Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C24/00—Coating starting from inorganic powder
  • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
  • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
  • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/17—Metallic particles coated with metal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/18—Non-metallic particles coated with metal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
  • B23K35/262—Sn as the principal constituent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
  • B23K35/3006—Ag as the principal constituent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
  • B23K35/3033—Ni as the principal constituent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
  • B23K35/3046—Co as the principal constituent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
  • B23K35/327—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C comprising refractory compounds, e.g. carbides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
  • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
  • B23K35/3613—Polymers, e.g. resins
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
  • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
  • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
  • C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
  • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
• • 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
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor
• • 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
  • Y10T428/12014—All metal or with adjacent metals having metal particles
  • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]

Definitions

• New wear protection films as well as a process for their production and their use
• the present invention relates to wear protection films made of metal-coated hard material particles, in particular of nickel-coated tungsten carbides and solder material particles, in particular nickel-chromium-based solder alloys, a process for their production using film casting and their use for the production of components with increased service life.
• MMCs metal matrix composites
• Wear protection layers of great importance The distribution of the hard materials, as well as the formation of the interface between material and solder and the formation of reaction phases in a molten metal alloy depends strongly on the materials to be mixed, the desired proportion of hard materials or the proportion of metal matrix on the hard metal alloy and the process conditions during of the manufacturing process. Therefore, reliable and simple methods have been and are being sought to produce such wear protection materials or wear protection coatings.
• No. 5,594,931 describes the production of prefabricated wear protection materials, which consist of at least two layers with different hard metal and solder material fractions, the layers being firmly joined by sintering.
• US 2007/0017958 A1 describes the use of layered materials which contain both hard metal particles, a metal alloy, a solder material and optionally a binder.
• the wear protection materials can be produced by slurrying the individual components in a solvent and then coating the material in layers.
• An alternative method that can be used to make metallic films is e.g. described in WO 2007/147792.
• the present invention has the object to provide wear protection films that are easy to manufacture and easy to handle. Furthermore, the wear protection layers produced with these films on a component should have the lowest possible porosity, low abrasion and high hardness.
• wear-protection foils which, on the one hand, have hard-material particles which have a metallic shell and, on the other hand, a brazing material, in particular a brazing alloy or a high-temperature braze.
• the wear-resistant films may also contain organic binders and plasticizers.
• metal-coated hard material particles together with Lotmaterialpulvern in the presence of a binder suspension containing an organic binder and optionally a plasticizer to a stable Process slip.
• the metal-coated hard material particles can be incorporated particularly well into the solder material matrix, wherein the cladding metal is chosen such that a slight wetting with the solder material takes place.
• metals are used as the hard material particle shell, which are also contained in the solder material.
• the improved wettability of the metal-coated hard material particles results in improved incorporation of the particles into the solder material matrix.
• the reaction behavior of the solder with the hard material can be controlled or avoided by a suitable metal shell. This also applies with regard to the further processing steps that are necessary for the production of wear protection layers from the claimed wear protection films.
• the resulting film may further be presintered, that is, the film is subjected to a sintering step before being applied to a component to produce the anti-wear layer in a subsequent step.
• the pre-sintering of the film reduces film shrinkage in the production of wear-resistant layers on the desired component.
• the pre-sintered films can also be easily glued to a component or soldered or welded using an additional solder on the component, for example by means of flame soldering.
• the wear protection films described here are thus particularly suitable for application to components by brazing or high temperature brazing, especially in vacuum furnaces.
• pre-sintered wear protection films these can also be glued, soldered or welded.
• Even after the high Temperatures during sintering, presintering, brazing or Hochtemperaturlötvones show the obtained wear protection layers a nearly isotropic microstructure in the particle distribution and a very low porosity, whereby a low abrasion and high hardness over the entire surface to be refined of the component is achieved.
