JP7627992B2 - Method for manufacturing thermal sprayed film-coated member and thermal sprayed film-coated member - Google Patents

Description

The present invention relates to a method for manufacturing a thermal sprayed film-coated member and a thermal sprayed film-coated member.

For the purpose of protecting the substrate and improving its performance, a thermal spray coating is formed on the surface of the substrate. For example, ceramics such as yttria (Y ₂ O ₃ ), titania (TiO 2 ), and chromia (Cr ₂ O ₃ ) are sometimes sprayed onto the ceramic substrate made of silicon carbide (SiC), aluminum oxide (Al ₂ O ₃ ), aluminum nitride ( _AlN ), etc., to improve the plasma resistance, wear resistance, and heat insulation properties of the substrate.

Conventionally, in order to coat a substrate with a ceramic sprayed film, a process of roughening the substrate surface was essential before the sprayed film was formed in order to allow the sprayed film to adhere to the substrate. For example, it is possible to roughen the substrate surface by blasting, but blasting may not be sufficient for non-metallic substrates such as ceramic substrates, as cracks may occur, reducing the strength of the substrate material or causing damage to the substrate due to cracks. For this reason, there has been a demand for a blast-free method of forming a ceramic film on a ceramic substrate by spraying, without inducing cracks.

Patent Document 1 discloses a ceramic sprayed coating member in which a SiC sintered body is roughened by blasting, the surface is then oxidized, and _{a Y2O3} sprayed film is formed thereon, so that _SiO2 and _Y2O3 form a double oxide by oxidation and _bond at the atomic level to form an adhesive bond. Patent Document 2 discloses a method for manufacturing a sprayed coating member in which a thin oxide film _SiO2 layer is formed on the surface by irradiating a SiC substrate with a laser, filling microcracks, and obtaining chemical adhesive strength between the oxide film and the _Al2O3 sprayed film. Patent Document 3 discloses a slurry and a spraying method in which Al is used as the substrate, _and the relationship between the particle diameter D10 of the slurry raw material and the substrate is 0.4<D10/Ra≦0.9.

JP 2014-162934 A WO2016/170895 JP 2018-154895 A

However, Patent Document 1 limits the materials that can be used as the substrate and the thermal spray coating to materials that contain silicon and have a higher melting point than the siliceous layer, respectively, making it difficult to apply to general ceramic substrates and ceramic thermal spray materials. Furthermore, Patent Document 2 uses as the substrate a material that is prone to forming an oxide film by laser irradiation, making it difficult to apply to general ceramic substrates.

In addition, although Patent Document 3 describes that ceramics can be used for the substrate, the experiments were actually conducted on an aluminum substrate, and it is unclear whether similar results can be obtained with the combination of a ceramic substrate and a ceramic sprayed film, which tends to have weak adhesion.

The present invention was made in consideration of these circumstances, and aims to provide a method for manufacturing a sprayed film-coated member that can improve the adhesion strength of a ceramic sprayed film even when a blasting process is not performed on a substrate made of a ceramic sintered body, and can reduce the risk of a decrease in the substrate material strength of the ceramic sintered body substrate and damage to the substrate.

(1) In order to achieve the above-mentioned object, the manufacturing method of a thermal sprayed film coated member of ^the present invention includes an adjusting step of adjusting the spatial volume Vvv ( ^μm3 / μm2) of the surface to be sprayed of a ceramic sintered body substrate made of a sintered body containing SiC, AlN, or Al2O3 _to a predetermined _range , and a coating step of coating the surface to be sprayed of the substrate by plasma 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, wherein the adjusting step is characterized in that the spatial volume Vvv and the average particle diameter D50 are adjusted to be in the range of 0.001≦(Vvv/(D50) ³ )≦0.40.

This allows the sprayed film to adhere closely to the substrate without the need for a process of roughening the substrate surface by blasting, reducing the risk of a decrease in substrate material strength or substrate damage caused by blasting a ceramic substrate.

(2) In addition, in the manufacturing method of the thermal sprayed film-coated member of the present invention, the ceramic sintered body is a SiC sintered body. This makes it possible to form a ceramic sprayed film on the SiC sintered body, which is a brittle material that does not adhere well to other ceramic materials, while reducing the risk of a decrease in the strength of the substrate material or damage to the substrate.

(3) In the method for producing a thermal sprayed film-coated member of the present invention, the ceramic sintered body is an Al ₂ O ₃ sintered body. This makes it possible to form a ceramic thermal sprayed film on the Al ₂ O ₃ sintered body, which is a brittle material that does not adhere well to other ceramic materials, while reducing the risk of a decrease in the strength of the substrate material or damage to the substrate.

(4) In addition, in the manufacturing method of the thermal sprayed film-coated member of the present invention, the ceramic sintered body is an AlN sintered body. This makes it possible to form a ceramic sprayed film on the AlN sintered body, which is a brittle material that does not adhere well to other ceramic materials, while reducing the risk of a decrease in the strength of the substrate material or damage to the substrate.

(5) In addition, in the manufacturing method of the thermal sprayed film-coated member of the present invention, the plasma spraying is characterized by using a non-oxidizing gas. This makes it possible to prevent unnecessary oxidation of the substrate surface and prevent oxidative deterioration of the thermal spray gun parts, making it possible to perform stable thermal spraying while ensuring adhesion.

(6) In addition, in the manufacturing method of the thermal sprayed film coated member of the present invention, the ceramic raw material powder is a powder of alumina, yttria, zirconia, titania, chromia, and yttrium alumina garnet, or any mixed powder of these. These materials may not adhere well to substrates made of other ceramic materials, but the manufacturing method of the present invention can make them adhere firmly to the ceramic substrate.

