstück, das als Kathode geschaltet ist. Im Grenzbereich zwischen Elektrolyt und Kathode unmittelbar auf der Oberfläche der Kathode befindet sich der sogenannte Kathodenfilm. Gerät ein hydratisiertes Metallion in diese Phasengrenze, nimmt es Elektronen aus der Kathode auf und wird dadurch in der Diffusionszone ausgerichtet.The electrolytes used in galvanic processes contain salts which dissociate into anions and cations in the aqueous medium. A hydration shell forms around the dissociated ions. During electrochemical deposition, hydrated metal ions of the electrolyte migrate to the workpiece to be coated, which is connected as a cathode. In the boundary region between the electrolyte and cathode directly on the surface of the cathode is the so-called cathode film. When a hydrated metal ion enters this phase boundary, it picks up electrons from the cathode and thereby aligns in the diffusion zone.

Unter dieser Diffusionszone und unmittelbar auf der Kathodenoberfläche ist eine elektrochemischen Doppelschicht, die "Helmholtzsche Doppelschicht" ausgebildet. Diese besteht aus einer elektrisch geladenen Zone an der Grenzfläche zwischen Elektrolyt und Kathode und ist ungefähr einige Atom- oder Moleküllagen dick. An ihrer Bildung sind Ionen, Elektronen oder gerichtete Dipolmoleküle beteiligt. Da die "Helmholtzsche Doppelschicht" auf der einen Seite positiv und auf der anderen Seite negativ geladen ist, verhält sie sich auf der Kathode wie ein Plattenkondensator mit sehr kleinem Plattenabstand.Under this diffusion zone and directly on the cathode surface is formed an electrochemical double layer, the "Helmholtz double layer". This consists of an electrically charged zone at the electrolyte-cathode interface and is about a few atomic or molecular layers thick. Their formation involves ions, electrons or directed dipole molecules. Since the "Helmholtz double layer" is positively charged on one side and negatively charged on the other side, it behaves on the cathode like a plate capacitor with a very small plate spacing.

Damit das Metallion auf die Werkstückoberfläche gelangen und in eine Wachstumsstelle auf der Oberfläche des Werkstücks eingebaut werden kann, muss es den Kathodenfilm überwinden. Dieser Vorgang kann durch eine geeignete Wahl der Abscheidebedingungen, wie chemische Zusammensetzung des Elektrolyten, Temperatur, Hydrodynamik und elektrische Stromstärke beeinflusst werden. Zur Ausbildung gleichmässig dicker Metallschichten auf dem Werkstück werden die Abscheidebedingungen für den Elektrolyt so gewählt, dass die Durchlässigkeit des Kathodenfilms für das Metallion so gleichmäßig wie möglich ist.In order for the metal ion to get onto the workpiece surface and be incorporated into a growth site on the surface of the workpiece, it must overcome the cathode film. This process can be influenced by a suitable choice of deposition conditions, such as chemical composition of the electrolyte, temperature, hydrodynamics and electric current. To form uniformly thick metal layers on the workpiece, the deposition conditions for the electrolyte are selected so that the transmissivity of the cathode film for the metal ion is as uniform as possible.

Wenn das Element Chrom aus einem wässrigen Elektrolyten auf einem Werkstück abgeschieden werden soll, liegt es in stark saurer Lösung als negativ geladener Hydrogendichromat-Komplex vor. Darin besitzt Chrom die Oxidationsstufe 6, wobei auch geringe Mengen an Chrom(III)-Verbindungen enthalten sein können.When the element chromium is to be deposited from an aqueous electrolyte on a workpiece, it is in strongly acidic solution as a negatively charged hydrodichromate complex. Here, chromium has the oxidation state 6, although small amounts of chromium (III) compounds may be included.

Elektrolysiert man eine solche Lösung, bildet sich jedoch auf der Kathode ein fester Film, der eine Chromabscheidung verhindert. Es entsteht lediglich Wasserstoff, der wegen seines kleinen Radius durch den festen Kathodenfilm hindurchtreten kann, im Gegensatz zu den großen Hydrogendichromationen. Erst durch den Zusatz von Fremdionen, z.B. Sulfat und Chlorid, wird der Kathodenfilm für die Chromionen durchlässig und es kommt über verschiedene Oxidationsstufen zur Abscheidung des Chroms (siehe " Chemie für die Galvanotechnik" Leutze Verlag, 2. Auflage, 1993 ).When such a solution is electrolyzed, however, a solid film is formed on the cathode which prevents chromium deposition. It only produces hydrogen, which can pass through the solid cathode film because of its small radius, in contrast to the large hydrodichrome ions. Only by the addition of foreign ions, such as sulfate and chloride, the cathode film for the chromium ions permeable and it comes through different oxidation states for the deposition of chromium (see " Chemistry for Electroplating "Leutze Verlag, 2nd edition, 1993 ).

