EP1565596B1 - Production de couches en chrome dur structurees - Google Patents

Production de couches en chrome dur structurees Download PDF

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Publication number
EP1565596B1
EP1565596B1 EP03773629A EP03773629A EP1565596B1 EP 1565596 B1 EP1565596 B1 EP 1565596B1 EP 03773629 A EP03773629 A EP 03773629A EP 03773629 A EP03773629 A EP 03773629A EP 1565596 B1 EP1565596 B1 EP 1565596B1
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EP
European Patent Office
Prior art keywords
layer
chromium
structured
electrolyte
hard chrome
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.)
Expired - Lifetime
Application number
EP03773629A
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German (de)
English (en)
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EP1565596A1 (fr
Inventor
Rudolf Linde
Stefan Dürdoth
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Federal Mogul Burscheid GmbH
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Federal Mogul Burscheid GmbH
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Publication of EP1565596A1 publication Critical patent/EP1565596A1/fr
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12389—All metal or with adjacent metals having variation in thickness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12389—All metal or with adjacent metals having variation in thickness
    • Y10T428/12396—Discontinuous surface component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12486—Laterally noncoextensive components [e.g., embedded, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12778—Alternative base metals from diverse categories
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the invention relates to a method for producing a structured hard chrome layer on a workpiece, structured hard chrome layers obtainable thereby and an electrolyte for carrying out the method.
  • Electrochemically or galvanically deposited chromium layers have been considered as prior art for many years in functional and decorative applications and applications for coating electrically conductive and non-conductive workpieces.
  • the structured layers used in the prior art all have a pronounced spherical layer structure.
  • the size of the spherical shapes varies between less than 1 micron and several microns.
  • the degree of coverage or the density of the spherical layer structure is more or less variable depending on the method.
  • structured chromium layers according to DE 33 077 48 A1, DE 42 11 881 A1 and DE 43 34 122 A1 are produced by varying the direct electrical currents, the structure of the structures being influenced by variation of current ramp and current pulse heights.
  • a process for the electrolytic coating of materials wherein a chromium alloy is deposited from an electrolyte containing at least chromic acid, sulfuric acid, a isopolyanionen auslagendes metal, a short-chain aliphatic sulfonic acid, its salt and / or their halogen derivative and Contains fluorides.
  • a structured hard chrome layer is not mentioned in this prior art.
  • the method according to the invention is ideally suited for use in the production of structured hard chrome layers.
  • a structured hard chrome layer is obtained by targeted influencing of the cathode film forming during the electrochemical deposition of metals, wherein the layer is formed in the shape of cups and / or labyrinth-like and / or columnar.
  • salts are dissolved in water, they dissociate into cations and anions. These dissociated ions surround simultaneously with a hydration shell, i. Water molecules (as dipoles) attach themselves to the cations or anions. During hydration, the charge of the ions is not changed. If a hydrated metal ion then begins to flow under the influence of current, it will be in the vicinity of the cathode in a boundary region between the electrolyte and the cathode.
  • This so-called cathode film is located directly on the surface of the workpiece to be coated, since the workpiece is electrically negatively connected.
  • the metal ions present in the electrolyte are first aligned by receiving electrons which are offered by the cathode from the electric current.
  • an electrochemical double layer also called "Helmholtz double layer”. It is a name for the approximately some atomic or molecular layers thick electrically charged zone at the interface electrolyte / electrode. Their formation is dependent on ions, electrons or directed dipole molecules. It is positive on the one hand and negatively charged on the other, and behaves like a plate capacitor with extremely low plate spacing.
  • the resulting metal atom is now on the workpiece surface. His condition is not yet comparable to that of an atom in the metal interior. Only when a so-called growth site is present, the resulting atoms arrange themselves in the existing metal lattice.
  • the deposition conditions of the electrolytes such as chemical composition, temperature, hydrodynamics and electric current, are chosen so that a uniform coverage of the base material takes place with the metal to be deposited.
  • the cathode film is influenced by this measure so that its permeability to the ions present is as uniform as possible.
  • the element chromium is present in aqueous solution, compared to most electrochemically depositable elements, as negatively charged complexion mainly as hydrodichromate in strongly acidic solution.
  • the chromium in this complex has the oxidation state 6.
  • smaller amounts of chromium (III) compounds are contained in electrolytes.
  • the formation of the cathode film is controlled so that it becomes permeable to chromium ions, so that initially forms a very dense barrier layer, which thenteurabel depending on the applied electrical coating current density and the metal structure of different thickness or layer thickness can arise.
  • structured chromium layers which are cup-shaped and / or labyrinth-like and / or columnar are obtained.
  • the chromium layer obtained by the method according to the invention has a high resistance to wear and corrosion, excellent sliding properties and seizure resistance as well as an aesthetically favorable appearance, which is hardly achieved by any other coating. Due to the cup-shaped and / or labyrinth-like and / or columnar structured hard chrome layer, it can be used for many functional or decorative applications. For example, the special structure of the layer ensures better absorption of liquids. Furthermore, the construction of a gas cushion allows as well as an improved anchoring possibility for explicatlagemde there substances, such as plastics, dyes, metals, ceramics, electronic components, the body's own tissue as implant coating, can be achieved. Furthermore, this surface structure allows specific optical effects, such as high adsorption capacity for light and heat radiation when using solar collectors, as well as decorative applications in the field of design.
  • electrolyte in the context of the present invention means aqueous solutions whose electrical conductivity is due to electrolytic dissociation in ions. Accordingly, the electrolyte in addition to the components (a) to (d) and optionally further present additives as the remainder of water.
  • component (a) preferably CrO 3 is used, which has proven to be particularly favorable for the electrolytic deposition of chromium.
  • An aliphatic sulfonic acid preferably used as component (c) is methanesulfonic acid. This has proven to be particularly favorable for the formation of the structured hard chrome layers with the above properties.
  • component (d) Li + , Na + and K + can be used.
  • alkaline earth ions are Mg 2+ and Ca 2+ .
  • component (d) (NH 4 ) 6 Mo 7 O 24 .4H 2 O, which has been found to be particularly favorable for the formation of the patterned hard chrome layer having the above properties.
