JP2021075783A - Manufacturing method of spray coating film coated member and spray coating film coated member - Google Patents

Abstract

To provide a manufacturing method of a spray coating film coated member capable of increasing an adhesion strength of a ceramic spray coating film, and reducing a strength reduction of a base material and a risk of a base material breakage of a ceramic sintered base material even when a blast processing for a base material composed of a ceramic sintered body is not performed.SOLUTION: A manufacturing method includes: an adjustment step of adjusting a space volume Vvv(μm3/μm2) of a surface to be spray coated 10 of a ceramic sintered base material 1 to a predetermined range; and a coating step of coating the surface to be spray coated 10 of the base material 1 with a slurry composed of water and a ceramic raw material powder of which average particle diameter D50 is in a range of 0.5 μm or more and 6 μm or less by plasma spraying. In the adjustment step, the space volume Vvv and the average particle size D50 are adjusted in a range of 0.001≤(Vvv/(D50)3)≤0.40.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for manufacturing a thermal spray film coating member and a thermal spray film coating member.

A thermal spray coating is formed on the surface of the base material for the purpose of protecting the base material and improving the function. For example, yttria (Y) is used to improve the plasma resistance, abrasion resistance, heat insulation, etc. of a ceramic base material made of silicon carbide (SiC), aluminum oxide (Al ₂ O _{3), aluminum nitride (AlN), or the like. Ceramics such as 2} O ₃ ), titania (TIO ₂ ), and chromia (Cr ₂ O ₃ ) may be sprayed.

Conventionally, in order to coat a base material with a ceramic sprayed film, a step of roughening the surface of the base material has been indispensable in order to bring the sprayed film into close contact before forming the sprayed film. For example, it is possible to roughen the surface of the base material by blasting, but it is caused by the decrease in strength and cracks of the base material due to the occurrence of cracks in non-metal base materials such as ceramic base materials. Since there is a possibility that the base material may be damaged, blasting may not be sufficiently performed. Therefore, there has been a demand for a blast-free method of forming a ceramic film on a ceramic base material by thermal spraying so as not to induce cracks.

In Patent Document 1, the SiC sintered body is roughened by blasting, and then the surface is oxidized _{to form a Y 2} O ₃ sprayed film on the surface, whereby SiO ₂ and Y ₂ O _{3 due to oxidation are formed.} A ceramic sprayed coating member that forms a double oxide and is bonded and adhered at the atomic level is disclosed. In Patent Document 2, a thin oxide film SiO ₂ layer is formed on the surface by irradiating the SiC base material with a laser to fill microcracks and obtain a chemical adhesion between the oxide film and the Al ₂ O _{3 sprayed film.} A method for manufacturing a thermal spray coating coating member that can be used is disclosed. Patent Document 3 discloses a slurry in which Al is used as a base material and the particle size D10 of the slurry raw material and the base material have a relationship of 0.4 <D10 / Ra ≦ 0.9, and a thermal spraying method.

Japanese Unexamined Patent Publication No. 2014-162934 WO2016 / 170895 JP-A-2018-154895

However, Patent Document 1 limits the materials that can be used as the base material and the thermal spray coating material to the material containing silicon and the material having a melting point higher than that of the siliceous layer, respectively, and therefore a general ceramic base material. And difficult to apply to ceramic sprayed materials. Further, since Patent Document 2 uses a material in which an oxide film is easily formed by laser irradiation as a base material, it is difficult to apply it to a general ceramic base material.

Further, although Patent Document 3 describes that ceramics can be used as a base material, an experiment is actually conducted on an aluminum base material, and a ceramic base material tends to have a weak adhesion. It is unclear whether similar results can be obtained with the combination of the ceramic sprayed film and the ceramic sprayed film.

The present invention has been made in view of such circumstances, and even when the base material made of the ceramics sintered body is not blasted, the adhesion strength of the ceramic sprayed film can be improved. It is an object of the present invention to provide a method for manufacturing a thermal sprayed film coating member capable of reducing a decrease in the strength of a base material of a ceramic sintered base material and a risk of damage to the base material.

(1) In order to achieve the above object, in the method for manufacturing a sprayed film coating member of the present invention, the space volume Vvv (μm ³ / μm ² ) of the sprayed surface of the ceramic sintered body base material is adjusted within a predetermined range. The adjustment step of thermal spraying and the coating step of coating the surface to be sprayed of the base material with a slurry composed of water and a ceramic raw material powder having an average particle diameter D50 of 0.5 μm or more and 6 μm or less are sprayed. Including, the adjusting step is characterized in that the space volume Vvv and the average particle size D50 are adjusted so as to be in the range of ^{0.001 ≦ (Vvv / (D50) 3) ≦ 0.40.} ..

As a result, the sprayed film can be brought into close contact with the base material without providing a step of roughening the surface to be sprayed of the base material by blasting, and the strength of the base material by blasting the ceramic base material. It is possible to reduce the risk of lowering and damage to the base material.

(2) Further, in the method for producing a thermal spray film coating member of the present invention, the ceramic sintered body is characterized in that it is a SiC sintered body. As a result, a ceramic sprayed film can be formed on a SiC sintered body, which is a brittle material and has poor adhesion to other ceramic materials, while reducing the risk of base material strength reduction and base material damage. Can be done.

(3) Further, in the method for producing a thermal spray film coating member of the present invention, the ceramic sintered body is characterized in that it _{is an Al 2} O _{3 sintered body. As a result, a ceramic sprayed film is formed on the Al 2} O ₃ sintered body, which is a brittle material and has poor adhesion to other ceramic materials, while reducing the risk of base material strength reduction and base material damage. Can be filmed.

(4) Further, in the method for producing a thermal spray film coating member of the present invention, the ceramic sintered body is characterized by being an AlN sintered body. As a result, a ceramic sprayed film can be formed on the AlN sintered body, which is a brittle material and has poor adhesion to other ceramic materials, while reducing the risk of base material strength reduction and base material damage. Can be done.

(5) Further, in the method for producing a thermal spray film coating member of the present invention, the plasma spraying is characterized by using a non-oxidizing gas. As a result, it is possible to prevent unnecessary oxidation of the base material surface, and by preventing oxidative deterioration of the thermal spray gun parts, it is possible to stably perform thermal spraying work with ensured adhesion.

(6) Further, in the method for producing a sprayed film coating member of the present invention, the ceramic raw material powder is a powder of alumina, yttria, zirconia, titania, chromia and yttrium alumina garnet, or an arbitrary mixed powder thereof. It is characterized by. These materials may not have good adhesion to a base material made of another ceramic material, but can be firmly adhered to the ceramic base material by the production method of the present invention.

(7) Further, in the method for producing a thermal spray film covering member of the present invention, the space volume Vvv is 0.01 or more and 0.30 or less. Thereby, the space volume Vvv of the sprayed surface of the ceramic sintered body base material can be adjusted within a predetermined range by polishing or grinding.

