EP2437904A1 - Process for producing a metal matrix composite material - Google Patents

Process for producing a metal matrix composite material

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Publication number
EP2437904A1
EP2437904A1 EP10724291A EP10724291A EP2437904A1 EP 2437904 A1 EP2437904 A1 EP 2437904A1 EP 10724291 A EP10724291 A EP 10724291A EP 10724291 A EP10724291 A EP 10724291A EP 2437904 A1 EP2437904 A1 EP 2437904A1
Authority
EP
European Patent Office
Prior art keywords
metal matrix
component
metal
matrix composite
composite material
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.)
Withdrawn
Application number
EP10724291A
Other languages
German (de)
French (fr)
Inventor
Isabell Buresch
Werner Krömmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wieland Werke AG
Original Assignee
Wieland Werke AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wieland Werke AG filed Critical Wieland Werke AG
Publication of EP2437904A1 publication Critical patent/EP2437904A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/115Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C24/00Coating starting from inorganic powder
    • C23C24/02Coating starting from inorganic powder by application of pressure only
    • C23C24/04Impact or kinetic deposition of particles
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129Flame spraying
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134Plasma spraying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967Inorganic matrix in void-containing component
    • Y10T428/24997Of metal-containing material

Definitions

  • the invention relates to a method for producing a metal matrix composite material having a metal matrix having at least one metal component and at least one reinforcing component arranged in the metal matrix, a corresponding material, in particular in the form of a coating, and the use of such a material.
  • MMC metal matrix composites or metal matrix composites
  • MMC often refers exclusively to appropriately reinforced aluminum, in special cases also referred to as reinforced magnesium and copper materials.
  • the metal component of the MMC is as elemental metal or in the form of an alloy.
  • reinforcement phase or component are usually particles (reinforcing particles) (diameter 0.01-150 microns), short fibers (diameter 1-6 microns, length 50-200 microns), continuous fibers (diameter 5-150 microns) or foams with of open porosity, which are usually made of ceramic material (SiC, Al 2 O 3 , B 4 C, SiO 2 ) or carbon in the form of fibers or graphite (see also and in the following: "Metal matrix composites: properties, Applications and Editing "by Dr. 0.
  • the reinforcing component is processed into a porous preform into which the molten metal is subsequently infiltrated with or without pressure.
  • fibers and foams with very high amplification volume fractions up to about 80% can be used as reinforcement in addition to particles become.
  • a local reinforcement in areas of highest stress is possible.
  • corresponding methods are expensive.
  • the powder metallurgy (PM) of MMC differs from commonly used PM processes only in that instead of a metal powder, a powder mixture of Keramik Inc. Reinforcement component and metal particles is used.
  • the PM is only suitable for fine particles (particle size 0.5-20 ⁇ m).
  • a subsequent formability of the MMC obtained by extruding, forging or rolling must be ensured, whereby the maximum volume content of the reinforcing particles is limited to about 40%.
  • Carbon nanotubes have outstanding properties. These include, for example, their mechanical tensile strength of about 40 GPa and their stiffness of 1 TPa (20 or 5 times steel). Both CNTs with conductive and those with semiconducting properties exist. CNTs belong to the family of fullerenes and have a diameter of 1 nm to a few 100 nm. Their walls, like the fullerenes or, like the planes of graphite, consist only of carbon. In particular, a mixture of CNT with other components allows composites and coatings with significantly improved properties.
  • Metal-based CNT composites such as those described in DE 10 2007 001 412 A1, comprise a metal matrix, such as Fe, Al, Ni, Cu or alloys thereof, and carbon nanotubes as a reinforcing component in the matrix. Due to the large density differences between metals and CNT and the resulting strong demixing tendencies as well as the lack of wettability of the CNT with metal, a melt metallurgical application for the production of corresponding metal-CNT composite materials is problematic.
  • DE 10 2007 001 412 A1 therefore proposes depositing a galvanically applied composite coating on a substrate by using a plating solution which contains metal cations of a metallic matrix to be deposited and carbon nanotubes. The composite coating then comprises the metallic matrix and carbon nanotubes disposed in the matrix, thereby improving the mechanical and tribological properties of the coating.
  • galvanic application is difficult or impossible to achieve in many areas.
  • the invention has for its object to provide a method for producing a metal matrix composite material, in particular with CNT as a reinforcing component, which allows to distribute the components used in a technically simple manner as evenly as possible, wherein
  • the reinforcing components should be as unchanged as possible in their physicochemical properties and contained in the metal matrix composite material to the highest possible percentage.
  • This object is achieved by a method for producing a metal matrix composite material and by such a metal matrix composite material, as such as a workpiece or as a coating of a workpiece or as a material for producing a
  • the invention includes the technical teaching, to
  • a metal matrix composite material for electrical components, electrical components or heat sinks with a metal matrix having at least one metal component and at least one reinforcing component arranged in the metal matrix to spray at least one of the components onto a substrate by a thermal spraying method, wherein at least one reinforcing component comprises carbon in the form of nanotubes, nanofibers, graphenes, fullerenes, flakes or diamond is used.
  • Composite particles such as single and multi-walled CNT (Single Walled / Multi Walled CNT, abbreviated SW / MW-CNT) with a length of 0.2 to 1000 ⁇ m, preferably of 0.5 to 500 ⁇ m and a bundle size of 5 to 1200 nm, preferably from 40 to 900 nm, have proven to be particularly advantageous.
  • SW-CNT or MW-CNT cold gas spray particles may also be previously used to improve their properties chemical processes with metals such as Cu or Ni sheathed or coated.
  • a further advantageous variant involves mixing and drying the metal powder with a CNT dispersion / suspension so that the metal powder particles are coated with the CNT.
  • the proportion of SW-CNT or MW-CNT in the carrier gas or in the powder stream for example, ranges from 0.1 to 30%, preferably from 0.2 to 10%.
  • an MMC coating or corresponding MMC strip with at least 0.3% SW or MW CNT produced in this way exhibits exceptional wear behavior with coefficients of friction and contact resistance values which are far below the previously known values of comparable metal layers.
  • reinforcing component carbon in the form of nanotubes, fullerenes, graphenes, flakes, nanofibers, diamond or diamond-like
  • Composite particles such as single wall and multiwalled CNT (single walled / multi walled CNT, abbreviated SW / MW CNT) having a length of 0.2 to 1000 ⁇ m, preferably 0.5 to 500 ⁇ m and a bundle size of 5 to 1200 nm, preferably from 40 to 900 nm, have proven to be particularly advantageous.
  • SW-CNT or MW-CNT cold spraying particles can also be previously coated or coated with metals such as Cu or Ni by means of chemical processes.
  • Another advantageous variant involves mixing and drying the metal powder with a CNT dispersion / suspension so that the metal powder particles are coated with the CNT.
  • the share of SW-CNT or MW CNT in the carrier gas or in the powder stream for example, ranges from 0.1 to 30%, preferably from 0.2 to 10%.
  • an MMC coating or corresponding MMC strip with at least 0.3% SW or MW CNT produced in this way exhibits exceptional wear behavior with coefficients of friction and contact resistance values which are far below the previously known values of comparable metal layers.
  • metal powders which were previously mixed, for example, with carbon components such as CNT or also ceramic reinforcing components can be used.
  • the proportion of metallic particles in the carrier gas can be, for example, in a range of 0.1 to 50%.
  • Spray processes such as flame, plasma, and cold gas spraying are known from the prior art for the production of coatings.
  • flame spraying a powder, lacing, rod or wire-shaped coating material is heated in a fuel gas flame and injected with the supply of additional carrier gas, for example compressed air, at high speed onto a base material.
  • additional carrier gas for example compressed air
  • plasma spraying a plasma powder is injected, which is melted by the high plasma temperature. The plasma stream entrains the powder particles and throws them onto the workpiece to be coated.
  • cold gas spraying as described, for example, in EP 0 484 533 B1, the spray particles are accelerated to high speeds in a comparatively cold carrier gas.
  • the temperature of the carrier gas is a few hundred 0 C and is below the melting temperature of the lowest-melting component sprayed.
  • the coating is formed with the impact of the particles on the high kinetic energy metal tape or component, the particles which do not melt in the cold carrier gas forming a dense and adherent layer upon impact. The plastic deformation and the resulting local heat release thereby ensure a very good cohesion and adhesion of the sprayed layer on the workpiece. Owing to the relatively low temperatures and the possibility of using argon or other inert gases as the carrier gas, oxidation and / or phase conversions of the coating material during cold gas spraying can be avoided.
  • the spray particles are added as a powder, usually with a particle size of 1 to 100 microns. The high kinetic energy get the
  • At least one of the components is preferably sprayed by cold gas spraying, flame spraying, in particular high-speed flame spraying (HVOF), and / or plasma spraying. It is also contemplated, especially in cold gas spraying, to use a carrier gas whose temperature is at room temperature or even below, whereby a thermal load of the sprayed components, in particular the
  • the temperature can be down to, for example, 10% below the Melting temperature of the lowest-melting component range.
  • the carrier gas should simultaneously create an inert or even reducing atmosphere in order to prevent oxidation of the powder particles and thus not adversely affect the later layer or material properties such as electrical conductivity, among other things.
  • a combination of two spraying methods can also be used.
  • a use of two spray nozzles with a mixture of the corresponding components at the coating site is also possible.
  • Friction corrosion resistance wherein the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal.
  • the invention provides a particularly flexible and cost-effective method, since, for example, in the production of printed conductors, lead frames and lead frames by the proposed spraying no prefabrication steps such as rolling, punching or annealing are required.
  • the substrate used in the process according to the invention may be a film or a substrate which is not wettable by the powder jet, which makes it possible to apply sprayed metal matrix composite materials from the substrate separate. In this way, a component or a pure material, for example in the form of a strip, can be obtained, which can then be further processed in a suitable manner.
  • tape materials and components such as electromechanical components, heatsinks, bearings, and bushings may also be adhesively coated which have improved properties through the metal matrix composite.
  • a metal strip or an electromechanical component is preferably used as the workpiece, which preferably consists of ceramic, titanium, copper, aluminum and / or iron and alloys thereof.
  • Semifinished products or 3D structures such as Molded Interconnection Devices (MID) can also be used for coating.
  • MID Molded Interconnection Devices
  • the method includes at least one surface processing step.
  • a surface processing step for example, on a metal strip or component made of a metallic material, an activation, a Budapest, Hungary, a Budapest, Hungary, a Budapest, Hungary, a о ⁇ ение, таком ⁇ онент ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Adhesive layer also be applied a non-stick coating.