Erfindungsgemäß führt die Verwendung eines Elektrolyts mit einer Chrom(VI)-Verbindung in einer Menge, die 50 bis 300 g/l, bevorzugt 50 bis 150 g/l, Chromsäureanhydrid entspricht, 0,5 bis 10 g/l Schwefelsäure und 5 g/l bis 15 g/l aliphatische Sulfonsäure mit 1 bis 6 Kohlenstoffatomen zur Ausbildung eines Kathodenfilms mit einer sehr dichten Sperrschicht. Legt man eine geeignet hohe Beschichtungsstromdichte an, schlägt die Sperrschicht durch, was zur Ausbildung einer Chromschicht ungleichmäßiger Schichtdicke auf dem Werkstück führt, wobei mit einer kathodischen Stromausbeute von 12 % oder weniger gearbeitet wird.According to the invention, the use of an electrolyte with a chromium (VI) compound in an amount corresponding to 50 to 300 g / l, preferably 50 to 150 g / l, chromic anhydride, 0.5 to 10 g / l sulfuric acid and 5 g / 1 to 15 g / l of aliphatic sulfonic acid having 1 to 6 carbon atoms to form a cathode film having a very dense barrier layer. Applying a suitably high coating current density, the barrier layer will strike, resulting in the formation of a layer of chromium of uneven thickness on the workpiece, operating at a cathodic current efficiency of 12% or less.

So entstehen ohne Verwendung von Additiven, die die Ausbildung der Sperrschicht des Kathodenfilms begünstigen, strukturierte Hartchromschichten mit näpfchenförmig und/oder labyrinthartig und/oder säulenförmig ausgebildeten Strukturen. Daher kann auf Verbindungen verzichtet werden, die die Ausbildung eines dichten Kathodenfilms fördern, wie beispielsweise Ammonium-, Alkali- und Erdalkalimolybdat, Ammonium-, Alkali- und Erdalkalivanadat und Ammonium-, Alkali- und Erdalkalizirkonat.Thus, without the use of additives which favor the formation of the barrier layer of the cathode film, structured hard chrome layers with cup-shaped and / or labyrinth-like and / or columnar structures are formed. Therefore, compounds promoting the formation of a dense cathode film such as ammonium, alkali and alkaline earth molybdate, ammonium, alkali and alkaline earth metal and ammonium, alkali and alkaline earth zirconate can be dispensed with.

Die kathodische Stromausbeute von 12 % oder weniger gewährleistet beim erfindungsgemäßen Verfahren die Ausbildung der strukturierten Hartchromschicht, da mit einer höheren Stromausbeute die Strukturierung der Hartchromschicht nicht erhalten wird.The cathodic current efficiency of 12% or less ensures the formation of the structured hard chrome layer in the method according to the invention, since structuring of the hard chrome layer is not obtained with a higher current efficiency.

Die mit dem erfindungsgemäßen Verfahren erzeugten strukturierten Hartchromschichten sind aufgrund der näpfchenförmigen und/oder labyrinthartigen und/oder säulenförmigen Struktur gleichmäßiger ausgebildet als die strukturierten Hartchromschichten des Stands der Technik. Nach dem erfindungsgemäßen Verfahren erhältliche strukturierte Hartchromschichten sind zur Beschichtung von Kolbenringen, insbesondere solche von Brennkraftmaschinen, bestens geeignet. Erfindungsgemäß hergestellte Schichten weisen neben einer hohen Korrosionsbeständigkeit auch hervorragende tribologische Eigenschaften auf, wie gute Gleiteigenschaften und Verschleiß- und Fressbeständigkeit, insbesondere im Falle einer Mangelschmierung. Ferner können die erfindungsgemäß erhaltenen Hartchromschichten für viele dekorative und funktionelle Anwendungen eingesetzt werden. Die Oberflächentopographie der erfindungsgemäß hergestellten Hartchromschichten ermöglicht beispielsweise ein hohes Absorptionsvermögen für Licht- und Wärmestrahlung beim Einsatz von Sonnenkollektoren. Des weiteren ermöglicht die spezielle Struktur der erfindungsgemäßen Hartchromschichten ein besseres Aufnahmevermögen für Flüssigkeiten. Auch können auf der strukturierten Oberfläche Gaspolster gut aufgebaut werden.The structured hard chrome layers produced by the method according to the invention are more uniform than the structured hard chrome layers of the prior art because of the cup-shaped and / or labyrinth-like and / or columnar structure. Structured hard chrome layers obtainable by the process according to the invention are best suited for coating piston rings, in particular those of internal combustion engines. In addition to a high corrosion resistance, layers produced according to the invention also have outstanding tribological properties, such as good sliding properties and wear and scuffing resistance, in particular in the case of insufficient lubrication. Furthermore, the hard chrome layers obtained according to the invention can be used for many decorative and functional applications. The surface topography of the hard chrome layers produced according to the invention makes it possible, for example, for a high absorption capacity for light and heat radiation when using solar collectors. Furthermore, the special structure of the hard chrome layers according to the invention allows a better absorption capacity for liquids. Also, gas cushions can be well constructed on the textured surface.