(8) Further, the thermal sprayed film coating member of the present invention is a thermal sprayed film coating member composed of a ceramics sintered body base material and a thermal sprayed film provided on the surface to be sprayed of the ceramics sintered body base material. ^{0.001 ≦ with respect to the space volume Vvv (μm 3} / μm ² ) of the sprayed surface of the ceramic sintered base material and the average particle size D50 (μm) of the ceramic raw material forming the sprayed film. (Vvv / (D50) ³ ) ≤0.40 is satisfied, and the ceramic sintered body base material and the elements constituting the sprayed coating are not chemically bonded to each other. As a result, it is possible to obtain a thermal spray film coating member in which the risk of the base material strength decrease and the base material breakage is reduced.

(9) Further, the sprayed film coating member of the present invention is a sprayed film coating member composed of a ceramics sintered body base material and a sprayed film provided on the surface to be exposed to the ceramics sintered body base material. ^{0.002 ≦ with respect to the space volume Vvv (μm 3} / μm ² ) of the surface to be exposed of the ceramic sintered base material and the average particle size D50 (μm) of the ceramic raw material forming the ceramic film. (Vvv / (D50) ³ ) ≤0.40 is satisfied, and the ceramic sintered body base material is a SiC sintered body, an AlN sintered body, or an Al ₂ O ₃ sintered body having a purity of 99.5% or more. It is characterized by being. As a result, it is possible to obtain a thermal spray film coating member in which the risk of the base material strength decrease and the base material breakage is reduced.

(10) Further, in the sprayed film coating member of the present invention, the ceramic sintered body base material is a SiC sintered body, an Al ₂ O ₃ sintered body, or an AlN sintered body, and the sprayed film is alumina. , Yttria, zirconia, titania, chromia, yttrium aluminum garnet, or any combination of two or more. As a result, it is possible to obtain a thermal spray film coating member in which the risk of the base material strength decrease and the base material breakage is reduced.

(11) Further, in the thermal spray film coating member of the present invention, the thermal spray film is characterized by being composed of any one or a combination of any one or more of alumina, yttria, zirconia, titania, chromia, and yttrium aluminum garnet. It is said. As a result, it is possible to obtain a thermal spray film coating member in which the risk of a decrease in the strength of the base material and the risk of damage to the base material is reduced.

According to the present invention, even when the base material made of the ceramic sintered body is not blasted, the adhesion strength of the ceramic sprayed film can be improved, and the base material strength of the ceramic sintered body base material can be improved. It is possible to manufacture a thermal sprayed film coating member in which a ceramic sprayed film is formed, while reducing the risk of deterioration and damage to the base material.

It is a schematic diagram which shows the thermal spray coating member of one Embodiment of this invention. It is a table which shows the manufacturing condition and evaluation of an Example and a comparative example. It is a table which shows the manufacturing condition and evaluation of an Example and a comparative example.

As a result of diligent research, the present inventors have adjusted the space volume Vvv (μm ³ / μm ² ) of the surface to be sprayed of the ceramic sintered body base material with respect to the average particle size D50 of the raw material particles to be sprayed. That is, by adjusting the relationship between the volume of the sprayed particles and the space volume of the base material so as to satisfy a certain range, even when the base material made of the ceramic sintered body is not blasted. It is possible to improve the adhesion strength of the ceramic sprayed film, reduce the risk of the base material strength of the ceramics sintered base material being lowered and the base material being damaged, and to manufacture the thermal sprayed film coating member on which the ceramic sprayed film is formed. Find out and complete the present invention.

That is, the method for manufacturing the thermal sprayed film coating member of the present invention ^{includes an adjusting step of adjusting the space volume Vvv (μm 3} / μm ² ) of the sprayed surface of the ceramic sintered body base material within a predetermined range, and the method of manufacturing the base material. The adjustment step includes a coating step of coating a surface to be sprayed by thermal spraying a slurry composed of water and a ceramic raw material powder having an average particle diameter D50 in the range of 0.5 μm or more and 6 μm or less. The volume is adjusted to be within the range of ^{0.001 ≦ (Vvv / (D50) 3} ) ≦ 0.40 with respect to the volume Vvv and the average particle size D50. Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the configuration diagram, the size of each component is conceptually represented, and does not necessarily represent the actual dimensional ratio.

[Manufacturing method of sprayed membrane coating member]
First, a ceramics sintered base material is prepared. As the ceramic sintered body base material, those formed of various materials can be used. For example, non-oxidizing ceramics such as SiC sintered body, silicon nitride sintered body and aluminum nitride sintered body, oxides such as Al ₂ O ₃ sintered body and Y ₂ O ₃ sintered body, YAG and the like. Double oxides and the like can be used. The ceramic sintered body base material is preferably formed of a SiC sintered body, an AlN sintered body, or an Al ₂ O ₃ sintered body. As a result, the strength of the base material is reduced and the base material is added to the SiC sintered body, the AlN sintered body, or the Al ₂ O _{3 sintered body, which is a brittle material and has poor adhesion to other ceramic materials.} A ceramic sprayed film can be formed while reducing the risk of breakage.

The ceramic sintered body base material may be produced by any method. The production conditions are appropriately selected depending on the type of the base material. For example, a hot press method or HIP can be used. For example, when the hot press method is used, a molded product can be produced by molding a mixed powder of a raw material powder and a sintering aid powder, and a sintered body can be produced by firing this. At this time, for example, the firing temperature is adjusted so as to be included in the temperature range of 1650 to 1950 ° C, more preferably 1750 to 1900 ° C. The firing time (holding time of firing temperature) is adjusted to be included in the time range of 2 to 10 hours. The press pressure at the time of firing is adjusted so as to be included in the pressure range of 1 to 15 MPa. The firing temperature and firing time are also changed depending on the type of raw material powder, sintering aid powder, and the like.

^{Next, the space volume Vvv (μm 3} / μm ² ) of the surface to be sprayed of the prepared ceramic sintered body base material is adjusted to a predetermined range. The space volume Vvv is adjusted to a predetermined range by, for example, polishing, grinding, or the like on the surface to be sprayed of the prepared ceramics sintered base material. In the present specification, the space volume Vvv means the void volume of the valley portion at a load area ratio of 80%. The measurement of the space volume Vvv (μm ³ / μm ² ) can be performed by using a coherence correlation interferometer or the like in accordance with ISO 25178.

The surface to be sprayed may be blasted, but depending on the abrasive used and the spraying strength, minute cracks may occur in the non-metal substrate such as the ceramic sintered substrate. .. Since such cracks may reduce the strength of the base material or damage the base material due to the cracks, sufficient care must be taken when performing the blasting process. That is, when the blasting process is performed, it is performed so that cracks do not occur depending on the material of the base material and the like. Since the method of the present invention does not need to roughen the surface to be sprayed, it is not necessary to perform blasting with a spray strength at which cracks occur. Therefore, it is also possible to use the blasting process after adjusting the strength.

