Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
  • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
• • 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 a piston ring, which is essentially formed from an electrolyte containing hexavalent chromium, with cracks on the layer and diamond particles embedded in these cracks.
• Galvanic hard chrome layers have been known from the prior art for a long time and are used, for example, as a surface coating for shock absorber pistons, hydraulic parts, piston rings and pressure rollers.
• galvanic chromium deposition is very economical with regard to the utilization of resources, since almost 100% of the chromium electrolyte can also be deposited as a chromium layer, which is why galvanic chromium layers are still used frequently today.
• European Patent EP 0 217 126 describes a galvanic hard chrome layer of the type mentioned at the outset with a crack network which extends through the entire layer thickness and in whose cracks solid particles are embedded.
• Such a chromium layer is produced by means of chrome-plating chromium baths known per se, such as preferably acidic chromic acid baths, with solid particles dispersed therein.
• the workpiece to be chrome plated is first connected cathodically, so that a micro-cracked chrome layer forms, then the workpiece is switched anodically, so that the micro cracks widen to the desired gap width and the cracks fill with solid particles, and then again occurs a cathodic circuit so that the solid particles are encapsulated and sealed by closing the cracks.
• This periodic current reversal can, if necessary, be repeated several times, the chromium plating parameters being varied according to the application in such a way that the desired crack width, crack density and crack filling are produced with, if necessary, different solid particle fillings.
• a method for producing a hard chrome composite coating on a substrate which comprises a disperse phase and is particularly suitable for mechanical components which are subjected to high-temperature friction is specified in European patent EP 0 668 375 B1.
• This method comprises the step of electrodeposition 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, together in the course of said deposition step the substrate is kept permanently at cathode potential and a pulsating cathode current which changes cyclically with time between a minimum and a maximum value is supplied in order to achieve a chromium layer which comprises a matrix with microcracks of a given distribution and a disperse phase which consists of said non-metal particles, some of which are enclosed in the microcracks and some are embedded directly in the matrix, the chromium plating bath being a bath based on chromic acid
• Another known piston ring which is described in European patent application EP 0 841 414 A1, differs from that from EP 0 841 413 A1 in that round aluminum particles are enclosed in the cracks, the average particle size being between 0.7 and 10 microns and the dispersion ratio of the round aluminum particles in the electrolyte is 3 to 15 vol .-%.
• German published patent application DE 197 45 811 A1 describes a galvanic hard chrome layer with a crack network that extends partially or completely through the layer thickness and solid particles embedded and encapsulated in the cracks, which consists of at least two layers of hard chrome, with at least one layer being deposited under pulsating direct current , so that the chromium in different crystallization form is present.
• the hard chrome can additionally be alloyed with the metals tungsten, vanadium and / or molybdenum.
• the object of the invention is to provide a galvanic hard chrome layer which has improved physical properties, such as, in particular, improved wear resistance and seizure resistance.
• 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 0.5 ⁇ m.
• the diamond particle size indicated does not mean that all the particles must necessarily have the same size, rather they can certainly have a different size, which should only be in the range from 0.25 to 0.5 ⁇ m.
• the galvanic chromium layer according to the invention is essentially formed from an electrolyte containing hexavalent chromium, the chromium formed from the hexavalent electrolyte having more lattice defects than a chromium formed from trivalent electrolyte, since the chromium formed from a hexavalent electrolyte is next to the body-centered cubic chromium contains more hexagonal chromium hydride, which is due to the strong hydrogen formation during the electrodeposition. This results in a larger number of lattice defects and thus an even greater hardness of the chromium deposited.
• the hard chrome layer according to the invention need not necessarily be pure chrome. On the contrary, the alloying of chromium, especially with the metals molybdenum, vanadium and tungsten, can be advantageous for certain applications.
• piston rings provided with a coating according to the invention were used in a 6-cylinder turbodiesel engine under full load for 85 hours.
