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WO2018159195A1 - Scellement, liquide d'application de scellement, film résistant à la corrosion, élément à haute température et procédés pour leur production - Google Patents

Scellement, liquide d'application de scellement, film résistant à la corrosion, élément à haute température et procédés pour leur production Download PDF

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Publication number
WO2018159195A1
WO2018159195A1 PCT/JP2018/003036 JP2018003036W WO2018159195A1 WO 2018159195 A1 WO2018159195 A1 WO 2018159195A1 JP 2018003036 W JP2018003036 W JP 2018003036W WO 2018159195 A1 WO2018159195 A1 WO 2018159195A1
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WIPO (PCT)
Prior art keywords
corrosion
sealing agent
resistant
resistant film
glass
Prior art date
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Ceased
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PCT/JP2018/003036
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English (en)
Japanese (ja)
Inventor
寛典 高瀬
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Publication date
Priority claimed from JP2017157036A external-priority patent/JP2018193606A/ja
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Publication of WO2018159195A1 publication Critical patent/WO2018159195A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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

Definitions

  • the present invention relates to a sealing agent for filling pores of a corrosion-resistant film, and a corrosion-resistant film and a high-temperature member produced using the same.
  • coal, oil, and LNG are burned in a boiler, and the turbine is rotated using the high-temperature and high-pressure gas, or the turbine is rotated by steam generated using the heat of the high-temperature gas. Is going. For this reason, high temperature members such as gas turbines and heat transfer tubes are exposed to corrosive and oxidizing combustion gas atmospheres of oxygen, sulfur oxides, hydrogen sulfide, etc. at 500 to 1000 ° C. As a result, there is a problem of a decrease in life due to so-called high temperature corrosion.
  • Patent Document 1 discloses a composite coating in which cermet or ceramics is formed by thermal spraying as a base layer, a sealing process is performed on the surface of the base layer with an oxide ceramic, and a glassy coating is further formed.
  • the composite coating described in Patent Document 1 has no through pores and exhibits not only excellent corrosion resistance against corrosive gas, but also the service life of the substrate is remarkably improved.
  • sealing agents include heat-resistant organic resin ceramic suspensions, chromic acid that generates Cr 2 O 3 by heating, inorganic metal compound solutions and colloidal solutions that generate metal oxides by firing, metal alkoxide alcohol solutions Metal chloride aqueous solution or alcohol solution, metal phosphate aqueous solution, metal hydroxide colloid solution, alcohol or water suspension containing metal oxide ultrafine powder, or a mixture of two or more of these are recommended .
  • these sealing agents have a problem that gas is generated even after solidification and complete sealing cannot be performed.
  • Na 2 SiO 3 , NaPO 3 , NaHSiO 3 as an inorganic binder has been proposed, these include alkali metals. As described in Patent Document 2, since alkali metals cause high-temperature corrosion, if the above-described inorganic binder is used, these may corrode a base material or a coating film.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sealing agent that can seal pores of a corrosion-resistant coating and that does not corrode a substrate.
  • Sealer of the present invention is a sealing agent for sealing the pores of the corrosion-resistant film, Bi 2 O 3 2 ⁇ 85 % in percent by mass, consisting of ZnO + B 2 O 3 10 ⁇ 75% content to glass It is characterized by that.
  • ZnO + B 2 O 3 means the total content of ZnO and B 2 O 3 .
  • the “glass” in the present invention may be a single glass or a glass mixture composed of a plurality of glasses. When “glass” is a glass mixture, the entire glass mixture is regarded as a single glass, and the content of each component is determined. When a glass mixture is used, there is an advantage that the composition can be easily adjusted.
  • the sealing agent having the above configuration is made of Bi 2 O 3 that significantly lowers the softening point, and glass containing ZnO or B 2 O 3 at an appropriate ratio that has a lower softening point lower effect than Bi 2 O 3. Become. Thereby, the pores of the corrosion-resistant film can be easily sealed, and the situation in which the viscosity of the glass is too low to react with the film or drop off from the surface of the film can be prevented.
  • the sealant of the present invention is preferably composed of a mixture of two or more kinds of glasses having different compositions. If it does in this way, adjustment of a composition will become easy as mentioned above.
  • the glass has a glass composition of Bi 2 O 3 2 to 85%, ZnO + B 2 O 3 10 to 75%, ZnO 0 to 55%, B 2 O 3 0 to 40 as a glass composition.