However, in the case of polishing or grinding, there is little possibility that a problematic crack will occur. Therefore, when processing the surface to be sprayed of the ceramic sintered body base material, polishing or grinding is preferable. .. Further, if the space volume Vvv of the sprayed surface of the sintered body is within a predetermined range in the state of the baked surface after sintering, processing may not be performed.

The surface to be sprayed is adjusted by 0.001 ≦ (Vvv / (Vvv /) with respect to the space volume Vvv and the average particle size D50 according to the average particle size D50 of the ceramic raw material powder contained in the slurry used in the coating step described later. D50) ³ ) Adjust so that the range is ≤0.40. In this adjustment, the surface to be sprayed is processed based on the average particle size D50 of the ceramic raw material powder to be used, and then the space volume Vvv is measured. If it is not included in the above range, the surface to be sprayed is further processed. After processing the surface to be sprayed, the space volume Vvv is measured, and the ceramic raw material powder used is changed based on the measurement result of the space volume Vvv. You may. The space volume Vvv (μm ³ / μm ² ) is preferably 0.01 or more and 0.30 or less.

Next, the ceramic raw material powder and water contained in the range of the average particle size D50 of 0.5 μm or more and 6 μm or less are prepared and mixed to prepare a slurry. The average particle size D50 of the ceramic raw material powder is preferably 0.5 μm or more and 6 μm or less. When D50 is smaller than 0.5 μm, the viscosity of the slurry becomes high, so that thermal spraying becomes difficult and the film quality deteriorates. On the other hand, if it is larger than 6 μm, the film quality deteriorates because the slurry cannot be stably transported. The average particle size D50 can be measured by using a dry measurement or a wet measurement of a laser diffraction / scattering particle size distribution measuring device. The particle size distribution of the ceramic raw material powder is preferably sharp.

Various materials can be used as the ceramic raw material powder. Ceramic raw material powders include, for example, alumina (Al ₂ O ₃ ), yttrium (Y ₂ O ₃ ), zirconia (ZrO ₂ ), titania (TIO ₂ ), chromia (Cr ₂ O ₃ ), and yttrium aluminum garnet (Y). ₃ Al ₅ O ₁₂ , also referred to as YAG), silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), aluminum nitride (AlN) powder, or any mixed powder thereof is preferably used. These materials are used for various purposes such as protection of a base material and improvement of functions, but when the base material is formed of a ceramic sintered body, adhesion to the base material may become a problem. In the production method of the present invention, even when the base material is formed of a ceramic sintered body, ceramic spraying using these materials is performed while reducing the risk of strength reduction and base material damage of the base material. A film can be formed.

The concentration of the slurry is preferably 10 wt% or more and 40 wt% or less, and more preferably 20 wt% or more and 40 wt% or less. If the concentration of the slurry is less than 10 wt%, the construction takes time and the productivity is reduced, so that it is not industrial. On the other hand, if it is larger than 40 wt%, the viscosity becomes high and the slurry cannot be stably transported.

Then, the prepared slurry is coated by plasma spraying on the surface to be sprayed of the base material. The gas used for thermal spraying is preferably a non-oxidizing gas. As the non-oxidizing gas, for example, Ar gas, H ₂ gas or N ₂ gas, or a mixed gas of any combination thereof can be used. The slurry is supplied to the nozzle via a tube pump and plasma sprayed using a gas.

Before the step of plasma spraying, a step of plasma-irradiating the surface to be sprayed of the base material with only the gas to which the slurry is not charged may be provided. By providing such a step, the surface to be sprayed of the base material is preheated, and the ceramic raw material powder melted during plasma spraying easily penetrates into the void.

As a result, as shown in FIG. 1, a ceramic sprayed film 2 derived from the slurry that covers the sprayed surface 10 of the base material 1 is formed. The thickness of the ceramic sprayed film 2 is preferably adjusted to 50 to 500 μm. This is because if the thickness of the sprayed film 2 is less than 50 μm, there is an increased risk that the functions of the sprayed film 2 such as plasma resistance, abrasion resistance, and heat insulating property will deteriorate. Further, if the thickness of the sprayed film 2 exceeds 500 μm, the internal stress of the sprayed film 2 becomes large, and the possibility that the adhesion force is lowered or peeling is increased increases. The porosity of the ceramic sprayed film 2 is preferably adjusted to 1 to 5%.

By such a manufacturing method, the adhesion strength of the ceramic sprayed film can be improved even when the base material made of the ceramic sintered body is not blasted, and the base material of the ceramic sintered body base material. It is possible to manufacture a thermal sprayed film coating member in which a ceramic sprayed film is formed, while reducing the risk of strength decrease and base material damage.

In the production method of the present invention, since the size of the space volume Vvv of the sprayed surface of the ceramic sintered body base material and the average particle size D50 of the raw material powder match, the molten particle size in which the raw material powder particles are melted is the base material. It is presumed that an appropriate amount of invading voids of several μm or less remaining on the surface of the ceramic, forming a pancake (splat) with this as a core, and adhering to the base material. That is, since a micron anchor effect is generated by the minute voids remaining on the surface in the state where the base material is ground and polished and adheres to the base material, it is not necessary to blast the base material for roughening. The risk of incentives for cracks can be avoided.

[Sprayed film coating member]
The thermal spray film coating member of the present invention comprises a ceramics sintered body base material and a thermal sprayed film provided on the surface to be sprayed of the ceramics sintered body base material. ^{0.001 ≦ (Vvv / (Vvv /) with respect to the space volume Vvv (μm 3} / μm ² ) of the surface to be sprayed of the ceramic sintered body base material and the average particle size D50 (μm) of the ceramic raw material forming the sprayed film. D50) ³ ) Satisfy ≤0.40. In addition, there are no chemical bonds between the elements that make up the ceramic sintered base material and the thermal spray film.

The absence of chemical bonds between the ceramic sintered base material and the elements constituting the sprayed film means that the sprayed film and the base material are in physical contact with each other due to the so-called anchor effect. That is, the sprayed particles in the molten state enter the fine valleys existing in the base material, and the sprayed particles solidify in the valleys. Then, the cooled and solidified sprayed particles exert a compressive stress on the base material, and as a result, the base material and the sprayed film are in close contact with each other due to the frictional force acting between the base material and the solidified sprayed particles. .. The absence of chemical bonds between the elements constituting the ceramic sintered body base material and the sprayed film can be confirmed by the fact that no reaction layer is formed between the ceramics sintered body base material and the sprayed film.

