WO2011105392A1 - Stratifié à film multicouche utilisant de l'aluminium ou un alliage d'aluminium comme substrat, et procédé de stratification permettant de l'obtenir - Google Patents

Stratifié à film multicouche utilisant de l'aluminium ou un alliage d'aluminium comme substrat, et procédé de stratification permettant de l'obtenir Download PDF

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WO2011105392A1
WO2011105392A1 PCT/JP2011/053902 JP2011053902W WO2011105392A1 WO 2011105392 A1 WO2011105392 A1 WO 2011105392A1 JP 2011053902 W JP2011053902 W JP 2011053902W WO 2011105392 A1 WO2011105392 A1 WO 2011105392A1
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layer
film
amorphous carbon
carbon film
plating layer
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Japanese (ja)
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晃一 稲葉
邦彦 渋澤
佐藤　剛
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Taiyo Chemical Industry Co Ltd
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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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/515—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
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    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • 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
    • C23C28/32—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
    • 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
    • C23C28/325—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with layers graded in composition or in physical properties
    • 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
    • C23C28/343—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 DLC or an amorphous carbon based layer, the layer being doped or not
    • 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
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing

Definitions

  • the present invention relates to a multilayer film stack using aluminum or an aluminum alloy as a substrate and a method for laminating the multilayer film laminate, and in particular, a multilayer film laminate including an amorphous carbon film or an amorphous carbon film containing silicon as the uppermost layer, and the multilayer film laminate.
  • the present invention relates to a lamination method.
  • a surface treatment method that replaces this anodizing treatment a surface treatment using an amorphous carbon film or an amorphous carbon film containing silicon or the like is known.
  • the amorphous carbon film is hard, has excellent wear resistance, has a small coefficient of friction, has an anti-adhesion property for soft metals, and has acid resistance and alkali resistance. Therefore, by coating the surface of a substrate such as a machine part with this amorphous carbon film, the properties of the substrate surface can be improved. For example, a machine part whose surface is coated with an amorphous carbon film can be cleaned with an acidic or alkaline detergent.
  • Patent Document 1 discloses that a base material is subjected to a solution treatment, and an aging treatment and an amorphous carbon film coating treatment are performed on the solution-treated base material. It is disclosed to do at the same time.
  • the base material of aluminum or aluminum alloy is soft, even if a hard amorphous carbon film is thinly formed on the surface, the difference in hardness between the base material and the amorphous carbon film is difficult. Therefore, the adhesion is inferior and the amorphous carbon film is easily peeled off from the substrate.
  • a load is applied, there is a problem that the amorphous carbon film cannot follow the deformation of the substrate and breakage easily occurs.
  • Patent Document 2 discloses that an electroless Ni—P plating layer or an ion nitride layer is used as an intermediate layer on the surface of aluminum or an aluminum alloy. It is disclosed that a diffusion layer and an electroless Ni—P plating layer are formed, and then an aging treatment of the substrate and a heat treatment of the electroless plating film are performed simultaneously when forming the amorphous carbon film.
  • the heat treatment of the electroless Ni—P plating layer causes the plating layer to crystallize and improve the hardness, so that the hardness distribution is graded stepwise and the load resistance is improved.
  • the adhesion is also improved.
  • a multilayer film laminating method capable of forming an amorphous carbon film on the uppermost part of an aluminum or aluminum alloy base material with good adhesion is provided.
  • a multilayer film structure in which an amorphous carbon film is provided on the uppermost part of an aluminum or aluminum alloy base material with good adhesion is provided.
  • the inventor performs electroless nickel plating on a base material made of aluminum or aluminum alloy in which a zinc layer is deposited by substitution reaction with aluminum or aluminum alloy, and further, hard chrome is formed on the electroless nickel plating layer.
  • a base material made of aluminum or aluminum alloy in which a zinc layer is deposited by substitution reaction with aluminum or aluminum alloy, and further, hard chrome is formed on the electroless nickel plating layer.
  • the multilayer film structure in one embodiment of the present invention obtained based on such knowledge is obtained by providing a zinc-substituted layer, an electroless nickel plating layer, a hard chromium plating layer, and an amorphous material on a base material made of aluminum or an aluminum alloy. A carbonaceous film or a silicon-containing amorphous carbon film is formed in this order.
  • a multilayer film laminating method capable of forming an amorphous carbon film on the uppermost part of an aluminum or aluminum alloy base material with good adhesion is provided. Further, various embodiments of the present invention provide a multilayer film structure in which an amorphous carbon film is provided with good adhesion on the uppermost part of an aluminum or aluminum alloy-based substrate.
  • an amorphous carbon film that is hard and has excellent wear resistance on the top of a soft class of aluminum or aluminum alloy base material among metals. are provided with good adhesion, and a multilayer film structure capable of improving the wear resistance and slidability of aluminum or an aluminum alloy and a method for producing the same are provided.
  • a zinc layer is deposited on the surface of aluminum or aluminum alloy by a substitution reaction with aluminum or aluminum alloy, and then electroless nickel plating is performed on the zinc substitution layer. Then, hard chrome plating is performed, and further, an amorphous carbon film is formed thereon to form a multilayer film structure having an inclined structure with an appropriate hardness. That is, in the formed amorphous carbon film, the hardness gradually increases from the base material side of the film toward the uppermost amorphous carbon film side.
  • the amorphous alloy is formed on the uppermost part of the aluminum alloy base material.
  • a carbon film can be formed with good adhesion.
  • both electroless nickel plating and hard chrome plating can be mass-produced in the air atmosphere, so compared to the case where solid chrome is used as a target, such as sputtering film deposition or vapor deposition film formation.
  • the method according to an embodiment of the present invention can be realized relatively inexpensively.
  • the electroless nickel plating and the hard chrome plating according to an embodiment of the present invention can be formed at a low temperature of 0.1 to 40 ⁇ m, respectively.
  • the amorphous carbon film or the silicon-containing amorphous carbon film can be formed by a plasma CVD method.
  • the multilayer film structure includes, for example, a primary layer on an aluminum or aluminum alloy-based base material (in this specification, sometimes simply referred to as an aluminum base material).
  • the secondary layer, the tertiary layer, and the uppermost layer are laminated in this order.
  • the primary layer is a zinc-substituted film having good adhesion to aluminum or an aluminum alloy
  • the secondary layer is an electroless nickel (Ni—P or Ni—B) plating layer.
  • the third layer is a hard chrome plating layer
  • the uppermost layer is an amorphous carbon film or an amorphous carbon film containing silicon (in this specification, simply referred to as “amorphous carbon film”). Yes.
  • the hardness of the aluminum substrate is approximately Hv100 and the hardness of the electroless nickel is amorphous or when the P content in the Ni—P plating film is precipitated as fine crystals with a low phosphorus type of approximately 1 to 4 wt%
  • the hardness of Hv is approximately 500 to 700
  • the hardness of hard chrome plating is approximately Hv 1000
  • the hardness of the amorphous carbon film formed by the plasma CVD apparatus is approximately Hv 1300 to 2000.
  • an amorphous carbon film can be formed with good adhesion on the uppermost layer of the aluminum substrate.
