EP3418421B1 - Cermet powder, protective film-coated member and method for producing same - Google Patents

Cermet powder, protective film-coated member and method for producing same Download PDF

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Publication number
EP3418421B1
EP3418421B1 EP17753182.9A EP17753182A EP3418421B1 EP 3418421 B1 EP3418421 B1 EP 3418421B1 EP 17753182 A EP17753182 A EP 17753182A EP 3418421 B1 EP3418421 B1 EP 3418421B1
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EP
European Patent Office
Prior art keywords
coating
mass
roll
cermet
protective
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EP17753182.9A
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German (de)
English (en)
French (fr)
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EP3418421A1 (en
EP3418421A4 (en
Inventor
Yuya Baba
Junichi Takeuchi
Yoshifumi Kobayashi
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JFE Steel Corp
Tocalo Co Ltd
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JFE Steel Corp
Tocalo Co Ltd
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Publication of EP3418421A1 publication Critical patent/EP3418421A1/en
Publication of EP3418421A4 publication Critical patent/EP3418421A4/en
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    • 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
    • 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
    • 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
    • C23C4/134—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
    • 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
    • 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
    • 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 disclosure relates to a cermet powder, a protective-coating-coated member and a method of producing the same, and an electroplating-bath-immersed roll.
  • JPH1198460A (PTL 1) describes a method in which plasma arc spraying is performed on a surface of a carbon steel roll using as a thermal spraying material an alloy containing Co or Ni as a main component and an additive of Cr, C, Fe, Mo, or the like under a low-pressure oxygen-free atmosphere, and the coating is then subjected to a hot melt treatment by plasma arc heating under the same atmosphere to form a nonporous thermal sprayed coating.
  • JPH5295592A (PTL 2) describes a method in which a thermal-spray coated layer is formed by thermal spraying a mixed powder composed of a carbide cermet powder and a C-containing nickel chromium alloy powder on the surface of a carbon-steel roll body portion, then causing redeposition of carbide by heating the thermal spray coating layer to form a redeposited-carbide-dispersed thermal sprayed coating, and subsequently shrink-fitting the roll body portion to the outside of the roll base member.
  • JP200288461A (PTL 3) describes a method of producing a conductor roll having enhanced corrosion resistance, in which a mixed powder composed of WC-Ni cermet and the balance consisting of a Ni-base self-fluxing alloy is thermal sprayed on the surface of a SS-400 roll, and thereafter a remelting treatment is carried out to form a coating layer.
  • JP2006183107A (PTL 4) describes a method of producing a conductor roll, in which a self-fluxing alloy thermal sprayed layer containing WC cermet is formed on the surface of a SS-400 roll and a WC cermet coating is further formed thereon.
  • PTL 5 describes a piston ring comprising a thermal spray coating that contains tungsten carbide and chrome carbide as a hard phase, and contains nickel as a metallic binder phase, wherein the thermal spray coating is formed by the spraying of a thermal spray powder that has been produced by means of a granulation sintering method, and that contains hard particles in which the mean particle diameter of the tungsten carbide has been adjusted by means of a BET method to fall within a range of not less than 0.15 ⁇ m and not more than 0.45 ⁇ m.
  • the thermal spray coating may have a composition that contains 7.0 wt% of nickel as the metallic binder phase, and 20 wt% of chromium carbide as the hard phase, and in which the remainder is made up of tungsten carbide as a hard phase and inevitable impurities.
  • PTL 6 describes a low binder, wear resistant material comprised of, in weight percent of raw materials, from about 15 to about 20 % of molybdenum carbide added in either elemental or compound form; an alloy of about 0.9 to about 3 % of cobalt, nickel or a combination of cobalt and nickel; of about 0 to about 0.1 % of chromium carbide and the balance of tungsten carbide.