• the pore formation is reduced by the good wettability of the metal-coated hard material particles by the solder material, since there is a good connection at the interface between the metal-coated hard material particles and the solder material.
• phase reactions or diffusion processes can occur at the interface between the metal shell of the hard material particle and the solder material, in particular if the hard material particles have a metal shell.
• the wear protection layer is further stabilized during the manufacturing process, which includes a treatment at high temperatures, the pore formation in the wear protection layer is minimized.
• the films according to the invention are easy to produce from a slurry by means of conventional film casting processes on an industrial scale.
• a wear protection film containing hard material particles which have a metallic shell and solder particles selected from the group of soft solders, brazing alloys or high-temperature solders, subject of the present invention.
• the hard material particles preferably contain carbides and / or borides of
• Transition metals with high melting points in particular carbides of tungsten, titanium, vanadium, chromium, tantalum, niobium, silicon or molybdenum but also borides, carbonitrides or nitrides of these metals come as hard material particles in question.
• tungsten carbides for example WC and / or WSC (tungsten carbides), wherein the WSC is a mixture of WC and W 2 C, which is in particular a eutectic structure of WC and W 2 C, titanium carbides, eg TiC, tantalum carbides, vanadium carbides , eg VC, chromium carbides, eg Cr 3 C 2 , Cr 7 C 3 , Cr 23 C 6 , silicon carbides, eg SiC, molybdenum carbides, such as Mo 2 C or titanium borides, eg TiB 2 , or mixtures of said hard material particles, wherein the tungsten carbides optionally mixed with tungsten borides, such as WB, are of particular importance.
• WSC tungsten carbides
• Particularly preferred hard material particles consist of the abovementioned carbides and / or borides.
• a particularly preferred tungsten carbide with a WC shell is Macroline tungsten carbide (MWC 1 of the Amperweld® powder series from HCStarck GmbH).
• MWC 1 of the Amperweld® powder series from HCStarck GmbH Macroline tungsten carbide
• the hard materials described are also referred to below as hard metals.
• WSCs tungsten carbide carbides
• the Macroline tungsten carbohydrates have a core of WSC and a shell of WC that largely protects the WSC core from reactions with the nickel base solder.
• Hard materials in spherical form are in particular obtainable by gas atomization or are produced in plasma from agglomerated hard materials.
• the hard material particles are surrounded by a metal shell, wherein the metal shell supports the connection to the solder material and the incorporation into the slurry.
• the shell has a similar composition as the solder material.
• the shell contains metals which are also contained in the solder material.
• Particularly preferred metals of the shell are nickel, cobalt, chromium, iron, copper, molybdenum, aluminum, yttrium or a mixture of these metals.
• Preferred mixtures of these sheath metals are cobalt / chromium, nickel / chromium, nickel / cobalt mixtures.
• the use of nickel-coated, chromium-coated or cobalt-coated hard material particles is particularly preferred.
• Metal-coated hard material particles are commercially available, eg nickel-coated or cobalt-coated .
• Tungsten carbide is marketed by HC Starck, Germany.
• the metal-coated hard materials used are usually present in powder form. Powders having an average particle diameter of about 0.05 ⁇ m to 200 ⁇ m, preferably between 10 ⁇ m and 150 ⁇ m, are used, the ideal particle diameter varying depending on the application.
• the hard materials are preferably completely coated with a metal shell, although partially metal-coated particles can be used. However, the surface of the latter particles should preferably be provided with at least 50% with a metal coating.
• the metallic coating of the hard material particles takes place by deposition of the metal intended for the coating on the hard material particles by conventional methods.
• Preferred solders according to the present invention are brazing alloys or
• solder powders from the group of nickel, titanium, cobalt, copper, tin or silver solders come into consideration as brazing materials.
• Suitable solders are e.g. Brazing alloys such as copper / tin solders, silver / cadmium / copper solders, silver / phosphor solders.
• high temperature solders such as e.g. Solders based on nickel or cobalt, such as nickel / chromium-containing solders or nickel / cobalt-containing solders used.