  • the electrolyte specified above in a particularly preferred embodiment, is substantially free of fluorides.
  • fluorides both simple and complex fluorides. If fluorides are present in the electrolyte, the formation of the structured hard chromium layer is disturbed. Accordingly, the term "substantially no fluorides" means that so much fluoride is tolerable in the electrolyte that the formation of the patterned hard chromium layer is unaffected.
  • the amount of fluorides that are tolerable can be readily determined by those skilled in the art. It has proved to be favorable if not more than 0.1 g / l is present in the electrolyte.
  • the electrolyte may further contain conventional catalysts which promote chromium deposition, such as SO 4 2- and / or Cl - . These can be present in the electrolyte in conventional amounts.
  • workpiece is understood to mean objects of any type that are to be provided with a structured chrome layer. These may be metallic or non-metallic objects. Should a non-metallic object structured hard chrome layer are formed, it is first made electrically conductive by applying a thin metal film.
  • the structured hard chromium layer is switched cathodically and immersed in the electrolyte.
  • a direct current for example a pulsating direct current with a frequency up to 1000 Hz, is applied to the workpiece.
  • the temperature for the deposition of the chromium may be 45 ° C to 95 ° C, in particular about 55 ° C.
  • the duration of the deposition is chosen as a function of the desired thickness of the structured hard chromium layer, the layer becoming thicker the longer the deposition takes place.
  • the cathodic current efficiency in the production of the structured hard chromium layer according to the method of the invention is 12% or less. If the current efficiency is higher, the desired structuring of the hard chrome layer is not obtained.
  • multiple layers may be applied to the workpiece, whereby the aforementioned patterned hard chromium layers and layers formed from conventional electrolytes may be alternately deposited one on top of the other.
  • the structured hard chrome layer obtainable by the process according to the invention and then a layer selected from a conventional chromium layer, black chrome layer, copper, nickel or tin layer.
  • a conventional chromium, copper and / or nickel layer can first be applied to the workpiece and then the hard chrome layer described in more detail above can be deposited thereon.
  • the subject matter of the present invention is furthermore a structured hard chrome layer, as obtainable by the process according to the invention described in more detail above.
  • the structured hard chrome layer is - in contrast to the hard chrome layers of the prior art, which have a pronounced spherical layer structure - cup-shaped and / or labyrinth-like and / or columnar.
  • the structured hard chromium layer according to the invention has the advantages described in connection with the method according to the invention.
  • the structured hard chrome layer according to the invention can be used to coat a variety of workpieces, such as piston rings, cylinders, pistons, bolts, camshafts, gaskets, composite materials, valves, bearings to protect against wear and to reduce friction, pressure cylinder for better wetting with colors, embossing rollers for better deep-drawing processes for the automotive industry, solar technology, decorative applications, medical technology, microtechnology and microelectronics.
  • workpieces such as piston rings, cylinders, pistons, bolts, camshafts, gaskets, composite materials, valves, bearings to protect against wear and to reduce friction, pressure cylinder for better wetting with colors, embossing rollers for better deep-drawing processes for the automotive industry, solar technology, decorative applications, medical technology, microtechnology and microelectronics.
  • FIGS. 1 to 8 show photographs according to the hard chrome layers of Examples 1 to 8.
  • a conventional chromium electrolyte of the following basic composition was prepared chromic anhydride CrO 3 250 g / l sulfuric acid H 2 SO 4 2.5 g / l
  • a part of the product is introduced into the electrolyte according to customary proviso and at 40 ° C. with 40 A / dm 2 for 30 min. coated.
  • the product coated under these conditions has, after the treatment, a conventional glossy uniform chromium layer, cf. Fig. 1.
  • Ammonium molybdate (NH 4 ) 6 Mo 7 O 24 .4H 2 O 100 g / l and methanesulfonic acid 4 g / l are additionally added to the electrolyte according to Example 1.
  • a product is coated according to the conditions described in Example 1.
  • the product described thus has a structured chromium layer after the treatment. This chrome layer has a shiny appearance on the protruding surface portions (supporting portion), and brown-colored cathode film is obtained in the recesses of the structure (Fig. 2).
  • a product is coated according to the conditions of Example 2. However, it is carried out instead of a coating current density of 40 A / dm 2 with 20 A / dm 2 .
  • the product thus coated has a structured chromium layer after the treatment.
  • the proportion of the protruding, glossy surface areas (supporting portion) is lower and the proportion of the deep areas is larger compared to the structural layer of Example 2 (FIG. 3).
  • a product is coated according to the conditions of Example 2. However, instead of a coating current density of 40 A / dm 2 , 60 A / dm 2 is used.
  • the product thus coated has a structured chromium layer after the treatment.
  • the proportion of the protruding, glossy surface areas (carrying portion) is greater and the proportion of the deep areas is lower compared to the structural layer of Example 2 (FIG. 4).
  • a product is coated according to the conditions of Example 2.
  • the product thus coated has a structured chromium layer after the treatment.
  • a conventional chromium electrolyte from Example 1 is now on this patterned chromium layer with chromium at 55 ° C and 50 A / dm 2 for 120 min. further coated.
  • the thus coated article has a significant increase in the structural height as compared with Example 2 (Fig. 5).
  • This graded layer has metallurgical properties on the surface such as conventional chrome and is additionally structured.
  • This layer structure is due to the fact that the profile height of the structural layer can be varied within a wide range, which is limited by the exclusive deposition according to Examples 2-4 by their low film growth rate.
  • a product is coated according to the conditions of Example 2.
  • the product thus coated has a structured chromium layer after the treatment.
  • a black chromium oxide-containing layer is now deposited on this structured chromium layer.
  • the thus coated article has a uniform, deep black surface with a very high light index (Figure 6).
  • a product is coated according to the conditions of Example 2.
  • the product thus coated has a structured chromium layer after the treatment.
  • a tin layer is now deposited on this patterned chromium layer, of sufficient thickness to fill the recesses of the structural chrome layer with tin.
  • the product thus coated has a surface which also has very good sliding properties with high wear resistance (FIG. 7).
  • a product is coated according to the conditions of Example 1 with a conventional chrome layer.
  • a structured chromium layer is applied with the conditions from Example 2 to the chromium layer from Example 1.
  • the structured chromium layer represents an entry layer for the conventional chromium layer and, depending on the tribological application, leads to an improvement of the layer system (FIG. 8).

