EP1114209B1 - Hard-chrome plated layer - Google Patents
Hard-chrome plated layer Download PDFInfo
- Publication number
- EP1114209B1 EP1114209B1 EP00943813A EP00943813A EP1114209B1 EP 1114209 B1 EP1114209 B1 EP 1114209B1 EP 00943813 A EP00943813 A EP 00943813A EP 00943813 A EP00943813 A EP 00943813A EP 1114209 B1 EP1114209 B1 EP 1114209B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chromium
- hard
- particles
- galvanic
- coat
- 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
Links
- 239000002245 particle Substances 0.000 claims abstract description 82
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 45
- 239000010432 diamond Substances 0.000 claims abstract description 45
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 37
- 239000011651 chromium Substances 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 102
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 229910052580 B4C Inorganic materials 0.000 claims description 2
- 238000005275 alloying Methods 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229910003470 tongbaite Inorganic materials 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 3
- 229910052582 BN Inorganic materials 0.000 claims 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims 1
- 229910001096 P alloy Inorganic materials 0.000 claims 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 description 16
- 238000007747 plating Methods 0.000 description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- -1 chrome hydride Chemical class 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 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 4
- 238000005461 lubrication Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
-
- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/625—Discontinuous layers, e.g. microcracked layers
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/923—Physical dimension
- Y10S428/924—Composite
- Y10S428/926—Thickness of individual layer specified
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/934—Electrical process
- Y10S428/935—Electroplating
-
- 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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49229—Prime mover or fluid pump making
- Y10T29/49274—Piston ring or piston packing making
- Y10T29/49281—Piston ring or piston packing making including coating or plating
-
- 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
- Y10T428/12458—All metal or with adjacent metals having composition, density, or hardness gradient
-
- 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
- Y10T428/12479—Porous [e.g., foamed, spongy, cracked, 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
- Y10T428/12486—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.]
- Y10T428/12639—Adjacent, identical composition, components
-
- 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
Definitions
- the invention relates to a galvanic hard chrome layer, in particular for one Piston ring, consisting essentially of an electrolyte containing hexavalent chromium is formed, with cracks on the layer and diamond cracks in these cracks are stored.
- Galvanic hard chrome layers have been in the prior art for a long time known and are used, for example, as a surface coating for shock absorber pistons, Hydraulic parts, piston rings and pressure rollers are used.
- the workpiece to be chrome-plated then becomes during chrome-plating first switched cathodically so that a micro-cracked chrome layer forms, then the workpiece is switched anodically, so that the microcracks extend to the desired gap width widen and the cracks fill with solid particles, and then again occurs a cathodic circuit so that the solid particles by closing the cracks encapsulated and enclosed.
- This periodic current reversal can if necessary, be repeated several times, the chrome plating parameters correspondingly the application can be varied so that the desired crack width, crack density and Crack filling with possibly different solid particle fillings arise.
- a method of making a hard chrome composite coating on a substrate the comprises a disperse phase and is particularly suitable for mechanical components which are subject to high temperature friction, is described in European patent EP 0 668 375 B1.
- This method includes the step of galvanic Deposition of at least one hard chrome layer in a chrome plating bath of the type which Forms microcracks and in which a predetermined concentration of particles of a given Size of a non-metal insoluble in the bath is dispersed in suspension, wherein together in the course of said deposition step, the substrate permanently Cathode potential maintained and a pulsating cathode current that cycled with time changed between a minimum and a maximum value, is supplied to a To achieve a chrome layer that has a matrix with microcracks of a given distribution and one comprises disperse phase, which consists of said non-metal particles, some of which are in the Microcracks included and some embedded directly into the matrix, the Chrome plating bath is a bath based on chromic acid, which is
- Another known piston ring which is described in European patent application EP 0 841 414 A1 is different from that from EP 0 841 413 A1 in that in the Cracked round aluminum particles are included, the average Particle size is between 0.7 and 10 ⁇ m and the dispersion ratio of the round Aluminum particles in the electrolyte is 3 to 15% by volume.
- German patent application DE 197 45 811 A1 finally describes a galvanic Hard chrome layer with one extending partially or entirely through the layer thickness Crack network and solid particles embedded and encapsulated in the cracks there is at least two layers of hard chrome, with at least one layer under pulsing Direct current is deposited, so that the chromium in different crystallization forms is present.
- the hard chrome can additionally with the metals tungsten, vanadium and / or Molybdenum alloyed.
- From US-A-4 846 940 is the use of diamond particles of a size about 0.5 - 15 ⁇ m for the production of galvanic hard chrome layers.
- EP-A-0 668 375 describes the production of hard chrome layers under Use of hard materials that can also consist of diamond. A particle size 0.1 - 20 ⁇ m is considered suitable.
- the object of the invention based on providing a galvanic hard chrome layer, the improved physical Properties such as improved wear resistance and Resistance to seizure.
- This object is achieved with a generic galvanic hard chrome layer in which the diamond particles have a size in the range from 0.25 to 0.4 ⁇ m.
- the diamond particle size indicated does not mean that all particles are necessarily one must have the same size, rather they can be of a different size have, which should only be in the range of 0.25 to 0.4 ⁇ m.
- the galvanic chrome layer according to the invention is essentially made of one hexavalent chromium-containing electrolytes formed, which from the hexavalent Chromium formed by electrolytes in contrast to one made from trivalent electrolyte Chromium formed has more lattice defects, since that from a hexavalent electrolyte formed chrome in addition to the cubic body-centered chrome more hexagonal chrome hydride contains what is due to the strong hydrogen formation during the electrodeposition is due. This results in a larger number of lattice defects and thus also in an even greater hardness of the deposited chrome.
- the hard chrome layer according to the invention does not necessarily have to be pure Act chrome. On the contrary, the alloying of the Chromium, especially with the metals molybdenum, vanadium and tungsten, may be advantageous.
- the galvanic according to the invention could Hard chrome layer can achieve significantly better results than with the coatings, such as they have so far been used.
- An electroplated hard chrome layer according to the invention with diamond inclusions shows also at high thermal loads, under which the layers previously used can reach their application limits with aluminum oxide particles, far improved Characteristics.
- Diamond converts to graphite at higher temperatures.
- the temperature of the Layer e.g. B. is applied to a piston ring tread, so high that a Burn marks appear.
- the diamond particles change advantageously in graphite, which then takes on lubrication tasks and thus the Prevention of burn marks.
- the layer according to the invention thus also has very good properties Emergency running properties, especially due to the conversion of diamond to graphite Temperatures of approx. 700 ° C or higher.
- the hard chrome layer according to the invention can preferably be produced by on and for known chromium plating baths with solid particles dispersed therein are used, as they have been known from the prior art for a long time.
- chrome plating the workpiece to be chromed is first switched cathodically, so that there is a Micro-cracked hard chrome layer forms, then the workpiece is anodically switched so that the micro cracks widen to the desired gap width and the cracks widen with the Fill diamond particles.
- the hard chrome layer according to the invention is not made of pure chrome, but of a Alloy elements are formed in the chromium plating electrolyte as Salts dissolved and galvanically deposited together with the chrome.
- the Alloy elements preferably in amounts of 0.1 to 30 percent by weight in the Chrome layer present. Such layers are still compared to pure chrome layers more wear-resistant and ductile.
- the entire thickness of the electroplated hard chrome layer according to the invention should preferably be used be several times larger than the particle size of the particles. This is desirable for yourself the particles can be completely embedded in the crack network formed in the hard chrome layer and not only individual particles are only partially embedded in the chrome layer. Most of the time it is it is also desirable that the cracks are filled with many diamond particles.
- the thickness of the Hard chrome layer according to the invention is preferably between 0.0005 and 1.0 mm.
- the gap width of the cracks in the galvanic chrome layer according to the invention should be larger than the particles to be stored.
- the galvanic hard chrome layer according to the invention is above 0.3 ⁇ m, in particular is above 0.5 ⁇ m, so that solid particles can be embedded in the cracks at all not the cracks are too small for the diamond particles.
- Hard chrome layer can be achieved if it consists of at least two layers of chrome layer consists. It was observed that the cracks in the chrome layer were not always continuous be formed. If thinner layers are applied and the particles each in the cracks of the individual layers, a coating can be achieved which better distribution of the diamond particles in the coating both in their entire thickness, as well as across their surface, since the cracks are not always in the same places be formed.