(7) In addition, in the manufacturing method of the thermal sprayed film-coated member of the present invention, the spatial volume Vvv is 0.01 or more and 0.30 or less. This makes it possible to adjust the spatial volume Vvv of the sprayed surface of the ceramic sintered body substrate to a predetermined range by polishing or grinding.

(8) The sprayed film-coated member of the present invention is a sprayed film-coated member consisting of a ceramic sintered body substrate and a sprayed film provided on the sprayed surface of the ceramic sintered body substrate, wherein the spatial volume Vvv ( ^μm3 / ^μm2 ) of the sprayed surface of the ceramic sintered body substrate and the average particle diameter D50 (μm) of the ceramic forming the sprayed film satisfy 0.001≦(Vvv/(D50) ³ )≦0.40, the ceramic sintered body substrate is a sintered body containing SiC, AlN, or Al2O3, and _{there is} no chemical bond between the elements constituting the ceramic sintered body substrate and the sprayed film. This makes it possible to obtain a sprayed film-coated member with reduced risk of deterioration of the substrate material strength or damage to the substrate.

(9) The sprayed film-coated member of the present invention is a member comprising a ceramic sintered body substrate and a sprayed film provided on the sprayed surface of the ceramic sintered body substrate, wherein the spatial volume Vvv ( ^μm3 / ^μm2 ) of the sprayed surface of the ceramic sintered body substrate and the average particle diameter D50 (μm) of the ceramic forming the sprayed film satisfy 0.002≦(Vvv/(D50) ³ )≦0.40, and the ceramic sintered body substrate is a SiC sintered body, an AlN sintered body, or _{an Al2O3} sintered body with a purity of 99.5% or more. This allows the sprayed film-coated member to be reduced in the risk of a decrease in the strength of the substrate material or damage to the substrate.

(10) In the thermal sprayed film-coated member of the present invention, the ceramic sintered body substrate is a SiC sintered body, _{an Al2O3} sintered body, or an AlN sintered body, and the thermal sprayed film is made of one or a combination of two or more of alumina, yttria, zirconia, titania, chromia, and yttrium aluminum garnet. This makes it possible to obtain a thermal sprayed film-coated member in which the risk of a decrease in the strength of the substrate material and a breakage of the substrate are reduced.

(11) In addition, in the thermal sprayed film-coated member of the present invention, the thermal sprayed film is characterized by being made of one or a combination of two or more of alumina, yttria, zirconia, titania, chromia, and yttrium aluminum garnet. This makes it possible to obtain a thermal sprayed film-coated member with reduced risk of deterioration of the substrate material strength and damage to the substrate.

According to the present invention, even if blasting is not performed on a substrate made of a ceramic sintered body, the adhesion strength of the ceramic sprayed film can be improved, and a sprayed film-coated member can be manufactured by forming a ceramic sprayed film while reducing the risk of a decrease in the substrate material strength of the ceramic sintered body substrate or damage to the substrate.

1 is a schematic diagram showing a thermal spray coated member according to one embodiment of the present invention. 1 is a table showing production conditions and evaluations of Examples and Comparative Examples. 1 is a table showing production conditions and evaluations of Examples and Comparative Examples.

As a result of intensive research, the inventors have discovered that by adjusting the spatial volume Vvv ( ^μm3 / ^μm2 ) of the sprayed surface of a ceramic sintered body substrate relative to the average particle diameter D50 of the raw material particles to be sprayed, i.e., by adjusting the relationship between the volume of the spray particles and the spatial volume of the substrate so that it falls within a certain range, it is possible to improve the adhesion strength of the ceramic sprayed film even when the substrate made of a ceramic sintered body is not subjected to blast processing, and to manufacture a sprayed film-coated component on which a ceramic sprayed film is formed while reducing the risk of a decrease in the substrate material strength of the ceramic sintered body substrate or damage to the substrate, and have completed the present invention.

That is, the manufacturing method of a thermal sprayed film coated member of the present invention includes an adjusting step of adjusting the spatial volume Vvv ( ^μm3 / ^μm2 ) of the surface to be sprayed of a ceramic sintered body substrate to a predetermined range, and a coating step of plasma spraying a slurry consisting of water and a ceramic raw material powder having an average particle diameter D50 in the range of 0.5 μm to 6 μm to coat the surface to be sprayed of the substrate, the adjusting step adjusting the spatial volume Vvv and the average particle diameter D50 to be in the range of 0.001≦(Vvv/(D50) ³ )≦0.40. Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Note that in the configuration diagram, the size of each component is represented conceptually and does not necessarily represent the actual dimensional ratio.

[Method of manufacturing thermal sprayed film coated member]
First, a ceramic sintered body substrate is prepared. The ceramic sintered body substrate can be made of 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, and composite oxides such as YAG can be used. The ceramic sintered body substrate is preferably made of SiC sintered body, AlN sintered body, or Al ₂ O ₃ sintered body. This makes it possible to form a ceramic sprayed film on SiC sintered body, AlN sintered body, or Al ₂ O ₃ sintered body, which are brittle materials and have poor adhesion to other ceramic materials, while reducing the risk of strength reduction of the substrate material and substrate damage.

The ceramic sintered body substrate may be produced by any method. The production conditions are appropriately selected depending on the type of substrate. For example, hot pressing or HIP can be used. For example, when using the hot pressing method, a mixed powder of raw material powder and sintering aid powder is molded to produce a molded body, which is then fired to produce a sintered body. In this case, for example, the firing temperature is adjusted to be within the temperature range of 1650 to 1950°C, more preferably 1750 to 1900°C. The firing time (the time for which the firing temperature is held) is adjusted to be within the time range of 2 to 10 hours. The pressing pressure during firing is adjusted to be within the pressure range of 1 to 15 MPa. Note that these firing temperatures and firing times can be changed depending on the types of raw material powder and sintering aid powder, etc.