  • MgO + CaO + SrO + BaO means the total content of MgO, CaO, SrO and BaO.
  • Li 2 O + Na 2 O + K 2 O means the total content of Li 2 O, Na 2 O and K 2 O.
  • the sealing agent coating liquid of the present invention is characterized by containing the above-mentioned sealing agent.
  • the corrosion-resistant film of the present invention is a corrosion-resistant film containing 50% by mass or more of one or more selected from ZrO 2 , Al 2 O 3, and SiO 2, and the powder composed of the above-described sealing agent is attached to the surface. It is characterized by that. “Adhering to the surface” includes not only the state where the sealant powder is chemically and physically bonded to the corrosion-resistant coating, but also the state where the sealant powder is geometrically caught by the corrosion-resistant coating and does not fall off. .
  • the high-temperature member employing the corrosion-resistant coating having the above-described configuration can seal the pores of the corrosion-resistant coating using a high-temperature atmosphere at the time of use, it is possible to omit a prior firing step.
  • the corrosion-resistant film of the present invention is a corrosion-resistant film containing 50% by mass or more of one or more selected from ZrO 2 , Al 2 O 3 and SiO 2, and some or all of the pores present on the surface are the above-mentioned It is characterized by being filled with a sealing agent.
  • the high-temperature member employing the corrosion-resistant coating having the above-mentioned configuration is because the sealing agent is fixed in the pores of the corrosion-resistant coating, so that the sealing agent layer may fall off during installation during installation or use, The situation where it breaks can be avoided effectively.
  • the method for producing a corrosion-resistant film of the present invention is characterized in that the above-described sealing agent coating solution is applied onto a corrosion-resistant film containing 50% by mass or more of at least one selected from ZrO 2 , Al 2 O 3 and SiO 2. And
  • the method for producing a corrosion-resistant film of the present invention it is preferable to have a step of baking after applying the sealant coating solution.
  • the high-temperature member of the present invention has a corrosion-resistant coating containing 50% by mass or more of at least one selected from ZrO 2 , Al 2 O 3 and SiO 2 on the surface of the base material, and the powder comprising the above-described sealing agent is It has adhered to the surface of the said corrosion-resistant film.
  • the high-temperature member of the present invention has a corrosion-resistant coating containing 50% by mass or more of one or more selected from ZrO 2 , Al 2 O 3 and SiO 2 on the surface of the base material, and exists on the surface of the corrosion-resistant coating. Part or all of the pores are filled with the sealing agent described above.
  • the method for producing a high-temperature member of the present invention includes the steps of forming a corrosion-resistant film containing 50% by mass or more of one or more selected from ZrO 2 , Al 2 O 3 and SiO 2 on the substrate, and the above-described method on the corrosion-resistant film. And a step of applying a sealant coating solution. In addition, it is preferable to dry a sealing agent coating liquid after sealing agent application
  • baking after applying the sealant coating solution includes the case where baking is carried out after drying a sealing agent coating liquid.
  • Sample No. 7 is a photograph showing the results of SEM observation and EDS analysis at ⁇ 2000 of the corrosion-resistant film of No. 7.
  • Sample No. 7 is a photograph showing the result of SEM observation at ⁇ 500 of a corrosion-resistant film of No. 7.
  • Sample No. It is a photograph which shows the result of SEM observation by x500 of 17 corrosion-resistant films.
  • the sealing agent of this invention seals the pore which exists in a corrosion-resistant film.
  • the corrosion resistant coating to which the sealing agent of the present invention can be applied is not particularly limited, and can be used as a sealing agent for a corrosion resistant coating containing 50% by mass or more of at least one selected from ZrO 2 , Al 2 O 3 and SiO 2 .
  • the proportion of Bi 2 O 3 in the glass composition is 2 to 85% by mass.
  • Bi 2 O 3 is a component that contributes to glass formation as a modified oxide or an intermediate oxide, and is a component that lowers the viscosity of the glass to lower the temperature at which it softens and flows.
  • Bi 2 O content of 3 becomes too lower the temperature at which softening and fluidization with too much, which may result in runoff from the surface of the corrosion-resistant film.
  • the content of Bi 2 O 3 contained in the glass composition is 2 to 85% by mass percentage, preferably 5 to 80%, 10 to 75%, particularly preferably 20 to 60%.