Die vorstehend angegebenen Mengen der Komponenten (a) bis (c) beziehen sich auf den Elektrolyt. Unter einem Elektrolyt werden vorliegend wässrige Lösungen verstanden, die durch dissoziierte Ionen elektrisch leitfähig sind.The amounts of components (a) to (c) given above are based on the electrolyte. Under an electrolyte are presently understood aqueous solutions which are electrically conductive by dissociated ions.

Für die Komponente (a), d.h. die Cr(VI)-Verbindung, wird bevorzugt CrO3 verwendet, da sie für die elektrolytische Abscheidung besonders geeignet ist.For component (a), ie the Cr (VI) compound, CrO 3 is preferably used, since it is particularly suitable for the electrodeposition.

Als Komponente (c), d.h. als aliphatische Sulfonsäure, werden vorzugsweise Methansulfonsäure, Ethansulfonsäure, Methandisulfonsäure, oder Ethandisulfonsäure eingesetzt, was sich für die Ausbildung der vorteilhaften dekorativen und funktionellen Eigenschaften der erzeugten Hartchromschicht als besonders günstig erwiesen hat.As component (c), i. As aliphatic sulfonic acid, methanesulfonic acid, ethanesulfonic acid, methanedisulfonic acid, or ethanedisulfonic acid are preferably used, which has proven to be particularly favorable for the formation of the advantageous decorative and functional properties of the hard chromium layer produced.

Der Elektrolyt kann in einer Ausführungsform im wesentlichen frei von Fluoriden sein. Letztere erschweren nämlich häufig die Ausbildung der strukturierten Hartchromschicht. Daher sind nur soviel Fluoride im Elektrolyten tolerabel, die die Abscheidung der strukturierten Hartchromschicht nicht beeinflussen. Als günstig hat es sich erwiesen, wenn nicht mehr als 0,1 g/l Fluoride im Elektrolyten vorliegen.The electrolyte may in one embodiment be substantially free of fluorides. The latter often complicate the formation of the structured hard chrome layer. Therefore, only as many fluorides in the electrolyte are tolerable that do not affect the deposition of the structured hard chrome layer. It has proven to be favorable if not more than 0.1 g / l fluorides are present in the electrolyte.

Außerdem können übliche Katalysatoren für die Chromabscheidung, wie SO4 2- und/oder Cl-, im Elektrolyten in üblichen Mengen enthalten sein.In addition, conventional catalysts for the separation of chromium, such as SO 4 2- and / or Cl - , may be present in the electrolyte in conventional amounts.

Erfindungsgemäß werden strukturierte Hartchromschichten mit dem vorstehend beschriebenen Verfahren auf Werkstücken abgeschieden. Dabei sind mit dem Begriff "Werkstück" metallische oder nicht metallische Gegenstände gemeint, die mit einer strukturierten Hartchromschicht versehen werden sollen. Im Falle eines nicht metallischen Gegenstands wird dieser vor dem Aufbringen der strukturierten Hartchromschicht mit einem dünnen Metallfilm beschichtet, um ihn elektrisch leitend zu machen.According to the invention, structured hard chrome layers are deposited on workpieces by the method described above. In this case, the term "workpiece" means metallic or non-metallic objects which are to be provided with a structured hard chrome layer. In the case of a non-metallic article, it is coated with a thin metal film prior to application of the patterned hard chromium layer to render it electrically conductive.

Um die strukturierte Hartchromschicht auf dem Werkstück abzuscheiden, wird letzteres als Kathode geschaltet und in den Elektrolyten eingetaucht. Dann wird an das Werkstück ein Gleichstrom, wie z.B. ein pulsierender Gleichstrom mit einer Frequenz bis 1000 Hz, angelegt. Während der Abscheidung des Chroms wird die Temperatur auf 45°C bis 95°C, bevorzugt 55°C gehalten. Je länger die Abscheidung durchgeführt wird, desto größer ist die Schichtdicke der Hartchromschicht.In order to deposit the structured hard chrome layer on the workpiece, the latter is connected as a cathode and immersed in the electrolyte. Then a DC current is applied to the workpiece, e.g. a pulsating direct current with a frequency up to 1000 Hz, applied. During the deposition of the chromium, the temperature is maintained at 45 ° C to 95 ° C, preferably 55 ° C. The longer the deposition is carried out, the greater the layer thickness of the hard chrome layer.