• soft solders in particular tin-based soft solders, e.g. Tin / lead or tin / silver solders which also contain other metals, e.g. Contain antimony, bismuth and / or copper.
• phosphorus additives are also common for common soft solders.
• metal-coated hard material particles are used in combination with nickel-containing solder materials.
• the nickel solders with additives such as Boron, chromium and silicon
• hard material particles such as e.g. Tungsten carbides, in particular the
• Tungsten carbide attack and thus render ineffective.
• metal-coated hard material particles By using metal-coated hard material particles, the dissolution of the hard material in the solder material can be reduced.
• tungsten carbides in nickel-based solders in particular creates the envelope
• WC shell tungsten carbide shell
• the use of nickel-clad tungsten carbides with a WC shell, such as MWC, is particularly suitable for producing particularly good wear-resistant coatings.
• the wear protection films described here generally contain, based on the total weight of the film, from 5% by weight to 95% by weight, preferably from 10% by weight to 90% by weight, of metal-coated hard material particles and 5% by weight. to 95 wt .-%, preferably 10 wt .-% to 50 wt .-%, of solder material particles.
• the films contain between 60% by weight and 80% by weight of metal-coated hard material particles and between 20% by weight and 40% by weight of solder material.
• the mixing ratio of the contained hard materials and solder materials can be varied depending on the respective wear protection application.
• the solder materials used can be selected based on the desired soldering temperature and on the material of the component to be coated.
• the solder materials should preferably have a solidus temperature above the decomposition temperature of organic additives used.
• the wear protection films may also, based on the total weight of the film, 0.1 wt .-% to 99.9 wt .-%, preferably between 10 wt .-% and 90 wt .-% of metal-coated hard material particles and 0.1 wt .-% to 99.9 wt. %, preferably 10 wt .-% to 50 wt .-%, of solder material particles.
• Such wear protection films may also contain from 0.1% to 20% by weight of organic binders and plasticizers.
• the described wear protection foils can also be laminated with further layers containing hard material and / or solder material.
• two or more films according to the invention which are characterized by a different content of metal-coated hard material particles or solder material, are laminated to form a composite film.
• composite materials comprising at least one of the described wear protection films, wherein the individual layers of the composite have different proportions of hard material particles and / or solder particles.
• Such composite materials preferably have a layer with a proportion of between 40% by weight and 95% by weight, particularly preferably between 60% by weight and 90% by weight, of metal-coated hard material particles and from 5% by weight to 60% by weight. -% of solder material.
• the composite materials also have at least one further layer, which mainly contains solder material, preferably with a proportion of between 40% by weight and 100% by weight, particularly preferably between 60% by weight and 90% by weight.
• This layer may also contain hard material particles, in particular with a proportion by weight of between 10% and 40%, which are preferably also coated with metal.
• such composite materials can be sintered on the component and / or pre-sintered. Sintered composite materials can also simply be glued, soldered or welded onto the component.
• the claimed wear protection foils in addition to other additives, may also contain organic binders and plasticizers.
• the proportion of organic binders and plasticizers is 0 wt .-% to 20 wt .-% based on the total weight of the film.
• organic binders and plasticizers are preferably used in a weight ratio of between 100: 0 and 50:50.
• an organic binder is contained in the wear protection film, this is particularly preferably present in a proportion by weight of between 0.5% by weight and 15% by weight, in particular between 2% by weight and 10% by weight, of the plasticizer particularly preferably with a weight fraction of between 0.1% by weight and 10% by weight, in particular between 0.5% by weight and 5% by weight, based on the total weight of the film.
• Preferred organic binders and plasticizers are those which decompose at temperatures below 400 ° C., preferably below 350 ° C.