  • the ratio of the total amount of ZnO and B 2 O 3 in the glass composition is 10 to 75% by mass.
  • ZnO and B 2 O 3 are components for lowering the viscosity of the glass to lower the temperature at which it softens and flows, but the effect of lowering the temperature at which it softens and flows is smaller than that of Bi 2 O 3 . For this reason, it becomes possible to optimize the temperature at which the glass softens and flows by adding appropriate amounts of these components together with Bi 2 O 3 .
  • the content of ZnO + B 2 O 3 contained in the glass composition is 10 to 75% by mass percentage, preferably 10 to 60%, 12 to 55%, 14 to 52%, particularly preferably 20 to 45%. .
  • the softening flow temperature becomes high, and there is a possibility that it cannot be sufficiently sealed.
  • the softening flow temperature is too low, There is a possibility that the sealing agent reacts with the coating or falls off from the coating surface.
  • the glass constituting the sealant is, for example, as a glass composition Bi 2 O 3 2 to 85% by mass, ZnO + B 2 O 3 10 to 75%, ZnO 0 to 55%, B 2 O 3 0 to 40%, MgO + CaO + SrO + BaO 0-40%, Li 2 O + Na 2 O + K 2 O 0-20%, SiO 2 0-40%, Al 2 O 3 0-30%, Fe 2 O 3 0-10% may be used. it can.
  • % means mass%.
  • ZnO is a component contributing to glass formation as an intermediate oxide. Moreover, it is a component for lowering
  • the content of ZnO is preferably 0 to 55%, 0 to 40%, 0.5 to 35%, 1 to 30%, particularly preferably 3 to 27%.
  • B 2 O 3 is a glass network-forming oxide. Moreover, it is a component for lowering
  • the content of B 2 O 3 is preferably 0 to 40%, 0.5 to 35%, 1 to 30%, particularly preferably 5 to 28%.
  • the content of MgO + CaO + SrO + BaO is preferably 0 to 40%, particularly preferably 0 to 25%. When there is too much MgO + CaO + SrO + BaO, it will become easy to devitrify.
  • MgO is a component that lowers the melting temperature of glass. When there is too much content of MgO, it will become easy to devitrify.
  • the MgO content is preferably 0 to 40%, 0 to 25%, particularly preferably 0 to 10%.
  • CaO is a component that lowers the melting temperature of glass. When there is too much content of CaO, it will become easy to devitrify.
  • the CaO content is preferably 0 to 40%, 0 to 30%, particularly preferably 0 to 20%.
  • SrO is a component that lowers the melting temperature of glass. When there is too much content of SrO, it will become easy to devitrify.
  • the SrO content is preferably 0 to 40%, 0 to 30%, particularly preferably 0 to 20%.
  • BaO is a component having a large effect of lowering the melting temperature of glass. When there is too much content of BaO, it will become easy to devitrify.
  • the BaO content is preferably 0 to 40%, 0 to 30%, particularly preferably 1 to 25%.
  • Li 2 O, Na 2 O, and K 2 O are components for lowering the viscosity of the glass to lower the temperature at which it softens and flows, but cause high-temperature corrosion.
  • the content of Li 2 O + Na 2 O + K 2 O is preferably 0 to 20%, 0 to 15%, 0.1 to 13%, particularly 1 to 12%.
  • the Li 2 O content is preferably 0 to 20%, 0 to 15%, 0 to 13%, particularly preferably 0.1 to 12%.
  • the content of Na 2 O is preferably 0 to 20%, 0 to 15%, 0.01 to 13%, particularly preferably 0.1 to 12%.
  • the content of K 2 O is preferably 0 to 20%, 0.01 to 10%, particularly preferably 0.1 to 12%.
  • SiO 2 is a network-forming oxide of glass, and is a component that contributes to glass formation and simultaneously increases water resistance. When the content of SiO 2 is too large it tends to be devitrified.
  • the content of SiO 2 is preferably 0 to 40%, 0.5 to 40%, particularly 1 to 35%.
  • Al 2 O 3 is a component that increases water resistance and increases the viscosity of the glass. When the content of Al 2 O 3 is too large it tends to be devitrified.
  • the content of Al 2 O 3 is preferably 0 to 30%, 0.1 to 20%, particularly preferably 0.5 to 10%.
  • Fe 2 O 3 is a component that stabilizes glass and suppresses devitrification. Tends to be devitrified on the contrary the content of Fe 2 O 3 is too large.