  • Corresponding MMC tapes or coatings can also be used subsequently for smoothing the surface of an additional treatment such as leveling or a reflow / heat treatment. be subjected to treatment.
  • an additional treatment such as leveling or a reflow / heat treatment.
  • be subjected to treatment for forming, for example, a soft annealing step, for example at about 0.4 times the melting temperature of the matrix metal, can also be carried out subsequently.
  • a soft annealing step for example at about 0.4 times the melting temperature of the matrix metal, can also be carried out subsequently.
  • the material can be re-rolled, for example with a degree of deformation of 0.1 to 10%.
  • Reinforcement component provided in particle form.
  • the size and shape of the particles as well as their quantity can be the same
  • a first component can also be mixed with at least one further component before spraying.
  • gentle mixing for example of cold spray particles, may be accomplished by coating the particles with a dispersion or suspension containing the reinforcing particles, followed by drying.
  • mixing in a ball mill or in an attritor consisting of at least two different components under protective gas can cause the particle shape to be destroyed and thus the flow behavior of the powder to be adversely affected.
  • At least one organic and / or at least one ceramic reinforcing component can be used. This can be present in the sprayed mixture or can also be injected or co-injected.
  • An advantageous method involves using at least one reinforcing component selected from the group consisting of tungsten, tungsten carbide, tungsten carbide cobalt, cobalt, boron, boron carbide, invar, kovar, niobium, molybdenum, chromium, nickel, titanium nitride, alumina, copper oxide, silver oxide , Silicon nitride, silicon carbide, silicon oxide, zirconium tungstate and zirconium oxide.
  • at least one reinforcing component selected from the group consisting of tungsten, tungsten carbide, tungsten carbide cobalt, cobalt, boron, boron carbide, invar, kovar, niobium, molybdenum, chromium, nickel, titanium nitride, alumina, copper oxide, silver oxide , Silicon nitride, silicon carbide, silicon oxide, zirconium tungstate and zirconium oxide.
  • a reinforcing component together with at least one further reinforcing component and / or to mix or mix it accordingly.
  • ceramic components whose advantageous properties, in addition to those of other reinforcing components, can be exploited.
  • the thermal expansion coefficient of the composite can be positively influenced.
  • Metal matrix which comprises at least one metal and / or an alloy of a metal selected from the group of tin, copper, silver, gold, nickel, zinc, platinum, palladium, iron, titanium and aluminum.
  • a particularly advantageous wear resistance, corrosion resistance and / or a specific electrical or thermal conductivity and an adapted coefficient of expansion can be provided.
  • a metal matrix composite material produced by the method according to the invention with a metal matrix having at least one metal component and at least one reinforcing component arranged in the metal matrix is likewise provided by the invention.
  • a metal matrix composite material which has a proportion of from 0.1 to 20%, preferably from 0.1 to 5%, preferably from 0.2 to 5%, of carbon nanotubes is regarded as being particularly advantageous.
  • the abovementioned proportions have proven to be particularly advantageous in practice, as mentioned above.
  • a corresponding metal matrix composite material with advantageous properties has, for example, a residual porosity of 0.2 to 20% with respect to the
  • MMC with such residual porosities can be used with advantage when a particularly good abrasion resistance, such as in bearings or sliding surfaces, or a high electrical conductivity, such as in tracks, is required.
  • the metal matrix composite according to the invention is particularly suitable for a coating for a workpiece.
  • the coating can be used, for example, on bearings and sliding elements, heat sinks, connectors, punched grids and strip conductors, in particular as heating elements usable conductor tracks are applied.
  • Such MMC coatings can be made of, for example, Sn, Cu, Ag, Au, Ni, Zn, Pt, Pd, Fe, Ti, W and / or Al and their alloys such as solders, in particular with a content of SW-CNT or MW. CNT from 0.1 to 20%, preferably from 0.2 to 5%.
  • the metal strip may be a coated tape for use in electromechanical components such as connectors, springs, e.g. for relays, switching contacts, to act conductor tracks in punched grids and heating elements or heat sinks and elements.
  • the metal strip preferably has a thickness of 0.01 to 5 mm, particularly preferably 0.06 to 3.5 mm.
  • the components may for example be sprayed onto a non-wettable substrate such as films made of PEEK, polyimide or Teflon.
  • stamped grids, tracks, heating elements and strips may comprise Cu, Al, Ni and Fe and alloys thereof.
  • Printed circuit traces comprising at least one metal matrix composite material as prepared above may be printed locally on a printed circuit board, molded interconnection devices (MID), e.g. LSDS or other thermoplastics in particular stencils, sprayed or provided in the form of a sheet-like coating, which is later processed, for example by suitable photolithography process.
  • MID molded interconnection devices
  • An MMC tape or trace may advantageously be made of Cu, Ag, Al, Ni and / or Sn and their alloys a proportion of SW-CNT or MW-CNT from 0.1 to 20%, preferably from 0.1 to 5%.
  • a metal matrix composite material produced according to the method of the invention is particularly suitable for use in the production of workpieces, in particular of electro-mechanical ones
  • Such a use may either include making the workpiece completely out of the metal matrix composite or coating it with such material.
  • Figure 1 is a schematic representation of a device for
  • Embodiment of the invention is suitable, and
  • FIG. 1 Microscopic micrographs of the microstructure and scanning electron micrographs of the surfaces of metal matrix composites prepared by methods according to particularly preferred embodiments of the present invention.
  • a device for cold gas spraying suitable for carrying out the method according to a particularly preferred embodiment of the invention is shown in FIG.
  • the device has a vacuum chamber 4 in which, for example, a substrate 5 to be coated can be placed in front of the nozzle of a cold gas spray gun 3. It should be understood, however, that such a spraying process could also be carried out at atmospheric pressure, for which a vacuum chamber is not required.
  • the vacuum chamber 4 in which, for example, a substrate 5 to be coated can be placed in front of the nozzle of a cold gas spray gun 3. It should be understood, however, that such a spraying process could also be carried out at atmospheric pressure, for which a vacuum chamber is not required.
  • Placement of the workpiece 5 in front of the cold gas spray gun 3 takes place, for example, by means of a holder, not shown in Figure 1 for reasons of clarity.
  • the substrate 5 is movable, i. displaceable and rotatably arranged, so that a coating can take place at a plurality of positions, in particular band-shaped or flat.
  • the cold gas spray gun 3 may be movably arranged.
  • the vacuum chamber 4 is evacuated and generated by means of the cold gas spray gun 3, a gas jet, are fed into the particles for coating the workpiece 5.
  • the main gas flow for example a helium-nitrogen mixture with about 40% by volume of helium, passes via the gas supply line 1 into the vacuum chamber 4.
  • the spray particles for example a metal powder with admixed CNT, pass through the auxiliary gas flow
  • the supply lines 1, 2 are for this purpose in the vacuum chamber. 4 in which both the cold gas spray gun ' 3 and the substrate 5 is located. It can also be provided to supply a plurality of components to be sprayed via a plurality of auxiliary gas streams. The entire cold gas spraying process thus takes place in the vacuum chamber 4.
  • the particles are accelerated so much by the cold gas jet that adhesion of the particles on the surface of the workpiece 5 to be coated is achieved by converting the kinetic energy of the particles into thermal energy.
  • the particles can additionally be heated up to the maximum temperature indicated above.
  • the carrier gas which passes during the cold gas spraying together with the spray particles from the spray gun 3 and carries the spray particles to the workpiece 5, passes after the injection process in the vacuum chamber 4.
  • the spent carrier gas is removed via the gas line 6 from the vacuum chamber 4 by means of the vacuum pump 8.
  • a particle filter 7 is connected, which removes free spray particles from the spent carrier gas in order to prevent the spray particles from damaging the pump 8.
  • FIGS. 2A to 2C of FIG. 2 show results of tests in which metal powders with the addition of reinforcing components were injected in each case.
  • FIG. 2A shows the microstructure of a layer 200 obtained by spraying pure copper with 1.5% MW-CNT with a copper matrix 201 and CNT 202 discontinuously distributed therein in a 1000-fold magnification. Furthermore, in the coating 200 so-called oxide skins 203 formed on the Cu grains by a not completely avoidable oxidation of the Cu powder during the mixing process with the MWCNT can be seen.
  • the layers were injected at a nozzle exit temperature of 600 0 C and a pressure of 38 bar under N 2 -GaS.
  • the density of the layer is 99.5%, its thickness is 280 ⁇ m, the layer hardness is 1200 N / mm 2 . Due to the good friction behavior, this layer is suitable as a running surface of bearings and bushes.
  • After detachment of the 280 micron thick layer of the carrier material is a tape, which can be used as a conductor in stamped or electromechanical components use.
  • Figure 2B shows the surface of a layer 210 obtained by spraying pure Sn with 2.1% MW-CNT with a
  • FIG. 2C shows a detailed view of FIG. 2B at a magnification of 10,000 times.
  • the layer 210 has spherical Sn bodies 213 with CNTs 202 distributed therebetween.
  • the density of the layer is 99.4%. It has a hardness of 368 N / mm 2 and a coefficient of friction of 0.5 in the wear test.
  • N 2 -GaS When spraying this layer under N 2 -GaS with a pressure of 32 bar and a nozzle exit temperature of 350 0 C, a layer thickness of 5 microns was achieved.
  • Such produced layers can be optimized by a post-treatment such as leveling or remelting (reflow treatment) in their surface structure specifically targeted to the particular application. Partially or completely applied to Cu alloy strips, these layers can be used to reduce plugging and drawing forces in electromechanical components such as connectors, or after appropriate leveling and reflow steps to improve the

Abstract

The invention proposes a process for producing a metal matrix composite material (200, 210) composed of a metal matrix (201, 211) having at least one metal component and at least one reinforcing component (202) arranged in the metal matrix (201, 211), in which at least one of the components is sprayed onto a substrate (5) by means of a thermal spraying process, use being made of at least one reinforcing component comprising carbon in the form of nano tubes (202), nano fibers, graphenes, fullerenes, flakes or diamond. Also proposed is a corresponding material, in particular in the form of a coating, and the use of such a material.