Beim erfindungsgemäßen Verfahren kann mit einer Stromdichte von 20 A/dm2 bis 200 A/dm2 gearbeitet werden. Dieser Bereich der Stromdichte führt zur Abscheidung besonders günstig strukturierter Hartchromschichten. Je höher dabei die Stromdichte gewählt wird, desto dichter werden die hervorstehenden Bereiche der Oberfläche der erfindungsgemäßen Hartchromschicht.In the method according to the invention can be used with a current density of 20 A / dm 2 to 200 A / dm 2 . This range of current density leads to the deposition of particularly favorable structured hard chrome layers. The higher the current density is chosen, the denser the protruding areas of the surface of the hard chrome layer according to the invention.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird vor und/oder nach dem Abscheiden der strukturierten Hartchromschicht eine zweite Schicht abgeschieden. So können auf das Werkstück mehrere Schichten aufgebracht werden, beispielsweise eine Metallschicht aus einem herkömmlichen Elektrolyt auf die erfindungsgemäße strukturierte Hartchromschicht. Ferner können die beiden Schichten aus verschiedenen Werkstoffen bestehen, wobei, wenn eine herkömmliche Metallschicht auf die strukturierte Hartchromschicht aufgebracht wird, eine verbesserte Verankerung der herkömmlichen Metallschicht ermöglicht wird.In a preferred embodiment of the method according to the invention, a second layer is deposited before and / or after the deposition of the structured hard chromium layer. Thus, several layers can be applied to the workpiece, for example a metal layer of a conventional electrolyte on the structured hard chromium layer according to the invention. Further, the two layers may be made of different materials, and when a conventional metal layer is applied to the patterned hard chrome layer, improved anchoring of the conventional metal layer is enabled.

Des weiteren kann als die zweite Schicht eine herkömmliche Hartchromschicht oder eine erfindungsgemäße strukturierte Hartchromschicht jeweils mit Einlagerungen abgeschieden werden, wobei die Einlagerungen aus Aluminiumoxid, Diamant und/oder Bornitrid des hexagonalen Typs bestehen können. Im dafür verwendeten Elektrolyten sind die genannten Materialien suspendiert. Die Einlagerungen führen zu einer weiteren Verbesserung der tribologischen Eigenschaften.Furthermore, as the second layer, a conventional hard chromium layer or a structured hard chromium layer according to the invention can be deposited in each case with inclusions, wherein the inclusions can consist of aluminum oxide, diamond and / or boron nitride of the hexagonal type. In the electrolyte used for these materials are suspended. The deposits lead to a further improvement of the tribological properties.

Außerdem wird in einer besonders günstigen Ausführungsform der Erfindung auf eine konventionelle Hartchromschicht gleichmäßiger Schichtdicke eine erfindungsgemäße Hartchromschicht elektrolytisch aufgebracht. Dies führt zu einer sogenannten gradierten strukturierten Hartchromschicht, bei der der Korrosionsschutz durch die konventionelle Hartchromschicht gleichmäßiger Schichtdicke gewährleistet ist, während die erfindungsgemäße strukturierte Hartchromschicht für eine Verbesserung der tribologischen Eigenschaften des Werkstücks sorgt.In addition, in a particularly favorable embodiment of the invention, a hard chromium layer according to the invention is applied electrolytically to a conventional hard chrome layer of uniform layer thickness. This leads to a so-called graded structured hard chrome layer, in which the corrosion protection is ensured by the conventional hard chrome layer of uniform layer thickness, while the structured hard chrome layer according to the invention provides for an improvement in the tribological properties of the workpiece.

