WO2011125657A1 - Procédé de fabrication d'un article revêtu ayant une excellente résistance à la corrosion, et article revêtu - Google Patents

Procédé de fabrication d'un article revêtu ayant une excellente résistance à la corrosion, et article revêtu Download PDF

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Publication number
WO2011125657A1
WO2011125657A1 PCT/JP2011/057843 JP2011057843W WO2011125657A1 WO 2011125657 A1 WO2011125657 A1 WO 2011125657A1 JP 2011057843 W JP2011057843 W JP 2011057843W WO 2011125657 A1 WO2011125657 A1 WO 2011125657A1
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Prior art keywords
corrosion resistance
coated article
hard
coating
hard film
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PCT/JP2011/057843
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English (en)
Japanese (ja)
Inventor
サーレ アブスアイリキ
剛史 石川
謙一 井上
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日立ツール株式会社
日立金属株式会社
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Application filed by 日立ツール株式会社, 日立金属株式会社 filed Critical 日立ツール株式会社
Priority to KR1020127024799A priority Critical patent/KR101455142B1/ko
Priority to CN201180014742.4A priority patent/CN102803546B/zh
Priority to JP2012509486A priority patent/JP5498572B2/ja
Publication of WO2011125657A1 publication Critical patent/WO2011125657A1/fr

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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5873—Removal of material
    • C23C14/588—Removal of material by mechanical treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a coated article that requires corrosion resistance, such as a mold, a tool, and an injection molding part used for molding plastics and rubber, and a coated article.
  • PVD physical vapor deposition
  • Patent Document 1 there is a technique for improving wear resistance and film adhesion by nitriding the surface of a part for injection molding and then coating a CrN or TiN film by an arc ion plating method.
  • Patent Document 2 the CrN film having excellent adhesion and corrosion resistance to the base material is coated first, and then a high-hardness TiN film is coated in multiple layers, thereby improving the corrosion resistance.
  • Patent Document 2 There is a method of giving (Patent Document 2).
  • Patent Document 3 it is conceivable to introduce the ion etching of Patent Document 3 on the surface of the hard film of Patent Documents 1 and 2.
  • ion etching of Patent Document 3 it is conceivable to introduce the ion etching of Patent Document 3 on the surface of the hard film of Patent Documents 1 and 2.
  • removal of droplets or the like that still exerts its effect cannot be achieved.
  • the sandblasting of patent document 4 since this is a rough processing method exclusively by the grinding action of spraying particles on the surface of the film, it is difficult to obtain a smooth surface preferable for improving corrosion resistance.
  • an object of the present invention is to provide a method for producing a coated article and a coated article with improved corrosion resistance of a hard coating.
  • the present inventor examined a method for suppressing defects penetrating from the surface of the hard film coated with PVD toward the base material. As a result, in order to suppress this, it has been found that removing impurities such as droplets on the surface of the coating without leaving as much as possible during the coating process is important for improving the corrosion resistance. In addition to this, it was also found that the surface of the film after removing droplets and the like has a certain surface roughness that improves the corrosion resistance. And the present invention has been achieved by realizing a coating structure having excellent corrosion resistance as a coated article.
  • the present invention is a method for producing a coated article having excellent corrosion resistance, in which a hard film comprising at least two layers or more is coated on the substrate surface of the article by PVD. Coating the surface of the first hard coating with the step of coating the surface of the first hard coating with the step of coating the second hard coating on the surface of the first hard coating.
  • This is a method for producing a coated article excellent in corrosion resistance, further comprising a step of polishing to an average roughness Ra of 0.05 ⁇ m or less and a maximum height Rz of 1.00 ⁇ m or less.
  • each arithmetic average roughness Ra and maximum height Rz preferably satisfy the following formulas 1 to 3.
  • Formula 2 For Rz, C / B ⁇ 0.1 Equation 3
  • the surface of the first hard film is polished so that the number density of the peaks and valleys at a distance of 50 nm or more from the average line is 50 pieces / mm 2 or less, respectively, in the sectional curve obtained by measuring the section. It is desirable.
  • the first and / or second hard coating is preferably chromium nitride. Furthermore, it is desirable that these hard coatings are chromium-based nitrides containing one or more elements selected from Mo, Nb, W, Si, and B.