- the thickness of the individual layers is preferably about 0.0005 to 0.5 mm.
- the hard chrome layer according to the invention consists of at least two layers, then the individual layers z. B. also different heights or completely different Have alloy components. This can be done depending on the shift requirements or be suitably selected for the material to be coated.
- the galvanic chromium layer is now formed in such a way that the at least two chromium layer layers have a different crystal structure, the strength properties of the layer according to the invention can be further improved.
- the chromium is deposited from the electrolyte on the cathodically connected workpiece with pulsating direct current with current densities between 5 and 250 A / dm 2 , so that several layers of hard chromium with different crystallization forms are deposited in the chromium layer according to the current density.
- the workpiece is switched anodically, so that the crack network in hard chrome expands and fills with the solid particles.
- the layers of different crystal structures are preferably alternated deposited on top of each other.
- Such a galvanic hard chrome layer according to the invention showed even further improvements Properties such as a longer service life at extreme temperature and Wear loads. Perhaps this is due to the fact that the different crystal structures of the two layers, high lattice voltages, in particular occur at the interfaces, which not only makes the layer harder overall, but also also improved other mechanical properties of the hard chrome layer according to the invention become.
- the electroplated hard chrome layer according to the invention in particular then excellent properties, preferably very good seizure resistance and wear resistance, if the proportion of diamond particles in the chrome layer is not chosen too high.
- the layer according to the invention shows particularly good properties if the proportion of Diamond particles in the chrome layer is 0.1 to 10 wt .-%.
- Hard material particles can all particles of hard materials familiar to the person skilled in the art include, but in particular come tungsten carbide, chromium carbide, aluminum oxide, Silicon carbide, silicon nitride, boron carbide and / or cubic bomitride are possible.
- the inclusion of further hard material particles can occur, among other things, when high pressures and insufficient lubrication may be advantageous if the temperature is e.g. B. on the Piston ring running surface for which the layers according to the invention, for. B. can be used can, is so high that the diamond particles convert into graphite and Take on lubrication tasks. At this point, however, the diamond alone can no longer serve to improve wear resistance. Here the sit down excellent properties of the hard material particles present next to the diamond and prevent unnecessarily high wear of the galvanic according to the invention Hard chrome layer.
- Solid lubricant particles continued to crack solid particles to increase the ductility of the Corrosion resistance and / or solid particles are contained as dyes.
- the layer according to the invention can incorporate further particles in addition to the hard material particles suitable for the respective application.
- Solid lubricant particles for example hexagonal bomitride, graphite and / or Polymer particles, in particular made of polyethylene and / or polytetrafluoroethylene, additionally in the Cracks are introduced.
- Ductile metals can be used to increase the ductility of the hard chrome layer according to the invention or tin, titanium or aluminum alloys.
- the cracks can be coated with polyethylene, for example filled and then melted in the cracks, so that the cracks sealed and protected against corrosive attacks.
- Different particles can also be used in addition to the diamond particles to fill the cracks be used.
- the diamond particles embedded in the galvanic chrome layer are advantageously made of mono- and / or polycrystalline diamond.
- Polycrystalline diamond that is only synthetic is currently more expensive than monocrystalline diamond, however better results are achieved with polycrystalline diamond, since a polycrystalline Diamond has many sliding planes due to the many different crystals.
- the high wear resistance of the galvanic chrome layer according to the invention brings about however, that this layer runs in relatively slowly. This is particularly the case with Use of the layer on piston rings is not so desirable because of negative effects in oil consumption and emissions in this phase. Improvements can be made here with special surface topographies, such as those with a special lapping be realized, and / or with the development of piston ring coatings that improve the running-in achieve that on the wear-resistant base layers galvanically, by means of PVD or CVD or other methods familiar to a person skilled in the art are to be applied.
- a dispersion layer based on nickel-cobalt-phosphorus can be used for this Silicon nitride can be used as dispersants, which with high fire protection ensures the required fast running-in.
- the layer graded is.
- the grading can, for example, be chosen such that it is on the tread has reduced solids content. The solids can go out decrease and even not at all in the outermost layer area layer according to the invention may be present.
- the solids content can also toward the free surface of the hard chrome layer to accept.
- the layer according to the invention can also be graded Lubricants and / or the other particles contained in the layer.
- the galvanic hard chrome layer according to the invention can also be advantageous if surface hardening is also carried out.
- nitriding since it can be carried out very well defined, i. H. it can either be nitrided the entire surface or only certain, exactly defined areas.
- the nitriding of surfaces is usually carried out by means of plasma nitriding carried out.
- the galvanic chrome layer according to the invention can also be one Surface hardening by means of ion implantation, for example with nitrogen become.
- the galvanic chrome layer according to the invention can be advantageously as a tread coating for temperature and wear Use machine parts and particularly preferably for piston rings, as they are at rubbing wear and has proven particularly effective when used in high temperatures.
- Chrome plating takes place at a temperature of 60 ° C.
- the workpiece to be chrome-plated is first switched cathodically in a first stage and chrome-plated for 8 minutes at a current density of 65 A / dm 3 .
- the polarity is reversed and the crack network of the previously deposited chromium layer is expanded and filled with diamond particles by anodic switching of the workpiece for one minute at a current density of 60 A / dm 3 .
- This cycle namely "cathodic chrome plating" for 8 minutes and "anodic etching" for 1 minute, is repeated a total of 20 times, resulting in a layer with a layer thickness of approximately 140 ⁇ m, which has a diamond content of 3-5% by weight. of the entire layer.
- the chrome plating takes place for a total of 5 hours at 55 ° C. to form a chrome layer with a total thickness of 0.2 mm.
- the workpiece to be chrome-plated is first connected cathodically in a first stage and chrome-plated for 30 minutes at a current density of 65 A / dm 3 .
- the polarity is reversed and the crack network of the previously deposited chromium layer is expanded by anodic switching of the workpiece for 30 seconds at a current density of 150 A / dm 3 and filled with diamond and aluminum oxide particles.
- This cycle is repeated a total of 10 times, resulting in a layer with a layer thickness of approximately 145 ⁇ m, which has a diamond content of 1-3% by weight of the entire layer.
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Abstract
Description
Die Erfindung bezieht sich auf eine galvanische Hartchromschicht, insbesondere für einen Kolbenring, die im wesentlichen aus einem sechswertiges Chrom enthaltenden Elektrolyten gebildet ist, wobei sich an der Schicht Risse befinden und in diese Risse Diamantpartikel eingelagert sind.The invention relates to a galvanic hard chrome layer, in particular for one Piston ring, consisting essentially of an electrolyte containing hexavalent chromium is formed, with cracks on the layer and diamond cracks in these cracks are stored.
Galvanische Hartchromschichten sind aus dem Stand der Technik schon seit längerer Zeit bekannt und werden beispielsweise als Oberflächenbeschichtung bei Stoßdämpferkolben, Hydraulikteilen, Kolbenringen und Druckwalzen verwendet.Galvanic hard chrome layers have been in the prior art for a long time known and are used, for example, as a surface coating for shock absorber pistons, Hydraulic parts, piston rings and pressure rollers are used.
Obwohl für galvanisches Chromabscheiden immer noch relativ viel Energie benötigt wird, ist die galvanische Chromabscheidung hinsichtlich der Verwertung von Resourcen sehr ökonomisch, da nahezu 100% des Chromelektrolyten auch als Chromschicht abgeschieden werden kann, weshalb galvanische Chromschichten auch heute noch häufig verwendet werden.Although a relatively large amount of energy is still required for electrodeposition of chrome, it is galvanic chromium deposition very economical with regard to the utilization of resources, since almost 100% of the chrome electrolyte can also be deposited as a chrome layer, which is why galvanic chrome layers are still used frequently today.