  • PTL 7 describes a thermal sprayed coating of a jig for producing a glass sheet, to be used for a jig for producing glass to be in contact with a glass sheet at a temperature of at least the strain point, which comprises tungsten carbide, at least one metal carbide selected from the group consisting of titanium carbide, zirconium carbide, hafnium carbide, niobium carbide, tantalum carbide, chromium carbide and molybdenum carbide, a metal containing N, and inevitable impurities.
  • a plating solution of a strong acid having a pH of less than 1 has the problem that the plating solution infiltrates from the surface of the coating after continuous use, causing the adhesion between the roll substrate and the thermal sprayed coating to decrease and the coating to peel off from the surface of the substrate.
  • the technique of PTL 1 is not implemented under severe circumstances such as a pH below 1, in which the implementation conditions are only demonstrated in the current density range as low as 5 A/dm 2 to 20 A/dm 2 , and the operation period is as short as 1,000 hours. This means that the technique of PTL 1 fails to address a long-term operation, such as one month continuous operation.
  • the thermal melting treatment of the coating is performed after thermal spraying, there is a problem of increased manufacturing cost.
  • a plating solution of a strong acid having a pH of less than 1 has the problem that the plating solution infiltrates from the surface of the coating after continuous use, causing the adhesion between the roll substrate and the thermal sprayed coating to decrease and the coating to peel off from the surface of the substrate.
  • the edge of the roll is acid corroded by the plating solution, leading to the problem of fragments lowering the product yield. It is also necessary to carry out remelting treatment on the roll after thermal spraying, causing a problem that the time and cost associated with roll regeneration including shrink-fitting are increased.
  • a plating solution of a strong acid having a pH of less than 1 has the problem that the plating solution infiltrates from the surface of the coating after continuous use, causing the adhesion between the roll substrate and the thermal sprayed coating to decrease and the coating to peel off from the surface of the substrate. It is also necessary to carry out remelting treatment on the roll after thermal spraying, causing a problem that the time and cost associated with roll regeneration are increased. In addition, when applying this coating to a stainless steel roll, the remelting treatment causes cracking at the crystal grain boundary due to heating of the stainless steel, and the roll is damaged. For this reason, carbon steel having low corrosion resistance has to be used, leading to the problem of fragments of acid-corroded carbon steel lowering the product yield.
  • a plating solution of a strong acid having a pH of less than 1 has the problem that the plating solution infiltrates from the surface of the coating after continuous use, causing the adhesion between the roll substrate and the thermal sprayed coating to decrease and the coating to peel off from the surface of the substrate.
  • the pH is 3.0, and no test was conducted under severe environments such as a pH below 1. It is also necessary to carry out remelting treatment on the roll after thermal spraying, causing a problem that the time and cost associated with roll regeneration are increased.
  • the conventional conductor rolls are primarily characterized in that carbon steel is used as the roll material, and for the purpose of preventing reaction of the carbon steel with the plating solution, a coated layer of a NiCr-based alloy is formed on the roll surface.
  • This coated layer is characterized by containing a carbide (or cermet) mainly composed of WC for the purpose of preventing wear due to rubbing against a steel sheet. This may greatly reduce reaction and wear in an acidic plating bath of pH ⁇ 1, secure the roll life, and reduce the defective rate.
  • cermet powder that enables preparation of a cermet coating having both high wear resistance and high corrosion resistance against a strong acid having a pH of less than 1. It would also be helpful to provide a protective-coating-coated member and an electroplating-bath-immersed roll that are compatible with high wear resistance and high corrosion resistance against a strong acid having a pH of less than 1, as well as their production methods.
  • the protective-coating-coated member and the electroplating-bath-immersed roll of the present disclosure can achieve both high wear resistance and high corrosion resistance against a strong acid having a pH of less than 1.