• the result shows that compared to previously used galvanic chrome layers with aluminum oxide particles, substantially the same cylinder wear of approximately 0.17 ⁇ m / 1000 km occurred with the galvanic hard chrome layer according to the invention, by more than half the wear on the rings , namely only 0.2 ⁇ m / 1000 km compared to 0.5 ⁇ m / 1000 km when using a conventional electroplated hard chrome coating with aluminum oxide particles as the piston ring coating.
• a galvanic hard chrome layer according to the invention with diamond inclusions also exhibits far improved properties under high thermal loads, under which the layers with aluminum oxide particles used hitherto can reach their application limits.
• 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 mark occurs.
• the diamond particles advantageously convert to graphite, which then takes on lubrication tasks and thus prevents the formation of burn marks.
• the layer according to the invention thus also has very good emergency running properties, in particular due to the conversion from diamond to graphite at temperatures of approximately 700 ° C. or higher.
• the hard chrome layer according to the invention can preferably be produced by using chromium plating baths known per se with solid particles dispersed therein, as have been known from the prior art for a long time.
• the chrome plating the workpiece to be chrome plated is first switched cathodically, so that a micro-cracked hard chrome layer forms, then the workpiece is switched anodically, so that the micro cracks widen to the desired gap width and the cracks fill with the diamond particles.
• the hard chrome layer according to the invention is not to be formed from pure chromium but from an alloy
• the alloy elements are dissolved in the chromium plating electrolyte as salts and galvanically deposited together with the chromium.
• the alloying elements are preferably present in the chromium layer in amounts of 0.1 to 30 percent by weight. Such layers are even more wear-resistant and ductile than pure chrome layers.
• the total thickness of the electroplated hard chrome layer according to the invention should preferably be several times larger than the particle size of the particles. This is desirable so that 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 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 embedded.
• a preferred gap width of the cracks of the electroplated hard chrome layer according to the invention is above 0.3 ⁇ m, in particular above 0.5 ⁇ m, so that solid particles can be incorporated into the cracks at all and the cracks are not too small for the diamond particles.
• the hard chrome layer according to the invention if it consists of at least two chrome layer layers. It has been observed that the cracks in the chrome layer are not always formed continuously. If thinner layers are applied and the particles are each introduced into the cracks of the individual layers, a coating can be achieved which better distributes the diamond particles in the coating both in their entire thickness, as well as across their surface, since the cracks are not always formed in the same places.
• 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
• the individual layers can, for. B. also have different high or completely different alloy components. Depending on the requirements of the layer or the material to be coated, this can be selected appropriately.
• 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 chrome 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 deposited alternately one above the other.
• Such a galvanic hard chrome layer according to the invention showed even further improved properties, such as, for example, a longer service life under extreme temperature and wear loads. This is perhaps due to the fact that the different crystal structures of the two layers result in high lattice stresses, in particular at the interfaces, which not only makes the layer harder overall but also improves other mechanical properties of the hard chrome layer according to the invention.
• the electroplated hard chrome layer according to the invention has excellent properties, particularly 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% by weight.
• further hard material particles are embedded in the cracks in the galvanic chrome layer.
• These other hard material particles can in this case include all hard material particles familiar to the person skilled in the art, but in particular tungsten carbide, chromium carbide, aluminum oxide, silicon carbide, silicon nitride, boron carbide and / or cubic boron nitride can be used.
• the storage of further hard material particles can be advantageous, inter alia, when high pressures and insufficient lubrication meet, if the temperature is, for. B. on the piston ring running surface, for which the layers according to the invention z. B. can be used so high that the diamond particles convert to graphite and take on lubrication tasks. At this point, however, the diamond alone can no longer serve to improve the wear resistance. The outstanding properties of the hard material particles present next to the diamond then prevail here and prevent unnecessarily high wear of the galvanic hard chrome layer according to the invention.
• solid lubricant particles, solid particles to increase ductility, corrosion resistance and / or solid particles can also be contained in the cracks in the galvanic hard chrome layer as dyes.
• the layer according to the invention can be suitably adapted for the respective application.
• hexagonal boron nitride, graphite and / or polymer particles, in particular made of polyethylene and / or polytetrafluoroethylene, can additionally be introduced into the cracks as solid lubricant particles.