  • the content of Fe 2 O 3 is preferably 0 to 10%, 0.1 to 5%, particularly preferably 0.3 to 3%.
  • P 2 O 5 , TiO 2 , MnO 2 , CoO, NiO, CuO, Y 2 O 3 , ZrO 2 , SnO 2 , La 2 O 3 , CeO 2 as long as desired properties are not impaired. Etc. up to 10% of each.
  • PbO is a component that contributes to glass formation as an intermediate oxide, and is a component that lowers the viscosity of the glass and lowers the temperature at which it softens and flows, but is listed as a substance with a high environmental load. Therefore, the content of PbO is particularly preferably less than 10%, less than 1%, and substantially not contained.
  • substantially does not contain means that PbO is not intentionally added to the glass, and does not mean that unavoidable impurities are completely eliminated. More objectively, it means that the content of these components including impurities is less than 0.1%.
  • the sealing agent of this invention becomes easy to adjust a composition, it is preferable to consist of a mixture of 2 or more types of glass from which a composition differs.
  • the glass constituting the sealing agent is preferably a glass powder having an average particle diameter of 100 nm to 500 ⁇ m, particularly 1 to 100 ⁇ m.
  • the “average particle size” is defined by D50 calculated on the basis of the number of particles when the particle size of an arbitrary powder is measured by the laser diffraction scattering method.
  • the sealing agent coating liquid of the present invention refers to a paste or slurry obtained by mixing a sealing agent with various resins, paints, organic solvents, sol-gel solutions, water glass, water, and other inorganic solvents. By making it into a paste or slurry, it becomes easy to apply uniformly on the corrosion-resistant coating. Resins, paints, and sol-gel solutions have a function of fixing the sealing agent on the coating until the sealing agent is softened and does not fall off from the corrosion-resistant coating.
  • Examples of such resins and paints, sol-gel solutions, and water glasses include vinyl resins such as unsaturated polyester resins, epoxy resins, polyvinyl butyral, polyvinyl alcohol, polybutyl methacrylate, polymethyl methacrylate, and polyethyl methacrylate.
  • Vinyl resins such as acrylic resins, ethyl cellulose and nitrocellulose, amide resins, silicone resins, polytitanocarboxylsilane solutions, solutions of metal alkoxides such as tetraethoxysilane and their partial condensates, sodium silicate as defined in JIS K1408 No. 1, No. 2, No. 3, etc. can be used.
  • boric acid powder or boron oxide powder may be added to the sealing agent coating solution.
  • the corrosion-resistant film of the present invention is a corrosion-resistant film containing 50% by mass or more of one or more selected from ZrO 2 , Al 2 O 3 and SiO 2 .
  • This type of corrosion-resistant coating can have corrosion resistance against corrosive and oxidizing combustion gas atmospheres of oxygen, sulfur oxides, hydrogen sulfide, etc. at 500 to 1000 ° C., for example.
  • the corrosion resistant coating examples include a corrosion resistant coating having stabilized ZrO 2 as a main constituent (hereinafter referred to as a stabilized ZrO 2 -based corrosion resistant coating).
  • Stabilized ZrO 2 is mainly composed of ZrO 2 , and one or more kinds of stable selected from Y 2 O 3 , MgO, CaO, SiO 2 , CeO 2 , Yb 2 O 3 , Dy 2 O 3 , HfO 2 and the like.
  • An agent is added.
  • the ZrO 2 content is 85% by mass or more, preferably 85 to 95% by mass
  • the stabilizer content is 15% by mass or less, preferably 5 to 15% by mass.
  • the corrosion resistance of the coating can be ensured, and the phase from the tetragonal or cubic to monoclinic phase of ZrO 2 generated near 1000 ° C. in the cooling process after plasma spraying. Metastasis can also be suppressed.
  • the content of ZrO 2 is less than 85 wt%, the corrosion resistance of the coating is reduced.
  • the porosity of the corrosion-resistant film is preferably 5% or less, particularly 4% or less.
  • the porosity of the corrosion-resistant film is preferably 5% or less, particularly 4% or less.
  • the thickness of the corrosion-resistant film is preferably 10 to 1000 ⁇ m, 10 to 500 ⁇ m, 50 to 400 ⁇ m, particularly preferably 70 to 300 ⁇ m. If the thickness of the corrosion-resistant film is too small, it is difficult to suppress permeation of acidic gas. On the other hand, when the film thickness of the corrosion-resistant film is too large, the thermal stress generated by the thermal cycle increases, and the corrosion-resistant film easily peels off.