  • a cermet powder according to one of the embodiments of the present disclosure consists of: tungsten carbide particles in an amount of 40 mass% to 70 mass%; molybdenum carbide particles in an amount of 10 mass% to 40 mass%; Ni or a Ni alloy as a matrix metal; and chromium either as a carbide or a metal or alloy element in the matrix, in an amount of 8 mass% to 20 mass%, wherein the content of Ni is 5 mass% to 20 mass%, and the content of molybdenum is not less than the content of chromium.
  • this cermet powder it is possible to produce a cermet coating that offers both high wear resistance and high corrosion resistance against a strong acid having a pH of less than 1.
  • Each component of the cermet powder of the present disclosure will be described below.
  • the tungsten carbide particles serve to impart high wear resistance and relatively high corrosion resistance to the cermet coating.
  • the tungsten carbide particles include for example WC particles.
  • the content of the tungsten carbide particles needs to be 40 mass% or more. The reason is that if it is less than 40 mass%, the cermet coating cannot provide sufficient wear resistance.
  • the content of the tungsten carbide particles is 70 mass% or less. The reason is that if it exceeds 70 mass%, the content of the other components becomes so small that the cermet coating cannot provide high corrosion resistance against a strong acid having a pH of less than 1.
  • the tungsten carbide particles preferably have a particle size distribution within a range of 0.1 ⁇ m to 6 ⁇ m.
  • the molybdenum carbide particles are important components in the present disclosure, which plays a role of imparting to the cermet coating not only high wear resistance but also high corrosion resistance to a strong acid having a pH of less than 1.
  • the molybdenum carbide particles include for example Mo 2 C particles.
  • the content of the molybdenum carbide particles needs to be 10 mass% to 40 mass%. The reason is that if the content is less than 10 mass%, the cermet coating cannot provide high corrosion resistance against a strong acid having a pH of less than 1, and if it exceeds 40 mass%, the content of the other components, in particular, tungsten carbide particles, must be reduced, resulting in insufficient wear resistance of the cermet coating.
  • the molybdenum carbide particles preferably have a particle size distribution within a range of of 0.1 ⁇ m to 6 ⁇ m.
  • the cermet powder of the present disclosure contains Ni or a Ni alloy as a matrix metal.
  • the Ni alloy include a NiCr-based alloy, a NiCrMo-based alloy, and a NiCoCrAlY-based alloy, containing Ni as a main component.
  • Ni as a matrix metal plays a role of imparting to the cermet coating high corrosion resistance to a strong acid having a pH of less than 1. From this viewpoint, the Ni content in the cermet powder is 5 mass% or more. Further, in view of the preferable content of the other components, the Ni content in the cermet powder is 20 mass% or less.
  • the cermet powder of the present disclosure contains chromium, either as a carbide or a metal or alloy element contained in the matrix metal, in an amount of 8 mass% or more.
  • This chromium plays a role of imparting to the cermet coating high corrosion resistance to a strong acid having a pH of less than 1, and from that viewpoint its content needs to be 8 mass% or more.
  • the content of chromium in the cermet powder is 20 mass% or less.
  • the particle size distribution thereof is preferably within a range of 0.1 ⁇ m to 6 ⁇ m.
  • the cermet powder of the present disclosure consists of the above components and inevitable impurities.
  • the molybdenum content is not less than the chromium content from the viewpoint of imparting to the cermet coating high corrosion resistance to a strong acid having a pH of less than 1.
  • the cermet powder of the present disclosure its production method is not particularly limited, and it 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-coating-coated member 100 comprises: a stainless steel base member 10; and a cermet coating 20 formed on the stainless steel base member.
  • the cermet coating 20 is formed by thermal spraying the cermet powder of the present disclosure as the thermal spray material onto the stainless steel base member 10. Consequently, in the cermet coating 20, carbide particles 24 containing tungsten carbide particles and molybdenum carbide particles, and optionally chromium carbide, are dispersed in a matrix 22 made of Ni or a Ni alloy.
  • an electroplating-bath-immersed roll according to an embodiment of the present disclosure comprises the protective-coating-coated member 100.