• suitable organic binders are polymers having a low blanket temperature, for example halogenated polyolefins, in particular teflon, polyacetals, polyacrylates or polymethacrylates or copolymers thereof, polyalkylene oxides, polyvinyl alcohols or derivatives thereof, polyvinyl acetates or polyvinyl butyrals.
• Particular preference is given to organic binders from the group of the polyalkylene carbonates, in particular polypropylene carbonate.
• the organic binder is used in particular during drying to connect the individual solid particles with each other.
• the binder should be readily soluble in the solvent and compatible with other additives, such as dispersants.
• the viscosity of the slurry is hardly increased by the addition of the binder and has achieved stabilizing effect on the suspension.
• the organic binder should preferably burn out without residue at low temperatures below 400 ° C.
• the binder provides improved durability and improved handleability of the green sheet, in particular to reduce the formation of cracks during drying, for example.
• plasticizers include, for example, phthalates, such as benzyl phthalate, glues, waxes, gelatin, dextrins, gum arabic, oils, such as paraffin oil or polymers, such as polyalkylenes, in particular polyethylenes.
• phthalates such as benzyl phthalate
• glues glues, waxes, gelatin, dextrins, gum arabic
• oils such as paraffin oil
• polymers such as polyalkylenes, in particular polyethylenes.
• preferred plasticizers are alkylene carbonates, in particular propylene carbonate.
• the plasticizer should in particular bring about the reduction of the glass transition temperature of the polymeric binder and a higher flexibility of the green film. The plasticizer penetrates into the network structure of the binder and thus reduces the viscosity of the slurry.
• plasticizers used preferably burn out completely at low temperatures below 400 ° C.
• metallic binders such as e.g. Metal powder, which may preferably contain tungsten, tantalum, niobium, molybdenum, chromium, vanadium, titanium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, aluminum or tin in question.
• metal oxides e.g. Silicates, alumina, zirconia or titanium oxide are added. Such metallic additives should not exceed a proportion of not more than 30% by weight of the total weight of the wear protection film.
• the wear protection films according to the invention may be flat films or else three-dimensionally formed films.
• the layer thickness of the films is between 10 .mu.m and 3000 .mu.m, in particular between 50 .mu.m and 2500 .mu.m, preferably between 200 .mu.m and 2000 .mu.m.
• Another object of the present invention is a Folieng automatisme for producing the wear protection films, which is simple, industrially feasible and, accordingly, inexpensive. For this purpose, first a binder suspension containing at least one solvent and an organic binder is prepared.
• Suitable solvents are in particular organic solvents.
• Preferred solvents are, for example, esters, ethers, alcohols or ketones, in particular methanol, ethanol, propanol, butanol, diethyl ether, butyl methyl ether, methyl acetate, ethyl acetate, acetone, methyl ethyl ketone (MEK) or mixtures thereof.
• Particularly preferred solvents are ketones, in particular from the group of alkyl ketones.
• Preferred organic binders are the compounds mentioned above, in particular polyalkylene carbonates.
• the binder suspension can also be added directly to a plasticizer. The resulting mixture is taken in a mixing unit, e.g. a ball mill, mixed and homogenized.
• the binder suspension thus prepared is then mixed with the hard material particles, which have a metallic shell, and the solder material and processed into a slurry.
• This can e.g. take place in a tumble mixer or in a ball mill, wherein the ball mill is filled with grinding media, which preferably have a higher density than the hard material particles to be processed.
• the binder suspension is preferably initially introduced in the ball mill, but can also be added later. Furthermore, the metal sheathed
• Hard material powder and the solder material powder filled into the ball mill wherein the resulting mixture is ground and stirred until a stable slurry is formed.
• sufficient mixing and homogenization of the slurry generally takes between 4 hours and 48 hours.
• the slip can then be degassed at low pressure.
• the storage, degassing or other processing steps are preferably carried out with constant stirring in order to prevent sedimentation of the solid constituents of the slurry.
• the hard material and / or solder material particles may also be pre-alloyed and the binder suspension added. A continuous or portionwise addition of the binder suspension during the slip production is conceivable.