  • the zinc-substituted film is very thin compared to other films. For example, the influence of a zinc-substituted film of about 200 nm on the adhesion of an amorphous carbon film can be ignored.
  • the secondary layer when the secondary layer is formed on the primary layer, the secondary layer is formed directly on the primary layer (without any other film).
  • a secondary layer may be provided on the primary layer via another film that is not specified in this specification.
  • a strike copper plating film having a thickness of about 10 to 300 nm, a copper film of the same thickness by a sputtering apparatus or a vapor deposition apparatus is used between the primary layer and the secondary layer.
  • An electrolytic Ni plating film a Ni film formed by a sputtering apparatus or a vapor deposition apparatus has a hardness of about Hv 200 to 500, so it may be harder than the secondary layer, but it is very thin compared to other films, so There is no substantial effect on the adhesion of the crystalline carbon film.
  • the tertiary layer when the tertiary layer is formed on the secondary layer, the tertiary layer may be formed directly on the secondary layer (without any other film), or it may be amorphous. As long as the adhesion of the carbonaceous film is not substantially deteriorated, a tertiary layer may be provided on the secondary layer via another film.
  • the uppermost layer when the uppermost layer is formed on the tertiary layer, the uppermost layer may be formed directly on the tertiary layer (without passing through another film), or the amorphous carbon film may be adhered.
  • the uppermost layer may be provided on the tertiary layer through another film as long as the property is not substantially deteriorated.
  • the multilayer film structure thus formed also has a gradual change in the coefficient of thermal expansion from the base material to the uppermost layer. That is, the thermal linear expansion coefficient of each layer is approximately 23 ⁇ 10 ⁇ 6 / ° C. in the base material aluminum, and approximately 13 ⁇ 10 ⁇ 6 / ° C. in the secondary electroless nickel layer, and the hard chromium plating of the tertiary layer.
  • the layer is approximately 7 ⁇ 10 ⁇ 6 / ° C.
  • the uppermost amorphous carbon film is approximately 2 ⁇ 10 ⁇ 6 / ° C.
  • the thermal expansion coefficient decreases stepwise from the aluminum base toward the uppermost layer.
  • the coefficient of thermal expansion of the zinc-substituted film is 26 ⁇ 10 ⁇ 6 / ° C., which is higher than that of the aluminum base material.
  • the zinc-substituted film is much thinner than other layers, for example, about 50 to 200 nm. Therefore, the influence on the adhesion between layers can be ignored.
  • the adhesion between the zinc-substituted layer and the aluminum or aluminum alloy base material can be improved by roughening the surface of the aluminum or aluminum alloy base material by sandblasting or the like.
  • an amorphous carbon film is directly formed on top of the electroless nickel plating, the carbon particles necessary for bonding the amorphous carbon film do not easily react with Ni to form carbides. And the bond between the amorphous carbon film is weakened. Therefore, in one embodiment of the present invention, a hard chrome plating layer is interposed between the electroless nickel plating layer and the amorphous carbon film. The amorphous carbon film is formed with good adhesion to the electroless nickel plating layer and its lower layer through this hard chrome plating layer.
  • a zinc replacement film as a primary layer is formed on the surface of a base material (aluminum base material) made of aluminum or an aluminum alloy.
  • This zinc replacement film is performed as a base treatment for electroless nickel plating described later, and includes a degreasing process, an acidic etching process, a nitric acid dipping process, a first zinc replacement process, a zinc nitrate stripping process, A dizinc replacement step.
  • the aluminum substrate is immersed in a weak alkaline solution for degreasing, then immersed in an acid solution such as sulfuric acid, etched, and then immersed in nitric acid, and then a strong alkali containing NaOH as a main component.
  • a zinc substitution layer is deposited with a zinc substitution solution (primary substitution).
  • the aluminum substrate after the primary substitution is immersed in nitric acid to remove the smut, and further zinc substitution (secondary substitution) is performed with the same zinc substitution solution as before.
  • the zinc substitution layer functions as a primer layer.
  • the zinc-substituted layer can be formed by any known method.
  • an anodized film on the aluminum base material in order to insulate the aluminum base material from the upper layer structure.
  • the anodized film is made of, for example, anodized or hard anodized.
  • a zinc-substituted film can be formed on the aluminum substrate on which the anodized film is formed.
  • the processing time for each step of forming the zinc-substituted film may be adjusted. Thereby, in the completed multilayer film structure, it is possible to electrically insulate between the aluminum base portion and the portion above the anodized film.
  • the anodized film is dissolved in the above-described nitric acid dipping step and zinc replacement using a strong alkaline solution. It can also be removed from the material.
  • the steps of degreasing, etching, acid soaking, primary zinc substitution, acid soaking and secondary zinc substitution are performed in approximately 30 seconds to 1 minute 30 seconds, Can be dissolved.
  • anodized aluminum or aluminum alloy base material can be reused.
  • the aluminum base material is immersed in an alkaline and acidic solution, so that burrs and cutting powder generated during processing of the base material can be removed.
  • the base treatment of electroless nickel plating and the removal of burrs and cutting powder can be performed at once. Leaving burrs or cutting powder generated during the processing of an aluminum base material may cause the upper amorphous carbon film to peel off.
  • the adhesion between the layers can be reduced.
  • the effect of preventing peeling of the amorphous carbon film by removing burrs and cutting powder can be obtained.
  • an electroless nickel plating layer as a secondary layer is formed on the above-described zinc replacement film.
  • the electroless nickel plating layer is, for example, an electroless Ni—P plating layer or an electroless Ni—B plating layer.
  • the aluminum substrate with the zinc replacement film as the primary layer is immersed in a plating solution containing nickel ions and hypophosphite ions to replace the zinc.
  • Electroless Ni—P plating is formed on the film. In electroless Ni—P plating, the plating proceeds continuously by the autocatalytic action of nickel.
  • the electroless Ni—B plating layer is formed on the same principle as the electroless Ni—P plating layer using an electroless plating solution containing nickel ions and a boron-based agent such as amine borane which is a reducing agent.
  • electroless Ni—B plating the decomposition and deterioration of the plating solution is severe and must be made disposable each time. Therefore, electroless Ni—P plating may be more suitable for actual production.
  • the electroless nickel plating layer of the present invention may have a two-layer structure in which an electroless Ni—B plating layer is formed on an electroless Ni—P plating layer.
  • the hardness of the electroless Ni—B plating layer is higher than the hardness of the electroless Ni—P plating layer and lower than the hardness of the hard chrome plating layer, so that an inclined structure having a more preferable hardness is formed. it can.
  • the thickness of the plating layer varies depending on the use and usage of the substrate, but is usually 0.1 to 40 ⁇ m, preferably 3 to 20 ⁇ m. However, the thickness of the plating layer is not limited to these.
  • an electrolytic nickel plating layer may be formed on the electroless nickel plating layer.
  • the electrolytic nickel plating layer is formed by energizing the base material on which the primary layer and the secondary layer are formed in a solution containing Ni sulfamate, Ni chloride and boric acid and maintained at about 55 ° C. Is done. This solution may contain an additive (glossy material) as necessary.
