WO2013042635A1 - Stratifié et procédé de fabrication du stratifié - Google Patents

Stratifié et procédé de fabrication du stratifié Download PDF

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Publication number
WO2013042635A1
WO2013042635A1 PCT/JP2012/073712 JP2012073712W WO2013042635A1 WO 2013042635 A1 WO2013042635 A1 WO 2013042635A1 JP 2012073712 W JP2012073712 W JP 2012073712W WO 2013042635 A1 WO2013042635 A1 WO 2013042635A1
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alloy
intermediate layer
titanium
metal
chromium
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PCT/JP2012/073712
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English (en)
Japanese (ja)
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智資 平野
教良 金田
年彦 花待
雄一郎 山内
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日本発條株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas

Definitions

  • the present invention relates to a laminate in which a hard film is formed on the surface of a substrate made of a metal or an alloy, and a method for manufacturing the laminate.
  • a laminate in which a hard film is formed on the surface of a base material made of a metal or an alloy has been used in various applications such as machine parts, tools, molds, medical members, and sports equipment.
  • the hard coating for example, ceramics (oxide ceramics, non-oxide ceramics, BCN ultra-hard materials), mixed materials of metals and ceramics, metals or alloys are used, and depending on the materials, corrosion resistance and heat resistance are used. Functions such as wear resistance can be imparted to the substrate.
  • Such a hard coating is formed on the substrate surface by chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, or the like.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • thermal spraying has been actively used because of the advantages that the film formation rate is fast, the film can be applied to a wide variety of substrates and coating materials, and there are few restrictions on the dimensions of the substrate.
  • Patent Document 1 discloses a metal substrate, a ceramic coating layer covering the surface of the metal substrate, and a metal substrate side.
  • a heat-resistant material comprising a fine particle aggregate layer and a metal bonding layer having a coarse particle aggregate layer disposed on the ceramic coating layer side is disclosed.
  • the film formed by thermal spraying adheres to the base material by a so-called anchor effect in which the material of the melted film enters the irregularities on the surface of the base material. Therefore, conventionally, when a laminate is produced by a thermal spraying method, as shown in FIG. 9, in order to increase the adhesion strength between a base material 91 such as a metal and a hard coating 93 formed on the surface thereof, The surface 92 of 91 is preliminarily roughened by blasting. However, the laminate produced by such a method has a problem that the adhesion strength between the base material 91 and the hard film 93 is not sufficient when mechanical stress is applied.
  • Patent Document 1 discloses that the metal base material is caused by cracks in the ceramic coating layer or cracks when the laminate is used in an environment where the temperature or the temperature fluctuates severely. In order to prevent peeling of the ceramic coating layer from the metal, it is disclosed that a metal bonding layer is provided between them. However, Patent Document 1 does not disclose any adhesion strength between the metal substrate and the ceramic coating layer when mechanical stress is applied to the laminate.
  • the present invention has been made in view of the above, and is a laminate having high adhesion strength between a base material made of a metal or an alloy and a thermal spray coating layer formed on the surface of the base material, and the laminate.
  • An object is to provide a manufacturing method.
  • a laminate according to the present invention is a substrate made of a metal or an alloy and a powder material of the metal or alloy heated to a temperature lower than the melting point of the powder material. It is characterized by comprising an intermediate layer which is accelerated together with gas and sprayed and deposited on the surface of the base material in a solid state, and a thermal spray coating layer formed on the intermediate layer by thermal spraying.
  • the base material is copper, copper alloy, zinc, zinc alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, nickel, nickel alloy, iron, iron alloy, titanium, titanium alloy, chromium, chromium alloy, It is characterized by comprising any one of niobium, niobium alloy, molybdenum, molybdenum alloy, silver, silver alloy, tin, tin alloy, tantalum, and tantalum alloy.
