JP3088652B2 - Vitreous sprayed material coated member having self-repairing action and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vitreous sprayed material coated member having a self-repairing action and a method for producing the same.
In particular, it is used as a component of municipal solid waste and industrial waste incineration plants that generate corrosive metal chlorides and hydrogen chloride gas by incineration, and as a component of waste heat recovery boilers. Including,
It is a thermal spray material coating member that is also applied to the sludge heating and volume reduction treatment plant of industrial water and sewage treatment plants.

[0002]

[Prior Art] There are ordinary households, restaurants,
Many kitchen residues from restaurants, including salt (NaCl)
Contains a large amount of seasonings. In addition, there are many plastics (for example, vinyl chloride, vinylidene chloride, etc.) used as wrapping paper and containers, and most of them are chlorinated. And sometimes a part of it is oxidized and changed to chlorine gas. Therefore, members used in municipal solid waste incineration facilities and waste heat recovery boilers are significantly corroded.

[0003] This municipal solid waste also includes metal products such as aluminum cans, zinc-plated and tin-plated products, and various types of used dry batteries, which are contained in combustion gas such as HCl and Cl _2. Reacts with water to produce low-melting-point, highly corrosive chlorides (eg, AlCl ₃ , ZnCl ₂ , SnCl ₂ ), which similarly adhere to the incinerators and heat transfer tube walls of waste heat boilers Corrode.

[0004] As described above, fire grate made of heat-resistant cast steel of a refuse incineration facility, as well as refractory brick support fittings, etc., are generally significantly corroded and worn, and lose their functions within a short period of time. The waste heat boiler also has a problem that stable operation cannot be performed for a long period of time because the combustion residue containing chloride as a main component is significantly corroded when adhered to the heat transfer surface. Moreover, such a corrosion reaction becomes more remarkable as the temperature becomes higher. For example, a waste heat boiler or the like must be operated with the steam temperature suppressed to about 330 to 350 ° C., and there is a problem that municipal solid waste combustion cannot be used effectively. there were.

Conventionally, the following countermeasures have been taken against such problems. (1) Improve the corrosion resistance by improving the grate material and boiler heat transfer tube material. (2) Cover boiler heat transfer tubes, especially high-temperature superheated tubes, with corrosion-resistant ceramics. (3) Ni-Cr alloy material is spray-coated on the boiler heat transfer surface. (4) Spray water into high temperature municipal waste flue gas to lower its temperature and reduce corrosiveness. (5) Separate municipal solid waste into general incineration materials and non-combustible products such as plastics and metals to minimize the generation of corrosive salts and exhaust gas. (6) Ca compound (Ca (OH) ₂ , CaCO ₃ ) is added to municipal waste and burned, and the generated HCl gas is solidified as CaCl ₂ and its corrosiveness is reduced.

However, the measure (1) for improving the corrosion resistance of the metal material is not economical because it causes an increase in the content of expensive Ni, Cr and the like. -Even if a Cr alloy tube is used, sufficient corrosion resistance to chlorides and hydrogen chloride gas cannot be expected. (2) When a ceramic is coated on a boiler superheated tube or the like, a sufficient effect cannot be exerted because cracks and local peeling occur due to a thermal shock accompanying operation and shutdown of the boiler. (3) Ni to boiler heat transfer tube
-Spraying of Cr alloy is valuable as a symptomatic treatment for corrosion-reduced heat transfer tubes, but is not enough as a countermeasure for raising the steam temperature of waste heat boilers. In addition, this thermal spray coating
The porosity is high, so the corrosion resistance to corrosive metal chlorides and hydrogen chloride gas is not sufficient. (4) Spraying of water into the high-temperature municipal waste combustion exhaust gas causes the loss of thermal energy possessed by the exhaust gas, and the dust collector, desulfurization, denitrification, desalination device and chimney provided at the boiler outlet. It promotes sulfuric acid dew point corrosion or hydrochloric acid dew point corrosion. (5) Separation of municipal waste
Although it contributes to the stability of combustion conditions and flue gas, it does not provide a drastic measure to reduce its corrosiveness. (6) The method of adding a Ca compound to municipal solid waste temporarily reduces the HCl component in the combustion gas, but the reaction product CaCl ₂ induces stress corrosion cracking of austenitic stainless steel. In addition, when the municipal solid waste incineration plant shuts down, it absorbs water in the air and hydrolyzes it to produce free hydrochloric acid, since it is very hygroscopic. For this reason, there is a problem that corrosion progresses even after the incineration plant is stopped, and the equipment operation rate is low.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a glass-sprayed material-coated member which can solve the problems of the prior art which is applied as a measure for preventing corrosion of members used in municipal solid waste incineration plants and waste heat recovery boilers. Is proposed. (1) Thermal spray coatings generally have pores, so highly corrosive metal chlorides and HCl generated by combustion of municipal solid waste.
Gas or Cl ₂ gas penetrates through the pores into the interior of the coating and contacts the substrate. As a result, even if a thermal sprayed material having excellent corrosion resistance is coated, the corrosion of the substrate proceeds through the pores, and the thermal spray coating is peeled off from the surface of the substrate, and the service life thereof is relatively short. . (2) In incineration plants, metal containers for beverages (for example, canned coffee and canned beer cans) are mixed in combustible municipal solid waste, and when these metallic materials fall onto the sprayed coating, Then, cracks and local peeling occur in the film. Further, at the time of repair of an incineration plant or the like, local cracks often occur in the thermal sprayed coating due to contact with a repair scaffold or a repair tool. However, conventionally, it has been difficult to repair such a damaged thermal spray coating during operation of an incineration plant, and no measures have been taken at present.

[0008] That is, a main object of the present invention is to provide a thermal spray material coating member that is resistant to a chloride corrosion environment. Another object of the present invention is to reduce the influence of pores by forming a composite film, and to further improve the corrosion resistance by spraying a glass material. Another object of the present invention is to improve the adhesion between the thermal spray coatings (substrate-undercoat-topcoat) and improve the durability of the member. Another object of the present invention is to improve the adhesion to the top coat by dispersing an oxide in the undercoat or forming an oxide layer on the surface of the undercoat. Another object of the present invention is to further improve the corrosion resistance by forming a re-melted glass layer by heating on the surface layer of the top coat. Another object of the present invention is to spray a vitreous mixed spray material on a mixture of a glass material and a metal or oxide, carbide, etc. during the top coat,
The purpose of the present invention is to provide a self-repairing action to the sprayed top coat to reduce the maintenance cost of the member. Still another object of the present invention is to provide a pure glass sprayed layer or an alkali metal silicate compound or borate compound, methyl silicate, ethyl silicate, silicon-containing resin, dimethyl Silicone, tetraethoxy silane,
Applying a sealing material such as tetra-butoxy-silane, which is a precursor for sealing, and applying a spray layer. (When this layer is subsequently heated, it forms SiO ₂ and B ₂ O ₃ to perform the sealing action. To improve corrosion resistance and self-repairing action.