So wird in der europäischen Patentschrift EP 0 217 126 eine galvanische Hartchromschicht der eingangs genannten Art mit einem durch die gesamte Schichtdicke sich erstreckenden Rißnetzwerk beschrieben, in deren Risse Feststoffpartikel eingelagert sind. Die Herstellung einer solchen Chromschicht erfolgt dabei durch an sich bekannte mikrorißbildende Verchromungsbäder, wie bevorzugt saure Chromsäurebäder, mit darin dispergierten Feststoffteilchen. Während des Verchromens wird dann das zu verchromende Werkstück zunächst kathodisch geschaltet, so daß sich eine mikrorissige Chromschicht bildet, danach wird das Werkstück anodisch geschaltet, so daß sich die Mikrorisse auf die gewünschte Spaltbreite aufweiten und die Risse sich mit Feststoffpartikeln füllen, und anschließend erfolgt wiederum eine kathodische Schaltung, so daß die Feststoffteilchen durch Schließen der Risse eingekapselt und eingeschlossen werden. Diese periodische Stromumkehr kann gegebenenfalls mehrfach wiederholt werden, wobei die Verchromungsparameter entsprechend dem Anwendungsfall so variiert werden können, daß die gewünschte Rißbreite, Rißdichte und Rißfüllung mit gegebenenfalls unterschiedlichen Feststoffpartikelfüllungen entstehen. For example, in European patent EP 0 217 126 a galvanic hard chrome layer is used initially mentioned type with one extending through the entire layer thickness Crack network described, in the cracks solid particles are embedded. The production Such a chromium layer takes place through microcracking agents known per se Chromium plating baths, such as preferably acidic chromic acid baths, with dispersed therein Solid particles. The workpiece to be chrome-plated then becomes during chrome-plating first switched cathodically so that a micro-cracked chrome layer forms, then the workpiece is switched anodically, so that the microcracks extend to the desired gap width widen and the cracks fill with solid particles, and then again occurs a cathodic circuit so that the solid particles by closing the cracks encapsulated and enclosed. This periodic current reversal can if necessary, be repeated several times, the chrome plating parameters correspondingly the application can be varied so that the desired crack width, crack density and Crack filling with possibly different solid particle fillings arise.
Ein Verfahren zum Herstellen eines Hartchrom-Kompositüberzuges auf einem Substrat, der eine disperse Phase umfaßt und besonders für mechanische Komponenten geeignet ist, die einer Hochtemperatur-Reibung unterworfen sind, wird in der europäischen Patentschrift EP 0 668 375 B1 angegeben. Dieses Verfahren umfaßt dabei den Schritt der galvanischen Abscheidung wenigstens einer Hartchromschicht in einem Chromplattierungsbad des Typs, der Mikrorisse bildet und in dem eine vorbestimmte Konzentration von Partikeln einer gegebenen Größe eines in dem Bad unlöslichen Nichtmetalls in Suspension dispergiert wird, wobei gemeinsam im Verlauf des besagten Abscheidungsschrittes das Substrat permanent bei Kathodenpotential gehalten und ein pulsierender Kathodenstrom, der sich zyklisch mit der Zeit zwischen einem Minimal- und einem Maximalwert verändert, zugeführt wird, um eine Chromschicht zu erzielen, die eine Matrix mit Mikrorissen einer gegebenen Verteilung und eine disperse Phase umfaßt, die aus besagten Nichtmetallpartikeln besteht, von denen einige in den Mikrorissen eingeschlossen und einige direkt in die Matrix eingebettet sind, wobei das Chromplattierungsbad ein auf Chromsäure basierendes Bad ist, das in Lösung vorherrschend sechswertiges Chrom enthält. Auch ein mit diesem Verfahren hergestellter Überzug, der einen relativ geringen Wasserstoffgehalt aufweist, wird in dieser Europäischen Patentschrift beschrieben.A method of making a hard chrome composite coating on a substrate, the comprises a disperse phase and is particularly suitable for mechanical components which are subject to high temperature friction, is described in European patent EP 0 668 375 B1. This method includes the step of galvanic Deposition of at least one hard chrome layer in a chrome plating bath of the type which Forms microcracks and in which a predetermined concentration of particles of a given Size of a non-metal insoluble in the bath is dispersed in suspension, wherein together in the course of said deposition step, the substrate permanently Cathode potential maintained and a pulsating cathode current that cycled with time changed between a minimum and a maximum value, is supplied to a To achieve a chrome layer that has a matrix with microcracks of a given distribution and one comprises disperse phase, which consists of said non-metal particles, some of which are in the Microcracks included and some embedded directly into the matrix, the Chrome plating bath is a bath based on chromic acid, which is predominant in solution contains hexavalent chromium. Also a coating made with this process, the one has a relatively low hydrogen content is described in this European patent described.
Es ist ferner aus der europäischen Patentanmeldung EP 0 841 413 A1 ein Kolbenring mit einer nitrierten Schicht über seiner gesamten Oberfläche bekannt, auf dessen Oberflächen eine Chrom-Verbund-Schicht ausgebildet ist. Diese Schicht weist ein Rißnetzwerk auf, das an ihrer Außenoberfläche und innen gebildet ist. Si3N4-Partikel sind in diesen Rissen eingeschlossen, wobei die durchschnittliche Größe der Si3N4-Partikel 0,8 bis 3 µm und das Dispersionsverhältnis dieser Partikel im Elektrolyten 3 bis 15 Vol.-% beträgt. Mit einer solchen Oberflächenbeschichtung soll eine verbesserte Abrieb- und Freßbeständigkeit erreicht werden.From the European patent application EP 0 841 413 A1 a piston ring with a nitrided layer over its entire surface is known, on the surfaces of which a chromium composite layer is formed. This layer has a crack network which is formed on its outer surface and on the inside. Si 3 N 4 particles are enclosed in these cracks, the average size of the Si 3 N 4 particles being 0.8 to 3 μm and the dispersion ratio of these particles in the electrolyte being 3 to 15% by volume. With such a surface coating, improved abrasion and seizure resistance is to be achieved.
Ein weiterer bekannter Kolbenring, der in der europäischen Patentanmeldung EP 0 841 414 A1 beschrieben wird, unterscheidet sich von dem aus der EP 0 841 413 A1 dadurch, daß in den Rissen runde Aluminium-Partikel eingeschlossen sind, wobei die durchschnittliche Partikelgröße zwischen 0,7 und 10 µm liegt und das Dispersionsverhältnis der runden Aluminium-Partikel im Elektrolyten 3 bis 15 Vol.-% beträgt.Another known piston ring, which is described in European patent application EP 0 841 414 A1 is different from that from EP 0 841 413 A1 in that in the Cracked round aluminum particles are included, the average Particle size is between 0.7 and 10 µm and the dispersion ratio of the round Aluminum particles in the electrolyte is 3 to 15% by volume.
Die deutsche Offenlegungsschrift DE 197 45 811 A1 beschreibt schließlich eine galvanische Hartchromschicht mit einem sich teilweise oder ganz durch die Schichtdicke erstreckenden Rißnetzwerk und in den Rissen eingelagerten und eingekapselten Feststoffpartikeln, die aus mindestens zwei Lagen Hartchrom besteht, wobei mindestens eine Lage unter pulsierendem Gleichstrom abgeschieden wird, so daß das Chrom in unterschiedlicher Kristallisationsform vorliegt. Das Hartchrom kann dabei zusätzlich mit den Metallen Wolfram, Vanadium und/oder Molybdän legiert sein.The German patent application DE 197 45 811 A1 finally describes a galvanic Hard chrome layer with one extending partially or entirely through the layer thickness Crack network and solid particles embedded and encapsulated in the cracks there is at least two layers of hard chrome, with at least one layer under pulsing Direct current is deposited, so that the chromium in different crystallization forms is present. The hard chrome can additionally with the metals tungsten, vanadium and / or Molybdenum alloyed.
Aus der US-A-4 846 940 ist die Verwendung von Diamant partikeln einer Größe von etwa 0,5 - 15 µm zur Herstellung galvanischer Hartchromschichten bekannt.From US-A-4 846 940 is the use of diamond particles of a size about 0.5 - 15 µm for the production of galvanic hard chrome layers.
