WO2021060005A1 - Matériau en poudre à pulvériser et procédé de fabrication de film pulvérisé - Google Patents

Matériau en poudre à pulvériser et procédé de fabrication de film pulvérisé Download PDF

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Publication number
WO2021060005A1
WO2021060005A1 PCT/JP2020/034374 JP2020034374W WO2021060005A1 WO 2021060005 A1 WO2021060005 A1 WO 2021060005A1 JP 2020034374 W JP2020034374 W JP 2020034374W WO 2021060005 A1 WO2021060005 A1 WO 2021060005A1
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Prior art keywords
particles
powder material
thermal
spraying
volume
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PCT/JP2020/034374
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English (en)
Japanese (ja)
Inventor
芙美 篠田
伸映 加藤
博之 伊部
和人 佐藤
拓弥 諌山
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株式会社フジミインコーポレーテッド
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Publication of WO2021060005A1 publication Critical patent/WO2021060005A1/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
    • 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
    • C23C4/18—After-treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C7/00—Features, components parts, details or accessories, not provided for in, or of interest apart form groups F02C1/00 - F02C6/00; Air intakes for jet-propulsion plants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C7/00—Features, components parts, details or accessories, not provided for in, or of interest apart form groups F02C1/00 - F02C6/00; Air intakes for jet-propulsion plants
    • F02C7/24—Heat or noise insulation