[0009]

Means for Solving the Problems As means effective for realizing the above-mentioned objects, the present invention provides: (1) After blasting the substrate surface to remove foreign substances such as iron rust and roughen the surface, Ni-Cr, Ni-Cr-Fe, Ni-Cr-Co, Ni
-Metal material such as Cr-Al-Fe or Cr ₃ C ₂ , WC, TiC
A thermal spray material composed of a carbide cermet and Al powder is sprayed to form an oxide-containing thermal spray coating. Then, on the undercoat sprayed film, as the topcoat, the undercoat sprayed material, for example, Ni, Cr, Ni-Cr.
Any one selected from oxides, borides, carbides, and carbide cermets, including alloys and carbide cermets
Spraying a mixed powder of more than one kind of powder and a glass material. Of course, it may be used for practical purposes as it is, but if the top coat sprayed film is heated to the melting point of the vitreous material or higher by the combustion flame of hydrocarbon to form a re-melted glass layer, it is possible to obtain a top coat without pores. (2) After blasting the surface of the base material, the undercoat thermal spray coating is applied, and when forming the top coat thermal spray coating thereon, the mixing ratio of the glass material is such that the lower the undercoat side, the less the glass material, and the outer surface side Thermal spraying is applied to the thermal spray material according to the gradient composition that is changed stepwise so as to be included as much as possible, and then the top coat thermal spray coating is heated to melt the glass material and form a re-melted glass layer on the outermost layer (3) After blasting the surface of the base material, the top coat sprayed coating of (2), that is, the mixing ratio of the corrosion-resistant metal material and the glass material is gradually inclined. The spray material sequentially sprayed in accordance with, then heated to forming the remelt layer on the outer surface by remelting the vitreous material layer is proposed. (4) After forming a pure glass sprayed layer composed of 100% glass on the composite sprayed coating of (1), (2), and (3), the pure glass layer is further melted by heating and melting. It may be a layer. (5) In the present invention, further, on the composite sprayed coating of the above (1), (2), and (3), a precursor sealing material that generates SiO ₂ and B ₂ O ₃ when heated. A coated or sprayed layer may be provided.

As described above, according to the present invention, by mixing a glass material in a thermal spray coating, only the glass material easily shows a melt softening phenomenon by heating. Therefore, if the composite sprayed coating is heated using the incineration heat generated during the operation of the municipal solid waste incineration plant, the defects such as pores and cracks contained in the coating are naturally eliminated by the self-repairing action. It becomes possible.

That is, the present invention provides (1) a member formed by forming a multilayer coating consisting of an undercoat sprayed coating and a topcoat sprayed coating coated thereon on the surface of a steel base material; The coat sprayed coating contains an oxide at all or at least a boundary portion with the top coat sprayed coating, while the top coat sprayed coating is selected from metals, oxides, borides, carbides, and carbide cermets. A self-repairing vitreous sprayed material coated member having a self-repairing action, formed by a vitreous mixed sprayed coating formed by spraying a mixture of at least one of the above and a glass material; and (2) a steel base In a member formed by forming a multilayer coating consisting of an undercoat sprayed coating and a topcoat sprayed coating coated on the undercoat sprayed coating on the surface of the material, The thermal spray coating contains an oxide entirely or at least at the boundary with the thermal spray coating, while the thermal spray coating comprises a metal, oxide, boride, carbide and carbide cermet. Formed in a vitreous mixed spray coating formed by spraying a mixture of any one or more selected and a glass material,
And a self-repairing vitreous sprayed material coating member having a self-repairing action, wherein the vitreous mixed sprayed coating has a remelted glass layer on a surface layer thereof. However, the undercoat sprayed coating contains Al ₂ O ₃ and is selected from Al and other metals and alloys or carbide cermets.
An oxide-containing thermal spray coating sprayed with more than one kind of material,
The thickness is 20 to 500 μm.

On the other hand, the above-mentioned top coat sprayed film has a thickness of 95%.
Vitreous thermal spraying by spraying a mixed powder of at least one powder selected from metals, oxides, borides, carbides, and carbide cermets of 5 to 95 vol% and a glass material of 5 to 95 vol%. A film having a thickness of 10 to 10
The top coat sprayed coating is characterized in that the mixing ratio between the powder of at least one selected from the group consisting of metals, oxides, borides, carbides and carbide cermets and the glass material is stepwise. It is characterized by being formed by spraying a gradually or gradually changing inclined compounding powder.

The above-mentioned inclined compound powder was formed by spraying.
Top coat thermal spray coating is compounded with glass material as the outer surface
Characterized in that the amount increases stepwise or gradually
You. And the above-mentioned top coat sprayed coating including a re-melted layer
The glass material is SiO_Two, Na _TwoOK_TwoO, B_TwoO_Three, Al_TwoO_Three, Li
_TwoO, CaO, MgO, TiO_Two, ZnO, ZrO_Two, SnO, SrO, BaO, CoO
At least one glass-forming oxide selected from the group consisting of:
And its linear expansion coefficient is 4 to 14 ×
Ten^-16/ ℃, melting point 450-750 ℃
You.

The member according to the present invention is a pure glass sprayed layer or an alkali metal spray formed by spraying a 100% glass material as an outermost layer on the top coat sprayed coating in each of the above inventions. A vitreous sprayed material-coated member having an adhesion layer of a precursor sealing material such as a silicate compound or a borate compound.

Next, the present invention proposes a method for manufacturing the above-mentioned member. That is, the present invention provides (1)
At least one material selected from metals, alloys and carbide cermets is sprayed on the surface of a steel base material to form an undercoat sprayed film, on which metal, oxide, boride, carbide and A method for producing a vitreous sprayed material coated member having a self-repairing action, characterized in that a mixture of one or more powders selected from carbide cermets and a glass material is sprayed to form a vitreous mixed sprayed coating; And (2) spraying an undercoat sprayed film by spraying at least one material selected from metals, alloys and carbide cermets on the surface of the steel base material, and forming a metal, oxide, boron Spraying a mixture of one or more powders selected from carbides, carbides and carbide cermets with a glass material to form a vitreous mixed spray coating, and then a vitreous mixed spray Heating the coating to a temperature equal to or higher than the melting point of the glass material, a self-repairing vitreous sprayed material coated member having a self-repairing action characterized by forming a remelted glass layer on the surface layer by remelting the glass material. Manufacturing method. However, in the above-mentioned manufacturing method, it is preferable that a sprayed material of 100% glass material is sprayed on the glassy mixed sprayed coating as the top coat, and a pure glass sprayed layer is formed on the outermost surface. It is.