Die Erfindung betrifft auch ein Verfahren zur Herstellung einer Beschichtung, wobei Chrom auf ein Werkstück unter Bildung einer strukturierten Hartchromschicht abgeschieden wird, und auf die strukturierte Hartchromschicht eine Zusammensetzung aufgebracht wird, die Epoxidharz, einen Festschmierstoff, einen Hartstoff oder Gemische davon enthält. Bei der strukturierten Hartchromschicht kann es sich um eine erfindungsgemäß hergestellte strukturierte Hartchromschicht handeln. Das Epoxidharz dient als Binder, um den Festschmierstoff und/oder den Hartstoff in den Vertiefungen der strukturierten Hartchromschicht zu halten. Als Festschmierstoff eignet sich insbesondere MoS2, Bornitrid, bevorzugt der hexagonale Typ des Bornitrids, oder Teflon, bzw. eine Mischung von zwei oder mehreren dieser Stoffe. Beispiele für Hartstoffe sind mikroskaliger Diamant, Aluminiumoxid, Si3N4, B4C, SiC oder eine Mischung von zwei oder mehrerer dieser Stoffe.The invention also relates to a method for producing a coating, wherein chromium is deposited on a workpiece to form a structured hard chrome layer, and to the structured hard chrome layer is applied a composition containing epoxy resin, a solid lubricant, a hard material or mixtures thereof. The structured hard chrome layer may be a structured hard chrome layer produced according to the invention. The epoxy resin serves as a binder to hold the solid lubricant and / or the hard material in the recesses of the patterned hard chrome layer. As a solid lubricant in particular MoS 2 , boron nitride, preferably the hexagonal type of boron nitride, or Teflon, or a mixture of two or more of these substances is suitable. Examples of hard materials are microscale diamond, alumina, Si 3 N 4 , B 4 C, SiC or a mixture of two or more of these substances.

Dieser Beschichtungsaufbau verbessert nicht nur die allgemeinen Verschleißeigenschaften, vielmehr ergeben sich bei Verwendung von MoS2 zusätzlich hervorragende Notlaufeigenschaften des Werkstücks im Falle einer Mangelschmierung. Insbesondere wenn Bornitrid in der Zusammensetzung enthalten ist, ergibt sich eine ausgezeichnete Selbstschmierung der Beschichtung, so dass je nach Anwendung auf den Einsatz weiterer Schmierstoffe verzichtet werden kann. Wird eine Mischung zweier oder mehrerer der genannten Festschmierstoffe in der Zusammensetzung verwendet, die auf die strukturierte Hartchromschicht aufgebracht wird, summieren sich die vorstehend genannten günstigen tribologischen Eigenschaften.This coating construction not only improves the general wear properties, but also provides excellent runflat properties when MoS 2 is used of the workpiece in case of insufficient lubrication. In particular, when boron nitride is included in the composition, there is an excellent self-lubrication of the coating so that it can be dispensed depending on the application on the use of other lubricants. If a mixture of two or more of said solid lubricants is used in the composition which is applied to the structured hard chrome layer, the favorable tribological properties mentioned above add up.

Die Erfindung umfasst ferner eine strukturierte Hartchromschicht, wie sie nach einem der vorstehenden Verfahren erhältlich ist.The invention further comprises a structured hard chrome layer as obtainable by one of the above methods.

Zudem betrifft die Erfindung eine Beschichtung, die nach dem vorstehenden Verfahren zur Herstellung einer Beschichtung erhältlich ist.In addition, the invention relates to a coating obtainable by the above process for producing a coating.

Der Elektrolyt zur Durchführung des erfindungsgemäßen Verfahrens zur Herstellung einer strukturierten Hartchromschicht besteht aus

  1. (a) Cr(VI)-Verbindung in einer Menge, die 50 bis 300 g/l Chromsäureanhydrid entspricht;
  2. (b) 0,5 g/l bis 10 g/l Schwefelsäure;
  3. (c) 5 g/l bis 15 g/l aliphatische Sulfonsäure mit 1 bis 6 Kohlenstoffatomen.
The electrolyte for carrying out the method according to the invention for producing a structured hard chrome layer consists of
  1. (a) Cr (VI) compound in an amount corresponding to 50 to 300 g / l of chromic anhydride;
  2. (b) 0.5 g / l to 10 g / l sulfuric acid;
  3. (c) 5 g / L to 15 g / L of aliphatic sulfonic acid having 1 to 6 carbon atoms.

Der Elektrolyt, der bevorzugt die Cr(VI)-Verbindung in einer Menge, die 50 bis 150 g/l Chromsäureanhydrid entspricht, enthalten kann, dient insbesondere zur galvanischen Abscheidung der vorstehend näher beschriebenen strukturierten Hartchromschichten auf Werkstücken.The electrolyte, which may preferably contain the Cr (VI) compound in an amount corresponding to 50 to 150 g / l of chromic anhydride, serves in particular for the electrodeposition of the structured hard chrome layers described in greater detail above on workpieces.

Die Erfindung wird in den nachfolgenden Beispielen unter Bezugnahme auf die Figuren näher erläutert, ohne sie jedoch darauf einzuschränken.The invention is explained in more detail in the following examples with reference to the figures, but without limiting it thereto.