  • the electrolytic nickel plating layer can be formed to have a hardness of about Hv 500 equivalent to that of the electroless nickel plating layer by adjusting the amount of additive (glossy material) added.
  • Electrolytic nickel plating has less plating waste liquid and is more environmentally friendly than electroless nickel plating. Therefore, part of the thickness of electroless nickel plating can be supplemented by electrolytic nickel plating.
  • the hardness of the electrolytic Ni—P plating layer may be slightly smaller than the hardness of the electroless Ni—P plating layer. However, since the difference in hardness is slight, even if the hardness is reversed, the adhesion of the amorphous carbon film is not substantially adversely affected.
  • amorphous carbon film when the amorphous carbon film is formed, for example, by using a low temperature plasma CVD method, a portion below the amorphous carbon film, that is, an aluminum base, a zinc substitution layer, An amorphous carbon film can be formed with the electroless nickel layer and the hard chromium plating layer kept at 300 ° C. or lower.
  • the portion below the amorphous carbon film when an amorphous carbon film is formed, for example, by using a low temperature plasma CVD method, the portion below the amorphous carbon film is kept at 260 ° C. or lower. An amorphous carbon film can be formed as it is.
  • Ni—P plating An electroless nickel plating layer having a phosphorus (P) content of approximately 8 wt% or more (in this specification, nickel plating containing phosphorus may be referred to as “Ni—P plating”) is approximately 260 ° C. or less. Although it is an amorphous structure, when it exceeds 260 degreeC, the transition from this amorphous structure to a crystal structure will begin. In this crystal structure, since hard Ni 3 P crystals are dispersed and precipitated, the electroless Ni—P plating layer begins to harden, and when heated to approximately over 300 ° C., in electroless Ni—P plating, The property as a crystal structure containing hard Ni 3 P becomes dominant.
  • the hardness of the electroless nickel plating layer changes according to the progress of crystallization.
  • the hardness of an electroless nickel plating layer (Ni-P plating layer) heated at a temperature exceeding 300 ° C. may reach Hv 900 to Hv 1000, and may be similar to or slightly higher than the hardness of a hard chrome plating layer. is there.
  • Ni—B plating An electroless nickel plating layer having a boron (B) content of approximately 3 wt% or more (in this specification, nickel plating containing boron may be referred to as “Ni—B plating”) is heated at 300 ° C. or more. The transition from the amorphous structure to the crystal structure begins. Hard Ni 3 B crystals are dispersed and precipitated in this crystal structure. The nature of the crystal structure containing heated by the hard Ni 3 B is dominant until approximately greater than 400 ° C.. Thus, the hardness of the electroless nickel plating layer (Ni—B plating layer) changes according to the progress of crystallization of the amorphous structure of nickel. For example, the hardness of an electroless nickel plating layer (Ni—B plating layer) heated at a temperature exceeding 400 ° C. may reach Hv 1200 to Hv 1400, which may exceed the hardness of the hard chrome plating layer.
  • the hardness of the electroless nickel plating (Ni—P plating or Ni—B plating) layer is produced by manufacturing the multilayer film structure with the workpiece always kept at 300 ° C. or lower. Does not exceed the hardness of the hard chrome plating layer, and the gradient structure of the hardness in the multilayer structure is maintained.
  • the amorphous nature is dominant in the electroless nickel plating (Ni—P plating, Ni—B plating) layer.
  • the gradient structure of hardness can be maintained.
  • the electroless nickel plating layer is not made amorphous. It can be precipitated as crystals.
  • the mass percentage concentration of phosphorus in the plating film is 1 to 4 wt%
  • the nickel plating layer is deposited as fine crystals.
  • the hardness of this nickel-plated layer of fine crystals is approximately Hv 650 to 700.
  • the secondary layer becomes harder than the hard chromium plating layer of the tertiary layer by forming the film while keeping the workpiece at 300 ° C. or lower or 260 ° C.
  • the multilayer film structure is manufactured so that the electroless nickel plating layer has an amorphous structure by adjusting the heating temperature when forming the multilayer film structure of the present application to 300 ° C. or lower or 260 ° C. or lower. Can do. Since the electroless nickel plating layer does not have crystallinity, the progress of corrosion from crystal defects can be further prevented.
  • a hard chromium plating layer as a tertiary layer is formed on the secondary layer.
  • the hard chrome plating layer as the third layer is formed by energizing the base material on which the first layer and the second layer are formed, for example, in a sulfuric acid aqueous solution containing chromic acid.
  • the thickness of the hard chrome plating layer to be formed varies depending on the use and usage of the substrate, but is usually 0.1 to 40 ⁇ m, preferably 0.2 to 20 ⁇ m. Hard chromium of about 0.2 ⁇ m is called flash. However, the thickness of the hard chrome plating layer is not limited to these.
  • the hard chromium plating to be formed is energized at a high current density during film formation, so that a large amount of hydrogen generated as a by-product is taken into the film.
  • hydrogen embrittlement becomes obvious and the hardness decreases.
  • the hard chrome plating immediately after the formation has a hardness of Hv 1000 or more, but the hardness of the hard chrome plating subjected to the heat treatment of 300 ° C. or more is reduced to about Hv 800.
  • the electrolytic hard chrome plating layer and the electrolytic nickel plating layer are characterized in that they are deposited thicker than the other flat portions at the end portions (in the vicinity of corners and edges) of the base material. Since stress concentrates on the edge of the base material and damage is likely to occur, forming an electrolytic hard chromium plating layer or electrolytic nickel plating layer thick on the edge of the base material results in the edge of the base material being easily damaged.
  • the part can be reinforced intensively. For example, when the base material is formed in a gear shape, an electrolytic hard chrome plating layer or an electrolytic nickel plating layer can be formed thickly on a tooth portion that is easily damaged. Furthermore, since the electrolytic hard chrome plating layer is excellent in weather resistance, it contributes to prevention of corrosion of the base material even if the amorphous carbon film provided in the upper layer has some defects.
  • FIG. 1 shows the heat treatment temperature and film hardness for each of the electroless Ni-P plating layer (- ⁇ -), the electroless Ni-B plating layer (- ⁇ -), and the hard chrome plating layer (- ⁇ -). It is a figure which shows the relationship.
  • the graph of FIG. 1 shows a primary layer, a secondary layer (electroless Ni—P plating layer or electroless Ni—B plating layer), and a tertiary layer (hard chrome plating) on the substrate by the method described above.
  • the layered product in which the layer was formed was subjected to heat treatment at a plurality of temperatures between room temperature and 400 ° C., and the hardness of each layer was measured after the heat treatment. Each heating time was 1 hour.
  • the thickness of each of the electroless Ni—P plating layer, the electroless Ni—B plating layer, and the hard chrome plating layer was 35 ⁇ m.
  • MVK-H3 manufactured by Akashi Co., Ltd. was used, and the load was set to 25 gf (loading time: 20 seconds).
  • the hard chromium plating layer of the third layer is softened by heating.
  • the Ni—P plating layer is hardened by heating.