  • the porosity of the corrosion-resistant coating can be adjusted by changing the particle size of the sprayed powder (stabilized ZrO 2 powder or inorganic glass powder).
  • the high temperature member of the present invention is provided with the above-mentioned corrosion resistant coating.
  • the metal material which has at least one of Fe, Ni, Co, and Cr as a main component is preferable.
  • the corrosion-resistant coating is preferably formed directly on the substrate, but for the purpose of improving adhesion and the like, one or more underlayers may be provided between the substrate and the corrosion-resistant coating.
  • an M—Cr—Al—Y-based alloy Ni, Co, or Fe
  • M Ni, Co, or Fe
  • M-Cr—Al—Y-based alloy Ni, Co, or Fe
  • the M-Cr-Al-Y alloy is an alloy containing Ni, Co, or the like, which has properties excellent in high temperature oxidation resistance and high temperature corrosion resistance, and added with Cr, Al and Y. This type of alloy is characterized in that it easily adheres to both SUS and the stabilized ZrO 2 -based corrosion resistant coating.
  • the porosity of the underlayer is preferably 1% or less. From the viewpoint of suppressing permeation of acid gas, the lower the porosity of the underlayer, the more advantageous.
  • the film thickness of the underlayer is preferably 10 to 500 ⁇ m, particularly 50 to 400 ⁇ m, more preferably 70 to 350 ⁇ m. From the viewpoint of suppressing permeation of acid gas, the thicker the base layer, the more advantageous.
  • the underlayer generally has an effect of relieving thermal stress due to the difference in thermal expansion characteristics generated at the interface between the base material and the corrosion-resistant film, but it is difficult to obtain a thermal stress mitigating effect if the underlayer is too thin. Become. On the other hand, if the film thickness of the underlayer is too large, thermal stress generated by a heat cycle or the like inside the power generation facility increases, and the underlayer is easily peeled off.
  • the porosity of the underlayer can be adjusted by changing the particle size of the M-Cr-Al-Y alloy powder to be sprayed.
  • the high-temperature member is a thermal power generation turbine or a heat transfer tube that generates power by collecting kinetic energy or heat energy via a fluid such as steam or air.
  • a thermal power generation turbine or a heat transfer tube that generates power by collecting kinetic energy or heat energy via a fluid such as steam or air.
  • it is not limited to these.
  • it is also suitable for various engines.
  • a method for producing a high-temperature member using the sealing agent of the present invention is a stabilized ZrO 2 -based corrosion-resistant coating film on a base material made of SUS and through an underlayer made of an M—Cr—Al—Y-based alloy.
  • An example of forming the case will be described.
  • a metal tube is used as the base material, a heat transfer tube with a corrosion-resistant coating can be produced.
  • the manufacturing method of this invention is not restrict
  • an underlayer made of an M—Cr—Al—Y alloy is formed on a base material made of SUS.
  • the formation of the underlayer is not particularly limited, but is preferably formed by gas spraying such as high-speed flame spraying (HVOF).
  • HVOF high-speed flame spraying
  • a powder made of an M—Cr—Al—Y alloy as the thermal spraying powder used at this time.
  • the M—Cr—Al—Y alloy is as described above, and the description thereof is omitted here.
  • the average particle size of the sprayed powder is preferably 10 to 75 ⁇ m, 10 to 53 ⁇ m, and particularly preferably 10 to 45 ⁇ m.
  • the particle size of the thermal spray powder When the particle size of the thermal spray powder is large, the porosity of the base layer formed by gas spraying is increased. In addition, if the particle size of the thermal spray powder is small, clogging of the jet port (port) for supplying the thermal spray powder to gas or plasma is likely to occur, and it takes time to form the thermal spray coating of any film thickness, resulting in thermal spraying. Cost is likely to increase.
  • a stabilized ZrO 2 -based corrosion resistant coating is formed on the underlayer made of the M—Cr—Al—Y alloy.
  • the stabilized ZrO 2 -based corrosion resistant coating can be formed by a plasma spraying method.
  • the plasma spraying method various methods such as an atmospheric pressure plasma spraying method and a vacuum plasma spraying method can be used. It is preferable to use stabilized ZrO 2 powder as the thermal spraying powder used at this time.