  • the second hard film is a chromium-based nitride whose component composition is (Cr 1 ⁇ a X a ) N (provided that the subscript number represents the atomic ratio of Cr to element X).
  • X is one or more elements selected from Mo, Nb, and W, and a is preferably 0.1 to 0.2.
  • X is one or more elements selected from Si and B, and a is preferably 0.03 to 0.10.
  • each of the arithmetic average roughness Ra and the maximum height Rz preferably satisfy the following formulas 1 to 3.
  • the physical vapor deposition method is preferably an arc ion plating method, and the coated article formed by these is preferably an injection molding part or a mold.
  • the coated article of the present invention is obtained by the above-described production method of the present invention, and is a coated article in which a hard film is coated on the surface of a base material of the article by a physical vapor deposition method. It comprises at least two layers of a first hard film coated on the surface of the material and a second hard film coated directly on the polished first hard film, and the first hard film and the second hard film It is a coated article excellent in corrosion resistance in which the number of droplets having a major axis of 1 ⁇ m or more straddling the interface of the hard coating is less than 2 (including 0) per 50 ⁇ m interface length in cross-sectional structure observation.
  • the first and / or second hard coating is preferably a chromium nitride. Furthermore, it is desirable that these hard coatings are chromium-based nitrides containing one or more elements selected from Mo, Nb, W, Si, and B.
  • the second hard film is a chromium-based nitride whose component composition is (Cr 1 ⁇ a X a ) N (provided that the subscript number represents the atomic ratio of Cr to element X).
  • X is one or more elements selected from Mo, Nb, and W, and a is preferably 0.1 to 0.2.
  • X is one or more elements selected from Si and B, and a is preferably 0.03 to 0.10.
  • the surface of the second hard coating is polished.
  • the physical vapor deposition method is preferably an arc ion plating method
  • the coated article of the present invention is preferably an injection molding part or a mold.
  • the surface of the first hard film in the middle of the coating of the hard film is optimally polished, so that there are very few defects penetrating toward the substrate after the second film is coated. Therefore, it exhibits excellent corrosion resistance.
  • the second hard coating can be given further improvement in corrosion resistance and high hardness by making the structure fine, it is a coating excellent in wear resistance in addition to corrosion resistance. Can be an article. Therefore, the present invention is useful for manufacturing injection molding parts, tools, and molds that are exposed to corrosive environments.
  • Sample No. of the present invention example It is an example of the cross-sectional curve of 1st 1st hard film. The arrow indicates the average line.
  • Sample No. of Comparative Example 8 is an example of a cross-sectional curve of the first hard coating of No. 8; The arrow indicates the average line.
  • Sample No. of the present invention example. 2 is a photomicrograph of the surface of a hard coating film showing the results of a corrosion test performed in 1.
  • Sample No. of the present invention example. 2 is a micrograph of the surface of a hard coating film showing the result of a corrosion test performed in 2.
  • Sample No. of Comparative Example 5 is a micrograph of the surface of a hard coating film showing the result of a corrosion test (immersion time is 10 hours) performed in 5.
  • Comparative Example 7 is a photomicrograph of the surface of a hard coating film showing the results of a corrosion test (immersion time is 10 hours) performed in 7.
  • Sample No. of Comparative Example 9 is a photomicrograph of the surface of a hard coating film showing the results of a corrosion test performed in No. 9.
  • Sample No. of Comparative Example 10 is a micrograph of the surface of a hard coating film showing the results of a corrosion test conducted in No. 10.
  • Sample No. of the present invention example. 12 is a photomicrograph of the surface of the hard coating film showing the results of the corrosion test conducted in No. 12.
  • Sample No. of the present invention example. 15 is a photomicrograph of the surface of the hard coating film showing the result of the corrosion test conducted in No. 15. Sample No. of the present invention example.
  • Sample No. of the present invention example. 27 is a photomicrograph of the surface of a hard coating film showing the results of a corrosion test performed in No. 27.
  • Sample No. of the present invention example. 2 is a micrograph of a hard coating surface showing the results of a corrosion test conducted in No. 28.
  • Sample No. of the present invention example. 3 is a photomicrograph of the surface of a hard coating film showing the results of a corrosion test performed at 32.