Next, the spatial volume Vvv (μm ³ /μm ² ) of the sprayed surface of the prepared ceramic sintered body base material is adjusted to a predetermined range. The sprayed surface of the prepared ceramic sintered body base material is processed, for example, by polishing, grinding, or the like, to adjust the spatial volume Vvv to a predetermined range. In this specification, the spatial volume Vvv refers to the void volume of the valley portion at a load areal ratio of 80%. The spatial volume Vvv (μm ³ /μm ² ) can be measured using a coherence correlation interferometer or the like in accordance with ISO 25178.

The surface to be sprayed may be processed by blasting, but depending on the abrasive used and the spraying strength, microcracks may occur in non-metallic substrates such as ceramic sintered substrates. Such cracks may reduce the strength of the substrate material or cause damage to the substrate due to the cracks, so great care must be taken when performing blasting. In other words, when performing blasting, it is necessary to avoid cracks depending on the material of the substrate. Since the method of the present invention does not require roughening of the surface to be sprayed, it is not necessary to perform blasting at a spraying strength that would cause cracks. Therefore, it is possible to use blasting after adjusting the strength.

However, since polishing or grinding is less likely to cause problematic cracks, polishing or grinding is preferable when processing the sprayed surface of a ceramic sintered body substrate. Also, if the spatial volume Vvv of the sprayed surface of the sintered body is within a specified range in the state of the baked surface after sintering, processing is not necessary.

The sprayed surface is adjusted according to the average particle diameter D50 of the ceramic raw material powder contained in the slurry used in the coating process described below, so that the spatial volume Vvv and average particle diameter D50 are in the range of 0.001≦(Vvv/(D50) ³ )≦0.40. This adjustment may be made by processing the sprayed surface based on the average particle diameter D50 of the ceramic raw material powder used, and then measuring the spatial volume Vvv, and if it is not within the above range, further processing the sprayed surface, or by processing the sprayed surface, measuring the spatial volume Vvv, and changing the ceramic raw material powder used based on the measurement result of the spatial volume Vvv. The spatial volume Vvv ( ^μm3 / ^μm2 ) is preferably 0.01 or more and 0.30 or less.

Next, prepare ceramic raw material powder with an average particle size D50 in the range of 0.5 μm to 6 μm and water, and mix them to prepare a slurry. The average particle size D50 of the ceramic raw material powder is preferably 0.5 μm to 6 μm. If D50 is smaller than 0.5 μm, the viscosity of the slurry increases, making thermal spraying difficult and deteriorating the film quality. If D50 is larger than 6 μm, the slurry cannot be transported stably, and the film quality deteriorates. The average particle size D50 can be measured using a laser diffraction/scattering type particle size distribution measuring device in dry or wet measurement. It is preferable that the particle size distribution of the ceramic raw material powder is sharp.

Various materials can be used as the ceramic raw material powder. For example, it is preferable to use alumina (Al ₂ O ₃ ), yttria (Y ₂ O ₃ ), zirconia (ZrO ₂ ), titania (TiO ₂ ), chromia (Cr ₂ O ₃ ), yttrium aluminum garnet (Y ₃ Al ₅ O ₁₂ , also written as YAG), silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), aluminum nitride (AlN) powder, or any mixed powder of these. These materials are used for various purposes such as protecting the substrate and improving its function, but when the substrate is formed of a ceramic sintered body, adhesion to the substrate may become a problem. The manufacturing method of the present invention can form a ceramic sprayed film using these materials while reducing the risk of strength reduction of the substrate material and substrate damage, even when the substrate is formed of a ceramic sintered body.

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%, application takes a long time and productivity decreases, making it unsuitable for industrial use. If the concentration is more than 40 wt%, the viscosity increases and the slurry cannot be transported stably.

The prepared slurry is then plasma sprayed onto the substrate surface to be sprayed. The gas used for spraying is preferably a non-oxidizing gas. As the non-oxidizing gas, for example, Ar gas, _H2 gas, _N2 gas, or a mixed gas of any combination of these gases can be used. The above slurry is supplied to a nozzle via a tube pump and plasma sprayed using the gas.

Before the plasma spraying process, a process may be performed in which the surface of the substrate to be sprayed is irradiated with plasma using only gas without adding slurry. By performing such a process, the surface of the substrate to be sprayed is preheated, and the molten ceramic raw material powder is more likely to penetrate into the voids during plasma spraying.

As a result, as shown in FIG. 1, a ceramic sprayed film 2 is formed from the slurry, covering the sprayed surface 10 of the substrate 1. The thickness of the ceramic sprayed film 2 is preferably adjusted to 50-500 μm. If the thickness of the sprayed film 2 is less than 50 μm, there is a high risk of the plasma resistance, abrasion resistance, heat insulation, and other functions of the sprayed film 2 decreasing. If the thickness of the sprayed film 2 exceeds 500 μm, the internal stress of the sprayed film 2 increases, increasing the risk of a decrease in adhesion or peeling. The porosity of the ceramic sprayed film 2 is preferably adjusted to 1-5%.

This manufacturing method can improve the adhesion strength of the ceramic sprayed film even when the substrate made of a ceramic sintered body is not subjected to blasting, and can produce a sprayed film-coated component with a ceramic sprayed film while reducing the risk of a decrease in the substrate material strength of the ceramic sintered body substrate or damage to the substrate.

In the manufacturing method of the present invention, the size of the spatial volume Vvv of the sprayed surface of the ceramic sintered body substrate is compatible with the average particle diameter D50 of the raw material powder, so it is presumed that the molten particle diameter of the molten raw material powder particles penetrates an appropriate amount into voids of several μm or less remaining on the surface of the substrate, forming pancakes (splats) with these as nuclei and adhering to the substrate. In other words, the minute voids remaining on the surface of the substrate after grinding and polishing create a micron-sized anchor effect, which allows for adhesion, so there is no need to blast the substrate to roughen it, and the risk of inducing cracks in the substrate can be avoided.