  • the corrosion resistant coating can be formed by a spraying technique other than plasma spraying (for example, gas spraying), a cold spray, an aerosol deposition method, or the like.
  • the average particle size of the stabilized ZrO 2 powder is preferably 10 to 75 ⁇ m, 10 to 53 ⁇ m, particularly 10 to 45 ⁇ m.
  • the average particle size of the stabilized ZrO 2 powder is large, the porosity of the corrosion-resistant coating formed by plasma spraying is increased.
  • the average particle size of the stabilized ZrO 2 powder is small, clogging of the spray port (port) for supplying the sprayed powder to the plasma is likely to occur, and it takes time to form a sprayed coating having an arbitrary film thickness. The thermal spraying cost tends to be high.
  • a paste or slurry (sealant coating solution) containing the above-described sealant is applied onto the corrosion-resistant film by a method such as brushing or spraying, and further dried as necessary.
  • a sealant layer can be formed.
  • the sealing agent can be formed by other methods as long as the sealing agent powder does not fall off the corrosion-resistant coating, such as sputtering or thermal spraying.
  • the sealant layer of the high temperature member thus produced is in a state where the sealant powder is adhered to the surface of the corrosion-resistant coating, and is not yet in a state of completely closing the pores, Can be installed. That is, when the use is started, it is exposed to a high temperature atmosphere, and the heat causes the sealing agent to soften and flow to fill pores existing on the surface of the corrosion-resistant coating.
  • firing may be performed after the sealing agent layer is dried (and before actual use).
  • firing conditions for example, 300 to 1000 ° C. and 10 minutes to 2 hours are preferable.
  • Table 1 shows examples of glass (glass samples A, B, C, D) constituting the sealant.
  • Tables 2 and 3 show examples of the present invention (sample Nos. 1 to 16).
  • Glass samples A, B, C, and D were produced as follows. First, a glass batch prepared to have the composition shown in Table 1 was melted at 1000 ° C. for 1 hour. Next, this was formed into a film, and then pulverized and classified to obtain a glass sample made of glass powder having an average particle size of 50 ⁇ m.
  • sealing agent samples No. 1 to 16
  • the softening point was measured using a differential thermal analyzer according to the method described by Masayuki Yamane, “For the first person who makes glass”.
  • the high temperature member was produced as follows. First, the SUS310S base material is degreased, washed, and then subjected to blasting, and an alloy powder having an average particle size of 10 to 45 ⁇ m made of a Co—Ni—Cr—Al—Y alloy is sprayed at high speed to provide high temperature oxidation resistance and resistance. An underlayer (Co—Ni—Cr—Al—Y alloy layer) excellent in high temperature corrosion resistance was formed. The thickness of the underlayer was 200 to 400 ⁇ m. In addition, the film thickness of the base layer was measured with a micrometer. The film thickness can be adjusted by first moving the thermal spraying device parallel to the substrate and spraying it, then measuring with a micrometer how much film thickness can be obtained with a single thermal spraying, and then spraying it. This was done by adjusting the number of times.
  • 8% Y 2 O 3 —ZrO 2 powder having an average particle size of 10 to 45 ⁇ m was sprayed at atmospheric pressure on the underlayer to form a corrosion-resistant coating.
  • the film thickness of the corrosion-resistant film was uniform and was 50 to 200 ⁇ m.
  • the adjustment and measurement of the thickness of the corrosion-resistant coating were performed in the same manner as when the Co—Ni—Cr—Al—Y alloy was sprayed.
  • a sealant layer was formed on the corrosion-resistant film by the following method. First, a polyvinyl butyral resin, a thinner, and a sealing agent sample were mixed to prepare a sealing agent paste. Next, a sealant paste was applied onto the corrosion-resistant film by brush coating, and then a sealant sample No. In No. 1, the sealing agent sample No. 24 at 550 ° C. for 24 hours. In Nos. 2 to 5, the sealing agent sample no. 6 to 16 were baked at 750 ° C. for 24 hours. In this way, high-temperature members (high-temperature member samples No. 1 to 16) in which the corrosion-resistant film was sealed with the sealing agent were obtained.
  • the corrosion-resistant film is not sealed with a sealant, and the other processes are performed at high temperature member sample no.
  • the high temperature member sample No. 17 was prepared and used as a comparison target.
  • the cut sample was embedded in a resin, the cut surface was polished, and then the cut surface was subjected to SEM observation and EDS analysis.