  • Sample No. of the present invention example. It is a scanning electron micrograph which shows the torn surface structure of 12 hard films. The upper side of the photograph is the second film, and the lower side is the first film.
  • Sample No. of the present invention example It is a scanning electron micrograph which shows the fracture surface structure of 11 hard coatings. The upper side of the photograph is the second film, and the lower side is the first film. It is the schematic of the film-forming apparatus used in the Example.
  • Sample No. of the present invention example. 1 is a microstructural photograph of 1 hard coating cross section. It is a base material, the 1st coat, and the 2nd coat from the bottom.
  • Sample No. of Comparative Example 8 is a microstructural photograph of 8 hard coating cross section. It is a base material, the 1st coat, and the 2nd coat from the bottom.
  • the present inventor found out that local corrosion is caused by irregularities originating from droplets, particles, and the like on the first hard film, while earnestly studying a method for suppressing the corrosion of the film. Then, in addition to the hard coating being divided into the first hard coating and the second hard coating, the second hard coating is continuously applied after the first hard coating is coated. Instead, first, the first hard film is polished and smoothed to have a certain surface roughness, and then the second hard film is coated thereon, whereby the corrosion resistance of the entire film can be greatly improved. In addition, the present inventors have also found a film structure having excellent corrosion resistance. Details will be described below.
  • the first hard film is polished on the first hard film by removing droplets and particles to obtain a smooth surface state. This is because it is coated so as to fill in the fine irregularities on the surface of the hard film, and the corrosion resistance of the entire film can be greatly improved.
  • Corrosion resistance can be improved by smoothing the surface of the first hard film to be coated by the production method of the present invention so that the film surface has a certain surface roughness. That is, the corrosion resistance is improved by polishing the arithmetic average roughness Ra in the surface roughness specified in JIS-B-0602-2001 to 0.05 ⁇ m or less and the maximum height Rz to 1.00 ⁇ m or less. I can do it.
  • the second hard coating is preferably in the same surface roughness range. In order to make the surface of the first hard film have this preferable surface roughness, the surface of the film is not sufficiently smoothed by a grinding action such as ion etching or sand blasting (shot blasting), and the corrosion resistance of the film is reduced. May be inferior.
  • a polishing means that precisely finishes the surface of the part to have a correct uniform surface when finishing machine parts. For example, using a surface plate, a lapping agent is placed between the hard film and the hard film.
  • a polishing agent having diamond particles and humidity is used.
  • the length of the interface in the cross-sectional structure observation is a droplet composed of at least two layers of the second hard film coated immediately above the film and having a major axis of 1 ⁇ m or more straddling the interface between the first hard film and the second hard film.
  • the coated article of the present invention having excellent corrosion resistance having a number per 50 ⁇ m of less than 2 (including 0) can be obtained. When coarse droplets are present, internal defects such as voids are formed between the film deposited on the upper surface thereof.
  • the average number of droplets having a major axis of 1 ⁇ m or more straddling the smoothed interface across the interface between the first hard film and the second hard film is less than 2 per 50 ⁇ m interface length in cross-sectional structure observation (0 Included). This is because the presence of about two droplets having a major axis of less than 1 ⁇ m and about two units having a major axis of 1 ⁇ m or more does not significantly affect the corrosion resistance.
  • the surface roughness of the substrate before coating is also polished smoothly.
  • the surface roughness of the base material before coating the hard film is A
  • the surface roughness before polishing of the first hard film is B
  • the surface roughness after polishing of the first hard film is C.
  • each of the arithmetic average roughness Ra and / or the maximum height Rz satisfy the relationship of A ⁇ C ⁇ B.
  • the surface roughness after polishing of the second hard film is defined as D, and A ⁇ It is preferable to satisfy the relationship C ⁇ D ⁇ B.
  • the surface roughness of the first hard coating is preferably smoother than the surface roughness of the second hard coating after polishing, and the surface roughness of the substrate before coating is the smoothest. It is preferable.
  • the droplets and the like on the surface at the time of coating are removed by polishing, and the degree of removal, that is, the surface roughness C after polishing is relative to the surface roughness B before polishing. It is desirable to finish so that C / B is less than 0.4 for Ra and C / B is less than 0.1 for Rz. By satisfying these equations, defects in the hard coating can be further reduced.