In these methods, it is a preferred embodiment that the re-melted layer in the top coat sprayed coating is formed by utilizing the combustion heat of a municipal solid waste incineration plant. In these methods, when forming an undercoat sprayed coating, Ni, Fe,
It is preferable to use, in addition to a metal / alloy or a carbide cermet that is Fe-Cr, Fe-Ni-Cr or Ni-Cr, a material to which 0.1 to 3 wt% of Al is added. On the other hand, when forming the top coat thermal spray coating, it is preferable to spray the inclined compound powder in which the compounding amount of the glass material in the thermal spray material is increased stepwise or gradually from the undercoat surface to the outer surface.

Further, in the present invention, at the site of a municipal solid waste incineration plant, after an undercoat of a metal spray coating is applied and a glassy spray coating is formed thereon, the structure of the plant and the base material In relation, when the application of the top coat becomes difficult due to the heat retained by the undercoat, the surface of the top coat is simply coated with the sealing material as a precursor, and is generated in a use environment. SiO ₂ and B ₂ O ₃ may be generated by heat to seal the surface. That is, even if a vitreous top coat spray coating is applied on a metallic tender comb spray coating at room temperature, this top coat spray coating tends to be porous. When the municipal solid waste incineration plant is operated, the corrosive gases (for example, HCl, C
l ₂ ) penetrates through the pores of the vitreous film. As a result, even if the temperature of the plant rises and becomes equal to or higher than the melting point of the glass and the pores are closed, the metal undercoat sprayed coating is corroded by the corrosive components that have penetrated inside, and the coating is destroyed from the inside. May be affected.

Therefore, in the present invention, when a top coat sprayed coating containing vitreous or vitreous material is applied without preheating the undercoat, a sealing material containing SiO ₂ and / or B ₂ O ₃ is applied thereon. Is applied.
The feature of this sealing material is that it contains a component constituting glass. When the above-mentioned sealing material is applied on the glassy top coat sprayed coating, the pores are filled, preventing the invasion of corrosive gas, and reacting with the glassy material when the temperature of the use environment rises due to plant operation. Fused, as a result, it is integrated with the surface layer of the glassy top coat sprayed coating to form a complete anticorrosion coating. The following are examples of SiO ₂ and B ₂ O ₃ compounds having such an action mechanism. In use, they are used as aqueous solutions, slurries, and melts (viscous states such as sols and gels). An adhesion layer of a sealing material which is applied or sprayed onto the glassy top coat sprayed coating and fused and integrated by post-heating is formed in advance.

The following materials can be used as the sealing material. (1) Alkali metal silicate compounds as inorganic compounds
(Eg, Na ₂ SiO ₃ , K ₂ SiO ₃ ), borate compounds of alkali metals (eg, Na ₂ B ₂ O ₇ , K ₂ B ₂ O ₇ ) (2) As organic compounds, methyl silicate, ethyl silicate, silicon Such as glass-containing resin, dimethyl silicone, tetra-ethoxy silane, tetra-butoxy silane, etc., when heated to a high temperature, eventually becomes SiO ₂ or B ₂ O ₃ and fuses with the vitreous component If it is, any of organic and inorganic substances can be used as a sealing material by mixing these compounds.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a member coated with a high corrosion-resistant sprayed material particularly suitable for a municipal solid waste incineration plant will be described. FIGS. 1 (a) and 1 (b) show the cross-sectional structure of a member coated with a high corrosion-resistant sprayed material according to the present invention. In this figure, 1 is a steel base material, 2 is an undercoat sprayed coating formed by spraying a sprayed powder of metal / alloy, oxide, carbide cermet, etc., 2a is an oxide layer, 3a
Is a top coat sprayed film formed by spraying a mixed powder of the above-mentioned sprayed powder and a glass material, 3a is a re-melted glass layer, and 4 is a pure glass sprayed layer of the outermost layer of 100% glass material. Hereinafter, the spray coating member shown in FIG. 1 will be described in more detail.

(1) FIG. 1 (a) shows that the surface of a steel substrate 1 is degreased, blasted and roughened, and then a metal or carbide cermet sprayed film is undercoated on the surface of the substrate 1. Is formed. Then, a composite type top coat sprayed film is formed thereon by using a mixed sprayed material obtained by mixing a glass material with at least one powder selected from metals, alloys, oxides, borides, carbides, carbide cermets and the like. Is formed.

Here, the purpose of the formation of the undercoat sprayed coating is to improve the adhesion to the substrate 1 and the adhesion to the topcoat sprayed coating 3 and to provide the undercoat sprayed coating itself with excellent heat resistance and corrosion resistance. It is necessary to be. For this reason, thermal spraying materials for undercoats include WC, Cr ₃ C ₂ , NbC, and metal-based materials such as Cr, Ni, Fe, Mo, and Co or alloys thereof and Al carbide cermet-based materials.
Mixtures or sinters of the above metals or their alloys and Al with carbides such as TiC, WTiC, ZrC, TaC, HfC and MoC are preferably used.

In the present invention, in order to improve the adhesion to the top coat, the undercoat sprayed coating contains an oxide in the entirety of the undercoat or at least at the boundary with the topcoat sprayed coating. Or an oxide layer is desirable. In general, a metal spray coating formed in the atmosphere generates an oxide by heating at a high temperature in a thermal spraying heat source and contact with oxygen in the air, so it is usually composed of a metal and its oxide. .

The presence of such an oxide helps to improve the adhesion to glass, but the formation of the oxide obtained under actual thermal spraying is not sufficient. Therefore, in the present invention, an oxide layer for improving adhesion is provided at least at the contact interface with the vitreous top coat sprayed coating which is the upper layer of the undercoat sprayed coating by taking the following means. Decided to form.