• the resulting slip can then be cast into a film using conventional film casting techniques.
• the binder suspension comprises at least 1 wt .-% to 60 wt .-%, more preferably between 5 wt .-% and 40 wt .-%, of organic binder based on the total weight of the binder suspension and 0 wt .-% to 15 wt. -%, more preferably between 2 wt .-% and 10 wt .-%, of plasticizer based on the total weight of the binder suspension (including solvent).
• the binder suspension contains a sufficient amount of solvent to ensure at least a suspension of the individual components of the binder suspension.
• solvent which are needed for the suspension of the hard particles and the Lotmaterialpumblen, is not contrary.
• binder slurry or solvent may also be added throughout the slurry production process as needed.
• the amount of the solvent is metered so that slips arise with a high solids content.
• the weight ratio between hard material particles and solder material particles is preferably between 40:60 and 90:10, that is, the slurry preferably contains approximately between 25% by weight and 90% by weight, particularly preferably between 50% by weight and 80% by weight % of hard material particles and approximately between 5% by weight and 60% by weight, particularly preferably between 10% by weight and 40% by weight, of solder material particles.
• the hard material particles and solder material particles can be added together or separately. The particles can be supplied both as solid to the binder suspension or in vorsuspensierter form.
• wear protection films can be produced such that a) a binder suspension containing a solvent and an organic binder is produced, b) the binder suspension prepared in step a) is mixed with hard material particles and solder material particles selected from the group of brazing alloys or high temperature solders and converted into a Slip processed and c) the slip obtained is poured into a film, wherein that for the production of the slip based on the total weight
• the binder suspension being from 0.1% by weight to 60% by weight of organic binder, based on the total weight of the binder suspension, and from 0% by weight to 15% by weight. based on plasticizer based on the total weight of the binder suspension and 60 wt .-% to 99.9 wt .-% of hard material particles and Lotmaterialpumblen are used, wherein the weight ratio between hard material particles and Lotmaterialpellen between 0: 100 and 100: 0 are used.
• the slurry or binder suspension may contain other useful additives, especially dispersants, defoamers or protective colloids, e.g. Polyester / polyamine condensation polymers, alkyl phosphate compounds, polyvinyl alcohols, dextrins or cellulose ethers.
• useful additives especially dispersants, defoamers or protective colloids, e.g. Polyester / polyamine condensation polymers, alkyl phosphate compounds, polyvinyl alcohols, dextrins or cellulose ethers.
• the slurry is filled into a reservoir under which a plastic carrier runs, which is carried out continuously at a controlled speed under the container.
• the slurry is poured from the reservoir onto the plastic film and coated with a casting squeegee to a certain thickness.
• a smooth and flat film is produced, which is then usually dried at variable temperatures, optionally stripped from the plastic film and rolled up or further processed or assembled.
• the method described is characterized by a high Production speed and thus by low production costs, the quality of the films produced has a good consistency.
• film thicknesses in particular in the range between 10 .mu.m and 3000 .mu.m and film widths can be set.
• the maximum film width is specified by the used Folieng discernstrom. Due to the pronounced pseudoplastic behavior of the slurry, however, film widths of up to 400 mm can be produced without difficulty.
• the film thickness and width can be adjusted by the following parameters: cutting height of the doctor blade, filling height and thus casting pressure of the slip in the casting chamber, pulling speed of the plastic backing, casting shoe width and viscosity of the slip.
• the film thickness variation in width and length are usually less than 10% in this method. If structured plastic carriers are used as the casting base, even simple structures can be introduced into the wear protection foil.
• An alternative method is the vacuum slip casting method, which is particularly suitable for the production of three-dimensionally shaped wear protection films.
• vacuum slip casting the process flow is considerably accelerated by applying a negative pressure.
• the slurry is poured into a porous mold, through which the solvent present is sucked by vacuum.