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

Claims (7)

  1. Procédé de fabrication d'une couche de chrome dur structurée, le chrome étant déposé sur une pièce d'oeuvre à partir d'un électrolyte qui contient :
    (a) un composé Cr(VI) en une quantité correspondant à 50 g/l à 600 g/l d'anhydride chromique ;
    (b) 0,5 g/l à 10 g/l d'UN acide sulfurique ;
    (c) 1 g/l à 20 g/l d'acide sulfonique aliphatique ayant de 1 à 6 atomes de carbone et
    (d) 10 g/l à 200 g/l d'au moins un composé formant un film cathodique dense choisi parmi le molybdate d'ammonium, de méral alcalin et de métal alcalino-terreux, le vanadate d'ammonium, de métal alcalin et de métal alcalino-terreux et le zirconate d'ammonium, de métal alcalin et de métal alcalino-terreux,
    où l'on travaille avec un rendement de courant cathodique de 12 % ou moins.
  2. Procédé selon la revendication 1, où le composé Cr(VI) est CrO3.
  3. Procédé selon l'une des revendications précédentes, où l'acide sulfonique aliphatique est l'acide méthanesulfonique.
  4. Procédé selon l'une des revendications précédentes, où le composé formant un film cathodique dense est (NH4)6Mo7O24 . 4 H2O.
  5. Procédé selon l'une des revendications précédentes, où l'électrolyte ne contient sensiblement pas de fluorures.
  6. Procédé selon l'une des revendications précédentes, où l'on travaille avec une densité de courant de 20 A/dm2 à 200 A/dm2.
  7. Couche de chrome dur structurée, obtenue d'après les procédés selon l'une des revendications 1 à 6.
EP03773629A 2002-11-29 2003-09-18 Production de couches en chrome dur structurees Expired - Lifetime EP1565596B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10255853 2002-11-29
DE2002155853 DE10255853A1 (de) 2002-11-29 2002-11-29 Herstellung strukturierter Hartchromschichten
PCT/EP2003/010425 WO2004050960A1 (fr) 2002-11-29 2003-09-18 Production de couches en chrome dur structurees