Description

Verfahren zur Herstellung eines Metallmatrix- Verbundwerkstoffs Method of making a metal matrix composite
Die Erfindung betrifft ein Verfahren zur Herstellung eines Metallmatrix-Verbundwerkstoffs mit einer zumindest eine Metallkomponente aufweisenden Metallmatrix und zumindest einer in der Metallmatrix angeordneten Verstärkungskomponente, einen entsprechenden Werkstoff, insbesondere in Form einer Beschichtung, sowie die Verwendung eines derartigen Werkstoffs.The invention relates to a method for producing a metal matrix composite material having a metal matrix having at least one metal component and at least one reinforcing component arranged in the metal matrix, a corresponding material, in particular in the form of a coating, and the use of such a material.
Der Trend zu zunehmender Miniaturisierung, der mit steigenden Materialkosten einhergehende Kostendruck sowie die immer anspruchsvolleren Anforderungen bei Applikationen in der Elektrik und Elektronik sowie bei der Herstellung von technischen Lagern erfordern neue Werkstoffe und Beschichtungen.The trend toward increasing miniaturization, the cost pressures associated with rising material costs, and the increasingly demanding requirements of applications in the electrical and electronic industries, as well as the manufacture of technical bearings, require new materials and coatings.
Metallmatrix-Verbundwerkstoffe bzw. Metallmatrix-Composite (Metal Matrix Composites, MMC) weisen gegenüber ausschließlich keramischen oder metallischen Werkstoffen herausragende Eigenschaftskombinationen auf . Aus diesem Grund besteht ein großes Interesse am Einsatz der ursprünglich für die Luft- und Raumfahrt sowie für die Wehrtechnik entwickelten MMC für eine Reihe von Anwendungen .Metal matrix composites or metal matrix composites (MMC) have outstanding combinations of properties compared to exclusively ceramic or metallic materials. For this reason, there is a great deal of interest in using the MMC, originally developed for the aerospace and defense industries, for a number of applications.
Die Bezeichnung MMC bezieht sich häufig ausschließlich auf entsprechend verstärktes Aluminium, in Sonderfällen werden damit auch verstärkte Magnesium- und Kupferwerkstoffe bezeichnet. Die Metallkomponente der MMC liegt als elementares Metall oder in Form einer Legierung vor. Als Verstärkungsphase bzw. -komponente kommen in der Regel Partikel (Verstärkungspartikel) (Durchmesser 0,01-150 um), Kurzfasern (Durchmesser 1-6 μm, Länge 50-200 μm) , Endlosfasern (Durchmesser 5-150 um) oder Schäume mit offener Porosität zum Einsatz, die in der Regel aus Keramikmaterial (SiC, Al2O3, B4C, SiO2) oder Kohlenstoff in Form von Fasern oder Graphit bestehen (siehe hierzu und auch im folgenden: "Metallmatrix-Verbundwerkstoffe: Eigenschaften, Anwendungen und Bearbeitung" von Dr. 0.The term MMC often refers exclusively to appropriately reinforced aluminum, in special cases also referred to as reinforced magnesium and copper materials. The metal component of the MMC is as elemental metal or in the form of an alloy. As reinforcement phase or component are usually particles (reinforcing particles) (diameter 0.01-150 microns), short fibers (diameter 1-6 microns, length 50-200 microns), continuous fibers (diameter 5-150 microns) or foams with of open porosity, which are usually made of ceramic material (SiC, Al 2 O 3 , B 4 C, SiO 2 ) or carbon in the form of fibers or graphite (see also and in the following: "Metal matrix composites: properties, Applications and Editing "by Dr. 0.
Beffort, 6. Internationales IWF-Kolloquium, 18. /19. April 2002, Egerkingen, Schweiz).Beffort, 6th International IMF Colloquium, 18. / 19. April 2002, Egerkingen, Switzerland).
Zur Herstellung von MMC-Bulkmaterialien sind aus dem Stand der Technik im Wesentlichen drei Verfahrensprozesse bekannt, nämlich das Einrühren von Keramikpartikeln in die Metallschmelze, die Schmelzinfiltration und die Pulvermetallurgie. Zur Herstellung von MMC-Beschichtungen ist aus dem Stand der Technik die galvanische Abscheidung bekannt .For the production of bulk MMC materials, essentially three process processes are known from the prior art, namely the stirring of ceramic particles into the molten metal, the melt infiltration and the powder metallurgy. For the production of MMC coatings, the prior art discloses the electrodeposition.
In entsprechenden Einrührverfahren muss häufig die mangelnde Benetzbarkeit zwischen Metallschmelze und Partikeln überwunden und eine Reaktion zwischen beiden Phasen begrenzt werden. Der Volumenanteil der Partikel ist aus Viskositätsgründen auf maximal 30% beschränkt.In corresponding stirring often the lack of wettability between molten metal and particles must be overcome and a reaction between the two phases are limited. The volume fraction of the particles is limited for viscosity reasons to a maximum of 30%.
Bei der Infiltration wird die Verstärkungskomponente zu einer porösen Vorform ("Preform") verarbeitet, in die anschließend mit oder ohne Druckeinsatz die Metallschmelze infiltriert wird. In diesem Fall können als Verstärkung neben Partikeln auch Fasern und Schäume mit sehr hohen Verstärkungsvolumenanteilen (bis ca. 80%) eingesetzt werden. Eine LokalVerstärkung in Bereichen höchster Beanspruchung ist möglich. Entsprechende Verfahren sind jedoch aufwendig.During infiltration, the reinforcing component is processed into a porous preform into which the molten metal is subsequently infiltrated with or without pressure. In this case, fibers and foams with very high amplification volume fractions (up to about 80%) can be used as reinforcement in addition to particles become. A local reinforcement in areas of highest stress is possible. However, corresponding methods are expensive.
Die Pulvermetallurgie (PM) von MMC unterscheidet sich von üblicherweise verwendeten PM-Verfahren nur dadurch, dass statt eines Metallpulvers ein Pulvergemisch aus Keramikbzw. Verstärkungskomponenten- und Metallpartikeln verwendet wird. Die PM ist grundsätzlich nur für feine Partikel (Korngröße 0.5-20 μm) geeignet. Darüberhinaus muss eine nachträgliche Umformbarkeit der erhaltenen MMC durch Extrudieren, Schmieden oder Walzen gewährleistet bleiben, wodurch der maximale Volumengehalt der Verstärkungspartikel auf ca. 40% beschränkt ist.The powder metallurgy (PM) of MMC differs from commonly used PM processes only in that instead of a metal powder, a powder mixture of Keramikbzw. Reinforcement component and metal particles is used. The PM is only suitable for fine particles (particle size 0.5-20 μm). In addition, a subsequent formability of the MMC obtained by extruding, forging or rolling must be ensured, whereby the maximum volume content of the reinforcing particles is limited to about 40%.
Bei der galvanischen Abscheidung von Dispersionsschichten besteht das Problem, die Partikel feinverteilt im Elektrolyten in Schwebe zu halten und gleichzeitig mit der Matrix abzuscheiden, um homogene Schichten zu erhalten. Die gleichzeitige Abscheidung von Partikeln und Matrix ist in vielen Fällen unmöglich aufgrund ihrer unterschiedlichen Potentiale .In the case of the electrodeposition of dispersion layers, there is the problem of levitating the particles finely distributed in the electrolyte and at the same time depositing them with the matrix in order to obtain homogeneous layers. The simultaneous deposition of particles and matrix is in many cases impossible because of their different potentials.
Kohlenstoff-Nanoröhrchen (Carbon Nanotubes, CNT) weisen herausragende Eigenschaften auf. Hierzu zählen z.B. ihre mechanische Zugfestigkeit von etwa 40 GPa und ihre Steifheit von 1 TPa (dem 20- bzw. 5-fachen von Stahl) . Es existieren sowohl CNT mit leitenden als auch solche mit halbleitenden Eigenschaften. CNT gehören zu der Familie der Fullerene und besitzen einen Durchmesser von 1 nm bis einigen 100 nm. Ihre Wände bestehen wie die der Fullerene oder wie die Ebenen des Graphits nur aus Kohlenstoff. Insbesondere eine Mischung von CNT mit weiteren Komponenten lässt Verbundwerkstoffe und BeSchichtungen mit signifikant verbesserten Eigenschaften erwarten.Carbon nanotubes (CNT) have outstanding properties. These include, for example, their mechanical tensile strength of about 40 GPa and their stiffness of 1 TPa (20 or 5 times steel). Both CNTs with conductive and those with semiconducting properties exist. CNTs belong to the family of fullerenes and have a diameter of 1 nm to a few 100 nm. Their walls, like the fullerenes or, like the planes of graphite, consist only of carbon. In particular, a mixture of CNT with other components allows composites and coatings with significantly improved properties.
Es ist bekannt, CNT mit herkömmlichem Kunststoff zur Verbesserung seiner mechanischen und elektrischen Eigenschaften zu mischen. CNT-Verbundwerkstoffe auf Metallbasis, wie sie beispielsweise in der DE 10 2007 001 412 Al behandelt werden, umfassen eine Metallmatrix, wie etwa Fe, AI, Ni, Cu oder entsprechende Legierungen, und Kohlenstoffnanoröhrchen als Verstärkungskomponente in der Matrix. Aufgrund der großen Dichteunterschiede zwischen Metallen und CNT und der hierdurch bedingten starken Entmischungstendenzen sowie aufgrund der mangelnden Benetzbarkeit der CNT mit Metall ist eine schmelzmetallurgische Applikation zur Herstellung von entsprechenden Metall-CNT-Verbundmaterialien problematisch. Die DE 10 2007 001 412 Al schlägt daher vor, auf einem Substrat eine galvanisch aufgebrachte Verbundbeschichtung abzuscheiden, indem eine Galvanisierlösung verwendet wird, die Metallkationen einer abzuscheidenden metallischen Matrix sowie Kohlenstoffnanoröhrchen enthält. Die Verbundbeschichtung umfasst dann die metallische Matrix und in der Matrix angeordnete Kohlenstoffnanoröhrchen, wodurch die mechanischen und tribologischen Eigenschaften der Beschichtung verbessert werden. Jedoch ist eine galvanische Aufbringung in vielen Bereichen nicht oder nur schwer durchführbar .It is known to mix CNT with conventional plastic to improve its mechanical and electrical properties. Metal-based CNT composites, such as those described in DE 10 2007 001 412 A1, comprise a metal matrix, such as Fe, Al, Ni, Cu or alloys thereof, and carbon nanotubes as a reinforcing component in the matrix. Due to the large density differences between metals and CNT and the resulting strong demixing tendencies as well as the lack of wettability of the CNT with metal, a melt metallurgical application for the production of corresponding metal-CNT composite materials is problematic. DE 10 2007 001 412 A1 therefore proposes depositing a galvanically applied composite coating on a substrate by using a plating solution which contains metal cations of a metallic matrix to be deposited and carbon nanotubes. The composite coating then comprises the metallic matrix and carbon nanotubes disposed in the matrix, thereby improving the mechanical and tribological properties of the coating. However, galvanic application is difficult or impossible to achieve in many areas.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung eines Metallmatrix-Verbundwerkstoffs, insbesondere mit CNT als Verstärkungskomponente, anzugeben, das es erlaubt, die eingesetzten Komponenten in technisch einfacher Weise möglichst gleichmäßig zu verteilen, wobei insbesondere die Verstärkungskomponenten in ihren physikalisch-chemischen Eigenschaften möglichst unverändert und zu einem möglichst hohen Prozentanteil in dem Metallmatrix-Verbundwerkstoff enthalten sein sollen.The invention has for its object to provide a method for producing a metal matrix composite material, in particular with CNT as a reinforcing component, which allows to distribute the components used in a technically simple manner as evenly as possible, wherein In particular, the reinforcing components should be as unchanged as possible in their physicochemical properties and contained in the metal matrix composite material to the highest possible percentage.