Die EP-A-0 668 375 beschreibt die Herstellung von Hartchromschichten unter Verwendung von Hartstoffen die auch aus Diamant bestehen können. Eine Partikelgröße von 0,1 - 20 µm wird als geeignet angesehen. Ausgehend von diesem bekannten Stand der Technik liegt der Erfindung die Aufgabe zugrunde, eine galvanische Hartchromschicht bereitzustellen, die verbesserte physikalische Eigenschaften, wie insbesondere eine verbesserte Verschleißbeständigkeit und Freßbeständigkeit, aufweist.EP-A-0 668 375 describes the production of hard chrome layers under Use of hard materials that can also consist of diamond. A particle size 0.1 - 20 µm is considered suitable. Starting from this known prior art, the object of the invention based on providing a galvanic hard chrome layer, the improved physical Properties such as improved wear resistance and Resistance to seizure.
Diese Aufgabe wird mit einer gattungsgemäßen galvanischen Hartchromschicht gelöst, bei der die Diamantpartikel eine Größe im Bereich von 0,25 bis 0,4 µm besitzen.This object is achieved with a generic galvanic hard chrome layer in which the diamond particles have a size in the range from 0.25 to 0.4 μm.
Die angegebene Diamantpartikelgröße bedeutet jedoch nicht, daß alle Partikel unbedingt eine gleiche Größe aufweisen müssen, vielmehr können sie durchaus eine unterschiedliche Größe besitzen, die lediglich im Bereich von 0.25 bis 0,4 µm liegen soll.However, the diamond particle size indicated does not mean that all particles are necessarily one must have the same size, rather they can be of a different size have, which should only be in the range of 0.25 to 0.4 µm.
Die erfindungsgemäße galvanische Chromschicht wird dabei im wesentlichen aus einem sechswertiges Chrom enthaltenden Elektrolyten gebildet, wobei das aus dem sechswertigen Elektrolyten gebildete Chrom im Gegensatz zum einem aus dreiwertigem Elektrolyten gebildeten Chrom mehr Gitterdefekte aufweist, da das aus einem sechswertigen Elektrolyten gebildete Chrom neben dem kubisch raumzentrierten Chrom mehr hexagonales Chromhydrid enthält, was auf die starke Wasserstoffbildung bei der galvanischen Abscheidung zurückzuführen ist. Dies resultiert in einer größeren Anzahl von Gitterdefekten und somit auch in einer noch größeren Härte des abgeschiedenen Chroms.The galvanic chrome layer according to the invention is essentially made of one hexavalent chromium-containing electrolytes formed, which from the hexavalent Chromium formed by electrolytes in contrast to one made from trivalent electrolyte Chromium formed has more lattice defects, since that from a hexavalent electrolyte formed chrome in addition to the cubic body-centered chrome more hexagonal chrome hydride contains what is due to the strong hydrogen formation during the electrodeposition is due. This results in a larger number of lattice defects and thus also in an even greater hardness of the deposited chrome.
Bei der erfindungsgemäßen Hartchromschicht muß es sich nicht notwendigerweise um reines Chrom handeln. Ganz im Gegenteil kann für bestimmte Anwendungsfälle das Legieren des Chroms, vor allem mit den Metallen Molybdän, Vanadium und Wolfram, vorteilhaft sein.The hard chrome layer according to the invention does not necessarily have to be pure Act chrome. On the contrary, the alloying of the Chromium, especially with the metals molybdenum, vanadium and tungsten, may be advantageous.
Durch die Verwendung von Diamantpartikeln einer Größe im Bereich von 0,25 bis 0,4 µm wurde überraschenderweise erreicht, daß im Vergleich zu aus dem Stand der Technik bekannten, eingesetzten Partikelgrößen Schichten mit noch besseren Eigenschaften erreicht werden können.By using diamond particles in the size range from 0.25 to 0.4 µm Surprisingly achieved that compared to known from the prior art used particle sizes layers with even better properties can be achieved can.
Bisher werden üblicherweise für Kolbenringe Beschichtungen aus galvanischen Hartchromschichten mit im Rißnetzwerk eingelagerten Al2O3-Partikel der Partikelgröße 2 bis 5 µm eingesetzt. Diese Schichten haben bisher die besten Eigenschaften bezüglich der Verschleiß- und der Freßbeständigkeit gezeigt. Up to now, coatings made of galvanic hard chrome layers with Al 2 O 3 particles of particle size 2 to 5 µm embedded in the crack network have usually been used for piston rings. These layers have so far shown the best properties in terms of wear and seizure resistance.
Versuche mit Diamantpartikeln waren bisher wenig erfolgreich, da sich bei Verwendung von Diamantpartikeln einer Größe von 2 bis 5 µm, wie sie für Aluminiumoxidpartikel üblicherweise eingesetzt werden, nur galvanische Hartchromschichten erzielen ließen, die im Vergleich zu den mit Aluminiumoxidpartikeln gebildeten Schichten schlechtere Eigenschaften aufweisen und zudem auch noch wesentlich teurer sind.Experiments with diamond particles have so far been unsuccessful, since when using Diamond particles with a size of 2 to 5 µm, as is usually the case for aluminum oxide particles can be used, only galvanic hard chrome layers can be achieved, which compared to the layers formed with aluminum oxide particles have poorer properties and are also much more expensive.
Bei einem Versuch unter motorischen Bedingungen wurden mit einer erfindungsgemäßen Beschichtung versehenen Kolbenringe in einem 6-Zylinder Turbodieselmotor unter Vollast 85 Stunden lang eingesetzt. Als Ergebnis zeigt sich, daß bei einem im Vergleich zu bisher verwendeten galvanischem Chromschichten mit Aluminiumoxidpartikeln im wesentlichen etwa gleichen Zylinderverschleiß von ca. 0,17 µm/1000 km auch bei ansonsten gleichen Bedingungen mit der erfindungsgemäßen galvanischen Hartchromschicht ein um über die Hälfte verringerter Ringverschleiß auftrat, nämlich nur 0,2 µm/1000 km im Vergleich zu 0,5 µm/1000 km bei Verwendung einer üblichen galvanischen Hartchrombeschichtung mit Aluminiumoxidpartikeln als Kotbenringbeschichtung.In an experiment under motor conditions with an inventive Coated piston rings in a 6-cylinder turbodiesel engine under full load 85 Used for hours. The result shows that one compared to the previous used electroplated chrome layers with aluminum oxide particles essentially same cylinder wear of approx. 0.17 µm / 1000 km even with otherwise the same Conditions with the galvanic hard chrome layer according to the invention in order to Half reduced ring wear occurred, namely only 0.2 µm / 1000 km compared to 0.5 µm / 1000 km when using a conventional galvanic hard chrome coating with Aluminum oxide particles as a potting ring coating.
Daneben konnte in einem Simulationstest zur Freßbeständigkeit gezeigt werden, daß eine Chromschicht mit Diamanteinlagerungen mit einer Partikelgröße zwischen 0,25 und 0,5 µm im Vergleich zu bisher verwendeten Chromschichten mit Aluminiumoxideinlagerungen einer Größe 2 bis 5 µm eine um über 20 % verbesserte Freßbeständigkeit (nämlich von 160 %) im Vergleich zu 130 % bei der Chromschicht mit Aluminiumoxidpartikeln eintrat.In addition, it could be shown in a simulation test on seizure resistance that a Chrome layer with diamond deposits with a particle size between 0.25 and 0.5 µm compared to previously used chrome layers Aluminum oxide deposits with a size of 2 to 5 µm improved by over 20% Resistance to seizure (namely of 160%) compared to 130% with the chrome layer Aluminum oxide particles entered.
Auch bezüglich der Brandspurfestigkeit konnten mit der erfindungsgemäßen galvanischen Hartchromschicht deutlich bessere Ergebnisse erzielt werden als mit den Beschichtungen, wie sie bisher Anwendung fanden.Also with regard to the resistance to burn marks, the galvanic according to the invention could Hard chrome layer can achieve significantly better results than with the coatings, such as they have so far been used.