  • the number density of the peaks (convex portions) and valley bottoms (concave portions) having a distance from the average line of 50 nm or more is 50 / mm 2 or less, respectively. It is preferable to polish.
  • the average line is the center line of the peak and valley bottom in the cross-sectional curve. The number of peaks at 50 nm or more from the center line was investigated, and the number density was measured.
  • the first and / or second hard coating that is coated by the production method of the present invention is preferably a chromium-based nitride that is excellent in corrosion resistance.
  • the chromium-based nitride means that the chromium content in the metal (including metalloid) portion is 50 atomic% or more.
  • the first and / or second hard coating is preferably a chromium nitride containing one or more elements selected from Mo, Nb, W, Si, and B. By adding Mo, Nb, and W into the film, the hardness is improved and the wear resistance is improved.
  • the chromium-based nitride in order to maintain the toughness and adhesion of the chromium-based nitride itself, it is a chromium-based nitride whose component composition is represented by (Cr 1 ⁇ a X a ) N (however, the subscript number is X represents an atomic ratio of Cr and element X), X is one or more elements selected from Mo, Nb, and W, and a is preferably 0.1 to 0.2.
  • Si and B are added in a film
  • the preferred film hardness is 2000HV 0.025 or more. And corrosion resistance improves more because a membrane
  • the chromium nitride When a reinforcing material such as glass fiber is added to the material to be molded, the hard film is likely to corrode due to wear. Therefore, by imparting high hardness to the hard coating, wear corrosion can be suppressed in addition to improvement of wear resistance.
  • a chromium nitride having a component composition represented by (Cr 1 ⁇ a X a ) N (however, subscript The number represents the atomic ratio of Cr to element X), X is one or more elements selected from Si and B, and a is preferably 0.03 to 0.10.
  • the coating means used in the production method of the present invention requires a physical vapor deposition method in which the hard film to be coated has high film adhesion.
  • a physical vapor deposition method in which the hard film to be coated has high film adhesion.
  • the arc ion plating method having particularly high film adhesion is preferable.
  • the film forming chamber 2 includes a plurality of arc discharge evaporation sources 3, 4, and 5 for mounting various targets (cathodes) 1, and a substrate holder 6 for mounting the substrate 7.
  • a rotation mechanism 8 is provided below the substrate holder 6, and the substrate 7 rotates and revolves through the substrate holder 6. And when the base material 7 opposes various targets, the film
  • the target used in this example is a metal target produced by a powder metallurgy method.
  • the evaporation sources 3 to 5 were appropriately equipped with a target constituting the metal component of the hard film and a target for metal ion etching.
  • JIS-SKD11 equivalent steel material tempered to 57-60HRC is used for the base material, and the surface of the base material is subjected to arithmetic mean roughness Ra 0.01 ⁇ m, Rz 0.07 ⁇ m before the first hard coating is coated on the base material. Polished. This was degreased and washed, and fixed to the substrate holder 7. And the base material was heated to 500 degreeC vicinity with the heater for heating (not shown) installed in the chamber 2, and it hold
  • Table 1 shows the prepared samples.
  • the hard coating is CrN.
  • Sample No. which is an example of the present invention.
  • 1 is an aero lapping process (manufactured by Yamashita Towers Co., Ltd.) as a means for removing the base material from the chamber after the first CrN coating and polishing the surface of the substrate (hereinafter abbreviated as intermediate surface treatment). Aero lapping machine (AERO LAP YT-300) is used, followed by polishing with 1 ⁇ m diamond paste, followed by SMAP treatment (using Kagami Tekko's specular shot machine SMAP-II) Went. Then, after degreasing and cleaning, the film was returned to the chamber again, and Ar ion etching and Ti metal ion etching were performed to cover the second CrN, thereby completing a hard film.
  • AERO LAP YT-300 Aero lapping machine
  • SMAP treatment using Kagami Tekko's specular shot machine SMAP-II
  • Sample No. 2-7 after the following intermediate surface treatment, Sample No. The second CrN was coated in the same manner as in 1. Sample No. 2 performed the intermediate surface treatment of only the above-described aero wrap treatment. Sample No. The intermediate surface treatment of Sample No. 3 Then the SMAP process was omitted. Sample No. For the intermediate surface treatment of No. 4, a nylon nonwoven fabric coated with an abrasive (Polishing pads # 1500 to # 3000 manufactured by Bell Star Abrasive Industry Co., Ltd.) was used.
