WO2017141925A1 - サーメット粉末、保護皮膜被覆部材及びその製造方法、並びに電気めっき浴中ロール及びその製造方法 - Google Patents

サーメット粉末、保護皮膜被覆部材及びその製造方法、並びに電気めっき浴中ロール及びその製造方法 Download PDF

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WO2017141925A1
WO2017141925A1 PCT/JP2017/005385 JP2017005385W WO2017141925A1 WO 2017141925 A1 WO2017141925 A1 WO 2017141925A1 JP 2017005385 W JP2017005385 W JP 2017005385W WO 2017141925 A1 WO2017141925 A1 WO 2017141925A1
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Prior art keywords
roll
cermet
carbide particles
mass
film
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PCT/JP2017/005385
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English (en)
French (fr)
Japanese (ja)
Inventor
雄也 馬場
竹内　純一
圭史 小林
Original Assignee
Ｊｆｅスチール株式会社
トーカロ株式会社
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Application filed by Ｊｆｅスチール株式会社, トーカロ株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to MYPI2018702770A priority Critical patent/MY186906A/en
Priority to KR1020187026279A priority patent/KR102177464B1/ko
Priority to EP17753182.9A priority patent/EP3418421B1/en
Priority to CN201780011768.0A priority patent/CN108699667B/zh
Priority to JP2017529403A priority patent/JP6232524B1/ja
Priority to US16/077,169 priority patent/US20190032239A1/en
Publication of WO2017141925A1 publication Critical patent/WO2017141925A1/ja
Priority to CONC2018/0009602A priority patent/CO2018009602A2/es

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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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/04—Electroplating with moving electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0657—Conducting rolls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12146—Nonmetal particles in a component

Definitions

  • the present invention relates to a cermet powder, a protective film-coated member and a production method thereof, and a roll in an electroplating bath and a production method thereof.
  • Patent Document 1 plasma arc spraying is performed in a low-pressure oxygen-free atmosphere using an alloy in which Co or Ni is the main component and Cr, C, Fe, Mo, or the like is added to the surface of a carbon steel roll.
  • a method of manufacturing a conductor roll is described in which after the application, the film is melted again by plasma arc heating in the same atmosphere to form a non-porous sprayed film.
  • a spray coating layer is formed by spraying a mixed powder composed of carbide cermet powder and C-containing nickel chromium alloy powder on the surface of a roll body made of carbon steel, and then heating the spray coating layer.
  • a method of manufacturing a conductor roll for electroplating is described, wherein the carbide is reprecipitated to form a reprecipitated carbide dispersion sprayed coating, and then the roll body is shrink-fitted into the outside of the roll base. ing.
  • Patent Document 3 discloses a conductor roll with improved corrosion resistance, in which a mixed powder composed of WC-Ni cermet and the remaining Ni-based self-fluxing alloy is sprayed on the roll surface made of SS400 and then remelted to form a coating layer. A manufacturing method is described.
  • Patent Document 4 describes a conductor roll manufacturing method in which a self-fluxing alloy sprayed layer containing WC cermet is formed on the SS400 roll surface, and further a WC cermet layer is formed thereon.
  • JP-A-1-198460 Japanese Patent Laid-Open No. 5-295592 JP 2002-88461 A JP 2006-183107 A
  • Patent Document 1 under strong acid plating solution with a pH of less than 1, the plating solution infiltrates from the surface of the coating by continuous use, so the adhesion between the roll base material and the thermal spray coating decreases, and the coating peels off from the surface of the base material. There was a problem of falling. In fact, Patent Document 1 does not carry out in a severe environment where the pH is less than 1, and the implementation conditions are also shown only in a low current density range of 5 to 20 A / dm 2 . Since the operation period is as short as 1000 hours, it has not been implemented for a long time, such as continuous operation for one month. Furthermore, since the coating is subjected to a thermal melting treatment after spraying, there is a problem that the manufacturing cost increases.