Definitions

  • the present invention relates to a thermal spraying powder material and a method for producing a thermal spray coating using the same. More specifically, the present invention is for thermal spraying capable of forming a thermal spray coating having both extremely high abrasion resistance and low thermal conductivity as compared with conventional products in a thermal spray coating of a heat resistant material used in a high temperature environment.
  • the present invention relates to a powder material and a thermal spray coating using the powder material.
  • heat-resistant members are coated with a heat-shielding coating to protect them from high temperatures.
  • the coating film is, for example, laminated with an undercoat layer and a topcoat layer above the undercoat layer, and the topcoat layer is a porous structure having many pores in order to reduce the thermal conductivity of the coating film.
  • thermal spraying is one of the surface modification techniques that have been put into practical use together with the physical vapor deposition method and the chemical vapor deposition method.
  • thermal spraying there are no restrictions on the size of the base material, a uniform sprayed coating can be formed even on a base material over a wide area, the film formation speed is high, on-site construction is easy, and it is relatively easy. Since it has features such as the ability to form a thick film, its application has expanded to various industries in recent years, and it has become an extremely important surface modification technology.
  • Patent Document 1 a thermal spray material composed of a mixed powder of a ceramic powder and a resin powder is sprayed onto an undercoat layer to form a topcoat layer, and then heat treatment is performed to vaporize the resin powder in the topcoat layer. A method of forming pores in the topcoat layer has been proposed.
  • an object of the present invention is to provide a thermal spraying powder material for forming a thermal spray coating having both low thermal conductivity and high abrasion resistance, and a method for producing a thermal spray coating using the same.
  • the present invention is a powder material for thermal spraying, which includes composite particles formed by coating the surface of resin particles with ceramic particles, and the content of the resin particles is 10% by volume or more.
  • a powder material for thermal spraying having a volume of 50% by volume or less.
  • a uniform porous structure can be formed in the topcoat layer, whereby a thermal spray coating having both low thermal conductivity and high abrasion resistance can be obtained. Can be formed.
  • FIG. 1A is a scanning electron microscope (SEM) photograph of ceramic (YSZ) particles having a Dv of 50% of 3 ⁇ m, (b) of ceramic (YSZ) particles having a Dv of 50% of 33 ⁇ m, and (c) of resin (PE) particles.
  • FIG. 2A shows composite particles constituting the thermal spraying powder material of the present invention
  • FIG. 2B shows mixed particles of ceramic (YSZ) particles and resin (PE) particles constituting the conventional thermal spraying powder material.
  • c) shows a scanning electron microscope (SEM) photograph of a cross section of the composite particles constituting the thermal spray powder material of the present invention.
  • SEM scanning electron microscope
  • SEM scanning electron microscope
  • One embodiment of the present invention is a powder material for thermal spraying, which comprises composite particles formed by coating the surface of resin particles with ceramic particles, and the content of the resin particles is 10% by volume or more and 50% by volume or less. A certain spraying powder material is provided.
  • ceramic particles and resin powder are mixed at a predetermined ratio, and the slurry is prepared by dispersing the mixed powder and an appropriate amount of binder resin in a solvent such as a mixed solution of water and alcohol. ..
  • the prepared slurry is granulated into droplets using a granulator such as a spray granulator and then dried. Thereby, composite particles in which the resin particles are coated with the ceramic particles can be obtained.
  • the type of ceramic that forms the ceramic particles is not particularly limited, and is ittium oxide (Y 2 O 3 ), aluminum oxide (Al 2 O 3 ), silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), and oxidation.
  • a metal oxide such as zirconium (ZrO 2 ) can be preferably used, but zirconia oxide (zirconia) is preferable.
  • yttria (Y 2 O 3 ) stabilized zirconia (YSZ), ittervia (Yb 2 O 3 ) stabilized zirconia (YbSZ), dyspria (Dy 2 O 3 ) stabilized zirconia (DySZ), and elvia ( Er 2 O 3 ) Stabilized zirconia (ErSZ), SmYbZr 2 O 7 is particularly preferable.
  • yttria-stabilized zirconia 8% by mass yttria-stabilized zirconia (5YSZ) is more preferable.
  • the volume-based median diameter of the ceramic particles is not particularly limited, but may be 1 ⁇ m or more and 10 ⁇ m or less, preferably 1 ⁇ m or more and 5 ⁇ m or less. If it is less than 1 ⁇ m, the flow of thermal spraying tends to be poor when the thermal spray coating is formed, and if it exceeds 10 ⁇ m, it tends to be difficult to form composite particles in which ceramic particles are coated on the surface of the resin particles.
  • FIG. 1 (a) shows a scanning electron microscope (SEM) photograph of particles of stabilized zirconia (YSZ) having a volume-based median diameter Dv of 50% of 3 ⁇ m
  • FIG. 1 (b) shows a scanning electron microscope (SEM) photograph.
  • a scanning electron microscope (SEM) photograph of stabilized zirconia (YSZ) particles with a volume-based median diameter Dv of 50% of 33 ⁇ m is shown.
  • the YSZ particles are formed on the surface of the PE particles.
  • the particles of stabilized zirconia (YSZ) shown in FIG. 1 (b) and the polyester (PE) resin particles shown in FIG. 1 (c) are mixed to produce a powder material for thermal spraying.
  • the type of resin forming the resin particles is not particularly limited as long as it is a resin that is thermally decomposed and vaporized by heating, but a resin having a thermal decomposition temperature in air of 200 ° C. or higher is preferable.
  • the thermal decomposition temperature in air can be measured, for example, by thermogravimetric differential thermal analysis (TG-DTA). If the 5% weight loss temperature due to TG-DTA in air is 200 ° C. or higher, it can be determined that the thermal decomposition temperature in air is 200 ° C. or higher.
  • Examples of the resin having a thermal decomposition temperature of 200 ° C. or higher in air include aliphatic polyamide, aromatic polyamide, polyimide, polyetherimide, polyamideimide, polysulfone, polyethersulfone, polyphenylene sulfide, and polyetheretherketone.
  • Examples thereof include polyarylate, polycarbonate, fluororesin, liquid crystal polymer, phenol resin, urea resin, silicon resin, epoxy resin, aromatic polyester, polyacetal, polybutylene terephthalate and the like.
  • the content of the resin particles is 10 to 50% by volume with respect to the entire powder material for thermal spraying. Preferably, it is 15 to 40% by volume. If it is less than 10% by volume, the porosity becomes low, so that the thermal conductivity does not become sufficiently low. On the other hand, if it exceeds 50%, sufficient wear resistance cannot be obtained.
  • the volume-based median diameter of the resin particles is not limited, but is preferably larger than the volume-based median diameter of the ceramic particles. When the volume-based median diameter of the resin particles is larger than the volume-based median diameter of the ceramic particles, it becomes easy to form composite particles in which the surface of the resin particles is coated with the ceramic particles.
  • FIG. 1 (c) shows a scanning electron microscope (SEM) photograph of polyester (PE) particle powder.
  • SEM scanning electron microscope
  • the volume-based median diameter of the resin particles may be 10 ⁇ m or more and 50 ⁇ m or less. If it is less than 10 ⁇ m, it tends to be difficult to form composite particles in which ceramic particles are coated on the surface of the resin particles, and if it exceeds 50 ⁇ m, the pore diameter tends to be large and the abrasion resistance tends to be deteriorated.
  • the volume-based median diameter is a cumulative particle size of 50% from the fine grain side (or coarse grain side) of the volume-based cumulative particle size distribution, and can be measured by, for example, a laser diffraction type particle size distribution measuring device. Specifically, as the laser diffraction type particle size distribution measuring device, Malvern Panalytical's laser diffraction type particle size distribution measuring device Mastersizer 3000 or the like can be used.