  • the protective-coating-coated member and the electroplating-bath-immersed roll thus formed according to the present disclosure can achieve both high wear resistance and high corrosion resistance against a strong acid having a pH of less than 1.
  • a roll member comprising a roll shaft portion 30 and a roll body portion 32, both made of stainless steel, is prepared, and a cermet coating 34 is formed only onto the roll body portion by thermal spraying the cermet powder disclosed herein to thereby produce a electroplating-bath-immersed roll 300.
  • the protective-coating-coated member of the present disclosure and the method of producing the same, and the electroplating-bath-immersed roll and the method of producing the same were completed based on our discoveries as described below.
  • the reactions of 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 increases locally (i.e., anode), while the electrodeposition reaction proceeds at a portion where the potential lowers locally (i.e., cathode).
  • the sites where these reactions take place can be regarded as being uniformly distributed in microscopic scales, and the corrosion uniformly proceeds over the entire surface. Consequently, the surface morphology can maintain an initial good state.
  • the plating solution is a strong acid with pH ⁇ 1 or the current density of plating is set excessively high, the reaction may proceed as a result of a cathode or anode reaction taking place in a locally fixed site. In such a case, the surface morphology changes greatly as described below, which may damage the plated product.
  • the reaction tends to concentrate at the site where deposition is initially generated, causing a metal to grow. Then, the grown metal deposit grows to a certain size, then falls off due to a load of, for example, rubbing against the steel sheet, and the site where the cathode reaction concentrates shifts to another place.
  • deposition of a plating metal such as Sn progresses non-uniformly on the surface, and at the same time fragments of the plating metal that fall off may damage the surface of the steel sheet as a product.
  • the reaction concentrates as a result of the anode reaction being fixed at a certain site, a particular element (such as Fe in the roll) constituting the site is selectively dissolved at the grain boundary or the like, which may cause the roll surface or the coated layer to partially fall off as fragments. These fragments that have fallen off from the surface may damage the surface of the steel sheet as a product.
  • a particular element such as Fe in the roll
  • the corrosion potential relatively decreases in a strong acid plating bath with pH ⁇ 1 or when the current density is excessively high, and the microscopic uniformity of the distribution of the anode and the cathode is reduced, adhesion/detachment of the plating metal and partial damage in the roll surface become conspicuous as a result of localized immobilization, and this may be the cause of decrease in the product yield.
  • reaction layer on the surface could be easily removed by washing with water and chemical washing, and deposition of metallic Sn on the removed surface was not observed.
  • the corrosion potentials at the time when 20 days passed after immersion were compared. As a result, it was found that stainless steel had a potential higher than that of carbon steel by 0.1 V or more, and maintained a potentially noble state.
  • carbide cermets are promising as such a material, it is known that good properties cannot be obtained with the ones described in PTLs 1 to 4. However, we determined that these carbide cermets may be able to improve the electrochemical characteristics in a strong acid plating bath by adjusting the components, and engaged in further studies.
  • samples were prepared by coating the surface of stainless steel as a base member with more than ten kinds of carbide cermet powders for thermal spraying including commercially available ones by HVOF thermal spraying, and immersion experiments were conducted using a strong acid plating solution with pH ⁇ 1.0.
  • the experimental results revealed that Ni or a NiCr-based alloy is superior for the matrix of the cermet, and when the carbide contains Mo carbide rather than WC particles alone, good corrosion resistance can be obtained.
  • carbide particles containing tungsten carbide particles and molybdenum carbide particles are dispersed in a matrix made of Ni or a Ni alloy, wherein the cermet coating contains the tungsten carbide particles in an amount of 40 mass% or more, the molybdenum carbide particles in an amount of 10 mass% to 40 mass%, and chromium either as a carbide or a metal or alloy element contained in the matrix, in an amount of 8 mass% or more.
  • a matrix containing Ni as a main component good results were obtained with a NiCr-based alloy, a NiCrMo-based alloy, and a NiCoCrA1Y-based alloy.