Eine erfindungsgemäße galvanische Hartchromschicht mit Diamanteinlagerungen zeigt außerdem bei hohen thermischen Belastungen, unter denen die bisher verwendeten Schichten mit Aluminiumoxidpartikeln an ihre Einsatzgrenzen kommen können, weitaus verbesserte Eigenschaften. Diamant wandelt sich bei höheren Temperaturen zu Graphit um. Beim Zusammentreffen von hohen Drücken und Mangelschmierung, kann die Temperatur der Schicht, die z. B. auf einer Kolbenringlauffläche aufgebracht wird, so hoch werden, daß eine Brandspurbildung auftritt. In dieser Situation wandeln sich die Diamantpartikel jedoch vorteilhafterweise in Graphit um, der dann Schmierungsaufgaben übernimmt und damit die Brandspurbildung verhindert. Somit besitzt die erfindungsgemäße Schicht auch noch sehr gute Notlaufeigenschaften, insbesondere aufgrund der Umwandlung von Diamant zu Graphit bei Temperaturen von ca. 700°C oder höher. An electroplated hard chrome layer according to the invention with diamond inclusions shows also at high thermal loads, under which the layers previously used can reach their application limits with aluminum oxide particles, far improved Characteristics. Diamond converts to graphite at higher temperatures. At the Coincidence of high pressures and insufficient lubrication, the temperature of the Layer, e.g. B. is applied to a piston ring tread, so high that a Burn marks appear. In this situation, however, the diamond particles change advantageously in graphite, which then takes on lubrication tasks and thus the Prevention of burn marks. The layer according to the invention thus also has very good properties Emergency running properties, especially due to the conversion of diamond to graphite Temperatures of approx. 700 ° C or higher.
Die erfindungsgemäße Hartchromschicht kann bevorzugt hergestellt werden, indem an und für sich bekannte Verchromungsbäder mit darin dispergierten Feststoffteilchen verwendet werden, wie sie aus dem Stand der Technik seit längerer Zeit bekannt sind. Während des Verchromens wird das zu verchromende Werkstück zunächst kathodisch geschaltet, so daß sich eine mikrorissige Hartchromschicht bildet, danach wird das Werkstück anodisch geschaltet, so daß sich die Mikrorisse auf die gewünschte Spaltbreite aufweiten und die Risse sich mit den Diamantpartikeln füllen.The hard chrome layer according to the invention can preferably be produced by on and for known chromium plating baths with solid particles dispersed therein are used, as they have been known from the prior art for a long time. During chrome plating the workpiece to be chromed is first switched cathodically, so that there is a Micro-cracked hard chrome layer forms, then the workpiece is anodically switched so that the micro cracks widen to the desired gap width and the cracks widen with the Fill diamond particles.
Soll die erfindungsgemäße Hartchromschicht nicht aus reinem Chrom, sondern aus einer Legierung gebildet sein, werden die Legierungselemente in dem Verchromungselektrolyten als Salze gelöst und zusammen mit dem Chrom galvanisch abgeschieden. Dabei sind die Legierungselemente, bevorzugt in Mengen von 0,1 bis 30 Gewichtsprozente in der Chromschicht vorhanden. Solche Schichten sind gegenüber reinen Chromschichten noch verschleißfester und duktiler.If the hard chrome layer according to the invention is not made of pure chrome, but of a Alloy elements are formed in the chromium plating electrolyte as Salts dissolved and galvanically deposited together with the chrome. Here are the Alloy elements, preferably in amounts of 0.1 to 30 percent by weight in the Chrome layer present. Such layers are still compared to pure chrome layers more wear-resistant and ductile.
Die gesamte Dicke der erfindungsgemäßen galvanischen Hartchromschicht sollte vorzugsweise um ein Mehrfaches größer sein als die Korngröße der Teilchen. Dies ist erwünscht, damit sich die Partikel vollständig in das in der Hartchromschicht gebildete Rißnetzwerk einlagern können und nicht nur einzelne Partikel nur teilweise in die Chromschicht eingelagert sind. Meist ist es durchaus auch erwünscht, daß die Risse mit vielen Diamantpartikeln ausgefüllt sind.The entire thickness of the electroplated hard chrome layer according to the invention should preferably be used be several times larger than the particle size of the particles. This is desirable for yourself the particles can be completely embedded in the crack network formed in the hard chrome layer and not only individual particles are only partially embedded in the chrome layer. Most of the time it is it is also desirable that the cracks are filled with many diamond particles.
Besonders vorteilhafte Ergebnisse lassen sich erreichen, wenn die Dicke der erfindungsgemäßen Hartchromschicht bevorzugt zwischen 0,0005 und 1,0 mm beträgt.Particularly advantageous results can be achieved if the thickness of the Hard chrome layer according to the invention is preferably between 0.0005 and 1.0 mm.
Die Spaltbreite der Risse in der erfindungsgemäßen galvanischen Chromschicht sollten größer als die einzulagernden Partikel sein. Eine bevorzugte Spaltbreite der Risse der erfindungsgemäßen galvanischen Hartchromschicht liegt oberhalb 0,3 µm, insbesondere oberhalb 0,5 µm ist, damit sich überhaupt Feststoffpartikel in die Risse einlagern können und nicht die Risse für die Diamantpartikel zu klein sind.The gap width of the cracks in the galvanic chrome layer according to the invention should be larger than the particles to be stored. A preferred gap width of the cracks The galvanic hard chrome layer according to the invention is above 0.3 μm, in particular is above 0.5 µm, so that solid particles can be embedded in the cracks at all not the cracks are too small for the diamond particles.
Es hat sich gezeigt, daß besonders hervorragende Eigenschaften bei der erfindungsgemäßen Hartchromschicht erzielt werden können, wenn sie aus mindestens zwei Chromschichtlagen besteht. Es wurde beobachtet, daß die Risse in der Chromschicht nicht immer durchgehend gebildet werden. Werden dünnere Schichten aufgetragen und die Partikel jeweils in die Risse der einzelnen Schichten eingebracht, so kann eine Beschichtung erreicht werden, die eine bessere Verteilung der Diamantpartikel in der Beschichtung sowohl in deren gesamter Dicke, als auch über deren Fläche hinweg, aufweist, da die Risse nicht immer an den selben Stellen gebildet werden.It has been shown that particularly excellent properties in the invention Hard chrome layer can be achieved if it consists of at least two layers of chrome layer consists. It was observed that the cracks in the chrome layer were not always continuous be formed. If thinner layers are applied and the particles each in the cracks of the individual layers, a coating can be achieved which better distribution of the diamond particles in the coating both in their entire thickness, as well as across their surface, since the cracks are not always in the same places be formed.
Die Dicke der einzelnen Lagen beträgt dabei bevorzugt etwa 0,0005 bis 0,5 mm.The thickness of the individual layers is preferably about 0.0005 to 0.5 mm.
Besteht die erfindungsgemäße Hartchromschicht aus mindestens zwei Schichten, so können die einzelnen Schichten z. B. auch verschieden hohe oder völlig unterschiedliche Legierungsbestandteile aufweisen. Dies kann je nach Anforderung an die Schicht beziehungsweise an den zu beschichtenden Werkstoff geeignet gewählt werden.If the hard chrome layer according to the invention consists of at least two layers, then the individual layers z. B. also different heights or completely different Have alloy components. This can be done depending on the shift requirements or be suitably selected for the material to be coated.
Wird die galvanische Chromschicht nun derart gebildet, daß die mindestens zwei Chromschichtlagen eine unterschiedliche Kristallstruktur aufweisen, so können die Festigkeitseigenschaften der erfindungsgemäßen Schicht noch weiter verbessert werden. Hierbei wird zur Herstellung mindestens einer Lage Hartchrom das Chrom aus dem Elektrolyten am kathodisch geschalteten Werkstück mit pulsierendem Gleichstrom mit Stromdichten zwischen 5 und 250 A/dm2 abgeschieden, so daß in der Chromlage entsprechend der Stromdichte mehrere Lagen Hartchrom mit unterschiedlicher Kristallisationsform abgeschieden werden. Nach jeweils einer Abscheidungsphase einer Lage wird das Werkstück anodisch geschaltet, so daß sich das Rißnetzwerk im Hartchrom aufweitet und mit den Feststoffpartikeln füllt.If the galvanic chromium layer is now formed in such a way that the at least two chromium layer layers have a different crystal structure, the strength properties of the layer according to the invention can be further improved. To produce at least one layer of hard chromium, the chromium is deposited from the electrolyte on the cathodically connected workpiece with pulsating direct current with current densities between 5 and 250 A / dm 2 , so that several layers of hard chromium with different crystallization forms are deposited in the chromium layer according to the current density. After each deposition phase of a layer, the workpiece is switched anodically, so that the crack network in hard chrome expands and fills with the solid particles.