  • the hardness of the hard chrome layer and the Ni—P plating layer are approximately the same at around 350 ° C. Therefore, in order to obtain a preferable hardness gradient structure, it is desirable to avoid heating at a temperature higher than 350 ° C. after the formation of the electroless Ni—P plating layer and the hard chrome plating layer.
  • an amorphous carbon film can be formed at 350 ° C.
  • the Ni—B plating layer is hardened by heating, and the hardness of the hard chromium layer and the Ni—B plating layer is approximately the same at about 320 ° C.
  • an amorphous carbon film can be formed at 320 ° C. or lower by using a low temperature plasma CVD method.
  • An amorphous carbon film or a silicon-containing amorphous carbon film that is the uppermost layer is formed on the tertiary layer.
  • the amorphous carbon film is formed by various methods such as a CVD (chemical vapor deposition) method such as a plasma CVD method or a physical vapor deposition (PVD) method such as an ion plating method or a sputtering method.
  • the amorphous carbon film according to one embodiment of the present invention is formed using a low temperature plasma CVD method at 350 ° C. or lower or 320 ° C. or lower depending on the type of the electroless nickel layer as the secondary layer. As described above, the hardness of the hard chrome plating layer is reduced by heating.
  • the hard chrome plating layer may be heated to 350 to 500 ° C. Therefore, instead of the PVD method, a plasma CVD method capable of forming a film at a low temperature of 350 ° C. or less can be used. .
  • the hard chrome plating layer contains a large amount of hydrogen in the film. Hydrogen contained in the hard chromium plating layer is not preferable for the film forming process by the PVD method.
  • the heat generated by the PVD method may cause warpage and distortion in the aluminum or aluminum alloy base material.
  • the amorphous carbon film is formed using the plasma CVD method, the problems associated with the manufacturing method using the PVD method do not occur.
  • an amorphous carbon film can be formed by low temperature sputtering.
  • the amorphous carbon film can be formed by keeping the workpiece at 350 ° C. or lower even by a method in which the workpiece becomes a high temperature of 350 ° C. or higher without the cooling device.
  • the plasma CVD method can form a film under a low temperature condition.
  • Plasma CVD methods used in various embodiments of the present invention include high pressure pulse plasma CVD, high frequency plasma CVD using high frequency discharge, direct current plasma CVD using direct current discharge, and microwave using microwave discharge.
  • a plasma CVD method is included. Since the direct current plasma CVD method is energized continuously, it is desirable to control the temperature of the substrate with a cooling device. In one embodiment of the present invention, it is desirable to use a high-pressure pulse plasma CVD method to form an amorphous carbon film.
  • the duty ratio of the power source can be controlled from 2% to 10% by increasing / decreasing the pulse frequency, so that the film forming temperature can be easily lowered as compared with other film forming methods.
  • carbon ions and the like can be implanted into a lower layer than the amorphous carbon film at a high pressure, adhesion between the lower layer and the amorphous carbon film is easily obtained.
  • the formed amorphous carbon film or the amorphous carbon film containing silicon is formed in various thicknesses depending on the use of the substrate, but is usually formed to 10 nm to 10 ⁇ m, preferably 0.1 ⁇ m. Formed to ⁇ 3 ⁇ m.
  • the thickness of the amorphous carbon film is not limited to these.
  • an amorphous carbon film containing silicon can be used as the intermediate adhesive layer.
  • the thickness of the intermediate adhesive layer varies depending on the use and usage of the substrate, and it is not necessary to particularly limit it, but it is usually 10 nm to 1 ⁇ m, preferably 0.1 ⁇ m to 0.5 ⁇ m. .
  • Amorphous carbon film can use hydrocarbon gas, such as methane, acetylene, and benzene, as a reaction gas in the case of forming using the CVD method.
  • hydrocarbon gas such as methane, acetylene, and benzene
  • a silicon compound gas such as Si (CH 3 ) 4 or SiH 4 can be used as a reaction gas when the CVD method is used.
  • Argon gas can be used as the carrier gas.
  • a mixture of argon gas and hydrocarbon gas can also be used as the carrier gas.
  • the measurement of the thickness and hardness of each film formed on the base material is performed by forming a single film on a silicon (100) substrate juxtaposed with the base material, It is measured.
  • a base material (hereinafter referred to as “cylindrical base material”) in which a 5000 series aluminum alloy base material (5052 material) was formed into a cylindrical shape having a diameter of 10 mm and a height of 10 mm was prepared.
  • a 5000 series aluminum alloy base material 5052 material
  • a zinc-substituted film was formed on the side surface of this cylindrical substrate by the method described above.
  • the cylindrical substrate was immersed in a weak alkaline solution and degreased at 70 ° C., and then immersed in a sulfuric acid solution at 70 ° C. to etch the substrate surface. Further, the substrate was acid-immersed with 50% nitric acid at room temperature, and a zinc-substituted layer was deposited at room temperature with a strong alkaline zinc-substituted solution mainly composed of NaOH. Subsequently, in order to remove the smut, it was immersed in 50% nitric acid at room temperature. Furthermore, the second zinc substitution was performed with the same zinc substitution solution as before.
  • the cylindrical substrate after the zinc substitution layer was formed in this way was further subjected to the following treatment to obtain each sample. That is, an electroless Ni—P plating layer having a thickness of 5 ⁇ m is formed on the cylindrical substrate after the zinc substitution layer is formed, and an amorphous carbon film (including an intermediate layer containing silicon of 0.1 ⁇ m) is formed thereon. Was formed to a thickness of 0.4 ⁇ m to obtain test sample 1 (1).
  • an electroless Ni—P plating layer is formed to a thickness of 5 ⁇ m on the cylindrical base material after the zinc-substituted layer is formed, and an amorphous carbon film (including the intermediate layer of 0.1 ⁇ m) thereon is 0.8 ⁇ m.
  • test Sample 1 (2) A film was formed with a thickness to obtain Test Sample 1 (2). Further, an electroless Ni—P plating layer having a thickness of 5 ⁇ m is formed on the cylindrical base material after the zinc-substituted layer is formed, and an amorphous carbon film (including the intermediate adhesive layer of 0.1 ⁇ m) is formed thereon. A film was formed with a thickness of 6 ⁇ m to obtain Test Sample 1 (3). Since test samples 1 (1) to 1 (3) do not have a hard chrome plating layer, all are comparative examples.
  • An electroless Ni—P plating layer is formed on the cylindrical base material after the zinc substitution layer is formed to a thickness of 5 ⁇ m, and a hard chromium plating layer is formed thereon to a thickness of 5 ⁇ m.
  • a carbon film (including an intermediate layer of 0.1 ⁇ m) was formed to a thickness of 0.4 ⁇ m to obtain Test Sample 2 (1).
  • an electroless Ni—P plating layer is formed on the cylindrical base material after the zinc substitution layer is formed to a thickness of 5 ⁇ m, and a hard chromium plating layer is formed thereon to a thickness of 5 ⁇ m.
  • a crystalline carbon film (including 0.1 ⁇ m of the intermediate layer) was formed to a thickness of 0.8 ⁇ m to obtain Test Sample 2 (2).
  • test samples 2 (1) to 2 (3) are examples of the present invention.