Die Figuren 1 bis 10 zeigen Fotografien der Hartchromschichten aus den Beispielen 1 bis 4.The FIGS. 1 to 10 show photographs of the hard chrome layers of Examples 1 to 4.

Beispiel 1:Example 1: (Vergleich)(Comparison)

Zur Erzeugung einer herkömmlichen Hartchromschicht wird folgender wässriger Elektrolyt hergestellt: Chromsäureanhydrid CrO3 250 g/l Schwefelsäure H2SO4 2,5 g/l. Das zu beschichtende Warenteil wird nach einer üblichen Vorbehandlung in den Elektrolyten eingetaucht. Bei 55°C wird mit einer Stromdichte von 40 A/dm2 30 Minuten lang Chrom auf das Warenteil abgeschieden.To produce a conventional hard chrome layer, the following aqueous electrolyte is prepared: chromic anhydride CrO 3 250 g / l sulfuric acid H 2 SO 4 2.5 g / l. The product to be coated is immersed in the electrolyte after a standard pretreatment. At 55 ° C., chromium is deposited on the product part for 30 minutes at a current density of 40 A / dm 2 .

Das resultierende Warenteil besitzt eine herkömmliche glänzende und gleichmäßig ausgebildete Chromschicht, wie in Fig. 1 dargestellt.The resulting article has a conventional glossy and uniform chrome layer, as in Fig. 1 shown.

Beispiel 2:Example 2:

Für die Ausbildung erfindungsgemäßer strukturierter Hartchromschichten wird ein erfindungsgemäßer Elektrolyt verwendet, der enthält: Chromsäureanhydrid CrO3 200 g/l Schwefelsäure H2SO4 3 g/l Methansulfonsäure CH3SO3H (70 %ig) 9 ml/l. Bei einer Temperatur von 70 °C, einer kathodischen Stromausbeute von 10 % und einer Expositionszeit von 30 Minuten werden erfindungsgemäße strukturierte Hartchromschichten auf Werkstücken abgeschieden. Für die in Fig. 2 bis 6 gezeigten Fotografien werden die Stromdichten folgendermaßen variiert: Fig. 2: 30 A/dm2; Fig. 3: 40 A/dm2; Fig. 4: 50 A/dm2; Fig. 5: 60 A/dm2; Fig. 6: 70 A/dm2. Es entstehen typische Oberflächenstrukturen mit in den Fotografien dunkel erscheinenden Strukturtälern, d.h. Vertiefungen.
Wird die Stromdichte konstant gelassen und werden stattdessen die Elektrolytbestandteile verändert, zeigt sich ebenfalls ein Einfluss auf die Strukturbildung, der aber im Ergebnis zu Strukturen führt, die mit denjenigen der Fig. 2 bis 6 vergleichbar sind.For the formation of structured hard chrome layers according to the invention, an electrolyte according to the invention is used, which contains: chromic anhydride CrO 3 200 g / l sulfuric acid H 2 SO 4 3 g / l methane CH 3 SO 3 H (70% pure) 9 ml / l. At a temperature of 70 ° C., a cathodic current efficiency of 10% and an exposure time of 30 minutes, structured hard chrome layers according to the invention are deposited on workpieces. For the in Fig. 2 to 6 In the photographs shown, the current densities are varied as follows: Fig. 2 : 30 A / dm 2 ; Fig. 3 : 40 A / dm 2 ; Fig. 4 : 50 A / dm 2 ; Fig. 5 : 60 A / dm 2 ; Fig. 6 : 70 A / dm 2 . The result is typical surface structures with structures that appear dark in the photographs, ie depressions.
If the current density is left constant and instead the electrolyte constituents are changed, an influence on the structure formation also appears, but as a result leads to structures which correspond to those of the Fig. 2 to 6 are comparable.

Beispiel 3:Example 3:

Auf ein Warenteil werden abwechselnd konventionelle Hartchromschichten mit Einlagerungen aus Aluminiumoxid und erfindungsgemäße strukturierte Hartchromschichten abgeschieden. Für letztere wird ein Elektrolyt verwendet, der Chromsäureanhydrid CrO3 100 g/l Schwefelsäure H2SO4 3,5 g/l Methansulfonsäure CH3SO3H (70 %ig) 6 ml/l enthält. Die strukturierten Hartchromschichten werden bei einer Temperatur von 60 °C, einer kathodischen Stromausbeute von 10 % und einer Stromdichte von 80 A/dm2 30 Minuten lang abgeschieden. Insgesamt werden sechs Schichten abwechselnd mit und ohne Einlagerungen aufgebracht. Fig. 7 und 8 zeigen einen typischen Querschliff dieser gradierten strukturierten Chromschichten in unterschiedlichen Vergrößerungen. Der Korrosionsschutz wird durch die konventionellen Hartchromschichten gewährleistet, während die günstigen tribologischen Eigenschaften aus den erfindungsgemäßen strukturierten Hartchromschichten resultieren. Anstelle von Aluminiumoxid kann auch Diamant oder hexagonales Bornitrid eingelagert werden.Conventional hard chrome layers with deposits of aluminum oxide and structured hard chrome layers according to the invention are alternately deposited on a product part. For the latter, an electrolyte is used which chromic anhydride CrO 3 100 g / l sulfuric acid H 2 SO 4 3.5 g / l methane CH 3 SO 3 H (70% pure) 6 ml / l contains. The structured hard chrome layers are deposited at a temperature of 60 ° C., a cathodic current efficiency of 10% and a current density of 80 A / dm 2 for 30 minutes. In total, six layers are applied alternately with and without deposits. Fig. 7 and 8th show a typical cross-section of these graded structured chromium layers in different magnifications. The corrosion protection is ensured by the conventional hard chrome layers, while the favorable tribological properties result from the structured hard chrome layers according to the invention. Instead of alumina, diamond or hexagonal boron nitride can also be incorporated.

Die entstandenen gradierten strukturierten Hartchromschichten können weiter wie im Beispiel 4 beschrieben behandelt werden, um die selbstschmierenden Eigenschaften der Oberfläche zu unterstützen.The resulting graded structured hard chrome layers can be further treated as described in Example 4 to aid the self-lubricating properties of the surface.

Beispiel 4:Example 4:

Bei einer nach Beispiel 2 auf einem Werkstück hergestellten erfindungsgemäßen strukturierten Hartchromschicht werden die Strukturtäler bzw. Vertiefungen der Oberfläche mit einem Gemisch aus Epoxidharz und Bornitrid des hexagonalen Typs gefüllt. Die Fotografien der Fig. 9 und 10 veranschaulichen die Füllung der Vertiefungen der Hartchromschicht. Die so entstandene Beschichtung weist hervorragende selbstschmierende Eigenschaften auf. Zudem kann abhängig von der Anwendung auf die zusätzliche Verwendung weiterer Schmierstoffe verzichtet werden.In a patterned hard chrome layer according to the invention produced on a workpiece according to Example 2, the structural valleys or depressions of the surface are filled with a mixture of epoxy resin and boron nitride of the hexagonal type. The photographs of Fig. 9 and 10 illustrate the filling of the recesses of the hard chrome layer. The resulting coating has excellent self-lubricating properties. In addition, depending on the application, the additional use of other lubricants can be dispensed with.

Beispiel 5:Example 5:

Ein Werkstück, das mit einer gemäß Beispiel 2 hergestellten strukturierten Hartchromschicht bedeckt ist, wird mit einem Gemisch aus Epoxidharz und MoS2 so behandelt, dass die Vertiefungen der Chromschicht mit dem Gemisch gefüllt werden. Das Epoxidharz dient als Binder, um das MoS2 in den Vertiefungen und zum Teil auch an den Erhebungen zu fixieren. Daraus resultieren gute Verschleißeigenschaften, wie auch hervorragende Notlaufeigenschaften, wenn eine Mangelschmierung des Werkstücks auftritt. Zudem ist im Vergleich zur unbehandelten strukturierten Hartchromschicht ein verbessertes Korrosionsverhalten gegeben.A workpiece covered with a patterned hard chrome layer prepared according to Example 2 is treated with a mixture of epoxy resin and MoS 2 so that the recesses of the chromium layer are filled with the mixture. The epoxy resin serves as a binder to fix the MoS 2 in the depressions and in part also on the elevations. This results in good wear properties, as well as excellent emergency running properties when a lack of lubrication of the workpiece occurs. In addition, compared to the untreated structured hard chrome layer, an improved corrosion behavior is given.

Beispiel 6:Example 6:

Die Vertiefungen einer nach Beispiel 2 auf einem Warenteil erzeugten strukturierten Hartchromschicht werden mit einem Gemisch aus Epoxidharz und mikroskaligem Diamant, d.h. Diamantkörnchen mit einer Größe im µm-Bereich, gefüllt. Auch hier zeigen sich gegenüber der nicht gefüllten strukturierten Hartchromschicht deutlich verbesserte Verschleißeigenschaften und ein wesentlich günstigeres Korrosionsverhalten.The wells of a patterned hard chrome layer produced on a product part according to Example 2 are filled with a mixture of epoxy resin and microscale diamond, ie diamond granules with a size in the micron range. Here, too, clearly improved wear properties and a significantly more favorable corrosion behavior are evident in comparison to the unfilled structured hard chrome layer.