Hierbei werden die Schichten unterschiedlicher Kristallstruktur bevorzugt abwechselnd übereinander abgeschieden.The layers of different crystal structures are preferably alternated deposited on top of each other.
Eine solche erfindungsgemäße galvanische Hartchromschicht zeigte noch weiter verbesserte Eigenschaften, wie beispielsweise eine höhere Lebensdauer bei extremen Temperatur- und Verschleißbelastungen. Dies ist vielleicht darauf zurückzuführen, daß durch die unterschiedlichen Kristallstrukturen der beiden Schichten hohe Gitterspannungen, insbesondere an den Grenzflächen entstehen, wodurch die Schicht insgesamt nicht nur härter wird, sondern auch andere mechanische Eigenschaften der erfindungsgemäßen Hartchromschicht verbessert werden.Such a galvanic hard chrome layer according to the invention showed even further improvements Properties such as a longer service life at extreme temperature and Wear loads. Perhaps this is due to the fact that the different crystal structures of the two layers, high lattice voltages, in particular occur at the interfaces, which not only makes the layer harder overall, but also also improved other mechanical properties of the hard chrome layer according to the invention become.
Es hat sich gezeigt, daß die erfindungsgemäße galvanische Hartchromschicht insbesondere dann hervorragende Eigenschaften, vorzugsweise sehr gute Freß- und der Verschleißfestigkeit, aufweist, wenn der Anteil der Diamantpartikel in der Chromschicht nicht zu hoch gewählt wird. Dabei zeigt die erfindungsgemäße Schicht besonders gute Eigenschaften, wenn der Anteil der Diamantpartikel in der Chromschicht 0,1 bis 10 Gew.-% beträgt. It has been shown that the electroplated hard chrome layer according to the invention in particular then excellent properties, preferably very good seizure resistance and wear resistance, if the proportion of diamond particles in the chrome layer is not chosen too high. The layer according to the invention shows particularly good properties if the proportion of Diamond particles in the chrome layer is 0.1 to 10 wt .-%.
Bei einer bevorzugten Ausführungsform der Erfindung sind in der galvanischen Chromschicht neben den Diamantpartikeln weitere Hartstoffpartikel in die Risse eingelagert. Diese anderen Hartstoffpartikel können hierbei alle den Fachmann geläufigen Partikel aus Hartstoffen umfassen, insbesondere kommen dabei aber Wolframkarbid, Chromcarbid, Aluminiumoxid, Siliziumkarbid, Siliziumnitrid, Borkarbid und/oder kubisches Bomitrid in Frage.In a preferred embodiment of the invention are in the galvanic chrome layer In addition to the diamond particles, other hard material particles are embedded in the cracks. These others Hard material particles can all particles of hard materials familiar to the person skilled in the art include, but in particular come tungsten carbide, chromium carbide, aluminum oxide, Silicon carbide, silicon nitride, boron carbide and / or cubic bomitride are possible.
Die Einlagerung weiterer Hartstoffpartikel kann unter anderem beim Zusammentreffen von hohen Drücken und Mangelschmierung vorteilhaft sein, wenn die Temperatur z. B. auf der Kolbenringlauffläche, für die die erfindungsgemäßen Schichten z. B. verwendet werden können, so hoch ist, daß sich die Diamantpartikel in Graphit umwandeln und Schmierungsaufgaben übernehmen. Zu diesem Zeitpunkt kann der Diamant alleine dann aber nicht mehr dazu dienen, die Verschleißbeständigkeit zu verbessern. Hier setzen sich dann die hervorragenden Eigenschaften der neben dem Diamant anwesenden Hartstoffteilchen durch und verhindern einen unnötig hohen Verschleiß der erfindungsgemäßen galvanischen Hartchromschicht.The inclusion of further hard material particles can occur, among other things, when high pressures and insufficient lubrication may be advantageous if the temperature is e.g. B. on the Piston ring running surface for which the layers according to the invention, for. B. can be used can, is so high that the diamond particles convert into graphite and Take on lubrication tasks. At this point, however, the diamond alone can no longer serve to improve wear resistance. Here the sit down excellent properties of the hard material particles present next to the diamond and prevent unnecessarily high wear of the galvanic according to the invention Hard chrome layer.
Vorteilhafterweise können in der erfindungsgemäßen galvanischen Hartchromschicht in den Rissen weiterhin Festschmierstoffpartikel, Feststoffpartikel zur Erhöhung der Duktilität, der Korrosionsfestigkeit und/oder Feststoffpartikel als Farbstoffe enthalten sind. Durch die Einlagerung weiterer Partikel neben den Hartstoffpartikein kann die erfindungsgemäße Schicht für die jeweilige Anwendung geeignet noch angepaßt werden. So können als Festschmierstoffteilchen beispielsweise hexagonales Bomitrid, Graphit und/oder Polymerteilchen, insbesondere aus Polyethylen und/oder Polytetrafluorethylen, zusätzlich in die Risse eingebracht werden.Advantageously, in the galvanic hard chrome layer according to the invention Solid lubricant particles continued to crack, solid particles to increase the ductility of the Corrosion resistance and / or solid particles are contained as dyes. Through the The layer according to the invention can incorporate further particles in addition to the hard material particles suitable for the respective application. So as Solid lubricant particles, for example hexagonal bomitride, graphite and / or Polymer particles, in particular made of polyethylene and / or polytetrafluoroethylene, additionally in the Cracks are introduced.
Zur Erhöhung der Duktilität der erfindungsgemäßen Hartchromschicht können duktile Metalle oder Metaillegierungen aus Zinn, Titan oder Aluminium eingelagert sein.Ductile metals can be used to increase the ductility of the hard chrome layer according to the invention or tin, titanium or aluminum alloys.
Zur Erhöhung der Korrosionsbeständigkeit können die Risse beispielsweise mit Polyethylen gefüllt und diese anschließend in den Rissen aufgeschmolzen werden, so daß die Risse damit versiegelt und gegenüber korrosiven Angriffen geschützt sind.To increase the corrosion resistance, the cracks can be coated with polyethylene, for example filled and then melted in the cracks, so that the cracks sealed and protected against corrosive attacks.
Es können auch unterschiedliche Teilchen neben den Diamantpartikeln zur Füllung der Risse eingesetzt werden.Different particles can also be used in addition to the diamond particles to fill the cracks be used.
Vorteilhafterweise sind die in der galvanischen Chromschicht eingelagerten Diamantpartikel aus mono- und/oder polykristallinem Diamant gebildet. Polykristalliner Diamant, der nur synthetisch hergestellt werden kann, ist zwar derzeit noch teurer als monokristalliner Diamant, jedoch werden mit polykristallinem Diamant die besseren Ergebnisse erzielt, da ein polykristalliner Diamant aufgrund der vielen verschiedenen Kristalle viele Gleitebenen aufweist.The diamond particles embedded in the galvanic chrome layer are advantageously made of mono- and / or polycrystalline diamond. Polycrystalline diamond that is only synthetic is currently more expensive than monocrystalline diamond, however better results are achieved with polycrystalline diamond, since a polycrystalline Diamond has many sliding planes due to the many different crystals.
Die hohe Verschleißfestigkeit der erfindungsgemäßen galvanischen Chromschicht bewirkt jedoch, daß das Einlaufen dieser Schicht relativ langsam erfolgt. Dies ist insbesondere bei der Verwendung der Schicht auf Kolbenringen nicht so wünschenswert, da negative Auswirkungen beim Ölverbrauch und der Emissionen in dieser Phase eintreten. Verbesserungen lassen sich hier mit speziellen Oberflächentopographien, wie sie bespielsweise mit einer Sonderläppung realisiert werden, und/oder mit der Entwicklung einlaufverbessemder Kolbenringbeschichtungen erreichen, die auf die verschleißbeständigen Basisschichten galvanisch, mittels PVD oder CVD oder anderen dem Fachmann geläufigen Verfahren aufzubringen sind.The high wear resistance of the galvanic chrome layer according to the invention brings about however, that this layer runs in relatively slowly. This is particularly the case with Use of the layer on piston rings is not so desirable because of negative effects in oil consumption and emissions in this phase. Improvements can be made here with special surface topographies, such as those with a special lapping be realized, and / or with the development of piston ring coatings that improve the running-in achieve that on the wear-resistant base layers galvanically, by means of PVD or CVD or other methods familiar to a person skilled in the art are to be applied.