Diese Aufgabe wird gelöst durch ein Verfahren zur Herstellung eines Metallmatrix-Verbundwerkstoffs und durch einen solchen Metallmatrix-Verbundwerkstoff, der als solches als Werkstück oder als Beschichtung eines Werkstücks oder als Werkstoff zur Herstellung einesThis object is achieved by a method for producing a metal matrix composite material and by such a metal matrix composite material, as such as a workpiece or as a coating of a workpiece or as a material for producing a
Werkstücks verwendet werden kann, mit den Merkmalen der unabhängigen Patentansprüche. Bevorzugte Ausgestaltungen sind in den jeweiligen abhängigen Ansprüchen angegeben.Workpiece can be used, with the features of the independent claims. Preferred embodiments are given in the respective dependent claims.
Die Erfindung beinhaltet die technische Lehre, zurThe invention includes the technical teaching, to
Herstellung eines Metallmatrix-Verbundwerkstoffs ) für elektrische Bauelemente, elektrische Komponenten oder Kühlkörper mit einer zumindest eine Metallkomponente aufweisenden Metallmatrix und zumindest einer in der Metallmatrix angeordneten Verstärkungskomponente zumindest eine der Komponenten durch ein thermisches Spritzverfahren auf ein Substrat zu spritzen, wobei zumindest eine Verstärkungskomponente Kohlenstoff in Form von Nanoröhrchen, Nanofasern, Graphenen, Fullerenen, Flakes oder Diamant verwendet wird.Producing a metal matrix composite material) for electrical components, electrical components or heat sinks with a metal matrix having at least one metal component and at least one reinforcing component arranged in the metal matrix to spray at least one of the components onto a substrate by a thermal spraying method, wherein at least one reinforcing component comprises carbon in the form of nanotubes, nanofibers, graphenes, fullerenes, flakes or diamond is used.
Composit-Partikel wie ein- und mehrwandige CNT (Single Walled/Multi Walled CNT, abgekürzt SW-/MW-CNT) mit einer Länge von 0,2 bis 1000 μm, vorzugsweise von 0,5 bis 500 μm und einer Bundlegröße von 5 bis 1200 nm, vorzugsweise von 40 bis 900 nm, haben sich hierbei als besonders vorteilhaft erwiesen. SW-CNT- oder MW-CNT- Kaltgasspritzpartikel können zur Verbesserung ihrer Eigenschaften auch zuvor über chemische Verfahren mit Metallen wie Cu oder Ni ummantelt bzw. beschichtet werden. Eine weitere vorteilhafte Variante beinhaltet, das Metallpulver mit einer CNT- Dispersion/_Suspension zu mischen und zu trocknen, so dass die Metallpulverpartikel mit den CNT ummantelt sind. Der Anteil der SW-CNT oder MW-CNT im Trägergas bzw. im Pulverstrom reicht beispielsweise von 0,1 bis 30%, vorzugsweise von 0,2 bis 10%.Composite particles such as single and multi-walled CNT (Single Walled / Multi Walled CNT, abbreviated SW / MW-CNT) with a length of 0.2 to 1000 μm, preferably of 0.5 to 500 μm and a bundle size of 5 to 1200 nm, preferably from 40 to 900 nm, have proven to be particularly advantageous. SW-CNT or MW-CNT cold gas spray particles may also be previously used to improve their properties chemical processes with metals such as Cu or Ni sheathed or coated. A further advantageous variant involves mixing and drying the metal powder with a CNT dispersion / suspension so that the metal powder particles are coated with the CNT. The proportion of SW-CNT or MW-CNT in the carrier gas or in the powder stream, for example, ranges from 0.1 to 30%, preferably from 0.2 to 10%.
Mit Hilfe eines der genannten Spritzverfahren ist es möglich, ein- und mehrwandige CNT in eine Metallmatrix einzubinden. Eine derart hergestellte MMC-Beschichtung oder entsprechendes MMC-Band mit mindestens 0,3% SW- oder MW-CNT zeigt nach Untersuchungen der Anmelderin ein außergewöhnliches Verschleißverhalten mit Reibkoeffizienten und Kontaktwiderstandswerten, welche weit unter den bisher bekannten Werten von vergleichbaren Metallschichten liegen. Mit besonderem Vorteil kann als Verstärkungskomponente Kohlenstoff in Form von Nanoröhrchen, Fullerenen, Graphenen, Flakes, Nanofasern, Diamant oder diamantähnlichenWith the aid of one of the spraying methods mentioned, it is possible to incorporate single-walled and multi-walled CNTs in a metal matrix. According to the Applicant's investigations, an MMC coating or corresponding MMC strip with at least 0.3% SW or MW CNT produced in this way exhibits exceptional wear behavior with coefficients of friction and contact resistance values which are far below the previously known values of comparable metal layers. With particular advantage can be used as reinforcing component carbon in the form of nanotubes, fullerenes, graphenes, flakes, nanofibers, diamond or diamond-like
Strukturen verwendet werden. Composit-Partikel wie ein- und mehrwandige CNT (Single Walled/Multi Walled CNT, abgekürzt SW- /MW-CNT) mit einer Länge von 0,2 bis 1000 μm, vorzugsweise von 0,5 bis 500 um und einer Bundlegröße von 5 bis 1200 nm, vorzugsweise von 40 bis 900 nm, haben sich hierbei als besonders vorteilhaft erwiesen. SW-CNT- oder MW-CNT- Kaltgasspritzpartikel können zur Verbesserung ihrer Eigenschaften auch zuvor über chemische Verfahren mit Metallen wie Cu oder Ni ummantelt bzw. beschichtet werden. Eine weitere vorteilhafte Variante beinhaltet, das Metallpulver mit einer CNT-Dispersion/_Suspension zu mischen und zu trocknen, so dass die Metallpulverpartikel mit den CNT ummantelt sind. Der Anteil der SW-CNT oder MW- CNT im Trägergas bzw. im Pulverstrom reicht beispielsweise von 0,1 bis 30%, vorzugsweise von 0,2 bis 10%.Structures are used. Composite particles such as single wall and multiwalled CNT (single walled / multi walled CNT, abbreviated SW / MW CNT) having a length of 0.2 to 1000 μm, preferably 0.5 to 500 μm and a bundle size of 5 to 1200 nm, preferably from 40 to 900 nm, have proven to be particularly advantageous. In order to improve their properties, SW-CNT or MW-CNT cold spraying particles can also be previously coated or coated with metals such as Cu or Ni by means of chemical processes. Another advantageous variant involves mixing and drying the metal powder with a CNT dispersion / suspension so that the metal powder particles are coated with the CNT. The share of SW-CNT or MW CNT in the carrier gas or in the powder stream, for example, ranges from 0.1 to 30%, preferably from 0.2 to 10%.
Mit Hilfe eines der genannten Spritzverfahren ist es möglich, ein- und mehrwandige CNT in eine Metallmatrix einzubinden. Eine derart hergestellte MMC-Beschichtung oder entsprechendes MMC-Band mit mindestens 0,3% SW- oder MW-CNT zeigt nach Untersuchungen der Anmelderin ein außergewöhnliches Verschleißverhalten mit Reibkoeffizienten und Kontaktwiderstandswerten, welche weit unter den bisher bekannten Werten von vergleichbaren Metallschichten liegen.With the aid of one of the spraying methods mentioned, it is possible to incorporate single-walled and multi-walled CNTs in a metal matrix. According to the Applicant's investigations, an MMC coating or corresponding MMC strip with at least 0.3% SW or MW CNT produced in this way exhibits exceptional wear behavior with coefficients of friction and contact resistance values which are far below the previously known values of comparable metal layers.
Durch entsprechende Spritzverfahren können Metallpulver, welche zuvor beispielsweise mit Kohlenstoffkomponenten wie CNT oder auch keramischen Verstärkungskomponenten gemischt wurden, zum Einsatz kommen. Der Anteil metallischer Partikel im Trägergas kann beispielsweise in einem Bereich von 0,1 bis 50% liegen.By means of appropriate spraying methods, metal powders which were previously mixed, for example, with carbon components such as CNT or also ceramic reinforcing components can be used. The proportion of metallic particles in the carrier gas can be, for example, in a range of 0.1 to 50%.