  • test sample 3 (1) 5 ⁇ m of electrolytic Ni plating layer is formed on the cylindrical substrate after the zinc substitution layer is formed, and an amorphous carbon film (including the intermediate adhesive layer of 0.1 ⁇ m) is formed thereon with a thickness of 0.4 ⁇ m.
  • Test sample 3 (1) was obtained. Further, an electrolytic Ni plating layer having a thickness of 5 ⁇ m is formed on the cylindrical base material on which the zinc replacement layer has been formed, and an amorphous carbon film (including the intermediate adhesive layer 0.1 ⁇ m) is formed thereon with a thickness of 0.8 ⁇ m. Film was obtained to obtain test sample 3 (2).
  • test sample 3 (3) was obtained.
  • Test samples 3 (1) to 3 (3) are comparative examples because they do not have an electroless nickel layer and a hard chromium plating layer.
  • a high-pressure DC pulse plasma CVD apparatus was used to form the amorphous carbon film.
  • the substrate was cleaned with argon gas plasma for about 5 minutes, and then using tetramethylsilane at a flow rate of 30 SCCM, gas pressure of 2 Pa, applied voltage
  • An intermediate layer containing silicon was formed under the conditions of ⁇ 5 kV, a pulse frequency of 10 kHz, and a pulse width of 10 ⁇ s.
  • an amorphous carbon film is formed by high-pressure DC pulse plasma CVD under the conditions of applied voltage -5 kV, pulse frequency 10 kHz, pulse width 10 ⁇ s, gas flow rate 40 SCCM, gas pressure 2 Pa. did.
  • the film formation time was adjusted so that a desired film thickness was obtained in each test sample.
  • the amorphous carbon film was formed so that the intermediate layer had the same thickness in each sample.
  • the temperature of the deposition chamber at the end of deposition was less than 160 ° C. for all samples.
  • An amorphous carbon film having a thickness of 1.6 ⁇ m has the outermost layer having the largest internal stress.
  • test samples 1 (2), 1 (3), and test samples 3 (1), 3 (2), and 3 (3) which are comparative examples, are based on an amorphous carbon film. It was confirmed that it peeled from the material. In particular, it was confirmed that peeling progressed from the site where the amorphous carbon film was formed thick.
  • exfoliation in the description of the present invention means a portion where the amorphous carbon film disappears or a state where the amorphous carbon film is turned up. This peeling was confirmed by 20 times observation with a CCD camera. For test sample 1 (1) and Examples 2 (1), 2 (2), and 2 (3), the peeling of the amorphous carbon film could not be confirmed.
  • Test sample 1 (1) which is a comparative example, was not confirmed to be peeled off, but test samples 1 (2) and 1 (3) manufactured by changing only the thickness of the amorphous carbon film under the same conditions. About peeling, as above-mentioned, peeling was confirmed.
  • test samples 2 (1) to 2 (3) which are examples of the present invention, no peeling occurred regardless of the film thickness of the amorphous carbon film.
  • improvement in the adhesion of the amorphous carbon film was observed.
  • a base material (hereinafter referred to as “cylindrical base material”) in which a 5000 series aluminum alloy base material (5052 material) was formed into a cylindrical shape with a diameter of 10 mm and a height of 10 mm was prepared.
  • a zinc-substituted film was formed on the cylindrical substrate by the method described above, and an electroless Ni—P plating layer was formed on the zinc-substituted film by 5 ⁇ m. Further, a hard chrome plating layer formed thereon with a thickness of 5 ⁇ m and a film formed with a thickness of 0.5 ⁇ m were prepared.
  • the cylindrical base material on which these two kinds of hard chromium plating layers are formed and the cylindrical base material on which neither the electroless nickel plating layer nor the hard chromium plating layer is formed are put into a high-pressure DC pulse plasma CVD apparatus. Then, an amorphous carbon film was formed on these cylindrical substrates by the following method. First, the reaction vessel of the CVD apparatus was evacuated to 7 ⁇ 10 ⁇ 4 Pa, and then the surface of the charged cylindrical substrate was cleaned with argon plasma for 10 minutes. An intermediate adhesive layer was formed on the surface of the cylindrical substrate under the conditions of a pressure of 2 Pa, an applied voltage of ⁇ 5 kV, a pulse frequency of 10 kHz, and a pulse width of 10 ⁇ s.
  • the intermediate adhesive layer was formed for 10 minutes.
  • the intermediate adhesive layer is formed between the amorphous carbon film and the lower layer in order to improve the adhesion of the amorphous carbon film.
  • an amorphous carbon film made of acetylene as a raw material is formed on the intermediate adhesive layer for 20 minutes under the conditions of an applied voltage of ⁇ 5 kV, a pulse frequency of 10 kHz, a pulse width of 10 ⁇ s, a gas flow rate of 40 SCCM, and a gas pressure of 2 Pa.
  • the amorphous carbon film having a thickness of 1.2 ⁇ m and a hardness of Hv 1500 including the intermediate adhesive layer (0.4 ⁇ m) was formed on each cylindrical substrate.
  • the temperature of the film formation chamber at the end of film formation was 125 ° C.
  • test sample 4 a sample containing a hard chromium plating layer of 5 ⁇ m is a test sample 4
  • a sample containing a hard chromium plating layer of 0.5 ⁇ m is a test sample 5
  • an amorphous carbon film is directly applied to a cylindrical substrate.
  • a sample obtained by film formation is designated as test sample 6.
  • test sample 6 A sample obtained by film formation is designated as test sample 6.
  • test sample 6 A sample obtained by film formation is designated as test sample 6.
  • test sample 6 A sample obtained by film formation is designated as test sample 6.
  • test sample 6 A sample obtained by film formation is designated as test sample 6.
  • test sample 6 the comparative test of the adhesive force by a heat cycle was done. First, each of test samples 4, 5, and 6 was heated to 260 ° C. with a hot plate and held at 260 ° C. for 10 minutes. Then, it was immersed in water at 17 ° C. and rapidly cooled. This heating to 260 ° C.
  • the adhesion to the lower layer of the amorphous carbon film is such that a zinc-substituted layer, an electroless Ni—P layer (5 ⁇ m), a hard chromium plating (5 ⁇ m), and an amorphous carbon film are formed on an aluminum substrate.
  • the multilayer film structure formed in this order is more than the multilayer film structure in which an amorphous carbon film containing silicon is directly formed on an aluminum substrate as an intermediate adhesive layer, and an amorphous carbon film is formed thereon. However, it was confirmed that it could be improved for practical use.
  • test samples 7 and 9 are an embodiment of the present invention, and test sample 8 is a comparative example.
  • test sample 8 is a comparative example.
  • a friction wear tester according to JIS K 7218 was used, and a hard ball (ball) with a diameter of 2 mm was used as the other party. was measured.
  • Test sample 7 was manufactured by the following method. First, plate-like aluminum alloy 5052 having a length and width of 100 mm ⁇ 40 mm and a thickness of 1 mm is dipped in a weak alkaline solution and degreased at 70 ° C., and then dipped in a sulfuric acid solution at 70 ° C. Etched. The substrate after etching was acid-immersed with 50% nitric acid at room temperature. Next, a zinc substitution layer was deposited on the surface of the base material after the acid immersion treatment at room temperature with a strong alkali zinc substitution solution mainly composed of NaOH. Subsequently, it was immersed in 50% nitric acid at room temperature to remove the smut.