The present invention uses the following means as a method for dispersing such an oxide in a film at a high concentration or for actively generating an oxide at least in a surface layer portion. (1) For example, a metal spray such as Ni, Fe, Fe-Cr, Fe-Ni-Cr, Ni-Cr and its alloys are sprayed with a sprayed metal material in which 0.1 to 3 wt% of Al having a high affinity for oxygen is added. I do.
In the thermal spray metal material to which Al is added, Al oxidizes faster than metals such as Ni, Fe, and Cr in the thermal spray heat source, and generates a large amount of Al ₂ O ₃ on the surface of the particles constituting the thermal spray coating. (2) In the powder of the thermal sprayed metal material in paragraph (1), add
After adding 3 wt%, these are mixed well and sprayed to form a sprayed coating containing Al ₂ O ₃ . (3) After forming a metal spray coating by a usual method, this is heated in an electric furnace or a combustion flame of a combustible gas (200 to 500 ° C.) to form a thick oxide on the surface of the spray coating. This treatment can be used as preheating (preheating) when applying a glassy thermal spray coating. (4) carbide cermets such as WC-Co, WC-Ni-Cr,
Thermal spray coatings such as Cr ₃ C ₂ —Ni—Cr also oxidize not only metal components but also carbides in a thermal spray heat source, and thus have good adhesion to the vitreous spray coating. However, if necessary, the carbide cermet film may be heated to 200 to 500 ° C. or Ni, Ni-C added as a binder.
0.1 to 3 wt% of Al with respect to metal components such as r and Co
Even if added, good adhesion to the vitreous film can be obtained.

The thickness of the undercoat sprayed coating is 20 to 500 μm. Particularly, a range of 50 to 300 μm is preferable. When the film thickness is less than 20 μm, the effect as undercoat is not sufficient.
Even if the thickness is larger than 0 μm, the effect of the action as the undercoat is saturated, which is economically disadvantageous. Further, the thickness of the surface oxide layer formed as required is preferably about 0.2 to 5 μm.

Next, the vitreous mixed thermal spray coating as a top coat formed on the undercoat thermal spray coating is the most characteristic component of the present invention. The above is a film formed in a mixed state with a glass material (glass-forming oxide that independently forms glass) powder. Cr, Ni, Fe, Mo, Co or Al
WC, Cr ₃ C ₂ , NbC, TiC, WTiC,
Al ₂ O ₃ , TiO ₂ , MgO, ZrO ₂ , Ta as a carbide or oxide material such as ZrC, TaC, HfC or MoC
Oxides such as ₂ O ₅ , Nb ₂ O ₅ or SiO _2, as borides, NiB ₂ , CrB ₂ , W ₂ B ₅ , TiB ₂ , Zr
Borides such as B ₂ , NbB ₂ or TaB ₂

Further, as the above glass material, Na ₂ O, K ₂
O, BaO, B ₂ O ₃ , SiO ₂ , MgO, CaO, PbO, LiO, SrO, SnO ₂
Glass-forming oxide such as is used as a main component. In addition, natural feldspar, natural silica, soda ash (Na ₂ CO ₃ ), borax (Na ₂ B ₂ O ₇ ), etc. are used as main raw materials, and SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ ,
Main component is CaF, Na ₂ O, K ₂ O, etc.
An enamel material to which O, MnO ₂ , NiO, TiO ₂ , ZnO, CoO, etc. are added can also be used.

These glass materials have a linear expansion coefficient of 4 to 4.
14 × 10^-6/ ° C with melting point in the range of 450 ° C to 750 ° C
It is desirable to use It has a linear expansion coefficient of 4 ×
Ten^-6If the temperature is less than / ° C, heating accompanying operation of the incineration plant
To be destroyed by repeated cooling
14 × 10 ^-6If the temperature is higher than / ℃,
Because it is difficult. Also, the melting point of the glass material is 450 ° C.
If it is too low, it may flow down during operation of the incineration plant
Conversely, glass materials with a melting point of 750 ° C or more
To SiO_TwoAnd the coefficient of linear expansion is
Small (4 × 10^-6/ ° C or less).
This is unsuitable as a light glass material.

The linear expansion coefficient and the melting point of the above glass material are adjusted by changing the contents of alkali metal components (Na ₂ O, K ₂ O) and SiO _2. Becomes larger and the melting point decreases, and the SiO ₂ component shows the opposite physical properties.

It is desirable that the particle diameter of the glass material powder including the above-described metals / alloys, oxides, borides, carbides, and carbide cermets be in the range of 5 to 150 μm. Particularly, those having a thickness of 10 to 60 μm are preferable. The reason is that if it is smaller than 5 μm, the probability of being superheated and scattered in the thermal spraying heat source is high, and the probability (yield) of adhering as a film becomes small. On the other hand, if the particle size is larger than 150 μm, the uniform dispersion of the various materials constituting the top coat will be poor, and the oxide and boride powders having a high melting point will be difficult to melt, and the affinity with the glass material will be reduced. It is because it causes.

The mixing ratio between the thermal spray material powder (metal / alloy, oxide, boride, carbide and carbide cermet) and the glass material is 95 to 5 vol% for the former and 5 to 95 vol% for the glass material. It is particularly preferable to mix the glass materials so that the average blending amount in the thickness direction of the glass material is 10 to 30 vol%. Because the glass material is 5
If the amount is less than vol%, the self-repairing effect (described later in detail) is not sufficient, while if it is more than 95 vol%, the effect as a mixed sprayed coating is saturated.

The thickness of the top coat sprayed coating is 10 to 10
When the thickness is less than 10 μm, the function as a top coat is insufficient.On the other hand, when the thickness is more than 1000 μm, the function as a top coat is maintained, but it takes a long time to form a film. It is not a good idea because it increases the cost.

In the case of the top coat mixed thermal spray coating formed on the under coat thermal spray coating, the surface layer may be reheated to form a re-melted glass layer having a thickness of 10 to 300 μm. A sprayed coating of 100% glass material may be formed as an outermost layer on the outermost portion of the coating. Such a mixed sprayed coating having a multilayer structure does not impair the performance of the highly corrosion resistant sprayed coating of the present invention at all. In addition, such a multilayered structure further improves the corrosion resistance and the self-repairing action.

When the top coat sprayed film formed as described above is heated to a temperature higher than the melting point of the glass material in a combustible gas flame or an electric furnace, only the vitreous material can be softened and melted. The pores generated during thermal spraying are completely eliminated by the treatment. Therefore, the use of such spray material covering members to the present invention as a member, such as municipal waste incineration plants, corrosive metal chlorides beginning gaseous HCl, such as Cl ₂ is able to penetrate into the solution morphism film Disappears.