  • Sample No. 6 and 7 correspond to Patent Document 4. That is, instead of the intermediate surface treatment of the present invention, sandblast treatment (projection material: # 400 to 600 sand) was performed.
  • Sample No. which is a comparative example. 8 and 9 correspond to Patent Document 3. That is, after coating with the first CrN, the sample No. As in 1 to 5, it is taken out from the chamber and returned to the chamber without intermediate surface treatment (however, No. 9 was only subjected to degreasing cleaning), and the same as the base material before coating with the second CrN Ar ion etching and Ti metal ion etching were performed.
  • Sample No. which is a comparative example. No. 10 corresponds to Patent Documents 1 and 2 and is formed without taking out from the chamber. Finally, the above sample No. The outermost surface of 1 to 10 was polished with diamond paste.
  • the measurement conditions are an evaluation length: 4.0 mm, a measurement speed: 0.3 mm / s, and a cut-off value: 0.8 mm. And about the 1st film
  • the measurement conditions are an evaluation length: 1.0 mm, a measurement speed: 0.15 mm / s, and a ⁇ s value: 0.8 mm.
  • Table 2 shows the relationship between the base material before coating the hard coating and the surface roughness Ra, Rz of the first and second hard coatings.
  • the surface of the film after the corrosion resistance evaluation test is shown in FIGS. 2A to 2F (in the figure, the light-colored portion confirmed to be spherical is pitting corrosion).
  • the hard coating satisfying the production method of the present invention has a smooth surface roughness on the outermost surface of the coating and is excellent in corrosion resistance.
  • the surface of the film after the corrosion resistance evaluation test is such that pitting corrosion with a very small diameter is confirmed as shown in FIGS. 2A to 2F.
  • Example 1 Various samples in which only the type of the hard coating was changed under the same film forming conditions as in No. 1 were prepared. The details are as shown in Table 3. Then, the hardness and corrosion resistance of the coating surface were evaluated. The hardness was measured according to JIS-Z-2244 by using a micro Vickers tester to measure the hardness HV0.025 of the coating surface. The test load is 0.2452N. The surface roughness and uneven defect density of the hard film were measured in accordance with JIS-B-0602-2001 as in Example 1, and the arithmetic average roughness Ra, the maximum height Rz, and the number of uneven defects were measured from the roughness curve. The corrosion resistance evaluation test is under the same conditions as in Example 1 except that the immersion time is 10 hours. These test results are shown in Table 3. The surface of the film after the corrosion resistance evaluation test is shown in FIGS. 3A to 3F (in the figure, the light-colored portion confirmed to be spherical is pitting corrosion).
  • sample No. satisfying the present invention is shown.
  • No. 11-34. 11 to 21 and 28 to 34 are particularly excellent in the balance between excellent corrosion resistance and high hardness.
  • sample no. 12-20 and 28-34 have high hardness.
  • 3A to F show sample No. 12, 15, 23, 27, 28, 32 shows the coating surface after the corrosion resistance evaluation test. No noticeable pitting corrosion is observed in 12, 15, 32.
  • Example 1 and Example 2 were subjected to cross-sectional observation of a plurality of visual fields in order to search for a factor for improving the corrosion resistance.
  • sample No. 1 and Comparative Example No. 6A and 6B show microstructural photographs taken with a scanning electron microscope in the cross-sectional observation of No. 8.
  • FIG. As shown in FIG. In No. 1, coarse droplets of 1 ⁇ m or more are not confirmed on the interface.
  • the number of droplets of 1 ⁇ m or more was 1 or less per 50 ⁇ m of interface length. Further, it was confirmed that the droplets present at the interface in the present invention example were removed or polished to constitute a smooth surface that did not cross the interface. On the other hand, the sample No. of the comparative example having poor corrosion resistance. In No. 8, four coarse droplets of 1 to 2 ⁇ m across the interface between the first hard film and the second hard film were confirmed per 50 ⁇ m of interface length in cross-sectional structure observation. When coarse droplets are present, internal defects such as voids are formed between the film deposited on the upper surface thereof. This defect promotes corrosion. In the example of the present invention, it can be seen that the influence of such coarse droplets can be eliminated by the polishing treatment, thereby improving the corrosion resistance.