^{Further, the spatial volume Vvv (μm 3} / μm ² ) of the sprayed surface of the ceramic sintered body base material can be measured using a coherence correlation interferometer. The space volume Vvv (μm ³ / μm ² ) of the sprayed surface in the present specification is a value measured with the load area ratio as 80%. Further, the average particle size D50 (μm) of the ceramic raw material forming the thermal spray film can be measured by a particle size measuring device by a laser diffraction / scattering method.

The ceramic sintered body base material can be selected from various materials. For example, non-oxidizing ceramics such as SiC sintered body, silicon nitride sintered body and aluminum nitride sintered body, oxides such as Al ₂ O ₃ sintered body and Y ₂ O ₃ sintered body, YAG and the like. It can be a compound oxide or the like. The ceramic sintered body base material is preferably formed of a SiC sintered body, an AlN sintered body, or an Al ₂ O ₃ sintered body. As a result, ceramics can be used as a ceramic sintered base material made _{of a SiC sintered body, an AlN sintered body, or an Al 2} O ₃ sintered body, which is a brittle material and has poor adhesion to other ceramic materials. It is possible to form a spray film coating member on which a spray film is formed, and it is possible to reduce the risk of a decrease in strength of the base material and damage to the base material.

The sprayed film preferably comprises any one or a combination of any one or more of alumina, yttria, zirconia, titania, chromia, and yttrium aluminum garnet. As a result, it is possible to obtain a sprayed film coating member in which the risk of a decrease in the strength of the base material and the risk of damage to the base material is reduced, and it can be applied to various uses. Combining two or more means that the sprayed film is formed by a mixture of particles made of different raw materials.

The thermal spray film coating member of the present invention is a thermal spray film coating member in which the ceramic sintered body base material and the thermal spray film are in close contact with each other by the anchor effect, so that the strength of the base material is reduced and the risk of base material damage is reduced. Can be done.

[Examples and Comparative Examples]
(Example 1)
(Base material preparation process)
98% purity, the SiC raw material powder having an average particle diameter of 0.5 [mu] m, by adding carbon and _{B 4} C, and an organic binder as a sintering aid, by CIP (cold isotropic pressure pressing) molding, 1 ton / cm ^{Hydrostatic molding was performed in step 2} to prepare a SiC molded body. Then, the SiC molded body _{N 2} atmosphere, to prepare a SiC sintered body form 3 hours atmospheric pressure at 2000 ° C.. Next, the SiC sintered body was processed into a substantially rectangular plate shape (or substantially square plate shape) having a length of 100 mm, a width of 100 mm, and a thickness of 5 mm to prepare a SiC sintered body base material. ^{At this time, the space volume Vvv (μm 3} / μm ² ) is adjusted to 0.010 by polishing one main surface of the SiC sintered body base material, and the average particle size of the raw material powder used in the plasma spraying step is adjusted. By setting the diameter D50 to 0.5 μm, the value of (Vvv / (D50) ³ ) was adjusted to 0.0800. The space volume Vvv was measured using a coherence correlation interferometer (manufactured by Taylor Hobson). In this way, the SiC sintered body base material of Example 1 was prepared.

(Plasma irradiation process)
Next, a non-oxidizing gas plasma was irradiated or sprayed onto the sprayed surface of the base material using a high-speed plasma sprayer to preheat the sprayed surface. As the non-oxidizing gas, a mixed gas of _{Ar gas, N 2} gas and H _{2 gas was used.} The supply amount of Ar gas to the nozzles constituting the thermal sprayer was controlled to 100 _{l / min, the supply amount of N 2} gas was controlled to 70 l / min, and _{the supply amount of H 2} gas was controlled to 70 l / min.

By controlling the current applied to the nozzles constituting the high-speed plasma sprayer to 250 A, the power supplied to the nozzles was adjusted to 65 kW. The distance between the tip of the nozzle and the sprayed surface of the base material was adjusted to 75 mm. The scanning speed or displacement speed of the nozzle with respect to the substrate was adjusted to 850 mm / s. As a result, _{a plasma of a mixed gas of Ar gas, N 2} gas and H ₂ gas was generated, and the plasma was irradiated or jetted from the tip of the nozzle to the sprayed surface of the base material. Preheating of the sprayed surface by plasma irradiation or injection was performed for 3 minutes.

(Plasma spraying process)
Then, the high-velocity plasma spray gun used as it is, the Y ₂ O ₃ slurry was plasma spray against surface to be thermal sprayed of the substrate using a non-oxidizing gas. The slurry had an average particle diameter D50 was adjusted with _Y 2 _{O 3} raw material powder 300g of 99.9% purity or higher is 0.5 [mu] m, the _Y 2 _{O 3} slurry by mixing water 700 g. As the non-oxidizing gas, a mixed gas of _{Ar gas, N 2} gas and H _{2 gas was used.} The supply amount of Ar gas to the nozzles constituting the thermal sprayer was controlled to 100 _{l / min, the supply amount of N 2} gas was controlled to 70 l / min, and _{the supply amount of H 2} gas was controlled to 70 l / min. As a result, the thermal spraying rate was controlled to 600 to 700 mm / s.

By controlling the current applied to the nozzles constituting the high-speed plasma sprayer to 250 A, the power supplied to the nozzles was adjusted to 65 kW. The distance between the tip of the nozzle and the sprayed surface of the base material was adjusted to 75 mm. The scanning speed or displacement speed of the nozzle with respect to the substrate was adjusted to 850 mm / s. As a result, _{a plasma of a mixed gas of Ar gas, N 2} gas and H ₂ gas was generated, and the raw material powder melted by the plasma was sprayed from the tip of the nozzle onto the sprayed surface of the base material. Thus, to form a sprayed film covering member in Example 1, the spray coat surface of the SiC ceramic substrate is coated with Y ₂ O ₃ sprayed coating.

(Example 2)
Example 2 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.190, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.1900 by setting the value to 1.0 μm. Other than that, the sprayed film covering member of Example 2 was formed according to the same conditions as in Example 1.

(Example 3)
Example 3 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.060, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0600 by setting the value to 1.0 μm. Other than that, the thermal spray film covering member of Example 3 was formed according to the same conditions as in Example 1.

(Example 4)
Example 4 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.190, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0070 by setting the value to 3.0 μm. Other than that, the sprayed film covering member of Example 4 was formed according to the same conditions as in Example 1.

(Example 5)
Example 5 is an example in which the type of thermal spraying raw material, the space volume Vvv, and the average particle size D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.190, and the type of raw material powder contained in the slurry is changed to Al ₂ O. ₃ and then, to adjust the average particle diameter D50 by a 3.0μm value of (Vvv / ^{(D50) 3)} to 0.0070. Other than that, the thermal spray film covering member of Example 5 was formed according to the same conditions as in Example 1.