  • the intermediate layer is made of copper, copper alloy, zinc, zinc alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, nickel, nickel alloy, iron, iron alloy, titanium, titanium alloy, chromium, chromium alloy, It is characterized by comprising any one of niobium, niobium alloy, molybdenum, molybdenum alloy, silver, silver alloy, tin, tin alloy, tantalum, and tantalum alloy.
  • the intermediate layer is made of the same metal or alloy as the base material.
  • the intermediate layer has a thickness of 5 to 100 ⁇ m.
  • the thermal spray coating layer is made of a ceramic material, a mixed material of metal and ceramic, a metal, or an alloy material.
  • the sprayed coating layer is made of alumina, magnesia, zirconia, yttria, yttria stabilized zirconia, steatite, forsterite, mullite, titania, silica, sialon, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, Titanium carbide, titanium carbonitride, titanium aluminum nitride, titanium nitride chromium, chromium nitride, zirconium nitride, chromium carbide, tungsten carbide, boron carbide, boron nitride, copper, copper alloy, zinc, zinc alloy, aluminum, aluminum alloy, magnesium, Magnesium alloy, nickel, nickel alloy, iron, iron alloy, titanium, titanium alloy, chromium, chromium alloy, niobium, niobium alloy, molybdenum, molybdenum alloy, silver, silver alloy,
  • a metal or alloy powder material is accelerated on a surface of a base material made of a metal or alloy together with a gas heated to a temperature lower than the melting point of the powder material, It includes an intermediate layer forming step of forming an intermediate layer by spraying and depositing as it is, and a thermal spray coating layer forming step of forming a thermal spray coating layer on the intermediate layer by thermal spraying.
  • a metal or alloy powder material is accelerated with a gas heated to a temperature lower than the melting point of the powder material to a base material made of a metal or alloy, and remains in a solid state on the surface of the base material. Since the intermediate layer is deposited by a so-called cold spraying method and a sprayed coating layer is formed on the intermediate layer, the adhesion strength between the substrate and the sprayed coating layer can be improved.
  • FIG. 1 is a schematic diagram showing a configuration of a laminate according to an embodiment of the present invention.
  • FIG. 2 is a flowchart showing a method for manufacturing a laminate according to the embodiment of the present invention.
  • FIG. 3 is a schematic diagram showing an outline of a cold spray apparatus used for manufacturing the laminate according to the embodiment of the present invention.
  • FIG. 4 is a schematic diagram illustrating the structure of the test piece according to the example.
  • FIG. 5 is an electron micrograph showing the surface of the intermediate layer (CS film).
  • FIG. 6 is a schematic diagram illustrating the structure of a test piece according to a comparative example.
  • FIG. 7 is an electron micrograph showing the blasted substrate surface.
  • FIG. 8 is a graph showing the results of a tensile test.
  • FIG. 9 is a schematic diagram showing a conventional structure of a laminate in which a thermal spray coating is formed on the substrate surface.
  • FIG. 1 is a schematic diagram showing a configuration of a laminate according to an embodiment of the present invention.
  • a laminate 10 shown in FIG. 1 includes a base material 11 made of a metal or an alloy, an intermediate layer (CS film) 12 formed on the surface of the base material 11 by a cold spray (CS) method, and the intermediate layer 12 And a thermal spray coating layer 13 formed by a thermal spraying method.
  • CS film intermediate layer
  • CS cold spray
  • the base material 11 is, for example, copper, copper alloy, zinc, zinc alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, nickel, nickel alloy, iron, iron alloy, titanium, titanium alloy, chromium, chromium alloy, niobium, niobium It is formed of a metal or an alloy such as an alloy, molybdenum, a molybdenum alloy, silver, a silver alloy, tin, a tin alloy, tantalum, or a tantalum alloy.
  • the base material 11 shown in FIG. 1 has comprised plate shape, the shape of the base material 11 will not be limited to plate shape, if the film formation by spraying is possible on the surface.