  • Patent Document 2 Even in Patent Document 2, the plating solution infiltrates from the coating surface by continuous use under a strong acid plating solution having a pH of less than 1, so that the adhesion between the roll base material and the thermal spray coating is lowered, and the coating is peeled off from the base material surface. There was a problem of falling. Further, since the edge of the roll is acid-corroded by the plating solution, there is a problem that the yield of the product is lowered due to the fragments. In addition, it is necessary to remelt the roll after thermal spraying, and there is a problem that time and cost associated with roll regeneration including shrink fit insertion are increased.
  • Patent Document 3 Even in Patent Document 3, the plating solution infiltrates from the surface of the coating under continuous use under a strong acid plating solution having a pH of less than 1. Therefore, the adhesion between the roll base material and the thermal spray coating decreases, and the coating peels off from the base material surface. There was a problem of falling. In addition, it is necessary to remelt the roll after thermal spraying, and there is a problem that time and cost associated with roll regeneration increase. Moreover, when it is going to apply this membrane
  • Patent Document 4 Even in Patent Document 4, the plating solution infiltrates from the coating surface by continuous use under a strong acid plating solution having a pH of less than 1. Therefore, the adhesion between the roll base material and the thermal spray coating decreases, and the coating peels off from the base material surface. There was a problem of falling. Actually, in the acid corrosion test by immersion in the plating solution in Patent Document 4, the pH is 3.0, and the test under a severe environment where the pH is less than 1 is not performed. In addition, it is necessary to remelt the roll after thermal spraying, and there is a problem that time and cost associated with roll regeneration increase.
  • the characteristics of conventional conductor rolls are that carbon steel is used as the roll material, and a NiCr alloy coating layer is applied to the roll surface to prevent reaction with the plating solution of the carbon steel. It is based on forming.
  • the coating layer is characterized by containing a carbide (or cermet) mainly composed of WC for the purpose of preventing wear due to rubbing with the steel plate. As a result, it is possible to significantly reduce reaction and wear in an acidic plating bath with pH ⁇ 1, and to ensure the roll life and reduce the defect rate.
  • the conventional product with a sprayed coating on a carbon steel roll base material is damaged due to acid corrosion because the sprayed coating and the base material are damaged. It was found that non-defective products were generated and the product yield was lowered.
  • tin ions in the plating solution change into metallic tin and cause an electrodeposition on the roll surface. Although this electrodeposited metal tin also causes defective products such as pressing irons, there is a problem that the tendency becomes prominent when the conventional roll is used.
  • an object of the present invention is to provide a cermet powder capable of producing a cermet film having both high wear resistance and high corrosion resistance against a strong acid having a pH of less than 1.
  • Another object of the present invention is to provide a protective film-coated member and a roll in an electroplating bath that have both high wear resistance and high corrosion resistance against a strong acid having a pH of less than 1, together with their production methods.
  • the gist configuration of the present invention for solving the above-described problems is as follows. (1) 40% by mass or more of tungsten carbide particles, 10-40 mass% molybdenum carbide particles, Ni or Ni alloy as matrix metal, Including The cermet powder further contains 8% by mass or more of chromium as a carbide or a metal or alloy element in the matrix metal.
  • a protective coating member having a stainless steel substrate and a cermet coating formed on the stainless steel substrate The cermet film is formed by dispersing tungsten carbide particles and molybdenum carbide particles in a matrix made of Ni or Ni alloy, In the cermet film, the content of the tungsten carbide particles is 40% by mass or more, the content of the molybdenum carbide particles is 10 to 40% by mass, and further chromium as a carbide or a metal or alloy element in the matrix.
  • a protective film-coated member containing at least mass%.
  • a method for producing a protective coating-coated member comprising a step of spraying the cermet powder according to any one of (1) to (4) above onto a stainless steel substrate.
  • a roll in an electroplating bath comprising the protective film-coated member according to any one of (5) to (9) above.