(Example 6)
Example 6 is an example in which the type of thermal spraying raw material, the space volume Vvv, and the average particle size D50 are different from those of Example 1. The space volume Vvv was adjusted to 0.190 by grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, and the type of raw material powder contained in the slurry was set to YAG. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0070 by setting the average particle size D50 to 3.0 μm. Other than that, the thermal spray film covering member of Example 6 was formed according to the same conditions as in Example 1.

(Example 7)
Example 7 is an example in which the type of thermal spraying raw material, the space volume Vvv, and the average particle size D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.190, and the type of raw material powder contained in the slurry is 8 mL% Y. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0070 by _{setting 2} O _3- ZrO ₂ and setting the average particle size D50 to 3.0 μm. Other than that, the sprayed film covering member of Example 7 was formed according to the same conditions as in Example 1.

(Example 8)
Example 8 is an example in which the type of thermal spraying raw material, the space volume Vvv, and the average particle size D50 are different from those of Example 1. The space volume Vvv was adjusted to 0.190 by grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, and _{the type of raw material powder contained in the slurry was set to TiO 2.} ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0070 by setting the average particle size D50 to 3.0 μm. Other than that, the thermal spray film covering member of Example 8 was formed according to the same conditions as in Example 1.

(Example 9)
Example 9 is an example in which the type of thermal spraying raw material, the space volume Vvv, and the average particle size D50 are different from those of Example 1. By grinding the one main surface of the SiC ceramic substrate surface to be thermal sprayed at a substrate preparation step, and adjust the space volume Vvv 0.190, the kind of the raw material powder contained in the slurry Cr ₂ O ₃ and then, to adjust the average particle diameter D50 by a 3.0μm value of (Vvv / ^{(D50) 3)} to 0.0070. Other than that, the sprayed film covering member of Example 9 was formed according to the same conditions as in Example 1.

(Example 10)
(Base material preparation process)
Example 10 is an example in which the type of raw material of the base material, the space volume Vvv, and the average particle size D50 are different from those of Example 1. MgO and an organic binder were added as sintering aids to _{Al 2} O ₃ raw material powder with a purity of 99.5% and an average particle size of 0.5 μm, and hydrostatic molding was performed at 1 ^{ton / cm 2 by the CIP molding method.} , Al ₂ O ₃ molded article was prepared. Next, the Al ₂ O ₃ molded product was fired at 1600 ° C. for 3 hours at normal pressure in an air atmosphere _{to prepare an Al 2} O ₃ sintered body. Next, the Al ₂ O ₃ sintered body was processed into a substantially rectangular plate shape (or substantially square plate shape) having a length of 100 mm, a width of 100 mm, and a thickness of 5 mm _{to prepare an Al 2} O ₃ sintered body base material. At this time, the space volume Vvv was adjusted to 0.150 by grinding one main surface of _{the Al 2} O _{3 sintered base material.} In this way, the Al ₂ O ₃ sintered body base material of Example 10 was prepared.

By setting the average particle size D50 of the _{Y 2} O ₃ raw material powder contained in the slurry _{to 3.0 μm with respect to the Al 2} O ₃ sintered base material prepared in the above base material preparation step (Vvv / (D50)). ^{The value of 3} ) was adjusted to 0.0056. Other than that, the sprayed film covering member of Example 10 was formed according to the same conditions as in Example 1.

(Example 11)
Example 11 is an example in which the space volume Vvv is different from that of Example 1. The value ^{of (Vvv / (D50) 3} ) was adjusted by adjusting the space volume Vvv to 0.042 by grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step. It was adjusted to 0.3360. Other than that, the sprayed film covering member of Example 11 was formed according to the same conditions as in Example 1.

(Example 12)
Example 12 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.042, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0420 by setting the value to 1.0 μm. Other than that, the thermal spray film covering member of Example 12 was formed according to the same conditions as in Example 1.

(Example 13)
Example 13 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 1. By sandblasting one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.550, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0204 by setting the value to 3.0 μm. Other than that, the thermal spray film covering member of Example 13 was formed according to the same conditions as in Example 1.

(Example 14)
Example 14 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 1. By sandblasting one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.550, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0060 by setting it to 4.5 μm. Other than that, the thermal spray film covering member of Example 14 was formed according to the same conditions as in Example 1.

(Example 15)
Example 15 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 1. By sandblasting one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.320, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0119 by setting the value to 3.0 μm. Other than that, the thermal spray film covering member of Example 15 was formed according to the same conditions as in Example 1.

(Example 16)
Example 16 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 1. By sandblasting one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.310, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0014 by setting the value to 6.0 μm. Other than that, the thermal spray film covering member of Example 16 was formed according to the same conditions as in Example 1.

(Comparative Example 1)
Comparative Example 1 is a comparative example in which the space volume Vvv is different from that of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.060, and the value ^{of (Vvv / (D50) 3) is adjusted.} It was adjusted to 0.4800. Other than that, the thermal spray film covering member of Comparative Example 1 was formed according to the same conditions as in Example 1.

(Comparative Example 2)
Comparative Example 2 is a Comparative Example in which the space volume Vvv and the average particle diameter D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.020, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0007 by setting the value to 3.0 μm. Other than that, the thermal spray film covering member of Comparative Example 2 was formed according to the same conditions as in Example 1.

(Comparative Example 3)
Comparative Example 3 is a Comparative Example in which the space volume Vvv and the average particle diameter D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.042, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0005 by setting it to 4.5 μm. Other than that, the thermal spray film covering member of Comparative Example 3 was formed according to the same conditions as in Example 1.

(Comparative Example 4)
Comparative Example 4 is a Comparative Example in which the space volume Vvv and the average particle diameter D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.042, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0002 by setting the value to 6.0 μm. Other than that, the thermal spray film covering member of Comparative Example 4 was formed according to the same conditions as in Example 1.

(Comparative Example 5)
Comparative Example 5 is a comparative example in which the space volume Vvv is different from that of Example 1. The value ^{of (Vvv / (D50) 3} ) was adjusted by adjusting the space volume Vvv to 0.550 by sandblasting one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step. Adjusted to 4.4000. Other than that, the thermal spray film covering member of Comparative Example 5 was formed according to the same conditions as in Example 1.

(Comparative Example 6)
Comparative Example 6 is a Comparative Example in which the space volume Vvv and the average particle diameter D50 are different from those of Example 1. By sandblasting one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.550, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.5500 by setting it to 1.0 μm. Other than that, the thermal spray film covering member of Comparative Example 6 was formed according to the same conditions as in Example 1.

(Comparative Example 7)
Comparative Example 7 is a Comparative Example in which the space volume Vvv and the average particle diameter D50 are different from those of Example 1. By grinding one main surface of the SiC sintered body base material on the surface to be sprayed in the base material preparation step, the space volume Vvv is adjusted to 0.190, and the average particle size D50 of the raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.0009 by setting the value to 6.0 μm. Other than that, the thermal spray film covering member of Comparative Example 7 was formed according to the same conditions as in Example 1.