One of the features of the vitreous mixed spray coating of the top coat according to the present invention is that even if the above-mentioned heat treatment is not performed, the combustion energy during operation of the municipal solid waste incineration equipment itself at the time of use is used. This also means that the sprayed coating easily exhibits a pore closing action, that is, a self-repair action. That is, this action is, for example, when the corrosion and wear portion of the waste heat recovery boiler of the municipal waste incineration plant is subjected to thermal spraying of the thermal spray coating member according to the present invention, the heat treatment step is omitted, and the municipal waste incineration plant is omitted. Exposure to combustion energy from municipal solid waste incinerators can also be replaced (self-repairing). Even if the sprayed coating is cracked due to heavy objects falling during operation or shutdown of the municipal solid waste incineration plant, when the garbage is restarted, the glass in the top coat sprayed coating is heated by the combustion heat of the municipal solid waste. The effect that only the material melts and softens to close the crack (hereinafter referred to as “the crack”).
This is called self-repairing action).

As described above, the feature of the present invention resides in the structure of the top coat sprayed coating. In particular, the composition of the material is not only a glass material but also a mixture of a metal and an alloy powder. The reason is that, since glass is generally an oxide, it does not deteriorate even after repeated heating and cooling, and even if a crack occurs in the coating, it can be softened and melted to repair the crack. . In addition, even if the metal powder contained in the top coat sprayed coating may be oxidized, it is contained as a glass component.
Since B ₂ O ₃ acts as a flux, the metal powder and the glass are not separated.

On the other hand, powders such as metals, alloys, oxides, borides, carbides, and carbide cermets among the constituents of the top coat sprayed film form a film by themselves and soften at high temperatures. It acts as an aggregate to compensate for the defects of glass with reduced erosion resistance, and these mixed materials complement each other to form a film that is both mechanically and chemically strong. ing.

(2) FIGS. 1 (b) and 1 (c) show the material in the top coat sprayed film formed on the undercoat sprayed film after the undercoat sprayed film is applied by the same material and the same method as in FIG. 1 (a). The composition ratio of the components is changed stepwise (b) or gradually (c). That is, the present invention relates to an example of a gradient composition in which a powder material such as a metal or an oxide is increased on the undercoat side in this film, and the ratio of the glass material is increased stepwise toward the surface side. Also, a gradient blending in which the blending ratio of a powder material such as a metal, an alloy, or an oxide and a glass material is continuously and gradually changed may be used. If necessary, a layer made of 100% glass material may be formed as the outermost layer. The mechanism of action of the thus sprayed top coat of the present invention is the same as that of the above-described coating of FIG. 1 (a), and has a self-repairing action.

As the thermal spraying method used for the high corrosion resistant thermal spray coating of the present invention, a flame spraying method using a combustible gas as a heat source, an arc spraying method using an electric heat source, a plasma spraying method, and the like for undercoating. For coating, the above-described flame spraying method, plasma spraying method, and sometimes explosive spraying method are effectively used.

[0041]

【Example】

 Example 1 In this example, penetration of a thermal spray coating which causes corrosion was performed.
The presence or absence of pores was confirmed by a salt spray test. (1) Base material: Carbon steel (SS400) 50mm wide x 100mm long x thickness
After cutting to 5mm, Al_TwoO _ThreeBrush the surface with powder
Strike processing. (2) Thermal spray material (spray coating according to the present invention) Thickness of undercoat thermal spray material and thermal spray film
did. a. 80wt% Ni-19.5wt% Cr-0.5wt% Al b. 50wt% Ni-20wt% Cr-29.5wt% Fe-0.5wt% Al c. 73wt% Cr_ThreeC_Two-20wt% Ni-6.5wt% Cr-0.5wt% Al Thickness of thermal spray coating and thermal spray coating 100μm thick by plasma spraying method using the following materials
did. a. (80wt% Ni-20wt% Cr) 80vol%-(the following component glass) 20
vol% b. (100wt% Al_TwoO_Three) 80vol%-(the following component glass) 20vol% c. (50wt% Ni-20wt% Cr-30wt% Fe) 70vol% −
(Las) 30 vol% d. (73wt% Cr_ThreeC_Two-20wt% Ni-7wt% Cr) 85vol%-(the following components
Glass) 30vol% 10wt% B as glass component_TwoO_Three-25wt% Na_TwoO-5wt% CaO-60wt
% SiO_TwoWas used. The glass component of the pure glass sprayed layer to be applied to the outermost layer
It was applied to a thickness of 30 μm by plasma spraying. (3) Heat treatment of thermal spray coating
For forming a lath layer, 820 ° C x 1 hour
Processed. The thermal spray coating of the comparative example is an undercoat.
The following materials are used as the d. 88wt% WC-12wt% Co e. 13wt% Cr-87wt% Fe 100% Al_TwoO_Three, 60wt% Al_TwoO_Three-40 wt% TiO_TwoTop Co
To plasma spray coating, 50μ for undercoat
m and the top coat were each formed to a thickness of 100 μm.

(4) Evaluation Test Method A 96-hour test was conducted according to the salt spray test method of JIS Z 2371 (1981), and then the appearance of the test piece was examined by visually observing the appearance of the test piece after standing for 24 hours. did. In addition, the occurrence of blue spots was investigated by contacting the surface of the test piece with filter paper containing ferroxil test solution (red blood salt 10 g / l, yellow blood salt 10 g / l, NaCl 60 g / l) as necessary. The occurrence of red rust was confirmed.

(5) Test Results Table 1 summarizes the test results. As is clear from these results, the coatings of Comparative Examples (Nos. 9 to 13) generated red rust on the coating surface regardless of the presence or absence of the thermal spray coating.
Its area reached 38% to 100% of the whole. The cause of the generation of red rust is that salt water penetrates into the through-holes present in the thermal sprayed coating, corrodes the SS400 of the base material, and the eluted iron ions become red rust and precipitate on the coating surface. Al ₂ O ₃ (No. 10), Al ₂ O ₃ -TiO ₂ (No. 1)
Even when 3) was applied, the area of red rust generation was slightly reduced due to the presence of through-holes in these oxide ceramic sprayed coatings, but the function as an anticorrosion coating was not recognized. On the other hand, in the case of having the glassy top coat mixed thermal spray coating member of the present invention, since the glass material is completely melted at the time of thermal spraying, through pores disappear and no generation of red rust is observed. In particular, those with a 100% glass film formed on the outermost layer (Nos. 2, 4, 3, and 8) and those completely melted at 820 ° C for 1 hour show no change from before the test. Did not. However, it was confirmed that three spots of fine spot-like red rust were generated on the film (No. 7) which was not subjected to the heat treatment even when the 100% glass film was formed. However, the extent was extremely minor.