[Thermal sprayed film coated member]
The thermal sprayed film-coated member of the present invention comprises a ceramic sintered body substrate and a thermal sprayed film provided on the surface to be sprayed of the ceramic sintered body substrate. The spatial volume Vvv ( ^μm3 / ^μm2 ) of the surface to be sprayed of the ceramic sintered body substrate and the average particle diameter D50 (μm) of the ceramic raw material forming the thermal sprayed film satisfy 0.001≦(Vvv/(D50) ³ )≦0.40. In addition, there is no chemical bond between the elements constituting the ceramic sintered body substrate and the thermal sprayed film.

The absence of chemical bonds between the elements that make up the ceramic sintered body substrate and the sprayed film refers to a state in which the sprayed film and the substrate are physically adhered to each other by the so-called anchor effect. In other words, the molten sprayed particles penetrate into the fine valleys in the substrate and solidify within these valleys. The cooled and solidified sprayed particles then exert a compressive stress on the substrate, and as a result, the substrate and the sprayed film are adhered to each other by the frictional force acting between the substrate and the solidified sprayed particles. The absence of chemical bonds between the elements that make up the ceramic sintered body substrate and the sprayed film can be confirmed by the absence of a reaction layer formed between the ceramic sintered body substrate and the sprayed film.

The spatial volume Vvv ( ^μm3 / ^μm2 ) of the sprayed surface of the ceramic sintered body substrate can be measured using a coherence correlation interferometer. The spatial volume Vvv ( ^μm3 / ^μm2 ) of the sprayed surface in this specification is a value measured with an areal load ratio of 80%. The average particle diameter D50 (μm) of the ceramic raw material forming the sprayed film can be measured with a particle diameter measuring device using a laser diffraction/scattering method.

The ceramic sintered body substrate can be selected from various materials. For example, it can be non-oxidizing ceramics such as SiC sintered body, silicon nitride sintered body, aluminum nitride sintered body, oxides such as Al ₂ O ₃ sintered body, Y ₂ O ₃ sintered body, and composite oxides such as YAG. The ceramic sintered body substrate is preferably formed of SiC sintered body, AlN sintered body, or Al ₂ O ₃ sintered body. This allows a sprayed film-coated member to be formed by forming a ceramic sprayed film on a ceramic sintered body substrate made of SiC sintered body, AlN sintered body, or Al ₂ O ₃ sintered body, which is a brittle material and has poor adhesion to other ceramic materials, and reduces the risk of strength reduction of the substrate material and substrate damage.

The sprayed film is preferably made of one or a combination of two or more of alumina, yttria, zirconia, titania, chromia, and yttrium aluminum garnet. This allows the sprayed film-coated member to be made with reduced risk of lowering the strength of the substrate material and of substrate damage, making it suitable for a variety of applications. "Made of a combination of two or more" means that the sprayed film is formed from a mixture of particles made from different raw materials.

The sprayed film-coated member of the present invention is a sprayed film-coated member in which the ceramic sintered body substrate and the sprayed film are adhered to each other by the anchor effect, reducing the risk of a decrease in the strength of the substrate material or damage to the substrate.

[Examples and Comparative Examples]
Example 1
(Substrate preparation process)
Carbon and _B4C and an organic binder were added as sintering aids to SiC raw material powder with a purity of 98% and an average particle size of 0.5 μm, and the powder was isostatically pressed at 1 ton/ ^cm2 by CIP (cold isostatic pressing) molding to produce a SiC molded body. Next, the SiC molded body was sintered at normal pressure for 3 hours at 2000°C in an _N2 atmosphere to produce a SiC sintered body. Next, the SiC sintered body was processed into a substantially rectangular plate (or substantially square plate) with a length of 100 mm, a width of 100 mm, and a thickness of 5 mm to produce a SiC sintered body base material. At this time, one of the main surfaces of the SiC sintered body base material was polished to adjust the spatial volume Vvv ( ^μm3 / ^μm2 ) to 0.010, and the average particle size D50 of the raw material powder used in the plasma spraying process was set to 0.5 μm, thereby adjusting the value of (Vvv/(D50) ³ ) to 0.0800. The spatial volume Vvv was measured using a coherence correlation interferometer (manufactured by Taylor Hobson Co., Ltd.) In this manner, the SiC sintered body substrate of Example 1 was prepared.

(Plasma irradiation process)
Next, a non-oxidizing gas plasma was irradiated or sprayed onto the substrate surface to be sprayed using a high-speed plasma spraying machine, and the surface to be sprayed was preheated. A mixture of Ar gas, _N2 gas, and _H2 gas was used as the non-oxidizing gas. The supply rate of Ar gas to the nozzle constituting the spraying machine was controlled to 100 l/min, the supply rate of _N2 gas was controlled to 70 l/min, and the supply rate of _H2 gas was controlled to 70 l/min.

The current applied to the nozzle constituting the high-speed plasma spraying machine was controlled to 250 A, and the power supplied to the nozzle was adjusted to 65 kW. The distance between the tip of the nozzle and the surface of the substrate to be sprayed was adjusted to 75 mm. The scanning speed or displacement speed of the nozzle relative to the substrate was adjusted to 850 mm/s. This generated plasma of a mixed gas of Ar gas, _N2 gas, and _H2 gas, and the plasma was irradiated or sprayed from the tip of the nozzle onto the surface of the substrate to be sprayed. The preheating of the surface to be sprayed by irradiating or spraying the plasma was performed for 3 minutes.