(Comparative Example 8)
Comparative Example 8 is a comparative example manufactured by a conventional manufacturing method. In the base material preparation process, the space volume Vvv is adjusted to 1.480 by sandblasting one main surface of the SiC sintered body base material to be sprayed, and the raw material powder is used as it is as a gas instead of wet spraying with a slurry. Thermal spraying was performed by dry spraying. _{Granular Y 2} O ₃ was used as the raw material powder. The average particle size D50 of the raw material powder granules was 30.0 μm. Formally, the value of (Vvv / (D50) ³ ) was calculated to be 0.0001.

(Example 17)
Example 17 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 10. The space volume Vvv is adjusted to 0.161 by grinding one main surface of the _{Al 2} O ₃ sintered base material with a purity of 99.5% of the surface to be sprayed in the base material preparation step, and is included in the slurry. The value of (Vvv / (D50) ³ ) was adjusted to 0.1610 by setting the average particle size D50 of the Y ₂ O _{3 raw material powder to 1.0 μm.} Other than that, the thermal spray film covering member of Example 17 was formed according to the same conditions as in Example 10.

(Comparative Example 9)
Comparative Example 9 is a comparative example in which the average particle size D50 is different from that of Example 17. The value of (Vvv / (D50) ³ ) was adjusted to 1.2880 by setting _{the average particle size D50 of the Y 2} O ₃ raw material powder contained in the slurry to 0.5 μm. Other than that, the thermal spray film covering member of Comparative Example 9 was formed according to the same conditions as in Example 17.

(Example 18)
Example 18 is an example in which the average particle size D50 is different from that of Example 17. The value of (Vvv / (D50) ³ ) was adjusted to 0.0060 by setting _{the average particle size D50 of the Y 2} O ₃ raw material powder contained in the slurry to 3.0 μm. Other than that, the thermal spray film covering member of Example 18 was formed according to the same conditions as in Example 17.

(Example 19)
Example 19 is an example in which the average particle size D50 is different from that of Example 17. The value of (Vvv / (D50) ³ ) was adjusted to 0.0018 by setting _{the average particle size D50 of the Y 2} O ₃ raw material powder contained in the slurry to 4.5 μm. Other than that, the thermal spray film covering member of Example 19 was formed according to the same conditions as in Example 17.

(Comparative Example 10)
Comparative Example 10 is a comparative example in which the average particle size D50 is different from that of Example 17. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0007 by setting the average particle size D50 of the _{Y 2} O ₃ raw material powder contained in the slurry to 6.0 μm. Other than that, the thermal spray film covering member of Comparative Example 10 was formed according to the same conditions as in Example 17.

(Example 20)
Example 20 is an example in which the type of thermal spraying raw material and the average particle size D50 are different from those of Example 17. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0060 by setting the sprayed raw material contained in the slurry as YAG and setting the average particle size D50 of the YAG raw material powder to 3.0 μm. Other than that, the thermal spray film covering member of Example 20 was formed according to the same conditions as in Example 17.

(Example 21)
Example 21 is an example in which the type of thermal spraying raw material and the average particle size D50 are different from those of Example 17. The thermal spraying raw material contained in the slurry is 8 mL% Y ₂ O _{3- ZrO 2} , and the average particle size D50 of the 8 mL% Y ₂ O _{3- ZrO 2} raw material powder is 3.0 μm (Vvv / (D50) ³ ). The value of was adjusted to 0.0060. Other than that, the thermal spray film covering member of Example 21 was formed according to the same conditions as in Example 17.

(Example 22)
Example 22 is an example in which the base material, the space volume Vvv, and the average particle size D50 are different from those of the example 17. In the base material preparation step of Example 17, the _{purity of the Al 2} O ₃ raw material powder was 99.8%. Then, by grinding one main surface of the 99.8% pure Al ₂ O ₃ sintered base material, the space volume Vvv is adjusted to 0.047, and the Y ₂ O ₃ raw material powder contained in the slurry is adjusted. The value of (Vvv / (D50) ³ ) was adjusted to 0.3760 by setting the average particle size D50 to 0.5 μm. Other than that, the sprayed film covering member of Example 22 was formed according to the same conditions as in Example 1.

(Example 23)
Example 23 is an example in which the average particle size D50 is different from that of Example 22. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0470 by setting the average particle size D50 of the _{Y 2} O ₃ raw material powder contained in the slurry to 1.0 μm. Other than that, the thermal spray film covering member of Example 23 was formed according to the same conditions as in Example 22.

(Example 24)
Example 24 is an example in which the average particle size D50 is different from that of Example 22. The value of (Vvv / (D50) ³ ) was adjusted to 0.0017 by setting _{the average particle size D50 of the Y 2} O ₃ raw material powder contained in the slurry to 3.0 μm. Other than that, the thermal spray film covering member of Example 24 was formed according to the same conditions as in Example 22.

(Comparative Example 11)
Comparative Example 11 is a comparative example in which the average particle size D50 is different from that of Example 22. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0005 by setting the average particle size D50 of the _{Y 2} O ₃ raw material powder contained in the slurry to 4.5 μm. Other than that, the sprayed film covering member of Example 22 was formed according to the same conditions as in Example 1.

(Comparative Example 12)
Comparative Example 12 is a comparative example in which the average particle size D50 is different from that of Example 22. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0002 by setting the average particle size D50 of the _{Y 2} O ₃ raw material powder contained in the slurry to 6.0 μm. Other than that, the thermal spray film covering member of Comparative Example 12 was formed according to the same conditions as in Example 22.

(Example 25)
(Base material preparation process)
Example 25 is an example in which the type of raw material of the base material, the space volume Vvv, and the average particle size D50 are different from those of Example 1. 98% purity, the AlN raw material powder having an average particle diameter of 0.5 [mu] m, were added _Y 2 _{O 3} and an organic binder as a sintering aid, by CIP molding, and the isostatic pressing at 1 ton / cm ^2, AlN A molded product was produced. Next, the AlN molded product was fired at 550 ° C. for 12 hours at normal pressure in an air atmosphere to prepare an AlN sintered body. Next, the AlN sintered body was processed into a substantially rectangular plate shape (or substantially square plate shape) having a length of 100 mm, a width of 100 mm, and a thickness of 5 mm to prepare an AlN sintered body base material. At this time, the space volume Vvv was adjusted to 0.158 by grinding one main surface of the AlN sintered body base material. In this way, the AlN sintered body base material of Example 25 was prepared.

To the above base material preparation step AlN sintered body base material prepared in the average particle diameter D50 of _Y 2 _{O 3} raw material powder contained in the slurry by a 1.0μm of (Vvv / ^{(D50) 3)} The value was adjusted to 0.1580. Other than that, the thermal spray film covering member of Example 25 was formed according to the same conditions as in Example 1.