  • a film component is adjusted to provide release properties from a molding material. It can be applied to metal injection molding dies and various machine parts.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Mounting, Exchange, And Manufacturing Of Dies (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'un article revêtu ayant une excellente résistance à la corrosion, dans lequel l'article revêtu est obtenu par revêtement de la surface d'un matériau de base pour l'article par un film de revêtement dur composé d'au moins deux couches par un procédé de déposition physique. Le procédé comprend une étape de revêtement de la surface du matériau de base par un premier film de revêtement dur et une étape de revêtement de la surface du premier film de revêtement dur par un second film de revêtement dur. Le procédé comprend en outre, avant l'étape de revêtement par le second film de revêtement dur, une étape de polissage de la surface du premier film de revêtement dur jusqu'à ce que la rugosité moyenne calculée (Ra) devienne de 0,05 µm ou moins et que la plus grande hauteur (Rz) devienne de 1,00 µm ou moins.
PCT/JP2011/057843 2010-03-31 2011-03-29 Procédé de fabrication d'un article revêtu ayant une excellente résistance à la corrosion, et article revêtu WO2011125657A1 (fr)

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KR1020127024799A KR101455142B1 (ko) 2010-03-31 2011-03-29 내식성이 우수한 피복 물품의 제조 방법 및 피복 물품
CN201180014742.4A CN102803546B (zh) 2010-03-31 2011-03-29 耐腐蚀性优异的被覆物品的制造方法及被覆物品
JP2012509486A JP5498572B2 (ja) 2010-03-31 2011-03-29 耐食性に優れた被覆物品の製造方法および被覆物品

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013132393A (ja) * 2011-12-26 2013-07-08 Polyplastics Co プレフィルドシリンジ用外筒の製造方法
WO2016027832A1 (fr) * 2014-08-20 2016-02-25 日立金属株式会社 Procédé de fabrication de moule revêtu pour moulage sous pression
JPWO2014192730A1 (ja) * 2013-05-30 2017-02-23 日立金属株式会社 冷間加工用金型の製造方法
JPWO2018096820A1 (ja) * 2016-11-22 2019-06-24 国立研究開発法人産業技術総合研究所 木質流動成形用金型及びそれを用いた木質流動成形用金型システム並びに植物系材料からなる成形体の製造方法
WO2019167674A1 (fr) 2018-02-27 2019-09-06 日立金属株式会社 Élément de revêtement et son procédé de fabrication
WO2020090475A1 (fr) * 2018-10-31 2020-05-07 東洋製罐グループホールディングス株式会社 Gabarit destiné au travail des métaux et du plastique

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016225449A1 (de) * 2016-12-19 2018-06-21 Robert Bosch Gmbh Verfahren zum Beschichten eines metallischen Bauteils mit einer Verschleißschutzschicht, metallisches Bauteil sowie Kraftstoffeinspritzsystem
JP6733844B1 (ja) * 2020-04-15 2020-08-05 マツダ株式会社 被覆金属材の耐食性試験方法及び耐食性試験装置

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5333777A (en) * 1976-09-07 1978-03-29 Tsuneo Nishida Production of hard exterior decorating parts with abrasive resistance
JPH06330348A (ja) * 1993-05-21 1994-11-29 Riken Corp 摺動部材
JP2001172766A (ja) * 1999-12-16 2001-06-26 Sumitomo Electric Ind Ltd 被覆摺動部材
JP2002348655A (ja) * 2001-05-18 2002-12-04 Sumitomo Metal Mining Co Ltd スケール付着防止膜付き部材およびその製造方法