  • the high-pressure DC pulse plasma CVD apparatus was depressurized to 1 ⁇ 10 ⁇ 3 Pa, and the substrate charged with argon gas plasma was cleaned for about 5 minutes.
  • the high-pressure DC pulse plasma CVD apparatus was depressurized to 1 ⁇ 10 ⁇ 3 Pa, and the substrate charged with argon gas plasma was cleaned for about 5 minutes.
  • an acetylene with a gas flow rate of 40 SCCM is used as a source gas, and an amorphous carbon film is formed under the conditions of an applied voltage of ⁇ 5 kV, a pulse frequency of 10 kHz, a pulse width of 10 ⁇ s, and a gas pressure of 2 Pa. did.
  • Film formation was performed such that the thickness of the intermediate adhesive layer was 25% of the total thickness of the intermediate adhesive layer and the amorphous carbon film.
  • the time required for the step of depositing the amorphous carbon film was about 20 minutes including the step of forming the intermediate adhesive layer.
  • the temperature of the aluminum substrate was made not to exceed 350 ° C.
  • thermolabel which can confirm the temperature change to 200 degreeC was attached to the aluminum base material, and it confirmed that the base material temperature did not reach 200 degreeC.
  • the amorphous carbon film was formed, the film was formed for 10 minutes, then stopped for 10 minutes, and the temperature of the substrate was lowered. Thereafter, the film formation was resumed to form an amorphous carbon film.
  • the amorphous carbon film had a thickness of 0.4 ⁇ m and a hardness of Hv1500.
  • the temperature of the film formation chamber at the end of film formation was 86 ° C.
  • Test sample 8 was produced by the following method. First, a plate-shaped aluminum alloy 5052 base material having a length and width of 100 mm ⁇ 40 mm and a thickness of 1 mm is prepared, and silicon is directly applied on the base material using the high-pressure DC pulse plasma CVD method under the same conditions as the test sample 7. An intermediate adhesion layer of amorphous carbon film and an amorphous carbon film were formed. Next, a test sample 9 was produced. An electroless Ni—P plating layer was deposited to a thickness of 5 ⁇ m on an aluminum substrate on which a zinc replacement layer was formed in the same manner as in test sample 7. The electroless Ni—P plating treatment was performed for 20 minutes.
  • an electrolytic nickel plating layer was deposited, and on this electrolytic nickel plating layer, a hard chromium electrolytic plating treatment was performed for 35 minutes so that the thickness of the electrolytic hard chromium plating layer was 10 ⁇ m.
  • an intermediate adhesion layer and an amorphous carbon film of an amorphous carbon film containing silicon were formed under the same conditions as in the test sample 7 by using a high-pressure DC pulse plasma CVD method.
  • FIG. 2 is a graph showing the change in the coefficient of friction according to the number of wears of the test sample 7, and FIG. 3 is a surface photograph of the test sample 7 taken after 100 times of wear.
  • the horizontal axis in FIG. 2 represents the number of wears, and the vertical axis represents the measured coefficient of friction.
  • a square point is a friction coefficient in the case of 502g, and a triangular point is a friction coefficient of 700g.
  • the frictional wear test was performed by using a frictional wear tester according to JIS K 7218 and reciprocating a super hard ball with a predetermined indentation load on the test sample.
  • the number of times the hard balls reciprocate on the test sample is defined as the number of wear.
  • the photograph in FIG. 3 was taken at a magnification of 200 times using a CCD camera.
  • the test sample 7 maintains a friction coefficient of approximately 0.04 ⁇ m or less until the number of frictions reaches 100.
  • the trajectory of the ball is hardly visible on the surface of the test sample 7 even after the test of 100 times of wear is performed. From these test results, it was found that the test sample 7 showed good frictional wear resistance.
  • FIG. 4 is a graph showing a change in the coefficient of friction according to the number of wears of the test sample 8.
  • the square point represents the friction coefficient at 700 g
  • the triangular point represents the friction coefficient at 502 g.
  • FIG. 5 is a photograph of the surface of the test sample 8 taken after 8 times of wear. The photograph in FIG. 5 was taken in the same manner as test sample 7. As shown in FIG. 4, the friction coefficient of the test sample 8 rapidly increased when the number of wear was 2. Further, as shown in FIG. 5, the trajectory of the ball clearly appeared as a white band extending in the left-right direction on the surface of the test sample 8. From these test results, it was confirmed that the surface of the test sample 8 was greatly sharpened and the surface of the aluminum alloy was exposed.
  • FIG. 6 is a graph showing a change in the coefficient of friction according to the number of wears of the test sample 9, and FIG. 7 shows a surface photograph of the test sample 9 taken after 100 times of wear.
  • the test sample 9 maintains a friction coefficient of approximately 0.15 ⁇ m or less until the number of frictions reaches 100.
  • the surface of the test sample 9 can be confirmed with a ball trajectory even after 100 wear tests, but there is no abnormality such as peeling on the amorphous carbon film. Not observed. From these test results, it was found that the test sample 9 showed good frictional wear resistance.
  • test samples 7 and 9 which are the examples of the present invention have a higher frictional wear resistance than the comparative examples. Since this excellent frictional wear resistance is due to the nature of the amorphous carbon film formed in the uppermost layer, the test samples 7 and 9 which are examples of the present invention are tested through a test for measuring the number of wears. It was shown that the amorphous carbon film did not peel off. Test sample 8 was unable to observe good frictional wear resistance. The reason why good frictional wear resistance was not obtained for test sample 8 was that the uppermost amorphous carbon film was peeled off and the friction coefficient of the softer substrate portion was measured. Thus, it was shown that the adhesion of the amorphous carbon film was improved in the examples of the present invention.
  • burrs and cutting powder could be removed in the film forming process of the zinc-substituted layer.
  • an aluminum alloy (5052) base material having a 100 mm square and a plate thickness of 5 mm is prepared, and a portion for forming a concave portion for storing components and a bottom of the concave portion is formed on one surface of the base material by three-dimensional countersink processing.
  • a part alignment pallet was created by forming a large number of part alignment holes like meshes. Six pallets for aligning the same parts were prepared. After cutting, heat treatment for warping correction was performed at 270 ° C.
  • a zinc-substituted film was formed on the surface of three of the six component alignment pallets after the heat treatment thus obtained as follows.
  • the three parts alignment pallets were degreased with an aluminum cleaner NE-6 manufactured by Meltex Co., Ltd., a Japanese company.
  • the chemicals for plating were those from Meltex Co., Ltd.
  • the parts alignment pallet was immersed in an aluminum cleaner NE-6 solution having a concentration of 60 g / L and degreased at 70 ° C. for 180 seconds.
  • the parts pallet after degreasing was washed with tap water for 30 seconds. Then, the tap water washing for 30 seconds was performed again.
  • the surface of the pallet for parts alignment after the water washing was immersed and etched using an acidic solution.