  • the roll shaft and the roll body are both made of stainless steel, and only the roll body is made of the protective film-coated member according to any one of (5) to (9). A roll in an electroplating bath.
  • the cermet powder of the present invention it is possible to produce a cermet film that achieves both high wear resistance and high corrosion resistance against a strong acid having a pH of less than 1. Moreover, the protective film covering member and the roll in the electroplating bath of the present invention can achieve both high wear resistance and high corrosion resistance against strong acid having a pH of less than 1.
  • FIG. 1 is a schematic cross-sectional view of a protective film covering member 100 according to an embodiment of the present invention.
  • (A) is a schematic cross-sectional view of a conventional roll 200 in an electroplating bath
  • (B) is a schematic cross-sectional view of a roll 300 in an electroplating bath according to an embodiment of the present invention.
  • the cermet powder according to an embodiment of the present invention includes 40% by mass or more of tungsten carbide particles, 10 to 40% by mass of molybdenum carbide particles, and Ni or Ni alloy as a matrix metal, and further includes chromium as a carbide or the above-mentioned It is characterized by containing 8% by mass or more as a metal or alloy element contained in the matrix metal. According to this cermet powder, it is possible to produce a cermet film that has both high wear resistance and high corrosion resistance against strong acids with a pH of less than 1.
  • each element of the cermet powder of the present disclosure will be described.
  • Tungsten carbide particles serve to impart high wear resistance and relatively high corrosion resistance to the cermet film.
  • tungsten carbide particles include WC particles.
  • the content of tungsten carbide particles needs to be 40% by mass or more. This is because if the amount is less than 40% by mass, sufficient wear resistance of the cermet film cannot be obtained.
  • the content of the tungsten carbide particles is preferably 70% by mass or less. This is because when the content exceeds 70% by mass, the content of other components becomes small, so that high corrosion resistance against strong acid having a pH of less than 1 cannot be obtained in the cermet film.
  • the particle size range of the tungsten carbide particles is preferably in the range of 0.1 to 6 ⁇ m.
  • Molybdenum carbide particles are an important component in the present invention that plays a role of imparting not only high abrasion resistance to a cermet film but also high corrosion resistance against a strong acid having a pH of less than 1.
  • Examples of molybdenum carbide particles include Mo 2 C particles.
  • the content of molybdenum carbide particles needs to be 10 to 40% by mass. If it is less than 10% by mass, high corrosion resistance to strong acid with a pH of less than 1 cannot be obtained in the cermet film. If it exceeds 40% by mass, the content of other components, particularly tungsten carbide particles, must be reduced. This is because sufficient wear resistance of the cermet film cannot be obtained. From the viewpoint of reliably obtaining the effects of the present invention, the particle size range of the molybdenum carbide particles is preferably within the range of 0.1 to 6 ⁇ m.
  • the cermet powder of the present disclosure contains Ni or a Ni alloy as a matrix metal.
  • the Ni alloy include NiCr-based alloys, NiCrMo-based alloys, and NiCoCrAlY-based alloys containing Ni as a main component.
  • Ni as a matrix metal plays a role of imparting high corrosion resistance to a strong acid having a pH of less than 1 to the cermet film.
  • the Ni content in the cermet powder is preferably 5% by mass or more.
  • it is preferable that Ni content in a cermet powder is 20 mass% or less from the relationship with suitable content of another component.
  • the cermet powder of this indication contains 8 mass% or more of chromium as a carbide or a metal or alloy element contained in the matrix metal.
  • This chromium plays a role of imparting high corrosion resistance to a strong acid having a pH of less than 1 to the cermet film, and from this viewpoint, the content is required to be 8% by mass or more.
  • the chromium content in the cermet powder is preferably 20% by mass or less.
  • the particle size range is preferably in the range of 0.1 ⁇ 6 [mu] m.
  • the cermet powder of the present disclosure is preferably composed of the above components and inevitable impurities.
  • the molybdenum content is preferably not less than the chromium content from the viewpoint of imparting high corrosion resistance to a strong acid having a pH of less than 1 to the cermet film.