[0044]

[Table 1]

Example 2 In this example, a confirmation test was performed on the effect of applying a shock to a thermal sprayed coating to generate a fine crack and then heating the same to repair the crack. (1) Substrate: Same as in Example 1 (2) Thermal spray material Undercoat thermal spray material and thermal spray coating thickness The following materials were applied to a thickness of 50 μm by plasma spraying, and then heated to 420 ° C. to spray the undercoat. Preheating was performed while promoting the formation of an oxide layer on the surface of the film, and subsequently, the top coat material was sprayed. a. 80wt% Ni-20wt% Cr b. _{73wt% Cr 3 C 2 -20wt%} Ni-7wt% Cr topcoat spray material and the sprayed coating thickness a. (80wt% Ni-20wt% Cr) 80vol%-(the following component glass) 20
vol% b. _{(100% Al 2 O 3)} 85vol% - ( following components Glass) 15 vol% c. (100% NiB) 85vol% − (the following component glass) 15vol% As glass component, 11wt% B ₂ O ₃ -14wt% Li ₂ O-3wt% Al ₂ O ₃ -2w
Glass components when applied to the outermost layer of t% SrO-70wt% SiO _{2 The} above glass components were applied to a thickness of 30 μm by plasma spraying. As a thermal spray coating of the comparative example, No. 10 in Table 1 (undercoat 80wt% Ni-20wt% Cr, topcoat 100% Al
₂ O _3), No.13 (undercoat 13wt% Cr -87wt% Fe, topcoat _{60wt% Al 2 O 3 -40wt%} TiO 2) was added, 88wt% WC-12wt% Co and 73 wt% Cr as a top coat ₃ C ₂ -20wt% Ni
-7wt% Cr was also tested. Heat treatment conditions for thermal spray coating: same as in Example 1.

(3) Evaluation test method A drop ball test method specified in JIS H 8663 (1961) Aluminum sprayed product test method (a steel ball having a diameter of 40 mm was tilted from a height of 1 m to 45 ° from all test pieces) After having cracked the sprayed coating in advance,
Heated at 0 ° C. × 1 hour. Thereafter, a salt spray test under the same conditions as in Example 1 was performed to investigate the occurrence of red rust.

(4) Test Results Table 2 summarizes the test results. As is clear from the results, in the thermal spray coatings of Comparative Examples (Nos. 7 to 10), a large amount of red rust was observed by the salt spray test in addition to the generation of cracks in the thermal spray coating due to the drop of steel balls. These thermal spray coatings contain porosity and fall into the top coat by falling steel balls.
Many cracks that can be distinguished visually are observed,
It is considered that since these cracks do not fuse even after the heat treatment, the inside of the salt water easily enters, and as a result of a corrosion reaction with the base material, a large amount of red rust is promoted. On the other hand, the coating of the present invention was formed as a vitreous and outermost layer contained in the top coat by heat treatment, although cracks occurred as in the sprayed coating of the comparative example due to the falling collision of the steel balls. No red rust was found in the salt spray test to completely fuse the glass layer and prevent internal penetration of the salt water. That is, even if the thermal spray coating of the present invention generates a crack due to a mechanical impact, the environment where the coating is heated to a temperature equal to or higher than the melting point of the vitreous contained in the coating, the crack generating portion itself is formed. It performs the function of repair.

[0048]

[Table 2]

Example 3 In this example, the corrosion resistance in a municipal solid waste combustion atmosphere was investigated. (1) Base material: 50 mm width using low alloy steel for boilers (STBA24)
A specimen cut into a length of 50 mm and a thickness of 3 mm was used as a test piece substrate. (2) Thermal spray material Undercoat thermal spray material and thermal spray coating thickness The following materials were applied to a thickness of 50 μm by the plasma spray method. a. 50wt% Ni-49.5wt% Cr-0.5wt% Al Top Coating Spray Material, Spray Coating Thickness, Spray Coating Structure The following materials were applied to the undercoat to a thickness of 200 μm by plasma spraying. a. 50wt% Ni-50wt% Cr / glassiness = 80/20 b. 100% CrB ₂ / glassy = 80/20 c. _{100% Al 2 O 3 / 27wt} % B 2 O 3 -18wt% L as glassy = 80/20 glass component to be mixed into the material
iO ₂ -4wt% SrO-3wt% CaO-2wt% Al ₂ O ₃ -2wt% TiO ₂ -2wt% ZnO-2wt
% ZrO ₂ -2 wt% SnO ₂ -2.5 wt% BaO- Remaining wt% SiO _{2 In} this example, a top coat was formed in which the mixing ratio of 50 wt% Ni-50 wt% Cr and the glass powder was changed stepwise. The structure was also tested. 50wt% Ni-50wt% Cr / glassiness = 95/5 50μm 50wt% Ni-50wt% Cr / glassiness = 80/20 50μm 50wt% Ni-50wt% Cr / glassiness = 50/50 50μm 50wt% Ni-50wt % Cr / glassiness = 20/80 50 μm Heat treatment conditions for sprayed coating: Same as in Example 1. As a comparative example, a film containing no glass component in the top coat and a low alloy steel for boilers not forming a sprayed coating are used. Was.

(3) Evaluation Test Method A chemical of the following composition simulating municipal waste incineration ash was applied as a corrosion medium to the surface of the test piece at a rate of 20 mg / cm ² , and in an atmosphere simulating the combustion gas of an incinerator. A high-temperature corrosion test was performed, and the corrosion resistance was evaluated by examining changes in the appearance and weight of the specimen surface. Corrosion _{medium: 65wt% PbCl 2 + 25wt%} KCl + 8wt% PbSO 4 + 2w
t% K ₂ SO ₄ corrosion Temperature and time: 550 ° C. × 20 hours Corrosion Atmosphere: 1000ppmHCl + 50ppmSO ₂ + remaining air

(4) Test results Table 3 summarizes the test results. from this result,
The untreated test piece (No. 12) of the comparative example suffered extremely severe corrosion damage, and had a thermal spray coating containing no glass component (No. 12).
9, 10, 11) but it is relatively strongly corroded, especially CrB ₂ , Al ₂
Topcoats such as O ₃ also showed localized exfoliation. On the other hand, in the thermal spray coatings (Nos. 1 to 8) according to the present invention, the action of the corrosive gas in the corrosive medium and atmosphere is weakened due to the presence of the glass component, the appearance change is small, and the corrosion amount is also comparative example. It was confirmed that it exhibited excellent corrosion resistance in municipal solid waste combustion gas.