Beispiel 7:Example 7:

Ein gemäß Beispiel 5 erzeugtes Werkstück wird zusätzlich mit einem Gemisch des Beispiels 6 behandelt. Die resultierende Beschichtung weist gegenüber den Beispielen 5 und 6 stark verbesserte tribologische Eigenschaften, z.B. eine ausgezeichnete Selbstschmierung, wie auch ein gegenüber der unbehandelten strukturierten Hartchromschicht günstigeres Korrosionsverhalten auf.A workpiece produced according to Example 5 is additionally treated with a mixture of Example 6. The resulting coating has greatly improved tribological properties, as compared to Examples 5 and 6, e.g. excellent self-lubrication, as well as compared to the untreated structured hard chrome layer more favorable corrosion behavior.

Claims (12)

  1. Method of producing a structured hard chromium layer having cup-shaped and/or labyrinthine and/or column-shaped structures on a workpiece, wherein chromium is deposited on a workpiece from an aqueous electrolyte by using direct current at a temperature of 45° - 95°, said electrolyte consisting of:
    (a) a Cr(VI) compound in an amount corresponding to 50 to 300 g/l of chromic acid anhydride;
    (b) 0.5 g/l to 10 g/l of sulfuric acid;
    (c) 5 g/l to 15 g/l of aliphatic sulfonic acid comprising 1 to 6 carbon atoms
    and water, wherein a cathodic current yield of 12 % or less is employed.
  2. Method according to claim 1, wherein the Cr(VI) compound is CrO3.
  3. Method according to any of the preceding claims, wherein the aliphatic sulfonic acid is selected from methane sulfonic acid, ethane sulfonic acid, methane disulfonic acid and ethane disulfonic acid.
  4. Method according to any of the preceding claims, wherein a current density of 20 A/dm2 to 200 A/dm2 is employed.
  5. Method according to claim 1, wherein a second layer is deposited before and/or after depositing the structured hard chromium layer.
  6. Method according to claim 5, wherein the structured hard chromium layer and the second layer consist of different materials.
  7. Method according to claim 5 or 6, wherein a hard chromium layer having uniform layer thickness is deposited as the second layer.
  8. Method of producing a coating, wherein chromium according to any of claims 1 to 7 is deposited on a workpiece to form a structured hard chromium layer, and wherein a composition containing epoxy resin, a solid lubricant, a hard substance, or mixtures thereof, is deposited on the structured hard chromium layer.
  9. Method according to claim 8, wherein MoS2, boron nitride, teflon, or a mixture thereof, is used as the solid lubricant.
  10. Method as claimed in claims 8 to 9, wherein microscale diamond, aluminum oxide, Si3N4, B4C, SiC, or a mixture thereof, is used as the hard substance.
  11. Structured hard chromium layer having cup-shaped and/or labyrinthine and/or column-shaped structures on a workpiece, obtainable by the method according to any one of claims 1 to 7.
  12. Coated structured hard chromium layer having cup-shaped and/or labyrinthine and/or column-shaped structures on a workpiece, wherein a coating containing epoxy resin, a solid lubricant, a hard substance, or mixtures thereof, obtainable by the method according to any one of claims 8 to 10, is deposited on the structured hard chromium layer.
EP05700700.7A 2004-04-21 2005-01-05 Production of a structured hard chromium layer and production of a coating Expired - Fee Related EP1738000B1 (en)

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DE102004019370A DE102004019370B3 (en) 2004-04-21 2004-04-21 Production of optionally coated structurized hard chrome layer, used e.g. for decoration, protection or functional coating on printing roller or stamping, embossing or deep drawing tool uses aliphatic sulfonic acid in acid plating bath
PCT/EP2005/000037 WO2005108648A2 (en) 2004-04-21 2005-01-05 Production of a structured hard chromium layer and production of a coating

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EP1738000B1 true EP1738000B1 (en) 2018-04-18

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JP (1) JP4542134B2 (en)
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PT (1) PT1738000T (en)
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JP4542134B2 (en) 2010-09-08
US8110087B2 (en) 2012-02-07
DE102004019370B3 (en) 2005-09-01
BRPI0506445A (en) 2006-12-26
WO2005108648A3 (en) 2006-03-30
WO2005108648A2 (en) 2005-11-17
US20080060945A1 (en) 2008-03-13
JP2007533852A (en) 2007-11-22
EP1738000A2 (en) 2007-01-03
BRPI0506445B1 (en) 2015-04-14
PT1738000T (en) 2018-07-03

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