  • the method for producing the spray powder material of the present invention is not particularly limited, but in general, spherical granule powder obtained by mixing and granulating each raw material powder is degreased, sintered, crushed, and classified.
  • a spherical powder having a uniform particle size that can be obtained is preferable.
  • it can be produced by a granulation sintering method, a sintering crushing method, a melt crushing method, or the like.
  • the granulation sintering method is a method in which raw material particles are granulated in the form of secondary particles and then sintered to firmly bond (sinter) the raw material particles to each other.
  • granulation can be carried out by using, for example, a granulation method such as dry granulation or wet granulation.
  • a granulation method such as dry granulation or wet granulation.
  • Specific examples of the granulation method include rolling granulation method, fluidized bed granulation method, stirring frame granulation method, crushing granulation method, melt granulation method, spray granulation method, and microemulsion granulation method. Law etc. can be mentioned.
  • a spray granulation method is mentioned as a preferable granulation method.
  • a molded product is first formed by mixing a plurality of raw material powders and compression molding. Next, the molded body is sintered to form a sintered body. Subsequently, the sintered body is crushed and classified to obtain the desired thermal spraying powder material.
  • the melt pulverization method first, a plurality of raw material powders are mixed, heated and melted, and then cooled to form a solidified product (ingot). Next, the solidified product is pulverized and classified to obtain the desired thermal spraying powder material.
  • the method of forming a thermal spray coating using the thermal spraying powder material of the present invention is a method of forming ceramic particles by spraying the thermal spraying powder material formed by the above method onto a base material.
  • the thermal spraying method is not particularly limited, but for example, atmospheric spraying (APS: atmospheric plasma spraying), suspension plasma spraying (SPS: suspension plasma spraying), reduced pressure plasma spraying (LPS: low pressure plasma spraying), and pressurized plasma spraying (high).
  • Plasma spraying method such as pressure plasma spraying, oxygen-supported high-speed frame (HVOP: High Velocity Oxygen Flame) spraying method, warm spray spraying method and air-supported high-speed frame spraying method (HVAF: High Velocity Air flame), etc.
  • High-speed frame thermal spraying and the like can be preferably used.
  • the thermal spraying powder material produced by the above method can be supplied to the thermal spraying apparatus in the form of powder, or may be supplied to the thermal spraying apparatus in the form of a slurry.
  • the thermal spray material when it is in the form of a slurry, it can be prepared by using a dispersion medium.
  • the dispersion medium include alcohols such as methanol and ethanol, toluene, hexane, kerosene and the like.
  • the slurry-like sprayed material may further contain other additives such as a dispersant, a coagulant, a viscosity modifier and the like.
  • the type of base material for which the thermal spray coating is formed is not particularly limited.
  • examples thereof include metal materials such as alloys, simple ceramic materials, composite ceramic materials, and ceramic matrix composites.
  • Specific examples of the metal material include alloys containing iron, nickel, cobalt and the like.
  • stainless steel, Hasteroy (manufactured by Haynes) which is an alloy in which molybdenum, chromium, etc. are added to a nickel group
  • Inconel manufactured by Special Metals
  • stellite manufactured by Delorosterite Group
  • Inver which is an alloy in which nickel, manganese, carbon and the like are added to iron.
  • ceramic materials include monolithic ceramics such as zirconia and alumina, and ceramic matrix composite materials (CMC).
  • the volume-based median diameter is using ZrO 2 -8 wt% Y 2 O 3 of 3 [mu] m (YSZ), volume-based median diameter as the resin particles to a polyester (PE) of 22 .mu.m, as a binder 2% by mass of polyvinyl alcohol (PVA) was added, and these were blended in the proportions shown in Table 1, mixed and granulated to prepare the spraying powder materials of Examples 1 to 3.
  • the ceramic particles and the resin particles are mixed in a predetermined composition, and are dispersed in a solvent consisting of a mixed solution of water and alcohol together with 2% by mass of PVA with respect to 100% by mass of the mixed powder.
  • Slurry was prepared.
  • this slurry was granulated into droplets using a spray granulator and then dried to produce a powder material for thermal spraying according to Examples 1 to 3 containing composite particles in which resin particles were coated with ceramic particles.
  • the volume-based median diameter is using ZrO 2 -8 wt% Y 2 O 3 (YSZ) of 33 .mu.m, median diameter on a volume basis as the resin particles to a polyester (PE) of 22 .mu.m, these
  • the powder materials for thermal spraying of Comparative Examples 1 to 4 were produced by mixing, stirring, and then drying at the volume ratios shown in Table 1.
  • Incidentally ceramic particles used in Comparative Example median diameter on a volume basis is prepared by granulation sintering ZrO 2 -8 wt% Y 2 O 3 (YSZ) of 3 [mu] m.
  • FIG. 2A shows a scanning electron microscope (SEM) photograph of the thermal spraying powder material of Example 1
  • FIG. 2C shows a scanning electron microscope (SEM) of a cross section of the thermal spraying powder material of Example 1. SEM) Photo is shown. As shown in FIG. 2C, it can be seen that the polyester (PE) resin particles have a composite particle structure in which the periphery is coated with YSZ particles.
  • FIG. 2B shows a scanning electron microscope (SEM) photograph of the thermal spraying powder material of Comparative Example 2, in which YSZ particles and PE particles are mixed. I understand.
  • thermal spray coatings of Examples 1 to 3 and Comparative Examples 1 to 4 produced by the above method were used to form a thermal spray coating under the following conditions, and then pores were formed in the thermal spray coating by heat treatment.
  • Thermal spraying conditions SG-100 plasma manufactured by PRAXAIR was used as the thermal sprayer. The thermal spraying conditions are shown below.
  • Base material Stainless steel 316 blasted with alumina # 40
  • Thermal spraying distance 90 mm Film thickness: 500-600 ⁇ m
  • Example 3 (a) of Example 2 has a more uniform porous shape. It can be seen that the tissue is formed. Similarly, when FIG. 3 (b) of Example 3 and FIG. 3 (d) of Comparative Example 4 having the same PE resin content of 42 vol% are compared, FIG. 3 (b) of Example 3 is more. It can be seen that a uniform porous structure is formed.
  • the specific heat capacity Cp (J ⁇ kg -1 ⁇ K -1 ) of the sprayed coating formed under the above thermal spraying conditions and the above heat treatment conditions was measured by the DSC Q100 of TA instrument, and the thermal diffusivity (m 2 ⁇ S -1 ). Was measured using Netch's Flash analyzer LF447.
  • (3) Evaluation of Abrasion Characteristics The thermal spray coating formed under the above thermal spraying conditions and the above heat treatment conditions was subjected to a load of 1 kgf with # 180 abrasive paper using a Suga abrasion resistance tester, and the thermal spray coating due to abrasion was applied. The decrease in thickness was measured.
  • the sprayed coatings of Examples 1 to 3 are excellent in both thermal conductivity and abrasion resistance, but in Comparative Examples in which the content of the resin particles exceeds 50% by volume, they are produced by granulation. However, the wear rate is high and the wear resistance is reduced. Further, in Comparative Examples 2 to 4 produced by mixing the thermal spray powder material, both low thermal conductivity and abrasion resistance are not achieved at the same time.
  • a uniform porous structure can be formed in the topcoat layer as a thermal spray coating, whereby industrial applicability that achieves both low thermal conductivity and high abrasion resistance can be achieved. Can provide a high sprayed coating.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