  • the intermediate layer 12 is formed as a base of the sprayed coating layer 13 by a cold spray method described later.
  • the intermediate layer 12 is, for example, copper, copper alloy, zinc, zinc alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, nickel, nickel alloy, iron, iron alloy, titanium, titanium alloy, chromium. , Chromium alloy, niobium, niobium alloy, molybdenum, molybdenum alloy, silver, silver alloy, tin, tin alloy, tantalum, and tantalum alloy.
  • the material of the intermediate layer 12 may be the same type of metal or alloy as the base material 11, or may be a different type of metal or alloy from the base material 11.
  • the cold spray method is a film forming method in which a powder material is accelerated together with a gas heated to a temperature lower than the melting point of the powder material and sprayed on the surface of the base material 11 in a solid state to deposit the powder material. .
  • the powder material collides with the base material 11 at a high speed, so that plastic deformation occurs between the material powder and the base material 11. Is obtained.
  • the thermal spray coating layer 13 is a hard coating made of a ceramic material, a mixed material of metal and ceramics, or a metal or an alloy material, and is formed on the intermediate layer 12 by thermal spraying.
  • the material of the sprayed coating layer 13 is selected according to the function imparted to the base material 11 such as corrosion resistance, heat resistance, and wear resistance.
  • a metal or alloy material is used for the sprayed coating layer 13, a material different from the base material 11 and the intermediate layer 12 is selected.
  • Ceramic materials include oxide ceramics such as alumina, magnesia, zirconia, yttria, yttria stabilized zirconia, steatite, forsterite, mullite, titania, silica, sialon, aluminum nitride, silicon nitride, silicon carbide.
  • Non-oxide ceramics such as titanium nitride, titanium carbide, titanium carbonitride, titanium aluminum nitride, titanium chromium nitride, chromium nitride, zirconium nitride, chromium carbide, tungsten carbide, and BCN-based ultra-hard materials such as boron carbide and boron nitride Is mentioned.
  • metal or alloy materials include copper, copper alloy, zinc, zinc alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, nickel, nickel alloy, iron, iron alloy, titanium, titanium alloy, chromium, chromium alloy, niobium Niobium alloy, molybdenum, molybdenum alloy, silver, silver alloy, tin, tin alloy, tantalum, tantalum alloy, tungsten, tungsten alloy.
  • a mixed material of metal and ceramics a mixed material mainly composed of ceramics such as oxides, nitrides, carbides, borides, etc. (for example, the above-mentioned ceramic materials), and a metal or alloy as a binder phase (bonding material).
  • cermet a mixed material which disperse
  • a material such as a mixed composition of yttria-stabilized zirconia (YSZ) and a nickel (Ni) -chromium (Cr) alloy may be used.
  • FIG. 2 is a flowchart showing a method for manufacturing the laminate 10.
  • step S1 a base material 11 having a desired shape is produced from a desired material.
  • step S2 the intermediate layer 12 is formed on the surface of the substrate 11 by a cold spray method.
  • FIG. 3 is a schematic diagram showing an outline of the cold spray apparatus 40 used for forming the intermediate layer 12.
  • the cold spray device 40 includes a gas heater 41 that heats the compressed gas, a powder supply device 42 that contains the powder of the material to be injected onto the base material 11 and supplies the powder to the spray gun 43, and heating A gas nozzle 44 for injecting the compressed gas and the material powder supplied thereto onto the substrate 11, and valves 45 and 46 for adjusting the amount of compressed gas supplied to the gas heater 41 and the powder supply device 42, respectively.
  • the material powder for example, one having an average particle diameter of about 5 to 100 ⁇ m is prepared.
  • the compressed gas helium, nitrogen, air or the like is used.
  • the compressed gas supplied to the gas heater 41 is, for example, 50 ° C. or higher, heated to a temperature in a range lower than the melting point of the material powder of the intermediate layer 12, and then supplied to the spray gun 43.