• the solids contained in the slurry deposit on the mold surface and thus form a three-dimensionally shaped film, which can be released from the mold after drying.
• very thin films of up to 1 ⁇ m in thickness can be obtained by the vacuum process, and the solvent removed can also be reused.
• the vacuum process can also be used industrially.
• a suspension of solvent such as an alkyl ketone, a binder, preferably polypropylene carbonate and a plasticizer, preferably propylene carbonate is homogenized in a ball mill for several days and mixed.
• the prepared mixture of organic additives is the basis for the Folieng messschlicker.
• a ball mill is filled with grinding media and weighed the binder suspension produced. The amount of grinding media used should be up the amount of solids in the slurry should be adjusted and the media should have a higher density than the hard material used. Thereafter, the hard and solder powders are weighed.
• various tungsten carbides coated with nickel are preferably used.
• solder materials used are above all nickel / chromium solder powder, preferably NICROBRAZ solder powder (Wall Colmonoy).
• the resulting slurry is mixed with continuous stirring between 0.5 h and 24 h. Thereafter, the mixed slurry is transferred to a special casting vessel and degassed. Due to the high density of the powders used, the slurry must be constantly stirred slowly, so that sedimentation of the solid components is avoided. Then the degassed slurry is poured on a commercial casting machine to a solid and flexible carbide foil.
• a plastic carrier in particular a silicone-coated plastic film, for example made of PET, which withstand the tensile forces during the casting process and should have low adhesion to the dried slurry or the green sheet, so that they can be easily removed.
• the wet film is produced in a circulating air drying duct, preferably at temperatures between 25 0 C and 85 0 C dried.
• green films with a density of between 2.5 and 15 g / cm 3 can be produced.
• the proportion of solid organic additives in the green film is preferably between 1 wt .-% and 25 wt .-%, in particular between 2 wt .-% and 10 wt .-% of the mass of the green sheet.
• the production of wear protection films by means of film casting has many advantages.
• large amounts of hard material particles can easily be mixed into a matrix of solder material during the production of the slip.
• an organic binder By using an organic binder, the film obtained is further stabilized, in particular against a mechanical stress, thereby increasing the handling of the film, in particular facilitates the further processing of the film.
• the wear protective films described herein are particularly suitable for the production of wear-resistant coatings ⁇ by brazing at about 450 0 C, preferably by high-temperature soldering at about 900 0 C, whereby the generation of a solid bonding of the film to the component by liquid phase sintering, thereby forming a diffusion zone at the interface takes place. This results in particularly coherent connections between the wear protection layer and the component.
• the liquid phase sintering is usually carried out under inert gas and / or under reduced pressure, with a small amount of hydrogen is often added as oxidation protection.
• brazing and high-temperature brazing can be coated especially metallic components that have a steel surface or have a metal surface containing, for example, iron, copper, molybdenum, chromium, nickel, aluminum, silver or gold, the melting temperature of the surface or their solidus temperature above the
• Liquidus temperature of the solder material contained in the wear protection film should be.
• the binder-containing wear protection films can be applied directly to a component for the production of a wear protection layer, debinded and then further processed to the corresponding protective layer.
• the wear protection films are preferably pre-debinded and pre-sintered in order to minimize film shrinkage during the production of the wear protection layer on the component.
• Debinding means removal of the organic constituents required for film casting as far as possible without residue. However, if residues remain in the form of carbon, this leads to the formation of carbides in the following sintering process, which does not necessarily have to be troublesome. Debinding is carried out thermally according to a suitable temperature / time profile. The temperature rise should not go above 400 0 C.
• the binder removal under nitrogen or argon takes place partly with a low hydrogen content in order to remove any oxygen present from the atmosphere. The complete debinding of the film can take up to a day.
• the first method is based on a green, filled with solder material hardfoil.
• the green foil is cut to size according to the component size and attached to the component surface.