  • the production method of the cermet powder of the present disclosure is not particularly limited, and can be produced by a known or arbitrary method such as a melt pulverization method, a sintering pulverization method, or a granulation sintering method.
  • a protective film covering member 100 includes a stainless steel base material 10 and a cermet film 20 formed on the stainless steel base material.
  • the cermet film 20 is formed by spraying the cermet powder of the present disclosure on the base material 10 as a thermal spray material.
  • the cermet film 20 is in a state in which tungsten carbide particles and molybdenum carbide particles, and optionally carbide particles 24 containing chromium carbide are dispersed in a matrix 22 made of Ni or Ni alloy.
  • a roll in an electroplating bath includes the protective film covering member 100.
  • Such a protective coating-coated member and roll in an electroplating bath of the present disclosure can achieve both high wear resistance and high corrosion resistance against strong acid having a pH of less than 1.
  • the cermet powder of the present disclosure is provided only on the roll body 32 of a roll member in which the roll shaft 30 and the roll body 32 are both made of stainless steel. It is preferable to produce the roll 300 in the electroplating bath by spraying the cermet film 34 to form the cermet film 34.
  • the protective film covering member of the present disclosure and the manufacturing method thereof, and the roll in the electroplating bath and the manufacturing method thereof have been completed based on the following knowledge of the present inventors.
  • the reactions of the above formulas (1) and (2) are electrochemically equivalent, and the total amount of electrons (e ⁇ ) generated in the anode reaction is equal to the total amount of electrons consumed in the cathode reaction.
  • the dissolution reaction proceeds at a portion where the potential is locally increased (anode), and at the portion where the potential is locally decreased (cathode).
  • the analysis reaction proceeds.
  • the sites where these reactions occur can be considered to be uniformly distributed microscopically when the corrosion potential when the roll is immersed in the liquid is relatively high, and the corrosion is evenly distributed over the entire surface. As a result, the surface morphology can maintain the initial good state. However, under conditions where the plating solution is a strong acid with pH ⁇ 1 or the plating current density is set too high, the site where the cathodic or anodic reaction occurs is fixed locally and the reaction proceeds. There are things to do. In such a case, the surface form changes greatly as described below, which may damage the plated product.
  • the reaction tends to concentrate at the site where the precipitation first occurs and grow as a metal.
  • the grown metal deposit grows up to a certain size and then falls off due to a load such as rubbing with the steel plate, and the portion where the cathode reaction concentrates moves to another place.
  • the plating metal such as Sn is deposited on the surface non-uniformly.
  • the dropped pieces of the plating metal may damage the surface of the product steel plate.
  • the corrosion potential is relatively lowered in a strong acid plating bath where the pH is ⁇ 1 or when the current density is excessively high, and the microscopic uniformity of the anode and cathode distributions. Due to the destruction, the above-mentioned plating metal adheres and falls and the roll surface is partially broken due to local fixation, and as a result, the product yield may be lowered.
  • the reaction is simply performed. It is necessary to find a material that can prevent the phenomenon in which the reaction is concentrated as a result of locally fixing the site where the cathode reaction or the anode reaction proceeds as described above, without paying attention only to the amount. On the other hand, if such a material is used, it is possible to prevent the progress of the local corrosion as described above, and to secure the roll life and the product yield.
  • reaction layer on the surface could be easily removed by washing with water and chemical washing, and precipitation of metal Sn could not be confirmed on the removed surface.
  • corrosion potential at the time when 20 days passed after immersion was compared, it was found that stainless steel has a higher potential of 0.1 V or more than carbon steel and maintains a potential noble state.
  • a sample was prepared by using stainless steel as a base material and coating the surface with a dozen types of carbide cermet powders for thermal spraying, including those commercially available, by the HVOF thermal spraying method. Immersion experiments were performed. As a result, it has been found that Ni or NiCr-based alloys are excellent for the cermet matrix, and that when the carbide contains Mo carbide rather than WC particles alone, good corrosion resistance can be obtained.