Hierfür kann insbesondere eine Dispersionsschicht auf Nickel-Cobalt-Phosphor-Basis mit Siliziumnitrid als Dispersanten verwendet werden, die bei hoher Brandspursicherheit den geforderten schnellen Einlauf sicherstellt.In particular, a dispersion layer based on nickel-cobalt-phosphorus can be used for this Silicon nitride can be used as dispersants, which with high fire protection ensures the required fast running-in.
Eine weitere Möglichkeit, das Einlaufverhalten der erfindungsgemäßen galvanischen Chromschicht mit Diamanteinlagerungen zu verbessern besteht darin, daß die Schicht gradiert ist. Die Gradierung kann dabei beispielsweise derart gewählt sein, daß sie auf der Lauffläche reduzierte Feststoffanteile aufweist. Die Feststoffanteile können dabei nach außen hin abnehmen und im äußersten Schichtbereich sogar überhaupt nicht mehr in der erfindungsgemäßen Schicht vorhanden sein.Another possibility of the run-in behavior of the galvanic according to the invention Improving the chrome layer with diamond inclusions is that the layer graded is. The grading can, for example, be chosen such that it is on the tread has reduced solids content. The solids can go out decrease and even not at all in the outermost layer area layer according to the invention may be present.
Jedoch kann auch der Feststoffanteil in Richtung zur freien Oberfläche der Hartchromschicht hin zunehmen. Ferner kann die erfindungsgemäß Schicht aber auch eine Gradierung der Schmierstoffe und/oder der anderen in der Schicht enthaltenen Partikel aufweisen.However, the solids content can also toward the free surface of the hard chrome layer to accept. Furthermore, the layer according to the invention can also be graded Lubricants and / or the other particles contained in the layer.
Je nach Einsatz der erfindungsgemäßen galvanischen Hartchromschicht, kann es auch vorteilhaft sein, wenn zusätzlich eine Oberflächenhärtung durchgeführt wird. Hierbei ist bevorzugt das Nitrieren zu nennen, da es sehr gut definiert durchgeführt werden kann, d. h. es kann entweder die gesamte Oberfläche nitriert werden oder auch nur bestimmte, genau definierte Bereiche. Üblicherweise wird das Nitrieren von Oberflächen mittels Plasma-Nitrieren durchgeführt. Jedoch kann die erfindungsgemäße galvanische Chromschicht ebenso einer Oberflächenhärtung mittels Ionenimplantieren, beispielsweise mit Stickstoff, unterzogen werden.Depending on the use of the galvanic hard chrome layer according to the invention, it can also be advantageous if surface hardening is also carried out. Here is preferred to mention nitriding, since it can be carried out very well defined, i. H. it can either be nitrided the entire surface or only certain, exactly defined areas. The nitriding of surfaces is usually carried out by means of plasma nitriding carried out. However, the galvanic chrome layer according to the invention can also be one Surface hardening by means of ion implantation, for example with nitrogen become.
Wie schon erwähnt, läßt sich die erfindungsgemäße galvanische Chromschicht vorteilhafterweise als Laufflächenbeschichtung von temperatur- und verschleißbelasteten Maschinenteilen und dabei besonders bevorzugt für Kolbenringe verwenden, da sie sich bei reibendem Verschleiß und beim Einsatz in hohen Temperaturen besonders bewährt hat.As already mentioned, the galvanic chrome layer according to the invention can be advantageously as a tread coating for temperature and wear Use machine parts and particularly preferably for piston rings, as they are at rubbing wear and has proven particularly effective when used in high temperatures.
Im folgenden soll die Erfindung anhand bevorzugter Ausführungsbeispiele noch näher erläutert werden:The invention is to be explained in more detail below on the basis of preferred exemplary embodiments become:
Zur Verchromung wird ein rißbildender Elektrolyt eingesetzt, der folgende Bestandteile enthält:
In ihm werden durch Rühren 50 g/l monokristalline Diamantpartikel mit einer durchschnittlichen Korngröße von 0,3 bis 0,4 µm dispergiert und während des Verchromens in Schwebe gehalten.50 g / l monocrystalline diamond particles with an average Grain size of 0.3 to 0.4 µm dispersed and kept in suspension during chrome plating.
Das Verchromen erfolgt bei einer Temperatur von 60°C.Chrome plating takes place at a temperature of 60 ° C.
Dabei wird das zu verchromende Werkstück zunächst in einer ersten Stufe kathodisch geschaltet und während 8 Minuten bei einer Stromdichte von 65 A/dm3 verchromt. In einer zweiten Stufe wird umgepolt und durch anodische Schaltung des Werkstückes während einer Minute bei einer Stromdichte von 60 A/dm3 das Rißnetzwerk der vorher abgeschiedenen Chromschicht aufgeweitet und mit Diamantpartikeln gefüllt. Dieser Zyklus, nämlich 8 min lang "kathodisches Verchromen" und 1 min lang "anodisches Ätzen", wird insgesamt 20 mal wiederholt, wodurch eine Schicht mit einer Schichtdicke von ca. 140 µm entsteht, die einen Diamantanteil von 3 - 5 Gew.-% der gesamten Schicht aufweist.The workpiece to be chrome-plated is first switched cathodically in a first stage and chrome-plated for 8 minutes at a current density of 65 A / dm 3 . In a second stage, the polarity is reversed and the crack network of the previously deposited chromium layer is expanded and filled with diamond particles by anodic switching of the workpiece for one minute at a current density of 60 A / dm 3 . This cycle, namely "cathodic chrome plating" for 8 minutes and "anodic etching" for 1 minute, is repeated a total of 20 times, resulting in a layer with a layer thickness of approximately 140 μm, which has a diamond content of 3-5% by weight. of the entire layer.
Hier wird zur Verchromung ein rißbildender Elektrolyt mit
Das Verchromen erfolgt insgesamt während 5 Stunden bei 55°C unter Bildung einer Chromschicht von insgesamt 0,2 mm Dicke. Dabei wird das zu verchromende Werkstück zunächst in einer ersten Stufe kathodisch geschaltet und während 30 Minuten bei einer Stromdichte von 65 A/dm3 verchromt. In einer zweiten Stufe wird umgepolt und durch anodische Schaltung des Werkstückes während 30 Sekunden bei einer Stromdichte von 150 A/dm3 das Rißnetzwerk der vorher abgeschiedenen Chromschicht aufgeweitet und mit Diamant- und Aluminiumoxidpartikeln gefüllt. Dieser Zyklus wird insgesamt 10 mal wiederholt, wodurch eine Schicht mit einer Schichtdicke von ca. 145 µm entsteht, die einen Diamantenanteil von 1 - 3 Gew.-% der gesamten Schicht aufweist.The chrome plating takes place for a total of 5 hours at 55 ° C. to form a chrome layer with a total thickness of 0.2 mm. The workpiece to be chrome-plated is first connected cathodically in a first stage and chrome-plated for 30 minutes at a current density of 65 A / dm 3 . In a second stage, the polarity is reversed and the crack network of the previously deposited chromium layer is expanded by anodic switching of the workpiece for 30 seconds at a current density of 150 A / dm 3 and filled with diamond and aluminum oxide particles. This cycle is repeated a total of 10 times, resulting in a layer with a layer thickness of approximately 145 μm, which has a diamond content of 1-3% by weight of the entire layer.
Claims (15)
- Galvanic hard-chromium coat, especially for a piston ring which is substantially formed from an electrolyte containing hexavalent chromium, the coating having cracks therein and diamond particles being embedded in said cracks, characterised in that the diamond particles possess a size ranging from 0.25 to 0.4 µm.
- Galvanic hard-chromium coat according to Claim 1, characterised in that the hard-chromium coat has alloying elements
- Galvanic hard-chromium coat according to Claims 1 or 2, characterised in that the chrome coat has a thickness between 0.0005 and 1.0 mm.