Spritzverfahren, wie Flamm-, Plasma-, und Kaltgasspritzen sind aus dem Stand der Technik zur Herstellung von Beschichtungen bekannt. Beim Flammspritzen wird ein pulver- , schnür-, stab- oder drahtförmiger Beschichtungswerkstoff in einer Brenngasflamme erhitzt und unter Zuführung zusätzlichen Trägergases, beispielsweise Druckluft, mit hoher Geschwindigkeit auf einen Grundwerkstoff gespritzt. Beim Plasmaspritzen wird in einen Plasmaj et Pulver eingedüst, das durch die hohe Plasmatemperatur aufgeschmolzen wird. Der Plasmastrom reißt die Pulverteilchen mit und schleudert sie auf das zu beschichtende Werkstück. Beim Kaltgasspritzen, wie es beispielsweise in der EP 0 484 533 Bl beschrieben ist, werden die Spritzpartikel in einem vergleichsweise kalten Trägergas auf hohe Geschwindigkeiten beschleunigt. Die Temperatur des Trägergases beträgt wenige hundert 0C und liegt unter der Schmelztemperatur der niedrigstschmelzenden gespritzen Komponente. Die Beschichtung wird mit dem Auftreffen der Partikel auf das Metallband oder Bauteil mit hoher kinetischer Energie gebildet, wobei die Partikel, die in dem kalten Trägergas nicht schmelzen, beim Aufprall eine dichte und festhaftende Schicht bilden. Die plastische Verformung und die daraus resultierende lokale Wärmefreigabe sorgen dabei für eine sehr gute Kohäsion und Haftung der Spritzschicht auf dem Werkstück. Aufgrund der relativ niedrigen Temperaturen und der Möglichkeit, Argon oder andere Inertgase als Trägergas zu nutzen, lassen sich Oxidation und/oder Phasenumwandlungen des Beschichtungswerkstoffes beim Kaltgasspritzen vermeiden. Die Spritzpartikel werden als Pulver, in der Regel mit einer Partikelgröße von 1 bis 100 μm, zugegeben. Die hohe kinetische Energie erhalten dieSpray processes, such as flame, plasma, and cold gas spraying are known from the prior art for the production of coatings. In flame spraying, a powder, lacing, rod or wire-shaped coating material is heated in a fuel gas flame and injected with the supply of additional carrier gas, for example compressed air, at high speed onto a base material. During plasma spraying, a plasma powder is injected, which is melted by the high plasma temperature. The plasma stream entrains the powder particles and throws them onto the workpiece to be coated. In cold gas spraying, as described, for example, in EP 0 484 533 B1, the spray particles are accelerated to high speeds in a comparatively cold carrier gas. The temperature of the carrier gas is a few hundred 0 C and is below the melting temperature of the lowest-melting component sprayed. The coating is formed with the impact of the particles on the high kinetic energy metal tape or component, the particles which do not melt in the cold carrier gas forming a dense and adherent layer upon impact. The plastic deformation and the resulting local heat release thereby ensure a very good cohesion and adhesion of the sprayed layer on the workpiece. Owing to the relatively low temperatures and the possibility of using argon or other inert gases as the carrier gas, oxidation and / or phase conversions of the coating material during cold gas spraying can be avoided. The spray particles are added as a powder, usually with a particle size of 1 to 100 microns. The high kinetic energy get the
Spritzpartikel bei der Entspannung des Trägergases in einer Laval-Düse.Spray particles in the relaxation of the carrier gas in a Laval nozzle.
Bevorzugt wird bei vorliegender Erfindung zumindest eine der Komponenten durch Kaltgasspritzen, Flammspritzen, insbesondere Hochgeschwindigkeitsflammspritzen (HVOF) , und/oder Plasmaspritzen gespritzt. Es wird auch erwogen, insbesondere beim Kaltgasspritzen, ein Trägergas zu verwenden, dessen Temperatur bei Raumtemperatur oder auch darunter liegt, wodurch eine thermische Belastung der gepritzen Komponenten, insbesondere derIn the present invention, at least one of the components is preferably sprayed by cold gas spraying, flame spraying, in particular high-speed flame spraying (HVOF), and / or plasma spraying. It is also contemplated, especially in cold gas spraying, to use a carrier gas whose temperature is at room temperature or even below, whereby a thermal load of the sprayed components, in particular the
Verstärkungskomponenten, sicher vermieden werden kann. Die Temperatur kann bis auf beispielsweise 10% unterhalb der Schmelztemperatur der niedrigstschmelzenden Komponente reichen. Das Trägergas soll gleichzeitig eine inerte oder sogar reduzierende Atmosphäre schaffen, um eine Oxidation der Pulverteilchen zu verhindern und so die späteren Schicht- oder Werkstoffeigenschaften wie elektrische Leitfähigkeit u.a. nicht negativ zu beeinflussen. Insbesondere kann auch eine Kombination zweier Spritzverfahren verwendet werden. Eine Verwendung zweier Spritzdüsen mit einer Mischung der entsprechenden Komponenten an der Beschichtungsstelle ist ebenfalls möglich .Reinforcement components, can be safely avoided. The temperature can be down to, for example, 10% below the Melting temperature of the lowest-melting component range. The carrier gas should simultaneously create an inert or even reducing atmosphere in order to prevent oxidation of the powder particles and thus not adversely affect the later layer or material properties such as electrical conductivity, among other things. In particular, a combination of two spraying methods can also be used. A use of two spray nozzles with a mixture of the corresponding components at the coating site is also possible.
Durch die genannten Maßnahmen lassen sich signifikant verbesserte Eigenschaften der hierdurch hergestellten Beschichtungen und Werkstoffe erzielen. Die entsprechendenAs a result of the measures mentioned, significantly improved properties of the coatings and materials produced thereby can be achieved. The corresponding
Produkte weisen eine erhöhte Verschleißbeständigkeit, ein besseres Gleitverhalten und eine höhereProducts have an increased wear resistance, a better sliding behavior and a higher
Reibkorrosionsbeständigkeit auf, wobei der Reibkoeffizient bis auf etwa ein Zehntel des Wertes des jeweiligen Reinmetalls reduziert werden kann. Ferner wird dieFriction corrosion resistance, wherein the friction coefficient can be reduced to about one-tenth of the value of the respective pure metal. Furthermore, the
Leitfähigkeit und die Härte der Materialien erhöht.Conductivity and hardness of the materials increased.
Die Erfindung liefert ein besonders flexibles und kostengünstiges Verfahren, da beispielsweise bei der Herstellung von Leiterbahnen, Leadframes und Stanzgittern durch die vorgesehenen Spritzverfahren keine Vorfertigungsschritte wie Walzen, Stanzen oder Glühen erforderlich sind.The invention provides a particularly flexible and cost-effective method, since, for example, in the production of printed conductors, lead frames and lead frames by the proposed spraying no prefabrication steps such as rolling, punching or annealing are required.
Als Substrat kann beim erfindungsgemäßen Verfahren eine Folie oder ein durch den Pulverstrahl nicht benetzbarer Untergrund dienen, was es ermöglicht, aufgespritzte Metallmatrix-Verbundwerkstoffe von dem Substrat abzutrennen. Hierdurch kann ein Bauteil oder ein reiner Werkstoff, beispielsweise in Form eines Bandes, erhalten werden, der dann in geeigneter Weise weiterverarbeitet werden kann.The substrate used in the process according to the invention may be a film or a substrate which is not wettable by the powder jet, which makes it possible to apply sprayed metal matrix composite materials from the substrate separate. In this way, a component or a pure material, for example in the form of a strip, can be obtained, which can then be further processed in a suitable manner.
Es können jedoch auch gezielt Bandwerkstoffe und Bauteile wie elektromechanische Komponenten, Kühlkörper, Lager und Buchsen haftend beschichtet werden, die durch den Metallmatrix-Verbundwerkstoff verbesserte Eigenschaften aufweisen. Zur Beschichtung im Sinne dieser Erfindung wird vorzugsweise ein Metallband oder ein elektromechanisch.es Bauteil als Werkstück verwendet, das vorzugsweise aus Keramik, Titan, Kupfer, Aluminium und/oder Eisen sowie Legierungen hiervon besteht. Auch Halbzeuge oder 3D- Strukturen wie Molded Interconnection Devices (MID) können zur Beschichtung verwendet werden.However, tape materials and components such as electromechanical components, heatsinks, bearings, and bushings may also be adhesively coated which have improved properties through the metal matrix composite. For the purposes of this invention, a metal strip or an electromechanical component is preferably used as the workpiece, which preferably consists of ceramic, titanium, copper, aluminum and / or iron and alloys thereof. Semifinished products or 3D structures such as Molded Interconnection Devices (MID) can also be used for coating.
Entsprechend einer besonders bevorzugten Ausführungsform beinhaltet das Verfahren wenigstens einen Oberflächenbearbeitungsschritt. Hierbei kann beispielsweise auf ein Metallband oder Bauteil aus einem metallischen Werkstoff eine Aktivierung, eine Haftungsvermittlungs- und/oder eine DiffusiorisSperrschicht aufgetragen werden, auf die anschließend die MMC aufgespritzt werden. Wird keine haftende Beschichtung angestrebt, sondern soll, wie oben dargestellt, ein reiner Metallmatrix-Verbundwerkstoff erhalten werden, kann anstelle einerAccording to a particularly preferred embodiment, the method includes at least one surface processing step. Here, for example, on a metal strip or component made of a metallic material, an activation, a Haftungsvermittlungs- and / or a Diffusiorisperrschicht are applied to the then the MMC are sprayed. If no adhesive coating is desired, but should, as shown above, a pure metal matrix composite material can be obtained instead of a
Haftvermittlungsschicht auch eine Antihaftbeschichtung aufgebracht werden.Adhesive layer also be applied a non-stick coating.
Entsprechende MMC-Bänder oder Beschichtungen können auch zur Einglättung der Oberfläche nachträglich einer Zusatzbehandlung wie Egalisieren oder einer Reflow-/Wärme- behandlung unterworfen werden. Zur Umformung kann nachträglich etwa auch ein Weichglühschritt, beispielsweise beim ca. 0,4-fachen der Schmelztemperatur des Matrixmetalles , erfolgen. Zur Verdichtung des Materials und/oder zur Reduzierung der Porosität an der Oberfläche kann das Material, beispielsweise mit einem Umformgrad von 0,1 bis 10%, nachgewalzt werden.Corresponding MMC tapes or coatings can also be used subsequently for smoothing the surface of an additional treatment such as leveling or a reflow / heat treatment. be subjected to treatment. For forming, for example, a soft annealing step, for example at about 0.4 times the melting temperature of the matrix metal, can also be carried out subsequently. For compacting the material and / or for reducing the porosity at the surface, the material can be re-rolled, for example with a degree of deformation of 0.1 to 10%.
In entsprechenden Verfahren wird vorteilhafterweise zumindest eine Metallkomponente und/oder zumindest eineIn corresponding methods, advantageously at least one metal component and / or at least one
Verstärkungskomponente in Partikelform bereitgestellt.Reinforcement component provided in particle form.
Durch eine entsprechende Auswahl von Struktur, Ausrichtung,Through an appropriate selection of structure, orientation,
Größe und Form der Partikel sowie deren Menge können dieThe size and shape of the particles as well as their quantity can be the
Werkstoffeigenschaften von Matrixwerkstoffen positiv beeinflusst werden. Durch geeignete Randbedingungen kann gegebenenfalls auch die Ausbildung von Whisker-Kristallen begünstigt oder verhindert werden.Material properties of matrix materials are positively influenced. If appropriate, the formation of whisker crystals can also be promoted or prevented by suitable boundary conditions.