  • the heating temperature of the compressed gas is preferably 300 to 900 ° C.
  • the compressed gas supplied to the powder supply device 42 supplies the material powder in the powder supply device 42 to the spray gun 43 so as to have a predetermined discharge amount.
  • the heated compressed gas is made a supersonic flow (about 340 m / s or more) by the gas nozzle 44 having a divergent shape.
  • the gas pressure of the compressed gas is preferably about 1 to 5 MPa. This is because the adhesion strength between the base material 11 and the intermediate layer 12 can be improved by adjusting the pressure of the compressed gas to this level.
  • the powder material supplied to the spray gun 43 is accelerated by the injection of the compressed gas into the supersonic flow, and collides with the base material 11 at a high speed while being in a solid phase to deposit, thereby forming a film.
  • the apparatus is not limited to the cold spray apparatus 40 shown in FIG. 3 as long as the apparatus can collide the material powder with the base material 11 in a solid state to form a film.
  • the powder material collides with and binds to the lower layer (the base layer 11 and the intermediate layer 12 previously deposited on the base material 11) in the solid state, so that the surface of the intermediate layer 12 Has a convex shape toward the outside (the interface on the thermal spray coating layer 13 side to be formed later).
  • the thickness of the intermediate layer 12 is preferably about 5 ⁇ m or more. Thereby, the entire surface of the substrate 11 can be covered with the intermediate layer 12 and a convex shape sufficient for the sprayed coating layer 13 to adhere can be formed.
  • the upper limit of the thickness of the intermediate layer 12 if the intermediate layer 12 is in a state of covering the entire surface of the substrate 11, there is no significant difference in effect even if the intermediate layer 12 is thickened. In consideration of the time required for the formation process of the intermediate layer 12, the upper limit is preferably about 100 ⁇ m.
  • step S3 a thermal spray coating layer 13 having a desired thickness is formed on the intermediate layer 12 by a thermal spraying method. Thereby, the laminated body 10 shown in FIG. 1 is completed.
  • the laminate 10 produced in this way has the following characteristics. First, at the interface between the intermediate layer 12 and the base material 11 and inside the intermediate layer 12, a strong bond is obtained by an anchor effect and a metal bond. Further, the surface of the intermediate layer 12 has a complex convex shape toward the sprayed coating layer 13 side. Therefore, the anchor effect of the thermal spray coating 13 is improved by the material of the thermal spray coating layer 13 melted by the thermal spray flame entering the narrow concave portion between the convexity of the surface of the intermediate layer 12. Thereby, the intermediate layer 12 and the sprayed coating layer 13 are also firmly bonded to each other. As a result, high adhesion strength can be obtained between the base material 11 and the sprayed coating layer 13.
  • the intermediate layer 12 is formed by the cold spray method can be determined by observing the interface between the base material 11 and the intermediate layer 12 (the presence or absence of an anchor layer) and the surface of the intermediate layer 12. it can.
  • the thermal spraying method since a laminated structure having a so-called lamellar structure is formed by laminating flat fine particles, it is possible to distinguish the cold spray method from the thermal spraying method.
  • the base material 11 is formed by laminating the sprayed coating layer 13 by thermal spraying on the surface of the base material 11 made of metal or alloy via the intermediate layer 12 by the cold spray method. It is possible to improve the adhesion strength between the thermal spray coating layer 13 and the thermal spray coating layer 13.
  • a columnar aluminum test piece 20 having a diameter of about 25 mm and a thickness of about 20 mm is prepared, and a thickness of about 5 mm is formed on one bottom surface of the aluminum test piece 20.
  • the copper base material 21 was bonded with an adhesive.
  • oxygen-free copper C1020 was used.
  • a copper intermediate layer (CS film) 22 having a thickness of about 30 ⁇ m was formed on the copper base material 21 by a cold spray method as a base treatment. At this time, copper powder having an average particle diameter of about 30 ⁇ m was used as the raw material powder, and nitrogen having a gas pressure of about 800 ° C.