- Galvanic hard-chromium coat according to any one of Claims 1 to 3, characterised in that the gap width of the cracks is greater than 0.001 mm.
- Galvanic hard-chromium coat according to any one of the preceding claims, characterised in that the chrome coat consists of at least two chromium layers.
- Galvanic hard-chromium coat according to Claim 5, characterised in that the at least two chromium layers have a different crystal structure.
- Galvanic hard-chromium coat according to any one of the preceding claims, characterised in that the amount of diamond particles in the chromium coat is 0.1 to 10% by weight.
- Galvanic hard-chromium coat according to any one of the preceding claims, characterised in that further hard material particles are embedded in the cracks in addition to the diamond particles.
- Galvanic hard-chromium coat according to any one of the preceding claims, characterised in that the hard material particles contain tungsten carbide, chromium carbide, aluminium oxide, silicon carbide, silicon nitride, boron carbide and/or cubic boron nitride.
- Galvanic hard-chromium coat according to any one of the preceding claims, characterised in that lubricant particles, particles for increasing ductility and corrosion resistance and/or particles as dyes are also contained in the cracks.
- Galvanic hard-chromium coat according to any one of the preceding claims, characterised in that the diamond particles are formed of mono and/or polycrystalline diamond.
- Galvanic hard-chromium coat according to any one of the preceding claims, characterised in that a running-in coat is applied thereon.
- Galvanic hard-chromium coat according to Claim 12, characterised in that the running-in coat is an electrodeposited Ni-Co-P alloy coat with embedded silicon nitride.
- Galvanic hard-chromium coat according to any one of the preceding claims, characterised in that said coat is graduated.
- Use of the galvanic hard-chromium coat according to any one of the preceding claims for a piston ring.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19931829 | 1999-07-08 | ||
| DE19931829A DE19931829A1 (en) | 1999-07-08 | 1999-07-08 | Galvanic hard chrome layer |
| PCT/EP2000/005524 WO2001004386A1 (en) | 1999-07-08 | 2000-06-15 | Hard-chrome plated layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1114209A1 EP1114209A1 (en) | 2001-07-11 |
| EP1114209B1 true EP1114209B1 (en) | 2004-08-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00943813A Expired - Lifetime EP1114209B1 (en) | 1999-07-08 | 2000-06-15 | Hard-chrome plated layer |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6503642B1 (en) |
| EP (1) | EP1114209B1 (en) |
| JP (1) | JP4406520B2 (en) |
| AT (1) | ATE272734T1 (en) |
| BR (1) | BR0006828B1 (en) |
| DE (2) | DE19931829A1 (en) |
| ES (1) | ES2223540T3 (en) |
| PT (1) | PT1114209E (en) |
| WO (1) | WO2001004386A1 (en) |
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| DE102007038188A1 (en) | 2007-08-13 | 2009-02-19 | Federal-Mogul Burscheid Gmbh | Coated machine element e.g. piston ring with a surface useful in internal combustion engine, comprises a structured hard chrome layer, a physical vapor deposition- or a chemical vapor deposition layer, and a chromium-solid particle layer |
| DE102008017270B3 (en) * | 2008-04-04 | 2009-06-04 | Federal-Mogul Burscheid Gmbh | Structured chromium solid particle layer and method for its production and coated machine element |
| DE102011084052A1 (en) | 2011-10-05 | 2013-04-11 | Federal-Mogul Burscheid Gmbh | Coated piston ring for use in combustion engine such as reciprocating piston engine, has base body whose outer circumferential surface and flank surface form outer edge, which exhibits ridge or ablation having specific range width |
| DE102011084051A1 (en) | 2011-10-05 | 2013-04-11 | Federal-Mogul Burscheid Gmbh | Coated piston ring for use in internal combustion engine, has metallic base unit with outer peripheral surface and flank surfaces that are provided partly with electrochemically deposited metallic wear protection layer |
| DE102012204156A1 (en) | 2012-03-16 | 2013-09-19 | Federal-Mogul Burscheid Gmbh | Piston ring with chrome solid particle wear protection layer and corrosion resistant flank surface |
| EP2660362B1 (en) | 2010-12-27 | 2019-06-26 | Nippon Piston Ring Co., Ltd. | Composite chromium plating film, and sliding member equipped with the film |
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- 1999-07-08 DE DE19931829A patent/DE19931829A1/en not_active Withdrawn
-
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- 2000-06-15 DE DE50007283T patent/DE50007283D1/en not_active Expired - Lifetime
- 2000-06-15 ES ES00943813T patent/ES2223540T3/en not_active Expired - Lifetime
- 2000-06-15 EP EP00943813A patent/EP1114209B1/en not_active Expired - Lifetime
- 2000-06-15 WO PCT/EP2000/005524 patent/WO2001004386A1/en active IP Right Grant
- 2000-06-15 JP JP2001509580A patent/JP4406520B2/en not_active Expired - Lifetime
- 2000-06-15 AT AT00943813T patent/ATE272734T1/en active
- 2000-06-15 BR BRPI0006828-4A patent/BR0006828B1/en not_active IP Right Cessation
- 2000-06-15 PT PT00943813T patent/PT1114209E/en unknown
- 2000-06-15 US US09/786,570 patent/US6503642B1/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007038188A1 (en) | 2007-08-13 | 2009-02-19 | Federal-Mogul Burscheid Gmbh | Coated machine element e.g. piston ring with a surface useful in internal combustion engine, comprises a structured hard chrome layer, a physical vapor deposition- or a chemical vapor deposition layer, and a chromium-solid particle layer |
| DE102008017270B3 (en) * | 2008-04-04 | 2009-06-04 | Federal-Mogul Burscheid Gmbh | Structured chromium solid particle layer and method for its production and coated machine element |
| US8337687B2 (en) | 2008-04-04 | 2012-12-25 | Federal-Mogul Burscheid Gmbh | Structured chrome solid particle layer and method for the production thereof |
| EP2660362B1 (en) | 2010-12-27 | 2019-06-26 | Nippon Piston Ring Co., Ltd. | Composite chromium plating film, and sliding member equipped with the film |
| DE102011084052A1 (en) | 2011-10-05 | 2013-04-11 | Federal-Mogul Burscheid Gmbh | Coated piston ring for use in combustion engine such as reciprocating piston engine, has base body whose outer circumferential surface and flank surface form outer edge, which exhibits ridge or ablation having specific range width |
| DE102011084051A1 (en) | 2011-10-05 | 2013-04-11 | Federal-Mogul Burscheid Gmbh | Coated piston ring for use in internal combustion engine, has metallic base unit with outer peripheral surface and flank surfaces that are provided partly with electrochemically deposited metallic wear protection layer |
| DE102011084051B4 (en) * | 2011-10-05 | 2020-03-12 | Federal-Mogul Burscheid Gmbh | Coated piston ring with radially increasing layer thickness and process for its production |
| DE102011084052B4 (en) | 2011-10-05 | 2024-05-29 | Federal-Mogul Burscheid Gmbh | Coated piston ring with sharp oil scraper edge |
| DE102012204156A1 (en) | 2012-03-16 | 2013-09-19 | Federal-Mogul Burscheid Gmbh | Piston ring with chrome solid particle wear protection layer and corrosion resistant flank surface |
| WO2013135325A1 (en) | 2012-03-16 | 2013-09-19 | Federal-Mogul Burscheid Gmbh | Piston ring with chromium solid particle wear-prevention layer and corrosion-resistant flank surface |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001004386A1 (en) | 2001-01-18 |
| US6503642B1 (en) | 2003-01-07 |
| PT1114209E (en) | 2004-10-29 |
| ES2223540T3 (en) | 2005-03-01 |
| JP2003504517A (en) | 2003-02-04 |
| DE19931829A1 (en) | 2001-01-18 |
| JP4406520B2 (en) | 2010-01-27 |
| DE50007283D1 (en) | 2004-09-09 |
| BR0006828A (en) | 2001-06-05 |
| EP1114209A1 (en) | 2001-07-11 |
| BR0006828B1 (en) | 2011-08-23 |
| ATE272734T1 (en) | 2004-08-15 |
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