  • a mixed solution of Actan E-10 having a concentration of 100 ml / L and Actan 70 having a concentration of 10 g / L was used as the acidic solution, and the component alignment palette was etched at 70 ° C. for 60 seconds.
  • tap water washing for 30 seconds was performed twice on the parts alignment pallet.
  • the pallet for parts alignment was placed in a mixed solution of 67.5% nitric acid with a concentration of 500 ml / L, 98% sulfuric acid with a concentration of 250 ml / L, and actin 70 with a concentration of 120 g / L at room temperature for 30 seconds. Soaked.
  • the component alignment pallet after the acid immersion treatment was immersed in a zinc replacement solution containing Almon EN having a concentration of 200 ml / L as a main component at 25 ° C. for 90 seconds to deposit a zinc replacement layer on the surface of the component alignment pallet. .
  • tap water washing for 30 seconds was performed twice on the parts alignment pallet.
  • the component alignment pallet on which the zinc replacement layer was formed was immersed in 67.5% nitric acid having a concentration of 500 ml / L at room temperature for 30 seconds, and the smut was dropped. Then, tap water washing for 30 seconds was performed twice on the parts alignment pallet.
  • the parts alignment pallet was immersed in a zinc replacement solution mainly composed of Almon EN having a concentration of 200 ml / L for 60 seconds at 25 ° C., and a second zinc replacement treatment was performed.
  • the zinc replacement layer was formed on the three parts alignment pallets by the method according to the embodiment of the present invention.
  • each of the three parts alignment pallets on which no film was formed was placed in a mixed solution of Melplate NI-2280LF M1 and Melplate NI-2280LF M2 having a concentration of 55 ml / L at 90 ° C. for 40 minutes. It was immersed, 10 ⁇ m of electroless nickel plating was deposited on the zinc-substituted layer, and electrolytic hard chromium plating was further performed for 35 minutes to form a hard chromium plating layer having a thickness of 10 ⁇ m. Subsequently, an amorphous carbon film was formed by the following method on the three component alignment pallets and the three component alignment pallets on which only the zinc replacement layer was formed. Prior to the formation, each of these six component alignment palettes was immersed in isopropyl alcohol and subjected to ultrasonic cleaning for 5 minutes.
  • the six parts alignment palettes after the ultrasonic cleaning were respectively put into a high-pressure DC pulse plasma CVD apparatus, and a carbon film was formed under the following conditions.
  • Deposition chamber vacuum 7 ⁇ 10-4 Pa
  • Argon base material cleaning Gas flow rate 30 SCCM, gas pressure 2 Pa, Applied voltage: -3.5 Kv Pulse frequency 10 kHz, Pulse width 10 ⁇ s, 5 minutes
  • Trimethylsilane intermediate adhesion layer Gas flow rate 30 SCCM, Gas pressure: 2 Pa Applied voltage: ⁇ 4.5 Kv Pulse frequency 10 kHz, pulse width 10 ⁇ s, 15 minutes
  • Carbon film layer with acetylene gas flow rate: 30 SCCM, gas pressure: 2 Pa Applied voltage: ⁇ 5 Kv, pulse frequency 10 kHz, pulse width 10 ⁇ s, 35 minutes.
  • test samples 10, 11, and 12 The three parts alignment pallets on which the zinc replacement layer, the electroless nickel plating layer, the hard chrome plating layer, and the amorphous carbon film are formed in this way are referred to as test samples 10, 11, and 12, respectively. Further, the remaining three component alignment pallets on which the amorphous carbon film is formed directly on the substrate are referred to as test samples 13, 14, and 15, respectively.
  • Test samples 10 to 15 were allowed to stand at room temperature and normal pressure for 3 days after the formation of the amorphous carbon film. Holes for aligning parts of the test samples 10 to 15 were observed at a magnification of 200 times using a CCD camera. As a result, no peeling of the amorphous carbon film was observed in the test samples 10, 11, and 12. On the other hand, in each of the test samples 13, 14 and 15, peeling was observed in the amorphous carbon film formed on the vicinity of the hole or on the part where the burr or cutting powder was attached to the hole wall. In addition, swell of the amorphous carbon film was observed.
  • the anodic oxide film formed on the aluminum substrate by the step of forming the zinc-substituted film according to one embodiment of the present invention can be removed, and the anodic oxide film was left. It was confirmed that a zinc-substituted film can be formed as it is.
  • an aluminum alloy base material 5052 material
  • the aluminum alloy base material was subjected to an anodic acid treatment to form an anodic oxide film having a thickness of 30 ⁇ m, and an anodic oxide film sample 1 was obtained.
  • an anodic acid treatment was performed on the aluminum alloy substrate to form an anodized film having a thickness of 10 ⁇ m, and an anodized film sample 2 was obtained.
  • a zinc-substituted film was formed on the anodized film sample 1 as follows. First, the anodized film sample 1 was immersed in an aluminum cleaner NE-6 having a concentration of 60 g / L for 180 seconds at 70 ° C. to be degreased. Next, the anodic oxide film sample 1 after degreasing was etched by immersing it in a mixed solution of 100 ml / L Actan E-10 and 10 g / L Actan 70 at 70 ° C. for 150 seconds. Next, the etched anodic oxide film sample 1 was immersed in 50% nitric acid at room temperature for 30 seconds.
  • the anodic oxide film sample 1 after the acid immersion treatment is immersed in a zinc-substituting liquid mainly composed of Almon EN having a concentration of 200 ml / L at room temperature for 100 seconds to deposit a zinc-substituting layer on the surface of the anodic oxide film sample 1. It was.
  • the anodized film sample 1 on which the zinc substitution layer was deposited was again immersed in 50% nitric acid at room temperature for 30 seconds.
  • the anodic oxide film sample 1 after the acid immersion was immersed in a zinc replacement solution mainly composed of Almon EN having a concentration of 200 ml / L at room temperature for 70 seconds to perform a second zinc replacement treatment.
  • the anodized film sample 1 after the second zinc substitution treatment was energized in a standard composition of pH 4.1 elpilite GS-6 at a current density of 55 ° C. and 3 A / dm 2 for 9 minutes.
  • a test sample 16 was prepared as a sample.
  • the photograph of the test sample 16 produced in this manner was photographed at a magnification of 3000 times using a CCD camera. As a result, there was no anodic oxide film that was 30 ⁇ m before the step of forming the zinc-substituted film. As a result, it was confirmed that the 30 ⁇ m anodic oxide film disappeared during the zinc substitution film forming step.
  • a zinc-substituted film was formed on the anodized film sample 2 as follows. First, the anodized film sample 2 was immersed in an aluminum cleaner NE-6 having a concentration of 60 g / L at 70 ° C. for 14 seconds to degrease. Next, the degreased anodic oxide film sample 2 was etched by being immersed in a mixed solution of 100 ml / L of Actane E-10 and 10 g / L of Actan 70 at 70 ° C. for 14 seconds. Next, the etched anodic oxide film sample 2 was immersed in 50% nitric acid at room temperature for 14 seconds.
  • the anodic oxide film sample 2 after the acid immersion treatment is immersed in a zinc-substituting liquid mainly composed of Almon EN having a concentration of 200 ml / L at room temperature for 14 seconds to deposit a zinc-substituting layer on the surface of the anodic oxide film sample 2.