  • FIG. 5 is an electron micrograph of the surface of the copper intermediate layer 22 taken.
  • the average surface roughness Ra of the surface of the copper intermediate layer 22 was about 5 to 8 ⁇ m.
  • an alumina (Al 2 O 3 ) layer 23 having a thickness of about 400 ⁇ m was formed on the copper intermediate layer 22 as a sprayed coating layer.
  • An aluminum test piece 20 was bonded to the upper surface of the alumina layer 23 with an adhesive.
  • a copper base 31 having a thickness of about 5 mm was adhered to one bottom surface of the aluminum test piece 20 with an adhesive.
  • oxygen-free copper C1020 was used as in the example.
  • the upper surface of the copper substrate 31 was blasted as a base treatment.
  • abrasive grains of white alumina having an average particle diameter of 350 ⁇ m were used.
  • FIG. 7 is an electron micrograph of the surface of the copper base 31 taken. At this time, the average surface roughness Ra of the surface of the copper base material 31 was about 4 to 6 ⁇ m.
  • an alumina layer 32 having a thickness of about 400 ⁇ m was formed on the copper base 31 as a sprayed coating layer.
  • the aluminum test piece 20 was bonded to the upper surface of the alumina layer 32 with an adhesive.
  • Al—Mg-based aluminum alloy A5052 was used instead of the copper base material 31 in the comparative example.
  • FIG. 8 is a graph showing the results of the tensile test, and shows the average value of peel strength measured by experiments on Examples, Comparative Examples, and Reference Examples.
  • the peeling strength when peeling occurred in the examples was about 18 MPa on average. All this peeling occurred between the copper intermediate layer 22 and the alumina layer 23. This is presumably because the copper intermediate layer 22 and the copper base material 21 are bonded by a metal bond, so that the adhesion strength is particularly high (for example, 70 MPa or more).
  • the peel strength in the comparative example was an average of about 5 MPa, which was less than 1/3 of the example. Further, the peel strength in the reference example was about 8.5 MPa on average, and remained at about 9 MPa at the maximum.

Abstract

L'invention concerne un stratifié et un procédé de fabrication dudit stratifié, le stratifié ayant une forte adhésion entre le substrat, qui est obtenu à partir d'un métal ou d'un alliage, et la couche de film pulvérisée thermiquement formée sur la surface du substrat. Le stratifié (10) comporte : un substrat (11) qui est formé à partir d'un métal ou d'un alliage ; une couche intermédiaire (12) déposée par accélération d'une matière pulvérulente d'un métal ou d'un alliage conjointement avec un gaz chauffé à une température au-dessous du point de fusion de la matière pulvérulente et pulvérisation dans l'état solide sur la surface du substrat ; et une couche de film pulvérisée thermiquement (13) formée par pulvérisation thermique sur la couche intermédiaire.