• the attachment of the film can be done without further aids, but it can also be used adhesives, which is preferred by remove thermal decomposition.
• the binder suspension can be used as an adhesive for applying the film to the component.
• the component is thermally treated with the green film.
• the binder removal process is preferably carried out at low temperatures of below 350 ° C.
• the debinding temperature is in preferred embodiments below the liquidus temperature of the solder material in the wear protection film.
• the organic additives used are preferably removed as completely as possible at reduced pressure (below one bar).
• sintering temperatures are usually in a range of 800 ° C and 2000 0 C, in particular from 1000 to 0 C and 1500 0 C, preferably from 1050 0 C to 1200 0 C.
• the brazing material used is The applied high vacuum promotes the wetting of the hard metal particles and the support with the liquid solder and reduces the porosity in the generated wear protection layer h thereby a pronounced diffusion layer.
• the diffusion layer determines the adhesion of the wear protection layer on the component surface.
• a presintered wear protection part is produced in a first step from the flexible green film produced analogously to the method just described.
• the pre-sintering of the green film is carried out, for example, on a ceramic sintered substrate, such as Al 2 O 3 or ZrO 2 .
• a high vacuum is applied and the hard metal foil is sintered on the sintered substrate to form the solid particle composite material.
• the thus pre-sintered wear protection film can then be applied to the component and processed by liquid phase sintering analogous to the previous method for wear protection layer.
• the pre-sintered Material also simply glued to the surface of the component or soldered using an additional solder or welded.
• the wear protection layers which can be produced with the aid of the wear protection films according to the invention are distinguished by a low porosity of preferably less than 5%, particularly preferably less than 1.5%, in particular less than 1%.
• the porosity can be optically determined on a wear protection layer section, the ratio of the area fraction of the pores to the area fraction of the solids on the cut surface being determined.
• Preferred wear protection layers that can be produced by the described methods have a density between 2.5 g / cm 3 and 25 g / cm 3 , preferably between 5 g / cm 3 and 15 g / cm 3 .
• the wear protection layers produced are characterized by a high hardness.
• Wear-resistant coatings with a Rockwell hardness of between 40 HRC and 70 HRC can be produced without problems, and preferred wear-resistant coatings have a Rockwell hardness of more than 50 HRC.
• the wear resistance of the layers produced can be determined by a two-body abrasion test according to ASTM G132-96 (Pin on Table). The wear resistance can be determined eg by the standard specification ASTM G65-04.
• organic additives including organic binders and plasticizers having a low decomposition temperature, and solder materials having a liquidus temperature above the decomposition temperature of the organic additives may be used in conjunction with the metal-coated ones
• Hard material particles which are evenly distributed in the solder material matrix, wear protection layers are produced with low porosity and high hardness.
• the liquidus temperature of the solder material is above 100 0 C, more preferably above 200 0 C, in particular above 400 0 C higher than the decomposition temperature of the organic binder or plasticizer. This is achieved with wear protection films that are easy to produce on an industrial scale and simply by thermal treatment, especially by separate debindering at low temperatures and subsequent brazing, high temperature brazing or Flame brazing at high temperatures, can be processed to the respective wear protection layers.
• FIG. 1 shows a wear protection layer (1) with a NICROBRAZ solder material and nickel-coated tungsten carbide hard metal particles on a steel carrier (3). It can be seen from the illustration in FIG. 1 that the coated tungsten carbide particles are distributed almost uniformly in the wear protection layer and the generated wear protection layer has a low residual porosity. Furthermore, it can be seen that the diffusion layer (2) between the wear protection layer and the steel support (3) is very well developed.
• FIG. 2 shows a presintered particle composite material between nickel-coated tungsten carbide hard metal particles and a nickel / chromium-containing solder material
• the Schlickerher too allows easy incorporation of metal-coated hard material particles in the solder material, which can be produced by the production of a wear protection film wear protection layer, which are characterized by an isotropic microstructure.