  • a test sample 17 was produced.
  • the removal amount of the anodic oxide film on the aluminum substrate can be adjusted by controlling the treatment time and the number of times of each step included in the zinc substitution treatment.
  • the removal amount of the anodized film can be increased by increasing the treatment time with an acidic or alkaline solution, and the anodized film can be completely removed as described above.
  • the aluminum substrate and the upper layer portion can be electrically connected.
  • an anodic oxide film can be left on the aluminum substrate by reducing the treatment time with an acidic or alkaline solution. The anodized film can insulate the aluminum substrate from the upper layer portion.
  • the multilayer structure according to various embodiments of the present invention can be applied to an index carrier.
  • the index carrier is configured by rotatably supporting a disk-shaped guide member on a rack.
  • a plurality of pockets for accommodating two sides of the square electronic component are formed at equal intervals on the outer periphery of the disc-shaped guide member. Since a negative pressure is applied to the pocket in the direction of the rotation center of the guide member, the electronic component can be accommodated in the pocket and transported in the rotation direction.
  • a CCD camera can be disposed outside the outer periphery of the guide member in the radial direction.
  • the guide member can accommodate an electronic component in a pocket and carry the electronic component to a photographing area of the CCD camera. With this CCD camera, it is possible to inspect the appearance of the electronic components being transported.
  • the index carrier itself is known and disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-307269.
  • the multilayer structure according to various embodiments of the present invention described above is formed on the surface of an index carrier.
  • the pockets of the guide member are susceptible to damage due to frequent contact with the electronic components.
  • an amorphous carbon film that is hard and excellent in wear resistance is formed on the top of a soft aluminum or aluminum alloy-based substrate as a metal with good adhesion.
  • the multilayer film structure which can improve the abrasion resistance of aluminum alloy, and sliding property, and its manufacturing method are provided.
  • all layers from the base material to the hard chrome plating can be wet-plated, so that the temperature during film formation is suppressed to 150 ° C. or lower. be able to. Thereby, film-forming of each layer can be made into less than 250 degreeC which is the recrystallization temperature of aluminum or an aluminum alloy base material.
  • the amorphous carbon film or the amorphous carbon film containing silicon according to various embodiments of the present invention is formed by the CVD method, it is not necessary to prepare an expensive solid target such as titanium, tungsten, or chromium.
  • an expensive solid target such as titanium, tungsten, or chromium.
  • the surface of the aluminum base material is hard chrome plated with excellent weather resistance. Since it is covered with a layer and a nickel plating layer, the aluminum substrate can be protected even if foreign matter enters from the pinhole.

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Abstract

L'invention concerne un procédé de stratification d'un film multicouche, suivant lequel un film de carbone amorphe peut être formé à la partie supérieure d'une base en aluminium ou en alliage d'aluminium avec adhésion élevée et la corrosion d'une couche située au-dessous du film de carbone amorphe peut être supprimée. De façon spécifique, on peut obtenir une structure de film multicouche avec un gradient adéquat de dureté en formant un film substitué par du zinc sur la surface d'une base qui est composée d'aluminium ou d'un alliage d'aluminium, en formant une couche de placage de nickel par un procédé de dépôt auto-catalytique à l'aide du film substitué par du zinc comme couche de primaire, puis en formant une couche dure de placage de chrome, et de manière supplémentaire en formant, comme dernière couche de recouvrement, un film de carbone amorphe de préférence à une température de 350°C ou moins et, de préférence, à l'aide d'un procédé de dépôt CVD sous plasma à faible température.
PCT/JP2011/053902 2010-02-23 2011-02-23 Stratifié à film multicouche utilisant de l'aluminium ou un alliage d'aluminium comme substrat, et procédé de stratification permettant de l'obtenir Ceased WO2011105392A1 (fr)

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JP2010037580A JP2013091811A (ja) 2010-02-23 2010-02-23 アルミニウム又はアルミニウム合金を基板とする多層膜積層体及びその積層方法
JP2010-037580 2010-02-23

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WO2014192916A1 (fr) * 2013-05-31 2014-12-04 本田技研工業株式会社 Élément recouvert de carbone et procédé de fabrication de ce dernier
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WO2015107256A1 (fr) * 2014-01-15 2015-07-23 Savroc Ltd Procédé pour la production d'un revêtement au chrome et objet revêtu
US10487412B2 (en) 2014-07-11 2019-11-26 Savroc Ltd Chromium-containing coating, a method for its production and a coated object
US20220176306A1 (en) * 2020-12-03 2022-06-09 National Taiwan Normal University Planar separation component for gas chromatography and manufacturing method and use thereof

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AT15858U1 (de) * 2017-05-19 2018-07-15 High Tech Coatings Gmbh Verfahren zur Verbesserung der Verschleißbeständigkeit eines Bauteils
JP6551766B2 (ja) * 2018-11-19 2019-07-31 三菱重工業株式会社 積層部材、並びに、これを用いた羽根車、圧縮機及びエンジン
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WO2014111624A1 (fr) * 2013-01-15 2014-07-24 Savroc Ltd Procédé de production d'un revêtement de chrome sur un substrat métallique
CN104995339A (zh) * 2013-01-15 2015-10-21 萨夫罗克有限公司 在金属衬底上产生铬涂层的方法
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WO2014192916A1 (fr) * 2013-05-31 2014-12-04 本田技研工業株式会社 Élément recouvert de carbone et procédé de fabrication de ce dernier
JP2017508879A (ja) * 2014-01-15 2017-03-30 サヴロック リミテッド クロム被覆を製造する方法および被覆物体
CN105917029A (zh) * 2014-01-15 2016-08-31 萨夫罗克有限公司 用于生产铬涂层的方法和涂覆的物体
CN105917030A (zh) * 2014-01-15 2016-08-31 萨夫罗克有限公司 用于生成含有铬的多层涂层的方法和涂覆的物体
WO2015107256A1 (fr) * 2014-01-15 2015-07-23 Savroc Ltd Procédé pour la production d'un revêtement au chrome et objet revêtu
WO2015107255A1 (fr) * 2014-01-15 2015-07-23 Savroc Ltd Procédé pour la production de revêtement multicouche contenant du chrome et objet revêtu
EA031842B1 (ru) * 2014-01-15 2019-02-28 Саврок Лтд Способ получения хромового покрытия и подложка с нанесенным покрытием
US10443143B2 (en) 2014-01-15 2019-10-15 Savroc Ltd Method for producing a chromium coating and a coated object
US10443142B2 (en) 2014-01-15 2019-10-15 Savroc Ltd Method for producing chromium-containing multilayer coating and a coated object
US10487412B2 (en) 2014-07-11 2019-11-26 Savroc Ltd Chromium-containing coating, a method for its production and a coated object
US20220176306A1 (en) * 2020-12-03 2022-06-09 National Taiwan Normal University Planar separation component for gas chromatography and manufacturing method and use thereof
US12145096B2 (en) * 2020-12-03 2024-11-19 National Taiwan Normal University Planar separation component for gas chromatography and manufacturing method and use thereof

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