PCT/JP2012/073712 2011-09-20 2012-09-14 Stratifié et procédé de fabrication du stratifié WO2013042635A1 (fr)

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WO2015001263A1 (fr) * 2013-07-03 2015-01-08 Snecma Procede de preparation a la depose d'un revetement metallique par projection thermique sur un substrat
CN104988493A (zh) * 2015-05-28 2015-10-21 山东建筑大学 一种通过纳米化因子使钛合金激光沉积层纳米化的方法
CN107488043A (zh) * 2016-06-12 2017-12-19 中国科学院宁波材料技术与工程研究所 多层复合膜、其制备方法以及作为碳化硅及其复合材料连接材料的应用
CN108559941A (zh) * 2018-04-27 2018-09-21 齐鲁工业大学 一种不锈钢汽车消音器表面高致密梯度金属陶瓷涂层及其制备方法
CN109111243A (zh) * 2018-09-20 2019-01-01 界首永恩机电科技有限公司 一种陶瓷工艺品表面喷施复合铜粉末的方法
US10315388B2 (en) 2014-06-11 2019-06-11 Nhk Spring Co., Ltd. Method of manufacturing laminate and laminate
CN115446319A (zh) * 2022-08-12 2022-12-09 南京大学 一种铜辅助制备钛合金和钛铝合金球形微粉的方法

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TW201500556A (zh) * 2013-06-30 2015-01-01 Teng-Fei Wu 鈦基複合材料及其製造方法
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JP2017001235A (ja) * 2015-06-08 2017-01-05 トヨタ自動車株式会社 断熱構造体
JP6662585B2 (ja) * 2015-06-23 2020-03-11 日本発條株式会社 クラッドパイプ及びクラッドパイプの製造方法
JP6109281B1 (ja) * 2015-11-26 2017-04-05 日本発條株式会社 積層体の製造方法
KR101746974B1 (ko) * 2015-12-15 2017-06-28 주식회사 포스코 강판의 금속 코팅 방법 및 이를 이용하여 제조된 금속 코팅 강판
EP3572555B1 (fr) * 2017-01-17 2021-03-03 Shinshu University Procédé de fabrication de carte de circuit imprimé en céramique
JP6868412B2 (ja) * 2017-02-03 2021-05-12 日産自動車株式会社 摺動部材、内燃機関の摺動部材、及び摺動部材の製造方法
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KR20190057753A (ko) * 2017-11-20 2019-05-29 (주)코미코 내플라즈마성 코팅막의 제조방법 및 이에 의해 형성된 내플라즈마성 부재
CN109628927B (zh) * 2019-02-01 2020-10-16 水利部杭州机械设计研究所 一种用于海工液压活塞杆的抗磨耐蚀镍基碳化硅复合涂层及其制备方法
CN110273149B (zh) * 2019-07-31 2021-06-01 安徽工业大学 一种钼基合金涂层及具有该合金涂层的基体

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WO2015001263A1 (fr) * 2013-07-03 2015-01-08 Snecma Procede de preparation a la depose d'un revetement metallique par projection thermique sur un substrat
FR3008109A1 (fr) * 2013-07-03 2015-01-09 Snecma Procede de preparation a la depose d'un revetement metallique par projection thermique sur un substrat
US9920431B2 (en) 2013-07-03 2018-03-20 Snecma Process for preparing a substrate for thermal spraying of a metal coating
RU2659521C2 (ru) * 2013-07-03 2018-07-02 Снекма Способ подготовки подложки для термического напыления металлического покрытия
US10315388B2 (en) 2014-06-11 2019-06-11 Nhk Spring Co., Ltd. Method of manufacturing laminate and laminate
CN104988493A (zh) * 2015-05-28 2015-10-21 山东建筑大学 一种通过纳米化因子使钛合金激光沉积层纳米化的方法
CN107488043A (zh) * 2016-06-12 2017-12-19 中国科学院宁波材料技术与工程研究所 多层复合膜、其制备方法以及作为碳化硅及其复合材料连接材料的应用
CN107488043B (zh) * 2016-06-12 2022-10-25 中国科学院宁波材料技术与工程研究所 多层复合膜、其制备方法以及作为碳化硅及其复合材料连接材料的应用
CN108559941A (zh) * 2018-04-27 2018-09-21 齐鲁工业大学 一种不锈钢汽车消音器表面高致密梯度金属陶瓷涂层及其制备方法
CN109111243A (zh) * 2018-09-20 2019-01-01 界首永恩机电科技有限公司 一种陶瓷工艺品表面喷施复合铜粉末的方法
CN109111243B (zh) * 2018-09-20 2020-12-11 界首永恩机电科技有限公司 一种陶瓷工艺品表面喷施复合铜粉末的方法
CN115446319A (zh) * 2022-08-12 2022-12-09 南京大学 一种铜辅助制备钛合金和钛铝合金球形微粉的方法

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