[0052]

[Table 3]

Embodiment 4 In this embodiment, after applying a metal-based undercoat sprayed coating on a steel base material, the presence of an oxide (oxide coating) of the undercoat sprayed coating when the glass material is sprayed thereon. The presence or absence and the adhesion of the vitreous spray coating were investigated. (1) Base material: Carbon steel (SS400) is width 50 x length 100 x thickness 5 mm
Then, the surface was blasted using Al ₂ O ₃ powder. (2) Thermal spray material Undercoat thermal spray material a. 80wt% Ni-20wt% Cr b. 80wt% Ni-19.5wt% Cr-0.5wt% Al c. _{73wt% Cr 3 C 2 -20wt%} Ni-7 wt% Cr d. _{73wt% Cr 3 C 2 -20wt%} Ni-6.5 wt% Cr- is 0.5 wt% Al undercoat after construction to Yotsute 100 [mu] m thick plasma spraying, oxidation to the undercoat sprayed coating surface is heated to 400 ° C. Preheating was performed while promoting the formation of the material layer, and then a pure glass sprayed layer was formed by plasma spraying a glass material to a thickness of 50 μm on the surface of the top coat sprayed film. Top coat sprayed material a. _{10wt% B 2 O 3 -25wt%} Na 2 O-5wt% CaO -60wt% SiO 2 heat treatment top After coating construction was subjected to a heat treatment at 820 ° C. × 1 hour in an electric furnace. As a comparative example, a film obtained by applying the following undercoat sprayed coating to a thickness of 100 μm by a plasma spraying method was used. a. 80wt% Ni-20wt% Cr b. 60wt% Ni-20wt% Cr-15wt% Co-5wt% Mo At the time of spraying glass material on top coat spraying, normal temperature (no heating), heat treatment at 820 ° C for 1 hour after forming pure glass sprayed layer Implemented.

(3) Evaluation test method After leaving still in an electric furnace maintained at 150 ° C. for 10 minutes, it is taken out of the furnace and blown with compressed air at room temperature (15 ° C.) for 10 minutes as one cycle. 20 cycles were repeated for all the test pieces. Thereafter, the adhesion between the undercoat and the glassy topcoat was investigated by visually observing the surface of the test piece.

(4) Test Results Table 4 shows the test results. As is clear from the results, the thermal sprayed coatings of Comparative Examples (Nos. 8 and 9) were finely cracked, and only the topcoat sprayed coating had a processing area of 50%.
Peeled over 100100%. On the other hand, in the thermal spray coatings (Nos. 1 to 7) according to the present invention, although fine cracks occur in the glassy coating of the top coat, the adhesion area with the undercoat is good, so that the peeling area is 8% or less. Was. This effect is considered to be due to the formation of an oxide film by heating the undercoat sprayed film and the preferential formation of Al ₂ O ₃ by the addition of the Al component.

[0056]

[Table 4]

Example 5 In this example, the effect of the sealing material layer in the case where a vitreous topcoat sprayed film was formed on a metallic undercoat sprayed film without preheating the same was tested. (1) Base material: The carbon steel of Example 1 was used. (2) Thermal spray material (thermal spray material according to the present invention) Thickness of undercoat thermal spray material and thermal spray coating. ・ 80 wt% Ni-19 wt% Cr-0.5 wt% Si- It was applied to a thickness of 50 μm by a plasma spraying method using a 0.5 wt% Al sprayed material. . Topcoat spray material and the sprayed coating thickness a (80wt% Ni-20wt% Cr) 80 vol% - (10wt% B 2 O 3 -25
_{wt% Na 2 O-5 wt} % CaO -60wt% SiO 2) 20 vol% b. Upon that construction to 100μm thickness by plasma spraying using a _{10wt% B 2 O 3 -25wt%} Na 2 O-5wt% CaO -60wt% topcoat sprayed material SiO ₂ above composition, pre-heating of all the undercoat was omitted . (3) Heat treatment of thermal spray coating The thermal spray coating applied as described above was subjected to the following treatment. a. Heat treated at 820 ° C for 1 hour b. Without performing the heat treatment, the sealing material of the present invention (Na ₂ SiO
₍₂ ) Apply 40 wt% aqueous solution and dry at 200 ℃ for 1 hour)
C. After the treatment of (b), a heat treatment of 820 ° C. × 1 hour was performed. (4) As a film of a comparative example a. 50μm as undercoat of 80wt% Ni-20wt% Cr
Thick construction b. After applying an undercoat of 80 wt% Ni-20 wt% Cr to a thickness of 50 μm, 8 wt% Y ₂ O ₃ -92 wt% ZrO ₂ was applied thereon to a thickness of 100 μm, and each was applied by a plasma spraying method. (5) Evaluation test method: The same salt spray test as in Example 1 was conducted to investigate the presence or absence of through holes in the thermal spray coating.

(6) Test Results Table 5 shows the test results. As is evident from the results, red rust was generated over the entire surface only with the metallic sprayed coating of the comparative example (No. 7), and 8 wt.
% Y ₂ O ₃ -92wt% ZrO ₂ coating (No.8)
58% of the test specimen area was covered with red rust. In contrast, the composite sprayed coatings of the present invention (Nos. 1 to 6) generally showed good corrosion resistance. In particular, when the glassy top coat sprayed coating was heated (Nos. 1, 3, 5, and 6), generation of red rust was not observed at all. However, the above-mentioned sealing material is coated and the glassy top coat sprayed coating is not heated (No. 2,
In 5), only the generation of small red rust was observed at one or two places. It was confirmed that the presence of the sealing material layer filled the pores of the undercoat sprayed coating and prevented the penetration of corrosive components. Was done. From these results, even if a glassy top coat sprayed coating is applied on it without preheating the metallic undercoat sprayed coating, if a sealing material is applied in advance, penetration of corrosive gas will occur before use. When the temperature gradually rises above the melting point of the glass, the thermal spray coating of the top coat and the sealing material are fused and integrated to form a thermal spray coating exhibiting a self-repairing action. As sealing material, in place of the Na ₂ SiO _3, even with a material obtained by adding 10wt% NaB ₂ O ₇ on Na ₂ SiO ₃ was obtained similar sealing effect as Na ₂ SiO _3.