(Plasma spraying process)
Then, the high-speed plasma spraying machine was used as it was to plasma spray the Y ₂ O ₃ slurry onto the substrate surface to be sprayed using a non-oxidizing gas. The slurry was prepared by mixing 300 g of Y _{2 O 3} raw material powder with a purity of 99.9% or more and an average particle size D50 of 0.5 μm with 700 g of water. 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 nozzle constituting the spraying machine 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 spraying speed was controlled to 600 to 700 mm/s.

The current applied to the nozzle constituting the high-speed plasma spraying machine was controlled to 250A, and the power supplied to the nozzle was adjusted to 65kW. The distance between the tip of the nozzle and the surface of the substrate to be sprayed was adjusted to 75mm. The scanning speed or displacement speed of the nozzle relative to the substrate was adjusted to 850mm/s. This resulted in the generation of plasma of a mixed gas of Ar gas, _N2 gas, and _H2 gas, and the raw material powder melted by the plasma was sprayed from the tip of the nozzle to the surface of the substrate to be sprayed. In this way, the sprayed film-coated member of Example 1 was formed, in which the surface of the SiC sintered body substrate to be sprayed was coated with a _Y2O3 sprayed _film .

Example 2
Example 2 is an example with a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.190, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 1.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.1900. Other than that, the thermal sprayed film-coated member of Example 2 was formed under the same conditions as Example 1.

Example 3
Example 3 is an example with a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.060, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 1.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0600. Other than that, the thermal sprayed film-coated member of Example 3 was formed under the same conditions as Example 1.

Example 4
Example 4 is an example with a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.190, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 3.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0070. Other than that, the thermal sprayed film-coated member of Example 4 was formed under the same conditions as Example 1.

Example 5
Example 5 is an example that differs from Example 1 in the type of thermal spray raw material, spatial volume Vvv, and average particle diameter D50. In the substrate preparation process, one main surface of the SiC sintered substrate to be thermal sprayed was ground to adjust the spatial volume Vvv to 0.190, the type of raw material powder contained in _the slurry was _Al2O3 , and the average particle diameter D50 was 3.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0070. The thermal sprayed film-coated member of Example 5 was formed under the same conditions as Example 1 otherwise.

Example 6
Example 6 is an example that differs from Example 1 in the type of thermal spray raw material, spatial volume Vvv, and average particle diameter D50. In the substrate preparation process, one main surface of the SiC sintered substrate to be thermal sprayed was ground to adjust the spatial volume Vvv to 0.190, the type of raw material powder contained in the slurry was YAG, and the average particle diameter D50 was 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0070. The thermal sprayed film-coated member of Example 6 was formed under the same conditions as Example 1 otherwise.

(Example 7)
Example 7 is an example that differs from Example 1 in the type of thermal spray raw material, spatial volume Vvv, and average particle diameter D50. In the substrate preparation step, one main surface of the SiC sintered substrate to be thermal sprayed was ground to adjust the spatial volume Vvv to 0.190, the type of raw material powder contained in the slurry was 8 mol% Y ₂ O ₃ -ZrO ₂ , and the average particle diameter D50 was 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0070. Other than that, the thermal sprayed film-coated member of Example 7 was formed under the same conditions as Example 1.

(Example 8)
Example 8 is an example that differs from Example 1 in the type of thermal spray raw material, spatial volume Vvv, and average particle diameter D50. In the substrate preparation process, one main surface of the SiC sintered substrate to be thermal sprayed was ground to adjust the spatial volume Vvv to 0.190, the type of raw material powder contained in the slurry was _TiO2 , and the average particle diameter D50 was 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0070. The thermal sprayed film-coated member of Example 8 was formed under the same conditions as Example 1 otherwise.

(Example 9)
Example 9 is an example that differs from Example 1 in the type of thermal spray raw material, spatial volume Vvv, and average particle diameter D50. In the substrate preparation process, one main surface of the SiC sintered substrate to be thermal sprayed was ground to adjust the spatial volume Vvv to 0.190, the type of raw material powder contained in the slurry _{was Cr2O3} , and the average particle diameter D50 was 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0070. The thermal sprayed film-coated member of Example 9 was formed under the same conditions as Example 1 otherwise.

(Example 10)
(Substrate preparation process)
Example 10 is an example in which the type of raw material, spatial volume Vvv and average particle diameter D50 of the substrate 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 diameter of 0.5 μm, and the Al ₂ O ₃ molded body was produced by isostatic pressing at 1 ton/cm ² using the CIP molding method. Next, the Al ₂ O ₃ molded body was sintered at normal pressure at 1600 ° C for 3 hours in an air atmosphere to produce an Al ₂ O ₃ sintered body. Next, the Al ₂ O ₃ sintered body was processed into a substantially rectangular plate (or substantially square plate) with a length of 100 mm, a width of 100 mm and a thickness of 5 mm to produce an Al ₂ O ₃ sintered body substrate. At this time, the spatial volume Vvv was adjusted to 0.150 by grinding one main surface of the _{Al 2} O ₃ sintered body substrate. In this manner, the Al ₂ O ₃ sintered body substrate of Example 10 was prepared.

The value of (Vvv/(D50) ³ ) was adjusted to 0.0056 by setting the average particle diameter D50 of _{the Y2O3 raw} material _powder contained in the slurry to 3.0 μm for the _Al2O3 sintered body substrate prepared in the above substrate preparation process. The thermal sprayed film coated member of Example 10 was formed under the same conditions as Example 1 except for the above.

Example 11
Example 11 is an example in which the spatial volume Vvv is different from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.042, thereby adjusting the value of (Vvv/(D50) ³ ) to 0.3360. The thermal sprayed film-coated member of Example 11 was formed under the same conditions as Example 1.

Example 12
Example 12 is an example with a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.042, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 1.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0420. Other than that, the thermal sprayed film-coated member of Example 12 was formed under the same conditions as Example 1.