• ductile metals or metal alloys made of tin, titanium or aluminum can be incorporated.
• the cracks can be filled with polyethylene, for example, and then melted into the cracks, so that the cracks are sealed and protected against corrosive attacks.
• different particles can also be used to fill the cracks.
• the diamond particles embedded in the galvanic chrome layer are advantageously formed from mono- and / or polycrystalline diamond.
• Polycrystalline diamond which can only be produced synthetically, 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 electroplated chrome layer according to the invention means that the running in of this layer takes place relatively slowly. This is not particularly desirable when using the layer on piston rings, since negative effects in oil consumption and emissions occur in this phase. Improvements can be achieved here with special surface topographies, such as those realized with special lapping, and / or with the development of piston ring coatings that improve the run-in, which can be applied to the wear-resistant base layers galvanically, by means of PVD or CVD or other methods familiar to the person skilled in the art.
• a dispersion layer based on nickel-cobalt-phosphorus with silicon nitride can be used as the dispersant, which ensures the required rapid run-in with high fire trace safety.
• the layer is graded.
• the grading can be chosen, for example, such that it has reduced solids content on the tread.
• the solids content may decrease towards the outside and may even no longer be present in the layer according to the invention in the outermost layer area.
• the solids content can also increase towards the free surface of the hard chrome layer.
• the layer according to the invention can also have a grading of the lubricants and / or the other particles contained in the layer.
• nitriding should preferably be mentioned, since it can be carried out in a very well-defined manner. H. Either the entire surface can be nitrided or only certain, precisely defined areas. The nitriding of surfaces is usually carried out by means of plasma nitriding.
• the galvanic chrome layer according to the invention can also be subjected to surface hardening by means of ion implantation, for example with nitrogen.
• the galvanic chrome layer according to the invention can advantageously be used as a tread coating for temperature and wear-stressed Use machine parts, particularly preferred for piston rings, as they have proven particularly effective in the case of abrasive wear and when used in high temperatures.
• a crack-forming electrolyte is used for chrome plating, which contains the following components:
• 50 g / l monocrystalline diamond particles with an average grain size of 0.3 to 0.4 ⁇ m are dispersed in it by stirring and kept in suspension during chrome plating.
• 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 and filled with diamond and aluminum oxide particles by anodic switching of the workpiece for 30 seconds at a current density of 150 A / dm 3 .
• This cycle is repeated a total of 10 times, resulting in a layer with a layer thickness of approx. 145 ⁇ m, which has a diamond content of 1-3% by weight of the entire layer.

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• Chemical & Material Sciences (AREA)
• Metallurgy (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Electroplating Methods And Accessories (AREA)
• Pistons, Piston Rings, And Cylinders (AREA)
• Dental Preparations (AREA)
• Electroplating And Plating Baths Therefor (AREA)
• Laminated Bodies (AREA)
• Physical Vapour Deposition (AREA)

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• 1999
  • 1999-07-08 DE DE19931829A patent/DE19931829A1/de not_active Withdrawn
• 2000
  • 2000-06-15 BR BRPI0006828-4A patent/BR0006828B1/pt not_active IP Right Cessation
  • 2000-06-15 EP EP00943813A patent/EP1114209B1/fr not_active Expired - Lifetime
  • 2000-06-15 US US09/786,570 patent/US6503642B1/en not_active Expired - Lifetime
  • 2000-06-15 WO PCT/EP2000/005524 patent/WO2001004386A1/fr active IP Right Grant
  • 2000-06-15 ES ES00943813T patent/ES2223540T3/es not_active Expired - Lifetime
  • 2000-06-15 AT AT00943813T patent/ATE272734T1/de active
  • 2000-06-15 DE DE50007283T patent/DE50007283D1/de not_active Expired - Lifetime
  • 2000-06-15 JP JP2001509580A patent/JP4406520B2/ja not_active Expired - Lifetime
  • 2000-06-15 PT PT00943813T patent/PT1114209E/pt unknown

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