  • Cr is desirably contained in an amount of 8% by mass or more as a carbide or alloy element of the matrix, and the content of Mo contained as a carbide is It has been found that it is desirable that the content is at least equivalent to the Cr content. Moreover, Mo 2 C is preferable as the Mo carbide, and even if the Mo content in the cermet is higher than the Cr content, the corrosion resistance is not impaired, but conversely the Mo content is higher than the Cr content. It has been found that desirable corrosion resistance is difficult to obtain when the amount is less than half.
  • Ni or Ni Tungsten carbide particles and molybdenum carbide particles are dispersed in a matrix made of an alloy.
  • the content of tungsten carbide particles is 40% by mass or more, and the content of molybdenum carbide particles is 10 to 40% by mass.
  • the matrix mainly composed of Ni good results were obtained with NiCr alloys, NiCrMo alloys, and NiCoCrAlY alloys.
  • adjusting the particle size of the tungsten carbide particles and molybdenum carbide particles, which are the main components of the cermet is important as a method for achieving both wear resistance and corrosion resistance in a trade-off relationship. That is, if a carbide having a particle size of less than 0.1 ⁇ m is used for the carbide which is the main component of cermet, the wear resistance is remarkably lowered, and if a particle having a particle size of 6 ⁇ m or more is used, the anode and cathode in the solution are used. There was a tendency that the microscopic uniformity of the distribution was not sufficiently maintained. It was confirmed that both wear resistance and corrosion resistance can be achieved when the particle sizes of tungsten carbide particles and molybdenum carbide particles are in the range of 0.1 to 6 ⁇ m.
  • high-speed flame spraying methods such as HVOF and HVAF are desirable as a method for forming the protective film.
  • high-speed flame spraying methods such as HVOF and HVAF
  • cermet coatings obtained by plasma spraying and other thermal spraying methods the porosity is greatly different, and high-speed HVOF, HVAF, etc.
  • a coating obtained by a thermal spraying method other than the flame it was difficult to maintain a good surface state because the solution penetrated into the coating.
  • the carbides are decarburized to form lower carbides or form a reaction phase with the matrix component, and the wear resistance and corrosion resistance are remarkably high. It will decline. Such a tendency was also confirmed in a coating formed by welding overlay or cladding. That is, as a method for forming the carbide cermet film, a high-speed flame spraying method such as HVOF or HVAF is desirable.
  • the surface roughness Ra of the carbide cermet film is preferably 0.5 to 10 ⁇ m.
  • Example 1 Samples of conventional roll specifications and roll specifications according to the present invention were prepared and immersed for 20 days in a strong acid plating solution (methanesulfonic acid 50 g / L, tin ion concentration 25 g / L) adjusted to pH ⁇ 1 A test was conducted. Five types of samples shown in Table 1 were produced. That is, No. 1 is a conventional carbon steel base material, and the protective film is also a conventional sample. On the other hand, in the samples Nos. 2 to 5, the base material was stainless steel. As for the protective coating, No. 2 uses the same conventional coating as No. 1, and No. 3 to No. 5 use HVOF coatings of various carbide cermets with Ni or Ni-based alloys as a matrix. No.
  • the Mo content is 9.4% by mass
  • the Cr content is 8.7% by mass
  • the WC particles have a minimum particle size of 0.1 ⁇ m and a maximum of 6 ⁇ m
  • the Mo 2 C particles have a minimum particle size of 0.1 ⁇ m.
  • the maximum was 6 ⁇ m
  • the surface roughness Ra was 3.0 ⁇ m.
  • Example 2 Paying attention to the compounding ratio of the protective film of No. 5 specification shown in Example 1, WC particles containing Ni or Ni-20Cr alloy as a matrix and having a particle size adjusted to a range of 0.1 to 6 ⁇ m, Cr 3 C 2 Various cermet powders containing particles and Mo 2 C particles were prepared. The cermet powder obtained on stainless steel was HVOF sprayed to form a protective coating. Table 2 shows the film composition of each sample. While performing the immersion test similar to Example 1, the Suga abrasion test was implemented. The evaluation results are shown in Table 2.