Example 13
Example 13 is an example with a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was sandblasted to adjust the spatial volume Vvv to 0.550, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 3.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0204. The remaining conditions were the same as those of Example 1, and the thermal sprayed film-coated member of Example 13 was formed.

(Example 14)
Example 14 is an example with a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was sandblasted to adjust the spatial volume Vvv to 0.550, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 4.5 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0060. The remaining conditions were the same as those of Example 1, and the thermal sprayed film-coated member of Example 14 was formed.

(Example 15)
Example 15 is an example with a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one of the main surfaces of the SiC sintered substrate to be sprayed was sandblasted to adjust the spatial volume Vvv to 0.320, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 3.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0119. The remaining conditions were the same as those of Example 1, and the thermal sprayed film-coated member of Example 15 was formed.

(Example 16)
Example 16 is an example with a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one of the main surfaces of the SiC sintered substrate to be sprayed was sandblasted to adjust the spatial volume Vvv to 0.310, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 6.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0014. The remaining conditions were the same as those of Example 1, and the thermal sprayed film-coated member of Example 16 was formed.

(Comparative Example 1)
Comparative Example 1 is a comparative example in which the spatial volume Vvv is different from that of Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.060, thereby adjusting the value of (Vvv/(D50) ³ ) to 0.4800. Other than that, the thermal sprayed film-coated member of Comparative Example 1 was formed under the same conditions as Example 1.

(Comparative Example 2)
Comparative Example 2 is a comparative example having a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.020, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 3.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0007. Other than that, the thermal sprayed film-coated member of Comparative Example 2 was formed under the same conditions as Example 1.

(Comparative Example 3)
Comparative Example 3 is a comparative example having a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.042, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 4.5 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0005. The remaining conditions were the same as those of Example 1, and the thermal sprayed film-coated member of Comparative Example 3 was formed.

(Comparative Example 4)
Comparative Example 4 is a comparative example having a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.042, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 6.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0002. The remaining conditions were the same as those of Example 1, and the thermal sprayed film-coated member of Comparative Example 4 was formed.

(Comparative Example 5)
Comparative Example 5 is a comparative example in which the spatial volume Vvv is different from that of Example 1. In the substrate preparation step, one main surface of the SiC sintered compact substrate to be sprayed was sandblasted to adjust the spatial volume Vvv to 0.550, thereby adjusting the value of (Vvv/(D50) ³ ) to 4.4000. Other than that, the thermal sprayed film-coated member of Comparative Example 5 was formed under the same conditions as Example 1.

(Comparative Example 6)
Comparative Example 6 is a comparative example having a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was sandblasted to adjust the spatial volume Vvv to 0.550, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 1.0 μm to adjust the value of (Vvv/(D50) ³ ) to 0.5500. Other than that, the thermal sprayed film-coated member of Comparative Example 6 was formed under the same conditions as Example 1.

(Comparative Example 7)
Comparative Example 7 is a comparative example having a different spatial volume Vvv and average particle diameter D50 from Example 1. In the substrate preparation step, one main surface of the SiC sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.190, and the average particle diameter D50 of the raw material powder contained in the slurry was set to 6.0 μm, adjusting the value of (Vvv/(D50) ³ ) to 0.0009. The thermal sprayed film-coated member of Comparative Example 7 was formed under the same conditions as Example 1 otherwise.

(Comparative Example 8)
Comparative Example 8 is a comparative example manufactured by a conventional manufacturing method. In the substrate preparation process, one of the main surfaces of the SiC sintered body substrate to be sprayed was sandblasted to adjust the spatial volume Vvv to 1.480, and the spraying was performed by dry spraying in which the raw material powder was sprayed directly with gas instead of wet _spraying with a slurry. Granular _Y2O3 was used as the raw material powder. The average particle diameter D50 of the granules of the raw material powder was 30.0 μm. The value of (Vvv/(D50) ³ ) was calculated formally to be 0.0001.

(Example 17)
Example 17 is an example with different spatial volume Vvv and average particle diameter D50 from Example 10. In the substrate preparation process, one main surface of the 99.5% pure _{Al2O3 sintered} compact substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.161, and the average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 1.0 μm to adjust the value of (Vvv/(D50) ³ ) to 0.1610. The remaining conditions were the same as those of Example 10 to form the thermal sprayed film-coated member of Example 17.

(Comparative Example 9)
Comparative Example 9 is a comparative example having a different average particle diameter D50 from Example 17. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 0.5 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 1.2880. The other conditions were the same as those of Example 17, and the thermal sprayed film coated member of Comparative Example 9 was formed.

(Example 18)
Example 18 is an example with a different average particle diameter D50 from Example 17. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0060. The other conditions were the same as those of Example 17, and the thermal sprayed film-coated member of Example 18 was formed.

(Example 19)
Example 19 is an example with a different average particle diameter D50 from Example 17. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 4.5 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0018. The other conditions were the same as those of Example 17, and the thermal sprayed film coated member of Example 19 was formed.

(Comparative Example 10)
Comparative Example 10 is a comparative example having a different average particle diameter D50 from Example 17. The average particle diameter D50 of _{the Y2O3 raw} material powder contained in the slurry was set to 6.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0007. The thermal sprayed film coated member of Comparative Example 10 was formed under the same conditions as Example 17.

(Example 20)
Example 20 is an example that differs from Example 17 in the type of thermal spray raw material and the average particle diameter D50. The thermal spray raw material contained in the slurry was YAG, and the average particle diameter D50 of the YAG raw material powder was set to 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0060. The rest of the conditions were the same as those of Example 17, and the thermal sprayed film-coated member of Example 20 was formed.

