EP1565596B1 - Production de couches en chrome dur structurees - Google Patents
Production de couches en chrome dur structurees Download PDFInfo
- 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
- Authority
- 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
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011651 chromium Substances 0.000 claims description 47
- 229910052804 chromium Inorganic materials 0.000 claims description 45
- 239000003792 electrolyte Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- -1 Cr(VI) compound Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 2
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims 1
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 81
- 238000000576 coating method Methods 0.000 description 10
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000004673 fluoride salts Chemical class 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical group 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005592 electrolytic dissociation Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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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
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- 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)
- 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.
- Procédé selon la revendication 1, où le composé Cr(VI) est CrO3.
- Procédé selon l'une des revendications précédentes, où l'acide sulfonique aliphatique est l'acide méthanesulfonique.
- Procédé selon l'une des revendications précédentes, où le composé formant un film cathodique dense est (NH4)6Mo7O24 . 4 H2O.
- Procédé selon l'une des revendications précédentes, où l'électrolyte ne contient sensiblement pas de fluorures.
- Procédé selon l'une des revendications précédentes, où l'on travaille avec une densité de courant de 20 A/dm2 à 200 A/dm2.
- Couche de chrome dur structurée, obtenue d'après les procédés selon l'une des revendications 1 à 6.
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 |
Family
ID=32318822
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP03773629A Expired - Lifetime EP1565596B1 (fr) | 2002-11-29 | 2003-09-18 | Production de couches en chrome dur structurees |
Country Status (8)
Country | Link |
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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) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Families Citing this family (11)
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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 |
DE102011084052B4 (de) | 2011-10-05 | 2024-05-29 | 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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DE10001888A1 (de) * | 2000-01-19 | 2001-07-26 | Rheinmetall W & M Gmbh | Verfahren zur Innenbeschichtung eines Waffenrohres |
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-
2002
- 2002-11-29 DE DE2002155853 patent/DE10255853A1/de not_active Withdrawn
-
2003
- 2003-09-18 JP JP2004556080A patent/JP4373923B2/ja not_active Expired - Fee Related
- 2003-09-18 PT PT03773629T patent/PT1565596E/pt unknown
- 2003-09-18 AU AU2003282018A patent/AU2003282018A1/en not_active Abandoned
- 2003-09-18 DE DE50304610T patent/DE50304610D1/de not_active Expired - Lifetime
- 2003-09-18 US US10/536,665 patent/US7699970B2/en not_active Expired - Fee Related
- 2003-09-18 WO PCT/EP2003/010425 patent/WO2004050960A1/fr active IP Right Grant
- 2003-09-18 EP EP03773629A patent/EP1565596B1/fr not_active Expired - Lifetime
- 2003-09-18 BR BRPI0315192A patent/BRPI0315192B1/pt not_active IP Right Cessation
-
2010
- 2010-01-07 US US12/683,890 patent/US8277953B2/en active Active
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Also Published As
Publication number | Publication date |
---|---|
US20060054509A1 (en) | 2006-03-16 |
JP4373923B2 (ja) | 2009-11-25 |
WO2004050960A1 (fr) | 2004-06-17 |
BRPI0315192B1 (pt) | 2015-10-13 |
PT1565596E (pt) | 2006-12-29 |
US7699970B2 (en) | 2010-04-20 |
US8277953B2 (en) | 2012-10-02 |
AU2003282018A1 (en) | 2004-06-23 |
EP1565596A1 (fr) | 2005-08-24 |
BR0315192A (pt) | 2005-08-23 |
JP2006508243A (ja) | 2006-03-09 |
DE10255853A1 (de) | 2004-06-17 |
US20100112376A1 (en) | 2010-05-06 |
DE50304610D1 (de) | 2006-09-21 |
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