  • Specimens were prepared with a carbide cermet coating satisfying the above conditions being formed on stainless steel by HVOF thermal spraying to form a protective coating, and were subjected to constant-current anode/cathode polarization dissolution experiments.
  • the experimental results demonstrated that the formation of a reaction layer was not significant and the surface morphology was still better than the stainless steel.
  • a potential higher by about 0.1 V than that of the stainless steel was obtained.
  • the above results indicate that the uniformity of the distribution of the anode and the cathode formed on the surface of the above-described carbide cermet coating formed by HVOF thermal spraying is achieved at a finer level than that of stainless steel. It was thus found that there is almost no possibility of the steel sheet being damaged by the reaction product. In this way, we discovered that a protective layer having good corrosion resistance can be formed even in a strong acid plating bath, while having excellent wear resistance.
  • a high-velocity flame spraying method such as HVOF or HVAF was found to be desirable.
  • HVOF or HVAF a high-velocity flame spraying method
  • the porosity greatly differs, and in the case of a layer obtained by a thermal spraying method other than the high-velocity flame spraying method such as HVOF or HVAF, it was difficult to maintain a satisfactory surface condition; for example, the solution infiltrated into the layer.
  • the carbide when heat treatment is performed on the resulting layer at a high temperature for the purpose of lowering the porosity, the carbide is decarburized into lower carbide or a reaction phase forms with the matrix components, causing a remarkable degradation in wear resistance and corrosion resistance.
  • a high-velocity flame spraying method such as HVOF or HVAF is preferable as the method of forming a carbide cermet coating.
  • the surface roughness Ra of the carbide cermet coating is preferably 0.5 ⁇ m to 10 ⁇ m.
  • Samples were prepared in conformity with conventional roll specifications and roll specifications according to the present disclosure, and subjected to immersion tests for 20 days in a strong-acid plating solution (methanesulfonic acid 50g/L, tin ion concentration 25 g/L) adjusted to pH ⁇ 1.
  • a strong-acid plating solution methanesulfonic acid 50g/L, tin ion concentration 25 g/L
  • Five samples listed in Table 1 were prepared. Specifically, in Sample No. 1, the base member was a conventional carbon steel and the protective layer was also a conventional sample. On the other hand, in Sample Nos. 2 to 5, the base member was made of stainless steel. Regarding the protective layers, Sample No. 2 adopted a conventional layer as in Sample No. 1, and Sample Nos. 3 to 5 used HVOF layers of various carbide cermets using Ni or a Ni base alloy as the matrix; among these, Sample No.
  • the Mo content was 9.4 mass%
  • the Cr content was 8.7 mass%
  • the WC particle size was 0.1 ⁇ m minimum and 6 ⁇ m maximum
  • the particle size of Mo 2 C particles was 0.1 ⁇ m minimum and 6 ⁇ m maximum
  • the surface roughness Ra was 3.0 ⁇ m.
  • Table 1 lists the results of observation of the surface conditions of the protective layer with the electron microscope after immersion for 20 days, as well as the measurements of the corrosion potential. Table 1 also lists the results of Suga wear tests (#120-SiC paper, load 3.25 kgf, 400 reciprocations) separately performed on the protective layers. The layer observation results were evaluated according to the following criteria: Excellent: almost no change Good: slightly changed Fair: changed Poor: significantly changed Table 1 Sample No. Base Member Coating components Coating observation results Corrosion potential (V vs.
  • FIGS. 2A and 2B illustrate a comparison between the structure of a conventional roll and the structure of a roll according to the present disclosure.
  • a shaft portion was formed by shrink-fitting a carbon steel tube to a copper shaft core
  • a body portion was formed by shrink-fitting a carbon steel sleeve with a protective layer formed thereon by thermal spraying to a roll body portion formed of a carbon steel tube, and these were combined to form a whole roll body.