  • the permeability was evaluated as “ ⁇ ”, and when the element was not detected as “X”.
  • the high temperature member sample no. FIG. 3 shows that a large number of pores are present in the corrosion-resistant coating.
  • high temperature member sample No. which is an embodiment of the present invention.
  • Tables 2 and 3 in Nos. 1 to 16, the sealing agent penetrated into the corrosion-resistant coating.
  • Sample No. It can be seen from FIG. 1 that 7 of the sealing agent penetrates into the corrosion-resistant film, and FIG. 2 that only a small number of pores are present in the corrosion-resistant film.
  • the pore which exists in a corrosion-resistant film is not connected with the exterior, it is thought that there is no problem practically.
  • the corrosion-resistant coating using the sealant of the present invention is a protective film for a thermal power generation turbine or heat transfer tube that recovers kinetic energy or thermal energy from a high-temperature combustion gas via a fluid such as steam or air. It is preferable to use it. Specifically, it is suitable as a protective film for turbines and heat transfer tubes of gas turbine power generation, coal thermal power generation, coal gasification combined power generation, oil thermal power generation, waste power generation, geothermal power generation, and the like. However, the present invention is not limited to these, and is also suitable as a protective film for various engines.
  • the high-temperature member of the present invention is suitable as a turbine or heat transfer tube for various types of engines such as gas turbine power generation, coal-fired power generation, coal gasification combined power generation, oil-fired power generation, waste power generation, and geothermal power generation.

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Abstract

L'invention concerne scellement pouvant sceller des pores dans un film résistant à la corrosion sans corroder un substrat. Le scellement est caractérisé en ce qu'il est destiné à sceller les pores dans un film résistant à la corrosion et en ce qu'il est formé d'un verre dans lequel le rapport de Bi2O3 dans la composition est de 2 à 85 % en masse et le rapport de la quantité combinée de ZnO et de B2O3 dans la composition est de 10 à 75 % en masse.
PCT/JP2018/003036 2017-02-28 2018-01-30 Scellement, liquide d'application de scellement, film résistant à la corrosion, élément à haute température et procédés pour leur production Ceased WO2018159195A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2017-036720 2017-02-28
JP2017036720 2017-02-28
JP2017-106317 2017-05-30
JP2017106317 2017-05-30
JP2017157036A JP2018193606A (ja) 2017-02-28 2017-08-16 封孔剤、封孔剤塗布液、耐食性被膜、高温部材及びこれらの製造方法
JP2017-157036 2017-08-16

Publications (1)

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WO2018159195A1 true WO2018159195A1 (fr) 2018-09-07

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PCT/JP2018/003036 Ceased WO2018159195A1 (fr) 2017-02-28 2018-01-30 Scellement, liquide d'application de scellement, film résistant à la corrosion, élément à haute température et procédés pour leur production

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WO (1) WO2018159195A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5893865A (ja) * 1981-12-01 1983-06-03 Agency Of Ind Science & Technol 表面処理防止方法
JPH07268594A (ja) * 1994-02-10 1995-10-17 Sumitomo Metal Ind Ltd 溶融金属めっき浴浸漬部材とその製造方法
JP2006335584A (ja) * 2005-05-31 2006-12-14 Nippon Electric Glass Co Ltd ビスマス系無鉛封着材料
JP2007210870A (ja) * 2005-03-09 2007-08-23 Nippon Electric Glass Co Ltd ビスマス系ガラス組成物およびビスマス系封着材料
JP2011173735A (ja) * 2010-02-23 2011-09-08 Nippon Electric Glass Co Ltd ビスマス系ガラス

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5893865A (ja) * 1981-12-01 1983-06-03 Agency Of Ind Science & Technol 表面処理防止方法
JPH07268594A (ja) * 1994-02-10 1995-10-17 Sumitomo Metal Ind Ltd 溶融金属めっき浴浸漬部材とその製造方法
JP2007210870A (ja) * 2005-03-09 2007-08-23 Nippon Electric Glass Co Ltd ビスマス系ガラス組成物およびビスマス系封着材料
JP2006335584A (ja) * 2005-05-31 2006-12-14 Nippon Electric Glass Co Ltd ビスマス系無鉛封着材料
JP2011173735A (ja) * 2010-02-23 2011-09-08 Nippon Electric Glass Co Ltd ビスマス系ガラス

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