(Example 21)
Example 21 is an example that differs from Example 17 in the type of spray raw material and the average particle diameter _{D50. The spray raw material contained in the slurry was 8 mol% Y2O3-ZrO2, and the average particle diameter D50 of the 8 mol% Y2O3-ZrO2 raw material powder was 3.0} μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0060. The rest of the conditions were the same as those of Example 17, and the sprayed film-coated member of Example 21 was formed.

(Example 22)
Example 22 is an example in which the substrate, spatial volume Vvv and average particle diameter D50 are different from those of Example 17. In the substrate preparation process of Example 17, the purity of the _Al2O3 raw _material powder was set to 99.8%. Then, one main surface of the 99.8% purity _{Al2O3 sintered} compact substrate was ground to adjust the spatial volume Vvv to 0.047, and the average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 0.5 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.3760. The sprayed film-coated member of Example 22 was formed under the same conditions as Example 1.

(Example 23)
Example 23 is an example with a different average particle diameter D50 from Example 22. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 1.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0470. The other conditions were the same as those of Example 22, and the thermal sprayed film-coated member of Example 23 was formed.

(Example 24)
Example 24 is an example with a different average particle diameter D50 from Example 22. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0017. The other conditions were the same as those of Example 22, and the thermal sprayed film coated member of Example 24 was formed.

(Comparative Example 11)
Comparative Example 11 is a comparative example in which the average particle diameter D50 is different from that of Example 22. The average particle diameter D50 of _{the Y2O3 raw} material powder contained in the slurry was set to 4.5 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0005. The thermal sprayed film coated member of Example 22 was formed under the same conditions as Example 1.

(Comparative Example 12)
Comparative Example 12 is a comparative example having a different average particle diameter D50 from Example 22. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 6.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0002. The other conditions were the same as those of Example 22, and the thermal sprayed film coated member of Comparative Example 12 was formed.

(Example 25)
(Substrate preparation process)
Example 25 is an example in which the type of raw material, spatial volume Vvv and average particle diameter D50 of the substrate are different from those of Example 1. Y ₂ O ₃ and an organic binder were added as sintering aids to AlN raw material powder with a purity of 98% and an average particle diameter of 0.5 μm, and the AlN molded body was produced by isostatic pressing at 1 ton/cm ² using the CIP molding method. Next, the AlN molded body was sintered at normal pressure at 550 ° C for 12 hours in an air atmosphere to produce an AlN sintered body. Next, the AlN sintered body was processed into a substantially rectangular plate shape (or a substantially square plate shape) with a length of 100 mm, a width of 100 mm and a thickness of 5 mm to produce an AlN sintered body substrate. At this time, the spatial volume Vvv was adjusted to 0.158 by grinding one of the main surfaces of the AlN sintered body substrate. In this way, the AlN sintered body substrate of Example 25 was prepared.

The value of (Vvv/(D50) ³ ) was adjusted to 0.1580 by setting the average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry to 1.0 μm for the AlN sintered body substrate prepared in the above substrate preparation process. The thermal sprayed film coated member of Example 25 was formed under the same conditions as Example 1 except for the above.

(Comparative Example 13)
Comparative Example 13 is a comparative example having a different average particle diameter D50 from Example 25. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 0.5 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 1.2640. The other conditions were the same as those of Example 25, and the thermal sprayed film coated member of Comparative Example 13 was formed.

(Example 26)
Example 26 is an example with a different average particle diameter D50 from Example 25. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0059. The other conditions were the same as those of Example 25, and the thermal sprayed film coated member of Example 26 was formed.

(Example 27)
Example 27 is an example in which the average particle diameter D50 is different from that of Example 25. The average particle diameter D50 of _{the Y2O3 raw} material powder contained in the slurry was set to 4.5 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0017. The other conditions were the same as those of Example 1, and the thermal sprayed film coated member of Example 25 was formed.

(Example 28)
Example 28 is an example that differs from Example 25 in the type of thermal spray raw material and the average particle diameter D50. The thermal spray raw material contained in the slurry was YAG, and the average particle diameter D50 of the YAG raw material powder was set to 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0059. The thermal sprayed film-coated member of Example 28 was formed under the same conditions as Example 25 otherwise.

(Example 29)
Example 29 is an example that differs from Example 25 in the type of spray raw material and the average particle diameter D50. The spray raw material contained in the slurry was 8 mol% Y ₂ O ₃ -ZrO ₂ , and the average particle diameter D50 of the 8 mol% Y ₂ O ₃ -ZrO ₂ raw material powder was set to 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0059. Otherwise, the thermal sprayed film-coated member of Example 29 was formed under the same conditions as Example 25.

(Comparative Example 14)
Comparative Example 14 is a comparative example having a different average particle diameter D50 from Example 25. The average particle diameter D50 of _{the Y2O3 raw} material powder contained in the slurry was set to 6.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0007. The thermal sprayed film coated member of Comparative Example 14 was formed under the same conditions as Example 25.

(Example 30)
Example 30 is an example with a different spatial volume Vvv and average particle diameter D50 from Example 25. In the substrate preparation process, one of the main surfaces of the AlN sintered substrate to be sprayed was ground to adjust the spatial volume Vvv to 0.042, and the average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 0.5 μm to adjust the value of (Vvv/(D50) ³ ) to 0.3360. The remaining conditions were the same as those of Example 25 to form the thermal sprayed film-coated member of Example 30.

(Example 31)
Example 31 is an example with a different average particle diameter D50 from Example 30. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 1.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.042. The other conditions were the same as those of Example 30, and the thermal sprayed film coated member of Example 31 was formed.

(Example 32)
Example 32 is an example with a different average particle diameter D50 from Example 30. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0016. The other conditions were the same as those of Example 30, and the thermal sprayed film coated member of Example 32 was formed.