In besonders vorteilhafter Weise kann auch eine erste Komponente vor dem Spritzen mit zumindest einer weiteren Komponente gemischt werden. Ein schonendes Mischen, beispielsweise von Kaltgasspritzpartikeln, kann durch Ummantelung der Partikel mit einer Dispersion oder Suspension, welche die Verstärkungspartikel enthält, und anschließendem Trocknen erfolgen. Das Mischen in einer Kugelmühle oder in einem Attritor aus mindestens zwei verschiedenen Komponenten unter Schutzgas kann je nach Härte der Partikel dazu führen, dass die Partikelform zerstört und damit das Fließverhalten des Pulvers negativ beeinflusst wird.In a particularly advantageous manner, a first component can also be mixed with at least one further component before spraying. Gentle mixing, for example of cold spray particles, may be accomplished by coating the particles with a dispersion or suspension containing the reinforcing particles, followed by drying. Depending on the hardness of the particles, mixing in a ball mill or in an attritor consisting of at least two different components under protective gas can cause the particle shape to be destroyed and thus the flow behavior of the powder to be adversely affected.
In einem derartigen Verfahren kann im Rahmen einer vorteilhaften Ausgestaltung zumindest eine organische und/oder zumindest eine keramische Verstärkungskomponente verwendet werden. Diese kann in dem gespritzen Gemisch vorliegen oder auch zugespritzt bzw. co-gespritzt werden.In such a method, in the context of an advantageous embodiment, at least one organic and / or at least one ceramic reinforcing component can be used. This can be present in the sprayed mixture or can also be injected or co-injected.
Ein vorteilhaftes Verfahren beinhaltet, dass wenigstens eine Verstärkungskomponente verwendet wird, die aus der Gruppe von Wolfram, Wolframcarbid, Wolframcarbid-Kobalt, Kobalt, Bor, Borcarbid, Invar, Kovar, Niob, Molybdän, Chrom, Nickel, Titannitrid, Aluminiumoxid, Kupferoxid, Silberoxid, Siliziumnitrid, Siliziumcarbid, Siliziumoxid, Zirkonwolframat und Zirkonoxid ausgewählt ist.An advantageous method involves using at least one reinforcing component selected from the group consisting of tungsten, tungsten carbide, tungsten carbide cobalt, cobalt, boron, boron carbide, invar, kovar, niobium, molybdenum, chromium, nickel, titanium nitride, alumina, copper oxide, silver oxide , Silicon nitride, silicon carbide, silicon oxide, zirconium tungstate and zirconium oxide.
Hierbei kann auch eine Verstärkungskomponente mit wenigstens einer weiteren Verstärkungskomponente zusammen verwendet und/oder entsprechend zugespritzt oder beigemischt werden. Durch die Verwendung von bekannten Keramikkomponenten können deren vorteilhafte Eigenschaften, auch zusätzlich zu denen anderer Verstärkungskomponenten, ausgenutzt werden. Durch Verwendung von Bor, Kobalt, Wolfram, Niob, Molybdän und seinen Legierungen und Invar oder Kovar kann der Wärmeausdehnungskoeffizient des Verbundwerkstoffs positiv beeinflusst werden.In this case, it is also possible to use a reinforcing component together with at least one further reinforcing component and / or to mix or mix it accordingly. Through the use of known ceramic components whose advantageous properties, in addition to those of other reinforcing components, can be exploited. By using boron, cobalt, tungsten, niobium, molybdenum and its alloys and Invar or Kovar, the thermal expansion coefficient of the composite can be positively influenced.
In vorteilhafter Weise kann ein Metallmatrix- Verbundwerkstoff oder eine Beschichtung mit einerAdvantageously, a metal matrix composite or a coating with a
Metallmatrix verwendet werden, die wenigstens ein Metall und/oder eine Legierung eines Metalls aufweist, das aus der Gruppe von Zinn, Kupfer, Silber, Gold, Nickel, Zink, Platin, Palladium, Eisen, Titan und Aluminium ausgewählt ist. Hierdurch kann beispielsweise eine besonders vorteilhafte Verschleißbeständigkeit, Korrosionsbeständigkeit und/oder eine spezifische elektrische oder thermische Leitfähigkeit sowie ein angepasster Ausdehnungskoeffizient bereitgestellt werden.Metal matrix can be used which comprises at least one metal and / or an alloy of a metal selected from the group of tin, copper, silver, gold, nickel, zinc, platinum, palladium, iron, titanium and aluminum. As a result, for example, a particularly advantageous wear resistance, corrosion resistance and / or a specific electrical or thermal conductivity and an adapted coefficient of expansion can be provided.
Ein durch das erfindungsgemäße Verfahren hergestellter Metallmatrix-Verbundwerkstoff mit einer zumindest eine Metallkomponente aufweisenden Metallmatrix und zumindest einer in der Metallmatrix angeordneten Verstärkungskomponente ist ebenfalls Gegenstand der Erfindung.A metal matrix composite material produced by the method according to the invention with a metal matrix having at least one metal component and at least one reinforcing component arranged in the metal matrix is likewise provided by the invention.
Als besonders vorteilhaft wird dabei ein Metallmatrix- Verbundwerkstoff angesehen, der einen Anteil von 0,1 bis 20%, vorzugsweise von 0,1 bis 5%, vorzugsweise von 0,2 bis 5% Kohlenstoff-Nanoröhrchen aufweist. Die genannten Anteile haben sich, wie oben erwähnt, in der Praxis als besonders vorteilhaft erwiesen.A metal matrix composite material which has a proportion of from 0.1 to 20%, preferably from 0.1 to 5%, preferably from 0.2 to 5%, of carbon nanotubes is regarded as being particularly advantageous. The abovementioned proportions have proven to be particularly advantageous in practice, as mentioned above.
Ein entsprechender Metallmatrix-Verbundwerkstoff mit vorteilhaften Eigenschaften weist beispielsweise eine Restporosität von 0,2 bis 20% in Bezug auf dieA corresponding metal matrix composite material with advantageous properties has, for example, a residual porosity of 0.2 to 20% with respect to the
Verstärkungskomponente und/oder von 0,2 bis 10% in Bezug auf die Metallkomponente auf. MMC mit derartigen Restporositäten können mit Vorteil dann verwendet werden, wenn eine besonders gute Abriebfestigkeit, wie beispielsweise in Lagern oder an Gleitflächen, oder eine hohe elektrische Leitfähigkeit, wie beispielsweise in Leiterbahnen, erforderlich ist.Reinforcement component and / or from 0.2 to 10% with respect to the metal component. MMC with such residual porosities can be used with advantage when a particularly good abrasion resistance, such as in bearings or sliding surfaces, or a high electrical conductivity, such as in tracks, is required.
Der erfindungsgemäße Metallmatrix-Verbundwerkstoff eignet sich besonders für eine Beschichtung für ein Werkstück. Die Beschichtung kann beispielsweise auf Lagern und Gleitelementen, Kühlkörpern, Steckverbindern, Stanzgittern und Leiterbahnen, insbesondere auf als Heizelemente verwendbaren Leiterbahnen, aufgebracht werden. Derartige MMC-Beschichtungen können etwa aus Sn, Cu, Ag, Au, Ni, Zn, Pt, Pd, Fe, Ti, W und/oder Al und ihren Legierungen wie etwa Loten, insbesondere mit einem Anteil von SW-CNT oder MW-CNT von 0,1 bis 20%, vorzugsweise von 0,2 bis 5% bestehen.The metal matrix composite according to the invention is particularly suitable for a coating for a workpiece. The coating can be used, for example, on bearings and sliding elements, heat sinks, connectors, punched grids and strip conductors, in particular as heating elements usable conductor tracks are applied. Such MMC coatings can be made of, for example, Sn, Cu, Ag, Au, Ni, Zn, Pt, Pd, Fe, Ti, W and / or Al and their alloys such as solders, in particular with a content of SW-CNT or MW. CNT from 0.1 to 20%, preferably from 0.2 to 5%.
Insbesondere kann es um ein beschichtetes Band zur Verwendung in elektromechanischen Bauelementen wie Steckverbindern, Federn, z.B. für Relais, schaltenden Kontakten, um Leiterbahnen in Stanzgittern und Heizelementen oder Kühlkörpern und -elementen handeln. Das Metallband besitzt vorzugsweise eine Dicke von 0,01 bis 5 mm, besonders bevorzugt von 0,06 bis 3,5 mm. Zur Herstellung von lediglich aus dem Metallmatrix- Verbundwerkstoff bestehenden Bändern können auch, wie erwähnt, die Komponenten beispielsweise auf einen nicht benetzbaren Untergrund wie Folien aus PEEK, Polyimid oder Teflon aufgespritzt werden. Entsprechend hergestellte Stanzgitter, Leiterbahnen, Heizelemente und Bänder können Cu, Al, Ni und Fe sowie Legierungen hiervon aufweisen.In particular, it may be a coated tape for use in electromechanical components such as connectors, springs, e.g. for relays, switching contacts, to act conductor tracks in punched grids and heating elements or heat sinks and elements. The metal strip preferably has a thickness of 0.01 to 5 mm, particularly preferably 0.06 to 3.5 mm. For the production of strips consisting only of the metal matrix composite material, as mentioned, the components may for example be sprayed onto a non-wettable substrate such as films made of PEEK, polyimide or Teflon. Correspondingly produced stamped grids, tracks, heating elements and strips may comprise Cu, Al, Ni and Fe and alloys thereof.
Leiterbahnen, die zumindest einen wie oben hergestellten Metallmatrix-Verbundwerkstoff aufweisen, können lokal auf eine Platine, MID-Strukturen (Moulded Interconnection Devices) aus z.B. LSDS oder anderen Thermoplasten insbesondere über Schablonen, aufgespritzt oder in Form einer flächigen Beschichtung vorgesehen werden, die später, etwa durch geeignete Photolithographieverfahren, weiterverarbeitet wird.Printed circuit traces comprising at least one metal matrix composite material as prepared above may be printed locally on a printed circuit board, molded interconnection devices (MID), e.g. LSDS or other thermoplastics in particular stencils, sprayed or provided in the form of a sheet-like coating, which is later processed, for example by suitable photolithography process.
Ein MMC-Band oder eine Leiterbahn kann vorteilhafterweise aus Cu, Ag, Al, Ni und/oder Sn und ihren Legierungen mit einem Anteil an SW-CNT oder MW-CNT von 0,1 bis 20%, vorzugsweise von 0,1 bis 5% bestehen.An MMC tape or trace may advantageously be made of Cu, Ag, Al, Ni and / or Sn and their alloys a proportion of SW-CNT or MW-CNT from 0.1 to 20%, preferably from 0.1 to 5%.