Publications (2)

Publication Number Publication Date
EP1565596A1 EP1565596A1 (fr) 2005-08-24
EP1565596B1 true EP1565596B1 (fr) 2006-08-09

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Country Status (8)

Country Link
US (2) US7699970B2 (fr)
EP (1) EP1565596B1 (fr)
JP (1) JP4373923B2 (fr)
AU (1) AU2003282018A1 (fr)
BR (1) BRPI0315192B1 (fr)
DE (2) DE10255853A1 (fr)
PT (1) PT1565596E (fr)
WO (1) WO2004050960A1 (fr)

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DE102007038188A1 (de) 2007-08-13 2009-02-19 Federal-Mogul Burscheid Gmbh Verschleißfest beschichtetes Maschinenelement und Verfahren zu dessen Herstellung
WO2011014897A1 (fr) 2009-08-04 2011-02-10 Technische Universität Wien Procédé de production de couches de chrome structurées
DE102009028223A1 (de) 2009-08-04 2011-02-24 Koenig & Bauer Aktiengesellschaft Verfahren und Herstellung strukturierter Chromschichten

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DE10255853A1 (de) 2002-11-29 2004-06-17 Federal-Mogul Burscheid Gmbh Herstellung strukturierter Hartchromschichten
DE102004019370B3 (de) * 2004-04-21 2005-09-01 Federal-Mogul Burscheid Gmbh Herstellung einer strukturierten Hartchromschicht und Herstellung einer Beschichtung
DE102004039056A1 (de) * 2004-08-11 2006-03-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung eines Substrats für Solarzellen, derartige Substrate sowie deren Verwendung
CN100344797C (zh) * 2004-09-20 2007-10-24 南京飞燕活塞环股份有限公司 一种球铁环镀铬工艺及其镀液
DE102005022692A1 (de) * 2005-05-18 2006-11-23 Robert Bosch Gmbh Verfahren zur Herstellung beschichteter Oberflächen und Verwendung derselben
DE102006042076A1 (de) * 2006-09-05 2008-03-20 Goldschmidt Tib Gmbh Ein neues Additiv für Chromelektrolyte
DE102008017270B3 (de) * 2008-04-04 2009-06-04 Federal-Mogul Burscheid Gmbh Strukturierte Chrom-Feststoffpartikel-Schicht und Verfahren zu deren Herstellung sowie beschichtetes Maschinenelement
DE102011084051B4 (de) 2011-10-05 2020-03-12 Federal-Mogul Burscheid Gmbh Beschichteter Kolbenring mit radial zunehmender Schichtdicke und Verfahren zu dessen Herstellung
DE102011084052A1 (de) 2011-10-05 2013-04-11 Federal-Mogul Burscheid Gmbh Beschichteter Kolbenring mit scharfer Ölabstreifkante
CN105734631B (zh) * 2014-12-10 2019-03-19 上海宝钢工业技术服务有限公司 冷轧轧辊毛化处理的电镀方法
CN109537002B (zh) * 2018-12-07 2020-10-27 重庆立道新材料科技有限公司 一种超高硬度镀铬添加剂及其应用

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DE102007038188A1 (de) 2007-08-13 2009-02-19 Federal-Mogul Burscheid Gmbh Verschleißfest beschichtetes Maschinenelement und Verfahren zu dessen Herstellung
WO2011014897A1 (fr) 2009-08-04 2011-02-10 Technische Universität Wien Procédé de production de couches de chrome structurées
DE102009028223A1 (de) 2009-08-04 2011-02-24 Koenig & Bauer Aktiengesellschaft Verfahren und Herstellung strukturierter Chromschichten

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BR0315192A (pt) 2005-08-23
US20100112376A1 (en) 2010-05-06
DE50304610D1 (de) 2006-09-21
US20060054509A1 (en) 2006-03-16
EP1565596A1 (fr) 2005-08-24
US8277953B2 (en) 2012-10-02
PT1565596E (pt) 2006-12-29
WO2004050960A1 (fr) 2004-06-17
US7699970B2 (en) 2010-04-20
BRPI0315192B1 (pt) 2015-10-13
JP2006508243A (ja) 2006-03-09
AU2003282018A1 (en) 2004-06-23
JP4373923B2 (ja) 2009-11-25
DE10255853A1 (de) 2004-06-17

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