L'invention concerne : un matériau en poudre à pulvériser, le matériau en poudre étant utilisé pour former un film pulvérisé qui présente à la fois une faible conductivité thermique et une haute résistance à l'abrasion ; et un procédé de fabrication d'un film pulvérisé dans lequel le matériau en poudre à pulvériser est utilisé. Un matériau en poudre à pulvériser, le matériau en poudre comprenant des particules composites configurées par la surface de particules de résine revêtue de particules de céramique, et étant tel que la teneur en particules de résine va de 10 à 50 % en volume (inclus).
PCT/JP2020/034374 2019-09-27 2020-09-10 Matériau en poudre à pulvériser et procédé de fabrication de film pulvérisé WO2021060005A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56102580A (en) * 1979-09-06 1981-08-17 Gen Motors Corp Abrasion resistant ceramic seal and method
JP2007327139A (ja) * 2006-06-08 2007-12-20 Sulzer Metco Us Inc 摩耗性を有するジスプロシア安定化ジルコニア
JP2014181348A (ja) * 2013-03-18 2014-09-29 Tocalo Co Ltd 溶射皮膜形成用複合粉末材料およびその製造方法、ならびに複合溶射皮膜
JP2016156046A (ja) * 2015-02-24 2016-09-01 株式会社フジミインコーポレーテッド 溶射用粉末

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56102580A (en) * 1979-09-06 1981-08-17 Gen Motors Corp Abrasion resistant ceramic seal and method
JP2007327139A (ja) * 2006-06-08 2007-12-20 Sulzer Metco Us Inc 摩耗性を有するジスプロシア安定化ジルコニア
JP2014181348A (ja) * 2013-03-18 2014-09-29 Tocalo Co Ltd 溶射皮膜形成用複合粉末材料およびその製造方法、ならびに複合溶射皮膜
JP2016156046A (ja) * 2015-02-24 2016-09-01 株式会社フジミインコーポレーテッド 溶射用粉末

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