(Comparative Example 13)
Comparative Example 13 is a comparative example in which the average particle size D50 is different from that of Example 25. The value of (Vvv / (D50) ³ ) was adjusted to 1.2640 by setting _{the average particle size D50 of the Y 2} O ₃ raw material powder contained in the slurry to 0.5 μm. Other than that, the thermal spray film covering member of Comparative Example 13 was formed according to the same conditions as in Example 25.

(Example 26)
Example 26 is an example in which the average particle size D50 is different from that of Example 25. The value of (Vvv / (D50) ³ ) was adjusted to 0.0059 by setting _{the average particle size D50 of the Y 2} O ₃ raw material powder contained in the slurry to 3.0 μm. Other than that, the thermal spray film covering member of Example 26 was formed according to the same conditions as in Example 25.

(Example 27)
Example 27 is an example in which the average particle size D50 is different from that of Example 25. The value of (Vvv / (D50) ³ ) was adjusted to 0.0017 by setting _{the average particle size D50 of the Y 2} O ₃ raw material powder contained in the slurry to 4.5 μm. Other than that, the thermal spray film covering member of Example 25 was formed according to the same conditions as in Example 1.

(Example 28)
Example 28 is an example in which the type of thermal spraying raw material and the average particle size D50 are different from those of Example 25. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0059 by setting the sprayed raw material contained in the slurry as YAG and setting the average particle size D50 of the YAG raw material powder to 3.0 μm. Other than that, the thermal spray film covering member of Example 28 was formed according to the same conditions as in Example 25.

(Example 29)
Example 29 is an example in which the type of thermal spraying raw material and the average particle size D50 are different from those of Example 25. The thermal spraying raw material contained in the slurry is 8 mL% Y ₂ O _{3- ZrO 2} , and the average particle size D50 of the 8 mL% Y ₂ O _{3- ZrO 2} raw material powder is 3.0 μm (Vvv / (D50) ³ ). The value of was adjusted to 0.0059. Other than that, the thermal spray film covering member of Example 29 was formed according to the same conditions as in Example 25.

(Comparative Example 14)
Comparative Example 14 is a comparative example in which the average particle size D50 is different from that of Example 25. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0007 by setting the average particle size D50 of the _{Y 2} O ₃ raw material powder contained in the slurry to 6.0 μm. Other than that, the thermal spray film covering member of Comparative Example 14 was formed according to the same conditions as in Example 25.

(Example 30)
Example 30 is an example in which the space volume Vvv and the average particle size D50 are different from those of Example 25. The space volume Vvv was adjusted to 0.042 by grinding one main surface of the AlN sintered base material on the surface to be sprayed in the base material preparation step, and the average of the _{Y 2} O _{3 raw material powders contained in the slurry was adjusted.} The value of (Vvv / (D50) ³ ) was adjusted to 0.3360 by setting the particle size D50 to 0.5 μm. Other than that, the thermal spray film covering member of Example 30 was formed according to the same conditions as in Example 25.

(Example 31)
Example 31 is an example in which the average particle size D50 is different from that of Example 30. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.042 by setting the average particle size D50 of the _{Y 2} O ₃ raw material powder contained in the slurry to 1.0 μm. Other than that, the thermal spray film covering member of Example 31 was formed according to the same conditions as in Example 30.

(Example 32)
Example 32 is an example in which the average particle size D50 is different from that of Example 30. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0016 by setting the average particle size D50 of the _{Y 2} O ₃ raw material powder contained in the slurry to 3.0 μm. Other than that, the thermal spray film covering member of Example 32 was formed according to the same conditions as in Example 30.

(Example 33)
Example 33 is an example in which the type of thermal spraying raw material and the average particle size D50 are different from those of Example 30. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0016 by setting the sprayed raw material contained in the slurry as YAG and setting the average particle size D50 of the YAG raw material powder to 3.0 μm. Other than that, the thermal spray film covering member of Example 33 was formed according to the same conditions as in Example 30.

(Example 34)
Example 34 is an example in which the type of thermal spraying raw material and the average particle size D50 are different from those of Example 30. The thermal spraying raw material contained in the slurry is 8 mL% Y ₂ O _{3- ZrO 2} , and the average particle size D50 of the 8 mL% Y ₂ O _{3- ZrO 2} raw material powder is 3.0 μm (Vvv / (D50) ³ ). The value of was adjusted to 0.0016. Other than that, the thermal spray film covering member of Example 34 was formed according to the same conditions as in Example 30.

(Comparative Example 15)
Comparative Example 15 is a comparative example in which the average particle size D50 is different from that of Example 30. ^{The value of (Vvv / (D50) 3} ) was adjusted to 0.0005 by setting the average particle size D50 of the _{Y 2} O ₃ raw material powder contained in the slurry to 4.5 μm. Other than that, the thermal spray film covering member of Comparative Example 15 was formed according to the same conditions as in Example 30.

The sprayed film coating members of each Example and each Comparative Example were evaluated by observing the appearance and measuring the adhesion. As for the appearance, the presence or absence of cracks and peeling of the sprayed film and the base material was visually observed. The adhesion was measured using a test piece having a diameter of 25 mm in which a sprayed film was formed on the base material in accordance with JIS H8402. The tables of FIGS. 2 and 3 show the evaluation results of the sprayed film coating members of each Example and each Comparative Example together with the manufacturing conditions.

In the sprayed film covering members of Examples 1 to 16, ^{the value of (Vvv / (D50) 3} ) is adjusted to 0.001 or more and 0.40 or less, and both the result by observing the appearance and the value of the adhesion force are both. It was good.

On the other hand, in the sprayed film covering members of Comparative Examples 1, 5 and 6, ^{the value of (Vvv / (D50) 3} ) is larger than 0.4. At this time, there was no problem in the result of observing the appearance, but the value of the adhesion was small. These comparative examples are considered to correspond to the case where the molten particle size is too small with respect to the Vvv of the base material, or the case where the base material is blasted and the Vvv is too large. In such a case, the molten particles invade the narrow portion of the surface of the base material and adhere to each other, but the base material cannot be completely covered as it is, and there is a risk that problems such as insufficient withstand voltage characteristics may occur. There is. Further, when molten particles are deposited on the molten particles, the anchor effect is not sufficiently exhibited and peeling occurs at the sprayed film interface. Therefore, it is presumed that sufficient adhesion to the ceramic sprayed film was not obtained, especially on the blasted surface of the base material.