  • the porosity is high, and the influence of the alteration of the carbide is strong, and regarding corrosion resistance and wear resistance, The properties as good as those of the coating prepared by HVOF spraying were not obtained.
  • Example 3 An example in which a conventional product and the present invention product are applied to a conductor roll of an electroplating line will be described.
  • 2A and 2B show a comparison between the structure of a conventional roll and the structure of a roll according to the present invention.
  • a carbon steel sleeve is formed by heat-spraying a carbon steel sleeve while a carbon steel tube is heat-fitted to a copper shaft core to form a shaft portion.
  • the body part was configured by shrink fitting to the part, and these were combined to form a roll body.
  • FIG. 2 (B) it is only necessary to form a thermal spray coating on the roll body made of stainless steel, and it can be seen that the production of the roll body is extremely easy.
  • the specification of the film according to the present invention was No. 6 in Example 2.
  • the failure rate of the products obtained using each roll was as high as 2.37% with the conventional roll, whereas the roll of the present invention succeeded in reducing it to 0.43% with 1/5 or less. This is presumably because the rate of occurrence of coating damage and coarse electrodeposited Sn debris, which are the cause of pressing creases, was significantly reduced by improving corrosion resistance.
  • the roll usage limit is about Ra 0.5 ⁇ m surface roughness, and if the initial surface roughness exceeds Ra 10 ⁇ m, the frequency of generating scratches on the product increases. ing. Accordingly, the surface roughness of the cermet film according to the present invention is preferably Ra 0.5 to 10 ⁇ m.
  • the cermet powder of the present invention can be suitably used as a material for a protective coating (cermet coating) on a protective coating covering member such as a roll in an electroplating bath.
  • the roll in the electroplating bath of the present invention can be suitably used, for example, as a conductor roll in a strong acid electroplating bath having a pH of less than 1.
  • Base material stainless steel
  • Cermet coating Matrix
  • Carbide particles WC particles, Mo 2 C particles, optionally Cr 3 C 2 particles
  • Roll shaft part 32
  • Roll body part 34
  • Cermet coating thermo spray coating

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PCT/JP2017/005385 2016-02-19 2017-02-14 サーメット粉末、保護皮膜被覆部材及びその製造方法、並びに電気めっき浴中ロール及びその製造方法 WO2017141925A1 (ja)

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MYPI2018702770A MY186906A (en) 2016-02-19 2017-02-14 Cermet powder, protective-coating-coated member and method of producing same, and electroplating-bath-immersed roll and method of producing same
KR1020187026279A KR102177464B1 (ko) 2016-02-19 2017-02-14 서멧 분말, 보호 피막 피복 부재 및 그 제조 방법과 전기 도금욕중 롤 및 그 제조 방법
EP17753182.9A EP3418421B1 (en) 2016-02-19 2017-02-14 Cermet powder, protective film-coated member and method for producing same
CN201780011768.0A CN108699667B (zh) 2016-02-19 2017-02-14 金属陶瓷粉末、保护被膜被覆部件及其制造方法以及电镀浴中辊及其制造方法
JP2017529403A JP6232524B1 (ja) 2016-02-19 2017-02-14 サーメット粉末、保護皮膜被覆部材及びその製造方法、並びに電気めっき浴中ロール及びその製造方法
US16/077,169 US20190032239A1 (en) 2016-02-19 2017-02-14 Cermet powder, protective-coating-coated member and method of producing same, and electroplating-bath-immersed roll and method of producing same
CONC2018/0009602A CO2018009602A2 (es) 2016-02-19 2018-09-13 Polvo cermet, miembro revestido con un recubrimiento protector y método de producirlos, y cilindro de inmersión en un baño electrolítico y método de producirlo

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