  • FIG. 2B it is only necessary to form a thermal sprayed coating on the roll body made of stainless steel, and it will be readily appreciated that the roll body can be extremely easily fabricated.
  • Sample No. 6 in Example 2 was adopted as the layer specification according to the present disclosure.
  • Heat generation by energization of each roll was measured with a thermoviewer, and both were determined to be within the range of 0.14 °C/min to 0.16 °C/min, in which operability is not impaired.
  • the composition of the plating bath was the same as in Example 1.
  • the roll pressing pressure on the steel sheet was 0.2 MPa and the sheet passing speed was in the range of 150 m/min to 490 m/min.
  • Each roll was used for 230 days. After completion of use, each roll was pulled up from the bath, and the surface roughness of the sheet passing portion and the amount of Sn adhesion were investigated. The results are presented in Table 3.
  • Table 3 Conventional product Our product Ra before use 3.0 ⁇ m 3.0 ⁇ m Ra after use 0.81 ⁇ m 1.08 ⁇ m Tin adhesion to roll surface 5.2 mass% 4.7 mass% Failure rate 2.37 % 0.43 %
  • the failure rate of the product was successfully lowered to 0.43 %, which is 1/5 or less, in the case of using rolls of the present disclosure, while it was as high as 2.37 % in the case of using conventional rolls.
  • the reason is considered to be that due to the improvement of corrosion resistance, the damage in the layer which would be the cause of defect and the occurrence rate of coarsen fragments of the electrodeposited Sn were greatly reduced.
  • the use limit of rolls was up to Ra of 0.5 ⁇ m in surface roughness, and that the frequency at which the product suffers scratches increased with a roll having an initial surface roughness Ra exceeding 10 ⁇ m. Therefore, the surface roughness Ra of the cermet coating according to the present disclosure is preferably from 0.5 ⁇ m to 10 ⁇ m.
  • the cermet powder of the present disclosure can be suitably used as the material of a protective layer (cermet coating) in a protective-coating-coated member such as an electroplating-bath-immersed roll.
  • a protective-coating-coated member such as an electroplating-bath-immersed roll.
  • the electroplating-bath-immersed roll of the present disclosure can be suitably used, for example, as a conductor roll or the like even in an electroplating bath of a strong acid having a pH of less than 1.

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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
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EP17753182.9A 2016-02-19 2017-02-14 Cermet powder, protective film-coated member and method for producing same Active EP3418421B1 (en)

Applications Claiming Priority (2)

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JP2016030368 2016-02-19
PCT/JP2017/005385 WO2017141925A1 (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

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CN109536871A (zh) * 2018-11-27 2019-03-29 广东省新材料研究所 锂电池极片生产中的传输辊的制造方法
CN110724983B (zh) * 2019-10-12 2022-02-08 天津大学 一种利用脉冲电沉积法制备纳米铜包覆碳化钨核壳结构粉体的方法
WO2021087133A1 (en) * 2019-11-01 2021-05-06 Exxonmobil Chemical Patents Inc. Bimetallic materials comprising cermets with improved metal dusting corrosion and abrasion/erosion resistance
CN117105673B (zh) * 2023-10-24 2023-12-29 内蒙古工业大学 一种氮化铝复相陶瓷及其制备方法

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US20190032239A1 (en) 2019-01-31
JPWO2017141925A1 (ja) 2018-02-22
EP3418421A1 (en) 2018-12-26
WO2017141925A1 (ja) 2017-08-24
CO2018009602A2 (es) 2018-09-28
CN108699667A (zh) 2018-10-23
TW201734223A (zh) 2017-10-01
JP6232524B1 (ja) 2017-11-15
CN108699667B (zh) 2021-06-15
KR20180110110A (ko) 2018-10-08
MY186906A (en) 2021-08-26
TWI623624B (zh) 2018-05-11
EP3418421A4 (en) 2018-12-26
KR102177464B1 (ko) 2020-11-11

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