Bezüglich weiterer Merkmale und Vorteile sei ausdrücklich auf die Ausführungen bezüglich des erfindungsgemäßen Herstellungsverfahrens verwiesen.With regard to further features and advantages, reference is expressly made to the statements relating to the production method according to the invention.
Ein entsprechend des erfindungsgemäßen Verfahrens hergestellter Metallmatrix-Verbundwerkstoff eignet sich in besonderer Weise zur Verwendung bei der Herstellung von Werkstücken, insbesondere von elektroraechanischenA metal matrix composite material produced according to the method of the invention is particularly suitable for use in the production of workpieces, in particular of electro-mechanical ones
Komponenten. Eine derartige Verwendung kann entweder umfassen, das Werkstück vollständig aus dem Metallmatrix- Verbundwerkstoff herzustellen, oder eine Beschichtung mit einem solchen Werkstoff vorzunehmen.Components. Such a use may either include making the workpiece completely out of the metal matrix composite or coating it with such material.
Figurencharacters
Die Erfindung und ihre Vorteile sowie weitere Ausgestaltungen der Erfindung werden im Folgenden anhand der in den Figuren dargestellten Ausführungsbeispiele näher erläutert. Im Einzelnen zeigt:The invention and its advantages as well as further embodiments of the invention are explained in more detail below with reference to the embodiments illustrated in the figures. In detail shows:
Figur 1 in schematischer Darstellung eine Vorrichtung zumFigure 1 is a schematic representation of a device for
Kaltgasspritzen, die zur Durchführung eines Verfahrens gemäß einer besonders bevorzugtenCold gas spraying, which for carrying out a method according to a particularly preferred
Ausführungsform der Erfindung geeignet ist, undEmbodiment of the invention is suitable, and
Figur 2 mikroskopische Schliff-Aufnahmen der Gefüge und rasterelektronenmikroskopische Aufnahmen der Oberflächen von Metallmatrix-Verbundwerkstoffen, die mittels Verfahren gemäß besonders bevorzugter Ausführungsformen der vorliegenden Erfindung hergestellt sind. Eine zur Durchführung des Verfahrens gemäß einer besonders bevorzugten Ausführungsform der Erfindung geeignete Vorrichtung zum Kaltgasspritzen ist in Figur 1 gezeigt. Die Vorrichtung weist eine Vakuumkammer 4 auf, in der beispielsweise ein zu beschichtendes Substrat 5 vor der Düse einer Kaltgasspritzpistole 3 platziert werden kann. Es sei jedoch zu verstehen gegeben, dass ein derartiges Spritzverfahren auch bei Atmosphärendruck erfolgen könnte, wozu eine Vakuumkammer nicht erforderlich ist. DieFigure 2 Microscopic micrographs of the microstructure and scanning electron micrographs of the surfaces of metal matrix composites prepared by methods according to particularly preferred embodiments of the present invention. A device for cold gas spraying suitable for carrying out the method according to a particularly preferred embodiment of the invention is shown in FIG. The device has a vacuum chamber 4 in which, for example, a substrate 5 to be coated can be placed in front of the nozzle of a cold gas spray gun 3. It should be understood, however, that such a spraying process could also be carried out at atmospheric pressure, for which a vacuum chamber is not required. The
Platzierung des Werkstücks 5 vor der Kaltgasspritzpistole 3 erfolgt beispielsweise mittels einer in Figur 1 aus Gründen der Übersichtlichkeit nicht gezeigten Halterung. Vorzugsweise ist das Substrat 5 beweglich, d.h. verschieb- und drehbar angeordnet, so dass eine Beschichtung an mehreren Positionen, insbesondere bandförmig oder flächig erfolgen kann. Alternativ oder zusätzlich hierzu kann auch die Kaltgasspritzpistole 3 beweglich angeordnet sein.Placement of the workpiece 5 in front of the cold gas spray gun 3 takes place, for example, by means of a holder, not shown in Figure 1 for reasons of clarity. Preferably, the substrate 5 is movable, i. displaceable and rotatably arranged, so that a coating can take place at a plurality of positions, in particular band-shaped or flat. Alternatively or additionally, the cold gas spray gun 3 may be movably arranged.
Zum Durchführen der Beschichtung des Substrats 5 wird die Vakuumkammer 4 evakuiert und mittels der Kaltgasspritzpistole 3 ein Gasstrahl erzeugt, in den Partikel zur Beschichtung des Werkstücks 5 eingespeist werden .For carrying out the coating of the substrate 5, the vacuum chamber 4 is evacuated and generated by means of the cold gas spray gun 3, a gas jet, are fed into the particles for coating the workpiece 5.
Hierbei gelangt der Hauptgasström, beispielsweise eine Helium-Stickstoff-Mischung mit etwa 40 VoI .-% Helium, über die Gaszuleitung 1 in die Vakuumkammer 4. Die Spritzpartikel, beispielsweise ein Metallpulver mit beigemischten CNT, gelangen im Hilfsgasstrom über dieIn this case, the main gas flow, for example a helium-nitrogen mixture with about 40% by volume of helium, passes via the gas supply line 1 into the vacuum chamber 4. The spray particles, for example a metal powder with admixed CNT, pass through the auxiliary gas flow
Zuleitung 2 in die Vakuumkammer 4, in der ein Druck von etwa 40 mbar herrscht, und dort in die Kaltgasspritzpistole 3. Die Zuleitungen 1, 2 sind hierzu in die Vakuumkammer 4 hineingeführt, in der sich sowohl die Kaltgasspritzpistole' 3 als auch das Substrat 5 befindet. Es kann auch vorgesehen sein, mehrere zu spritzende Komponenten über mehrere Hilfsgasströme zuzuführen. Der gesamte Kaltgasspritzprozess findet somit in der Vakuumkammer 4 statt. Die Partikel werden durch den Kaltgasstrahl so stark beschleunigt, dass ein Anhaften der Partikel auf der Oberfläche des zu beschichtenden Werkstücks 5 durch Umwandlung der kinetischen Energie der Partikel in Wärmeenergie erreicht wird. Die Partikel können zusätzlich bis zu der oben angegebenen Maximaltemperatur erwärmt werden.Feed line 2 in the vacuum chamber 4, in which a pressure of about 40 mbar prevails, and there in the cold gas spray gun 3. The supply lines 1, 2 are for this purpose in the vacuum chamber. 4 in which both the cold gas spray gun ' 3 and the substrate 5 is located. It can also be provided to supply a plurality of components to be sprayed via a plurality of auxiliary gas streams. The entire cold gas spraying process thus takes place in the vacuum chamber 4. The particles are accelerated so much by the cold gas jet that adhesion of the particles on the surface of the workpiece 5 to be coated is achieved by converting the kinetic energy of the particles into thermal energy. The particles can additionally be heated up to the maximum temperature indicated above.
Das Trägergas, das beim Kaltgasspritzen zusammen mit den Spritzpartikeln aus der Spritzpistole 3 tritt und die Spritzpartikel zum Werkstück 5 trägt, gelangt nach dem Spritzprozess in die Vakuumkammer 4. Das verbrauchte Trägergas wird über die Gasleitung 6 aus der Vakuumkammer 4 mittels der Vakuumpumpe 8 entfernt. Zwischen die Vakuumkammer 4 und die Vakuumpumpe 8 ist beispielsweise ein Partikelfilter 7 geschaltet, der freie Spritzpartikel aus dem verbrauchten Trägergas entfernt, um zu verhindern, dass die Spritzpartikel die Pumpe 8 beschädigen.The carrier gas, which passes during the cold gas spraying together with the spray particles from the spray gun 3 and carries the spray particles to the workpiece 5, passes after the injection process in the vacuum chamber 4. The spent carrier gas is removed via the gas line 6 from the vacuum chamber 4 by means of the vacuum pump 8. Between the vacuum chamber 4 and the vacuum pump 8, for example, a particle filter 7 is connected, which removes free spray particles from the spent carrier gas in order to prevent the spray particles from damaging the pump 8.
In den Teilfiguren 2A bis 2C der Figur 2 sind Ergebnisse von Versuchen dargestellt, in denen jeweils Metallpulver mit Zusatz von Verstärkungskomponenten gespritzt wurden.FIGS. 2A to 2C of FIG. 2 show results of tests in which metal powders with the addition of reinforcing components were injected in each case.
Die Figuren zeigen Bilder von Schliffen und rasterelektronenmikroskopische Aufnahmen der Oberfläche der hierdurch erhaltenen Schichten. Im Rahmen der Versuche wurde kommerziell erhältliches Cu-, SnAg3- und Sn-Pulver zusammen mit geeigneten MW-CNT des Herstellers AhwahneeThe figures show images of cuts and scanning electron micrographs of the surface of the layers obtained thereby. In the course of the experiments, commercially available Cu, SnAg 3 and Sn powders were used together with suitable MW-CNT from the manufacturer Ahwahnee
(P/N ATI-BMWCNT-002) verwendet. Figur 2A zeigt das Gefüge einer durch Spritzen von Rein- Kupfer mit 1,5% MW-CNT erhaltene Schicht 200 mit einer Kupfermatrix 201 und hierin diskontinuierlich verteilten CNT 202 in 1000-facher Vergrößerung im Schliff. Ferner sind in der Beschichtung 200 durch eine nicht vollständig vermeidbare Oxidation des Cu-Pulvers während des Mischungsvorganges mit den MWCNT gebildete sogenannte Oxidhäute 203 auf den Cu-Körnern zu sehen. Die Schichten wurden bei einer Düsenaustrittstemperatur von 600 0C und einem Druck von 38 bar unter N2-GaS gespritzt. Die Dichte der Schicht liegt bei 99,5%, ihre Dicke bei 280 um, die Schichthärte beträgt 1200 N/mm2. Aufgrund des guten Reibverhaltens eignet sich diese Schicht als Lauffläche von Lagern und Buchsen. Nach Ablösung der 280 um dicken Schicht vom Trägermaterial liegt ein Band vor, welches als Leiterbahn in Stanzgittern oder elektromechanischen Bauelementen Einsatz finden kann.(P / N ATI-BMWCNT-002). FIG. 2A shows the microstructure of a layer 200 obtained by spraying pure copper with 1.5% MW-CNT with a copper matrix 201 and CNT 202 discontinuously distributed therein in a 1000-fold magnification. Furthermore, in the coating 200 so-called oxide skins 203 formed on the Cu grains by a not completely avoidable oxidation of the Cu powder during the mixing process with the MWCNT can be seen. The layers were injected at a nozzle exit temperature of 600 0 C and a pressure of 38 bar under N 2 -GaS. The density of the layer is 99.5%, its thickness is 280 μm, the layer hardness is 1200 N / mm 2 . Due to the good friction behavior, this layer is suitable as a running surface of bearings and bushes. After detachment of the 280 micron thick layer of the carrier material is a tape, which can be used as a conductor in stamped or electromechanical components use.