Further, in the sprayed film covering members of Comparative Examples 2 to 4 and 7, ^{the value of (Vvv / (D50) 3} ) is smaller than 0.001. At this time, as a result of observing the appearance of Comparative Examples 2 to 4, peeling occurred. Therefore, effective adhesion cannot be measured. Further, in Comparative Example 7, there was no problem in the result of observing the appearance, but the value of the adhesive force was small. Comparative Examples 2 to 4 are considered to correspond to the case where the molten particle size is too large with respect to the Vvv of the base material. In such a case, the molten particles fill a minute void portion of several μm or less of the base material, and the remaining melt is thickly deposited and solidified. Since the stress acting during solidification cannot be retained by the anchor portion, it is presumed that a phenomenon in which a sprayed film cannot be formed on the base material occurs. Further, in Comparative Example 7, since the surface roughness Ra was larger than that in Comparative Examples 2 to 4, it is considered that the stress acting during solidification could be retained at the anchor portion, but the surface surface was sufficiently adhered. Since the roughness Ra was not large, it is presumed that the value of the adhesion force became small.

Further, in Comparative Example 8, since the surface roughness Ra was increased by blasting so that the adhesion could be increased by the conventional manufacturing method, the value of the adhesion was large, but cracks were generated by observing the appearance. confirmed.

The sprayed film coating members of Examples 1 to 15 had a Vvv value of 0.01 or more and 0.30 or less, but their adhesion was 10 MPa or more, indicating that even better adhesion could be obtained. It was.

Sprayed film covering member in Example 17 to 34 is, _Al 2 _{O 3} sintered purity of more than 99.5% of the base material, a purity of 99.8% or more of _Al 2 _{O 3} sintered body, AlN sintered body Therefore, the value of (Vvv / (D50) ³ ) was adjusted to 0.001 or more and 0.40 or less, and both the result of observing the appearance and the value of adhesion were good.

In particular, Examples 1 to 15, 17, 18, 20 to 23, 25, 26, 28 to 31, in which the value of (Vvv / (D50) ^{3) was 0.002 or more and 0.40 or less, have adhesive strength.} Was expensive.

On the other hand, in the sprayed film covering members of Comparative Examples 9 and 13, ^{the value of (Vvv / (D50) 3} ) is larger than 0.4. At this time, there was no problem in the result of observing the appearance, but the value of the adhesion was small. These comparative examples are considered to correspond to the case where the molten particle size is too small with respect to the Vvv of the base material, or the case where the base material is blasted and the Vvv is too large. In such a case, the molten particles invade the narrow portion of the surface of the base material and adhere to each other, but the base material cannot be completely covered as it is, and there is a risk that problems such as insufficient withstand voltage characteristics may occur. There is. Further, when molten particles are deposited on the molten particles, the anchor effect is not sufficiently exhibited and peeling occurs at the sprayed film interface. Therefore, it is presumed that sufficient adhesion to the ceramic sprayed film was not obtained, especially on the blasted surface of the base material.

Further, in the sprayed film covering members of Comparative Examples 10 to 12, 14 and 15 ^{, the value of (Vvv / (D50) 3} ) is smaller than 0.002. At this time, as a result of observing the appearance of Comparative Examples 10 to 12, 14 and 15, peeling occurred. Therefore, effective adhesion cannot be measured. Comparative Examples 10 to 12, 14 and 15 are considered to correspond to the case where the molten particle size is too large with respect to the Vvv of the base material. In such a case, the molten particles fill a minute void portion of several μm or less of the base material, and the remaining melt is thickly deposited and solidified. Since the stress acting during solidification cannot be retained by the anchor portion, it is presumed that a phenomenon in which a sprayed film cannot be formed on the base material occurs.

It goes without saying that the present invention is not limited to the above embodiments and extends to various modifications and equivalents included in the ideas and scope of the present invention. Further, the structure, shape, number, position, size, etc. of the components shown in each drawing are for convenience of explanation and can be changed as appropriate.

1 Ceramic sintered base material 2 Ceramic sprayed film 10 Sprayed surface

Claims (11)

It is a method of manufacturing a thermal spray film covering member.
^{An adjustment step for adjusting the spatial volume Vvv (μm 3} / μm ² ) of the surface to be sprayed of the ceramic sintered body base material within a predetermined range, and
The coating step of coating the surface to be sprayed of the base material by plasma spraying a slurry composed of water and a ceramic raw material powder having an average particle size D50 in the range of 0.5 μm or more and 6 μm or less is included.
The adjusting step is performed with respect to the space volume Vvv and the average particle size D50.
0.001 ≦ (Vvv / (D50) ³ ) ≦ 0.40
A method for manufacturing a sprayed film coating member, which comprises adjusting the temperature so as to fall within the range of. The method for manufacturing a thermal spray film coating member according to claim 1, wherein the ceramic sintered body base material is made of a SiC sintered body. The method for manufacturing a thermal spray film coating member according to claim 1, wherein the ceramic sintered body base material is made of an Al ₂ O _{3 sintered body.} The method for producing a thermal spray film coating member according to claim 1, wherein the ceramic sintered body base material is made of an AlN sintered body. The method for producing a thermal spray film coating member according to any one of claims 1 to 4, wherein the plasma spraying uses a non-oxidizing gas. The ceramic raw material powder according to any one of claims 1 to 5, wherein the ceramic raw material powder is a powder of alumina, yttria, zirconia, titania, chromia, yttrium aluminum garnet, or an arbitrary mixed powder thereof. A method for manufacturing a sprayed film coating member. The method for manufacturing a thermal spray film coating member according to any one of claims 1 to 6, wherein the space volume Vvv is 0.01 or more and 0.30 or less. A thermal sprayed film coating member composed of a ceramics sintered body base material and a thermal sprayed film provided on a sprayed surface of the ceramics sintered body base material.
With respect to the space volume Vvv (μm ³ / μm ² ) of the sprayed surface of the ceramics sintered base material and the average particle size D50 (μm) of the ceramic raw material forming the sprayed film.
0.001 ≦ (Vvv / (D50) ³ ) ≦ 0.40
The filling,
A thermal spray film coating member, characterized in that there is no chemical bond between the ceramic sintered base material and the elements constituting the thermal spray film. A thermal sprayed film coating member comprising a ceramics sintered body base material and a thermal sprayed film provided on the surface to be sprayed of the ceramics sintered body base material.
With respect to the space volume Vvv (μm ³ / μm ² ) of the sprayed surface of the ceramics sintered base material and the average particle size D50 (μm) of the ceramic raw material forming the sprayed film.
0.002 ≤ (Vvv / (D50) ³ ) ≤ 0.40
The filling,
The ceramics sintered body base material is a SiC sintered body, an AlN sintered body, or an Al ₂ O ₃ sintered body having a purity of 99.5% or more. The ceramic sintered body base material is a SiC sintered body, an Al ₂ O ₃ sintered body, or an Al N sintered body.
The sprayed film coating member according to claim 8, wherein the sprayed film comprises any one or a combination of any one or more of alumina, yttria, zirconia, titania, chromia, and yttrium aluminum garnet. The sprayed film coating member according to claim 9, wherein the sprayed film comprises any one or a combination of any one or more of alumina, yttria, zirconia, titania, chromia, and yttrium aluminum garnet.

Images