• wear protection film wear protection layer which are characterized by an isotropic microstructure.
• wear protection layers can be produced in which a gradient of the hard material content is present.
• the mixture of the two starting materials, the metal-coated hard material particles and the solder material can be freely defined depending on the application, in particular high contents of metal-coated hard material particles can be introduced into the wear protection layers.
• organic additives such as binders and plasticizers, which have a decomposition temperature below 350 0 C, the debinding of the green film can be done without the wear protection layer or the component is damaged.
• the film casting process is generally a low cost process for the production of large area planar components.
• the flexible green film allows a variety of different cost-effective processing steps (cutting, punching, laminating). Moreover, by laminating such films, it is possible to produce a material gradient in the wear protection layer.
• the uppermost layer can then have, for example, more carbide, so that the anti-wear properties can be greatly improved.
• the bottom layer accordingly has more solder material, so that the pronounced diffusion layer ensures excellent adhesion to the component surface.
• the shape of the wear protection film can be adapted in the green state to the component surface, which can be done with the sintering of the film in a single process step.
• Example 1 Slurry and film production
• a ball mill is filled with grinding media and the prepared binder suspension is weighed according to recipe specifications.
• the carbide and solder powders are then weighed.
• the hard metal powder used is a Ni-coated tungsten carbide WC-Ni 88-12 (H.C. Starck, Germany).
• the solder powder used is a NICROBRAZ solder powder from Wall Colmonoy. Table 2 shows the slip composition used to make a wear protection film with a 65:35 blend ratio of cemented carbide and solder powder.
• the slurry is mixed at a rotational speed of 20-30 rpm for 12-16 hours. Thereafter, the mixed slurry is transferred to a special casting vessel and degassed for 15 minutes at a reduced pressure of 500 mbar. Thereafter, the slurry is poured on a conventional casting to a solid and flexible carbide foil. The slip is poured onto a silicone-coated carrier film.
• the produced wet film is dried in a circulating air drying channel.
• the green carbide foil has no cracks.
• the density of the green film is between 4.5 and 5.8 g / cm 3 .
• the proportion of solid organic additives in the green film is between 4 and 5 mass. %.
• the wear protection layers on a component can be produced by two different methods.
• the first method is based on a prepared according to Example 1 green, filled with solder material carbide film.
• the green foil is cut to size according to the component size and mounted on the component surface of a steel beam. Thereafter, the organic additives contained in the green film are removed in vacuo and at a temperature up to 350 0 C.
• the debindered film in the subsequent liquid-phase sintering step, the debindered film in
• FIG. 1 shows the wear protection layer produced according to Example 2.1 with the NICROBRAZ solder material and tungsten carbide hard metal on a steel carrier. It can be seen that the residual porosity is less than 1% and the diffusion layer between the wear-resistant layer and the steel support is very good.
• the generated wear protection layer has a hardness of 60 HRC (Rockwell hardness).
• HRC Rockwell hardness
• a presintered wear protection part is produced from the flexible green film produced according to Example 1 in a first step.
• the organic additives are burned out to about 350 0 C.
• the presintering of the green sheet is carried out within 20 minutes on a ceramic AI 2 O 3 - sinter support under high vacuum at 10 "6 mbar and at a temperature of 1065 0 C.
• the pre-sintered particle composite of tungsten carbide and the NICROBRAZ solder material is shown in FIG. 2 the film is then cut and applied to a steel beam.
• the presintered film takes place on the sintering underlay in a 30-minute liquid phase sintering step in a high vacuum of 10 -5 mbar and 10 -6 mbar at a sintering temperature of 1180 0 It has been found that the use of the pre-sintered wear protection film significantly reduces the shrinkage of the protective layer due to the liquid-phase sintering.

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• 2009
  • 2009-10-06 WO PCT/EP2009/007156 patent/WO2010040498A1/de active Application Filing
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