Figur 2B zeigt die Oberfläche einer durch Spritzen von Rein-Sn mit 2,1% MW-CNT erhaltene Schicht 210 mit einerFigure 2B shows the surface of a layer 210 obtained by spraying pure Sn with 2.1% MW-CNT with a
Zinnmatrix und hierin diskontinuierlich verteilten CNT in 300-facher Vergrößerung. Figur 2C zeigt eine Detailansicht der Figur 2B in 10.000-facher Vergrößerung. Die Schicht 210 weist sphärische Sn-Körper 213 mit hierzwischen verteilten CNT 202 auf. Die Dichte der Schicht liegt bei 99,4%. Sie weist eine Härte von 368 N/mm2 und im Verschleißtest einen Reibkoeffizienten von 0,5 auf. Beim Spritzen dieser Schicht unter N2-GaS mit einem Druck von 32 bar und einer Düsenaustrittstemperatur von 350 0C wurde eine Schichtdicke von 5 μm erzielt. Durch Variation derTin matrix and herein discontinuously distributed CNT in 300x magnification. FIG. 2C shows a detailed view of FIG. 2B at a magnification of 10,000 times. The layer 210 has spherical Sn bodies 213 with CNTs 202 distributed therebetween. The density of the layer is 99.4%. It has a hardness of 368 N / mm 2 and a coefficient of friction of 0.5 in the wear test. When spraying this layer under N 2 -GaS with a pressure of 32 bar and a nozzle exit temperature of 350 0 C, a layer thickness of 5 microns was achieved. By variation of the
Düsenaustrittstemperatur, der Verfahrgeschwindigkeit und des Druckes kann die Schichtdicke, die Schichthärte und in Kombination mit dem CNT-Gehalt des Pulvers der Reibkoeffizient wesentlich verändert (reduziert) werden. Derartig hergestellte Schichten können durch eine Nachbehandlung wie Egalisieren oder Umschmelzen (Reflowbehandlung) in ihrer Oberflächenstruktur noch gezielt auf den jeweiligen Einsatzfall optimiert werden. Partiell oder vollflächig auf Cu-Legierungsbänder aufgebracht können diese Schichten zur Reduzierung von Steck- und Ziehkräften bei elektromechanisehen Bauelementen wie Steckverbindern, oder nach entsprechenden Egalisier- und Reflowschritten der Verbesserung desDie exit temperature, the travel speed and the pressure, the layer thickness, the layer hardness and in combination with the CNT content of the powder Friction coefficient significantly changed (reduced). Such produced layers can be optimized by a post-treatment such as leveling or remelting (reflow treatment) in their surface structure specifically targeted to the particular application. Partially or completely applied to Cu alloy strips, these layers can be used to reduce plugging and drawing forces in electromechanical components such as connectors, or after appropriate leveling and reflow steps to improve the
Verschleißverhaitens bei Gleitlagern und Buchsen dienen. Wear behavior in plain bearings and bushes are used.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung eines Metallmatrix- Verbundwerkstoffs (200, 210) für elektrische Bauelemente, elektrische Komponenten oder Kühlkörper mit einer zumindest eine Metallkomponente aufweisenden Metallmatrix (201, 211) und zumindest einer in der Metallmatrix (201, 211) angeordneten Verstärkungskomponente (202), dadurch gekennzeichnet, dass zumindest eine der Komponenten durch ein thermisches Spritzverfahren auf ein Substrat (5) gespritzt wird, und dass zumindest eine Verstärkungskomponente Kohlenstoff in Form von Nanoröhrchen (202) , Nanofasern, Graphenen, Fullerenen, Flakes oder Diamant verwendet wird.Method for producing a metal matrix composite material (200, 210) for electrical components, electrical components or heat sinks having a metal matrix (201, 211) comprising at least one metal component and at least one reinforcement component (202) arranged in the metal matrix (201, 211) , characterized in that at least one of the components is sprayed onto a substrate (5) by a thermal spray method, and that at least one reinforcing component of carbon in the form of nanotubes (202), nanofibers, graphenes, fullerenes, flakes or diamond is used.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Spritzverfahren Kaltgasspritzen, Flammspritzen und/oder Plasmaspritzen verwendet wird.2. The method according to claim 1, characterized in that is used as spraying cold gas spraying, flame spraying and / or plasma spraying.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass als Substrat (5) eine Folie oder ein Substrat mit nicht benetzbarer Oberfläche oder ein zu beschichtendes Werkstück, ein Halbzeug und/oder eine 3D- Struktur verwendet wird.3. The method according to claim 1 or 2, characterized in that as substrate (5) a film or a substrate with non-wettable surface or a workpiece to be coated, a semifinished product and / or a 3D structure is used.
4. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass wenigstens eine Oberfläche des Substrats (5) und/oder des Metallmatrix-Verbundwerkstoffs (200, 210) bearbeitet wird. 4. The method according to any one of the preceding claims, characterized in that at least one surface of the substrate (5) and / or the metal matrix composite material (200, 210) is processed.
5. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass zumindest eine Metallkomponente und/oder zumindest eine Verstärkungskomponente (202) in Partikelform bereitgestellt wird.5. The method according to any one of the preceding claims, characterized in that at least one metal component and / or at least one reinforcing component (202) is provided in particulate form.
6. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass eine erste Komponente vor dem Spritzen mit zumindest einer weiteren Komponente gemischt wird.6. The method according to any one of the preceding claims, characterized in that a first component is mixed before spraying with at least one further component.
7. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass zumindest eine organische und/oder zumindest eine keramische Verstärkungskomponente (202) verwendet wird.7. The method according to any one of the preceding claims, characterized in that at least one organic and / or at least one ceramic reinforcing component (202) is used.
8. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass wenigstens eine weitere Verstärkungskomponente verwendet wird, die aus der Gruppe von Wolfram, Wolframcarbid, Wolframcarbid-Kobalt , Kobalt, Kupferoxid, Silberoxid, Titannitrid, Chrom, Nickel, Bor, Borcarbid, Invar, Kovar, Niob, Molybdän, Aluminiumoxid, Siliziumnitrid, Siliciumcarbid, Siliziumoxid, Zirkonwolframat und Zirkonoxid ausgewählt ist.8. The method according to any one of the preceding claims, characterized in that at least one further reinforcing component is used, which consists of the group of tungsten, tungsten carbide, tungsten carbide-cobalt, cobalt, copper oxide, silver oxide, titanium nitride, chromium, nickel, boron, boron carbide, Invar , Kovar, niobium, molybdenum, alumina, silicon nitride, silicon carbide, silica, zirconium tungstate and zirconia.
9. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass eine Metallmatrixkomponente verwendet wird, die wenigstens ein Metall und/oder eine Legierung eines Metalls aufweist, das aus der Gruppe von Zinn, Kupfer, Silber, Gold, Nickel, Zink, Platin, Palladium, Eisen, Titan und Aluminium ausgewählt ist. 9. The method according to any one of the preceding claims, characterized in that a metal matrix component is used which comprises at least one metal and / or an alloy of a metal selected from the group of tin, copper, silver, gold, nickel, zinc, platinum, Palladium, iron, titanium and aluminum is selected.
10. Metallmatrix-Verbundwerkstoff (200, 210) mit einer zumindest eine Metallkomponente aufweisenden Metallmatrix (201, 211) und zumindest einer in der Metallmatrix (201, 211) angeordneten Verstärkungskomponente (202) , wobei der Metallmatrix-Verbundwerkstoff (200, 210) durch ein Verfahren nach einem der vorangehenden Ansprüche hergestellt ist.10. A metal matrix composite material (200, 210) having a metal matrix (201, 211) comprising at least one metal component and at least one reinforcement component (202) arranged in the metal matrix (201, 211), wherein the metal matrix composite material (200, 210) a method according to any one of the preceding claims is made.
11. Metallmatrix-Verbundwerkstoff (200, 210) insbesondere nach Anspruch 10, der einen Anteil 0,1 bis 20%, vorzugsweise 0,1 bis 5%, vorzugsweise 0,2 bis 5% Kohlenstoff-Nanoröhrchen (202) als Verstärkungskomponente aufweist .11. Metal matrix composite material (200, 210) in particular according to claim 10, which has a proportion of 0.1 to 20%, preferably 0.1 to 5%, preferably 0.2 to 5% carbon nanotubes (202) as a reinforcing component.
12. Metallmatrix-Verbundwerkstoff (200, 210) nach Anspruch 10 oder 11, der eine Restporosität von 0,2 bis 20% in Bezug auf die Verstärkungskomponente und/oder von 0,2 bis 10% in Bezug auf die Metallkomponente aufweist.A metal matrix composite (200, 210) according to claim 10 or 11, having a residual porosity of 0.2 to 20% with respect to the reinforcing component and / or from 0.2 to 10% with respect to the metal component.
13. Verwendung eines Metallmatrix-Verbundwerkstoffs nach einem der Ansprüche 10 bis 12 zur Herstellung eines Werkstücks, wobei das Werkstück durch den Metallmatrix- Verbundwerkstoff beschichtet und/oder aus dem Metallmatrix- Verbundwerkstoff gebildet wird. Use of a metal matrix composite according to any one of claims 10 to 12 for the manufacture of a workpiece, wherein the workpiece is coated by the metal matrix composite and / or formed from the metal matrix composite.
EP10724291A 2009-06-03 2010-05-27 Process for producing a metal matrix composite material Withdrawn EP2437904A1 (en)

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JP2012528934A (en) 2012-11-15
DE102009026655B3 (en) 2011-06-30
RU2536847C2 (en) 2014-12-27
CN102458719A (en) 2012-05-16
WO2010139423A1 (en) 2010-12-09
KR20120027350A (en) 2012-03-21
US20120077017A1 (en) 2012-03-29
EP2261397A1 (en) 2010-12-15
RU2011154031A (en) 2013-07-20

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