[0059]

[Table 5]

[0060]

As described above, Al and other metals and alloys or a carbide cermet are spray-coated as an undercoat, and then a metal, an alloy, a carbide cermet, an oxide, a boride and the like, and a glass material. The top coat is applied with a vitreous mixed thermal spray material mixed with, and, if necessary, a 100% glass layer is provided on the surface layer. As a result of the pores in the sprayed coating always disappearing, extremely excellent corrosion resistance is exhibited. In particular, the top coat spray coating containing a glass component unique to the present invention has a function of spontaneously fusing and repairing when heated to a temperature equal to or higher than the melting point of glass, even if a mechanical shock is applied for some reason and a crack occurs. So, even if applied to municipal solid waste incineration plant,
It is expected that the sprayed coating formed by the conventional technique will exhibit high corrosion resistance over the life of the coating.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a cross section of a vitreous high corrosion resistance thermal spray coating member according to the present invention.

[Description of Signs] 1 Base material 2 Undercoat sprayed coating 2a Oxide layer 3 Vitreous topcoat sprayed coating 3a Re-melted glass layer 4 Pure glass sprayed layer

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-62-222052 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 4/04, 4/10

Claims (16)

(57) [Claims] 1. A member comprising a steel base material and a multi-layer coating composed of an undercoat thermal spray coating and a top coat thermal spray coating coated thereon, wherein the undercoat thermal spray coating is entirely or The top coat spray coating contains at least 95 to 5 vol% of metal, oxide, boride, carbide and carbide cermet at least at the boundary with the top coat spray coating. One or more powders selected from among 5 to 95 vol
% Formed by spraying a mixture of a glass material, the film thickness is 10 to
A member coated with a glassy sprayed material having a self-repairing action, which is formed by a glassy mixed sprayed coating of 1000 μm . 2. A member formed by forming a multilayer coating consisting of an undercoat sprayed coating and a topcoat sprayed coating coated thereon on the surface of a steel base material, wherein the undercoat sprayed coating is entirely or The top coat spray coating contains at least 95 to 5 vol% of metal, oxide, boride, carbide and carbide cermet at least at the boundary with the top coat spray coating. One or more powders selected from among 5 to 95 vol
% Formed by spraying a mixture of a glass material, the film thickness is 10 to
A member coated with a self-repairing vitreous spray material, which is formed of a 1000 μm vitreous mixed spray coating and has a re-melted glass layer on the surface of the vitreous mixed spray coating. 3. The undercoat sprayed coating is formed on the entire or at least a boundary portion with the topcoat sprayed coating.
_{3. The} vitreous sprayed material-coated member according to claim 1, comprising ₂ O _{3. 4} . 4. The undercoat sprayed coating is an oxide-containing sprayed coating obtained by spraying Al and at least one material selected from other metals and alloys or carbide cermets, and has a thickness of 20%. The glassy sprayed material-coated member according to claim 1, 2, or 3, wherein the thickness is from 500 to 500 µm. 5. The top coat thermal spray coating according to claim 1, wherein a mixing ratio of a powder of at least one selected from metals, oxides, borides, carbides, and carbide cermets to the glass material is stepwise or gradual. The glassy sprayed material-coated member according to claim 1, wherein the coated member is formed by spraying a gradient compound powder that changes to: 6. The top coat sprayed coating formed by spraying the inclined compounding powder, wherein the compounding amount of the glass material is increased stepwise or gradually toward the outer surface. 6. The member coated with a vitreous spray material according to 5. 7. The glass material of the top coat sprayed coating including the re-melted layer is SiO ₂ , Na ₂ O, K ₂ O, B ₂ O ₃ , Al ₂
O ₃ , li ₂ O, CaO, MgO, TiO ₂ , ZnO, ZrO ₂ , SnO, SrO, B
It contains at least one glass-forming oxide selected from aO and CoO as a main component, and has a linear expansion coefficient of 4 to 14 × 10 ⁻¹⁶ / ° C and a melting point of 450 to 750 ° C. The vitreous sprayed material-coated member according to claim 1, 2, or 5, wherein: 8. The top coat sprayed coating according to any one of claims 1 to 7, further comprising:
A member coated with a glassy sprayed material, having a pure glass sprayed layer formed by spraying a glass material. 9. An applied / sprayed layer of a sealing material which generates SiO ₂ or B ₂ O ₃ by heating as an outermost layer on the thermal sprayed top coat film according to claim 1. A member coated with a vitreous spray material, comprising: 10. An undercoat sprayed film is formed by spraying at least one material selected from metals, alloys, and carbide cermets on the surface of a steel base material. boride, by spraying a mixture of 5 to 95 vol% 1 or more powder 95 to 5 vol% and a glass material selected from among carbides and carbide cermets, thickness 10
A method for producing a member coated with a glassy sprayed material having a self-repairing action, wherein a glassy mixed sprayed coating having a thickness of about 1000 μm is formed. 11. An undercoat sprayed film is formed by spraying at least one material selected from metals, alloys, and carbide cermets on the surface of a steel base material, and an undercoat sprayed film is formed thereon. boride, by spraying a mixture of 5 to 95 vol% 1 or more powder 95 to 5 vol% and a glass material selected from among carbides and carbide cermets, thickness 10
Forming a glassy mixed sprayed coating of ~ 1000 μm , then heating the glassy mixed sprayed coating to a temperature equal to or higher than the melting point of the glass material, and remelting the glass material to form a remelted glass layer on the surface layer. A method for producing a vitreous sprayed material-coated member having a self-repairing action. 12. A pure glass sprayed layer is formed on the outermost surface by spraying a sprayed material of 100% glass material on the glassy mixed sprayed coating as a top coat. Item 12. The production method according to item 10 or 11. 13. The method according to claim 10, wherein a sealing material that generates SiO ₂ or B ₂ O ₃ when heated is further applied or sprayed on the vitreous mixed thermal spray coating as the top coat. 12. The production method according to item 11. 14. The production method according to claim 10, wherein the re-melted layer in the thermal spray coating of the top coat is formed using combustion heat of a municipal solid waste incineration plant. 15. In the formation of the undercoat thermal spray coating, in addition to a metal / alloy or carbide cermet which is Ni, Fe, Fe-Cr, Fe-Ni-Cr or Ni-Cr as a thermal spraying material, Al is 0.1 to 0.1%. 14. The method according to claim 10, 11, 12 or 13, wherein 3 wt% is used. 16. In forming a top coat thermal spray coating, spraying a gradient compound powder in which the amount of glass material in the thermal spray material is increased stepwise or gradually from the undercoat surface to the outer surface. Claim 1.
15. The method according to 0, 11, 12, 13 or 14.