JP2003064469A (ja) * 2001-08-20 2003-03-05 Riken Corp 耐摩耗性皮膜及びその皮膜を有する摺動部材
JP2004349481A (ja) * 2003-05-22 2004-12-09 National Institute Of Advanced Industrial & Technology チタン酸ストロンチウム薄膜積層体及びその作製方法
JP2006216365A (ja) * 2005-02-03 2006-08-17 Sumitomo Electric Ind Ltd 超電導薄膜材料、超電導線材およびこれらの製造方法
JP2007136654A (ja) * 2005-10-19 2007-06-07 Mitsubishi Materials Corp 高硬度鋼の重切削加工で硬質被覆層がすぐれた耐チッピング性を発揮する表面被覆立方晶窒化ほう素基超高圧焼結材料製切削工具
JP2007162613A (ja) * 2005-12-15 2007-06-28 Mitsubishi Heavy Ind Ltd 表面平滑化皮膜を有する回転機械

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2771947B2 (ja) * 1994-04-21 1998-07-02 株式会社リケン 摺動部材
JP2007163613A (ja) * 2005-12-09 2007-06-28 Fujitsu Ltd レチクルの検査方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5333777A (en) * 1976-09-07 1978-03-29 Tsuneo Nishida Production of hard exterior decorating parts with abrasive resistance
JPH06330348A (ja) * 1993-05-21 1994-11-29 Riken Corp 摺動部材
JP2001172766A (ja) * 1999-12-16 2001-06-26 Sumitomo Electric Ind Ltd 被覆摺動部材
JP2002348655A (ja) * 2001-05-18 2002-12-04 Sumitomo Metal Mining Co Ltd スケール付着防止膜付き部材およびその製造方法
JP2003064469A (ja) * 2001-08-20 2003-03-05 Riken Corp 耐摩耗性皮膜及びその皮膜を有する摺動部材
JP2004349481A (ja) * 2003-05-22 2004-12-09 National Institute Of Advanced Industrial & Technology チタン酸ストロンチウム薄膜積層体及びその作製方法
JP2006216365A (ja) * 2005-02-03 2006-08-17 Sumitomo Electric Ind Ltd 超電導薄膜材料、超電導線材およびこれらの製造方法
JP2007136654A (ja) * 2005-10-19 2007-06-07 Mitsubishi Materials Corp 高硬度鋼の重切削加工で硬質被覆層がすぐれた耐チッピング性を発揮する表面被覆立方晶窒化ほう素基超高圧焼結材料製切削工具
JP2007162613A (ja) * 2005-12-15 2007-06-28 Mitsubishi Heavy Ind Ltd 表面平滑化皮膜を有する回転機械

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013132393A (ja) * 2011-12-26 2013-07-08 Polyplastics Co プレフィルドシリンジ用外筒の製造方法
TWI621455B (zh) * 2011-12-26 2018-04-21 Polyplastics Co., Ltd. 預填注射器用外筒的製造方法
JPWO2014192730A1 (ja) * 2013-05-30 2017-02-23 日立金属株式会社 冷間加工用金型の製造方法
WO2016027832A1 (fr) * 2014-08-20 2016-02-25 日立金属株式会社 Procédé de fabrication de moule revêtu pour moulage sous pression
JPWO2016027832A1 (ja) * 2014-08-20 2017-04-27 日立金属株式会社 ダイカスト用被覆金型の製造方法
CN106660110A (zh) * 2014-08-20 2017-05-10 日立金属株式会社 压铸用被覆模具的制造方法
JPWO2018096820A1 (ja) * 2016-11-22 2019-06-24 国立研究開発法人産業技術総合研究所 木質流動成形用金型及びそれを用いた木質流動成形用金型システム並びに植物系材料からなる成形体の製造方法
WO2019167674A1 (fr) 2018-02-27 2019-09-06 日立金属株式会社 Élément de revêtement et son procédé de fabrication
KR20200106537A (ko) 2018-02-27 2020-09-14 히다찌긴조꾸가부시끼가이사 피복부재 및 그 제조 방법
US11976350B2 (en) 2018-02-27 2024-05-07 Proterial, Ltd. Covering member and method for manufacturing the same
WO2020090475A1 (fr) * 2018-10-31 2020-05-07 東洋製罐グループホールディングス株式会社 Gabarit destiné au travail des métaux et du plastique
CN112930233A (zh) * 2018-10-31 2021-06-08 东洋制罐集团控股株式会社 金属塑性加工用夹具

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CN102803546B (zh) 2014-12-31
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KR101455142B1 (ko) 2014-10-27
CN102803546A (zh) 2012-11-28
KR20120120471A (ko) 2012-11-01

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