(Example 33)
Example 33 is an example that differs from Example 30 in the type of thermal spray raw material and the average particle diameter D50. The thermal spray raw material contained in the slurry was YAG, and the average particle diameter D50 of the YAG raw material powder was set to 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0016. The rest of the conditions were the same as those of Example 30, and the thermal sprayed film-coated member of Example 33 was formed.

(Example 34)
Example 34 is an example that differs from Example 30 in the type of thermal spray raw material and the average particle diameter D50. The thermal spray raw material contained in the slurry was 8 mol% _{Y2O3 - ZrO2} , and the average particle diameter D50 of the ₈ mol% _Y2O3 - _ZrO2 raw material powder was 3.0 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0016. The rest of the conditions were the same as those of Example 30, and the thermal sprayed film-coated member of Example 34 was formed.

(Comparative Example 15)
Comparative Example 15 is a comparative example having a different average particle diameter D50 from Example 30. The average particle diameter D50 of _{the Y2O3} raw material powder contained in the slurry was set to 4.5 μm, so that the value of (Vvv/(D50) ³ ) was adjusted to 0.0005. The other conditions were the same as those of Example 30, and the thermal sprayed film coated member of Comparative Example 15 was formed.

The sprayed film-coated members of each Example and Comparative Example were evaluated by observing their appearance and measuring their adhesion. The appearance was evaluated by visually inspecting the sprayed film and the substrate for cracks and peeling. Adhesion was measured using a φ25 mm test piece with a sprayed film formed on a substrate in accordance with JIS H8402. The tables in Figures 2 and 3 show the evaluation results of the sprayed film-coated members of each Example and Comparative Example, along with the manufacturing conditions.

The thermal sprayed film coated members of Examples 1 to 16 had a (Vvv/(D50) ³ ) value adjusted to be 0.001 or more and 0.40 or less, and both the results of the appearance observation and the adhesion values were good.

On the other hand, the sprayed film coated members of Comparative Examples 1, 5, and 6 have a value of (Vvv/(D50) ³ ) larger than 0.4. In this case, the results of the observation of the appearance were fine, but the adhesion value was small. These comparative examples are considered to correspond to the case where the molten particle diameter is too small compared to the Vvv of the substrate, or the substrate is blasted and Vvv is too large. In such a case, the molten particles penetrate into the narrow part of the substrate surface and adhere to it, but if left as it is, the substrate cannot be covered entirely, and there is a risk of problems such as insufficient voltage resistance characteristics. Furthermore, if the molten particles are deposited on it, the anchor effect is not fully exerted and peeling occurs at the sprayed film interface. Therefore, it is presumed that the adhesion to the ceramic sprayed film was not sufficient, especially on the blasted surface of the substrate.

In addition, the sprayed film coated members of Comparative Examples 2 to 4 and 7 had a value of (Vvv/(D50) ³ ) smaller than 0.001. In this case, the results of observing the appearance of Comparative Examples 2 to 4 showed that peeling had occurred. Therefore, effective measurement of adhesion was not possible. In Comparative Example 7, the results of observing the appearance were fine, but the adhesion value was small. Comparative Examples 2 to 4 are considered to correspond to a state in which the molten particle diameter is too large compared to the Vvv of the substrate. In such a case, the molten particles fill minute voids of the substrate of several μm or less, and the remaining molten liquid accumulates thickly and solidifies. It is presumed that a phenomenon occurs in which the anchor portion cannot hold the stress acting during solidification, and therefore the sprayed film cannot be formed on the substrate. In Comparative Example 7, the surface roughness Ra was larger than that of Comparative Examples 2 to 4, and therefore it is considered that the anchor portion was able to hold the stress acting during solidification, but the surface roughness Ra was not large enough to generate sufficient adhesion, and therefore it is presumed that the adhesion value was small.

In addition, in Comparative Example 8, the surface roughness Ra was increased by blasting to increase the adhesion strength using the conventional manufacturing method, so the adhesion strength value was high, but the occurrence of cracks was confirmed by observing the appearance.

The thermal sprayed film coated members of Examples 1 to 15 had Vvv values 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.

The sprayed film-coated members of Examples 17 to 34 were made of Al ₂ O ₃ sintered compacts with a substrate purity of 99.5% or more, Al ₂ O ₃ sintered compacts with a substrate purity of 99.8% or more, or AlN sintered compacts, and the (Vvv/(D50) ³ ) values were adjusted to 0.001 or more and 0.40 or less, and both the results of the appearance observation and the adhesion values were good.

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

On the other hand, the sprayed film coated members of Comparative Examples 9 and 13 have a value of (Vvv/(D50) ³ ) larger than 0.4. In this case, the results of the observation of the appearance were fine, but the adhesion value was small. These comparative examples are considered to correspond to the case where the molten particle diameter is too small compared to the Vvv of the substrate, or the substrate is blasted and Vvv is too large. In such a case, the molten particles penetrate into the narrow part of the substrate surface and adhere to it, but if left as it is, the substrate cannot be covered entirely, and there is a risk of problems such as insufficient voltage resistance characteristics. Furthermore, if the molten particles are deposited on it, the anchor effect is not fully exerted and peeling occurs at the sprayed film interface. Therefore, it is presumed that the adhesion to the ceramic sprayed film was not sufficient, especially on the blasted surface of the substrate.

Moreover, the sprayed film coated members of Comparative Examples 10 to 12, 14, and 15 had a value of (Vvv/(D50) ³ ) smaller than 0.002. In this case, in Comparative Examples 10 to 12, 14, and 15, peeling was observed by visual inspection. Therefore, effective measurement of adhesion was not possible. Comparative Examples 10 to 12, 14, and 15 are considered to correspond to cases in which the molten particle diameter is too large compared to the Vvv of the substrate. In such cases, the molten particles fill minute voids in the substrate of several μm or less, and the remaining molten liquid accumulates thickly and solidifies. It is presumed that the anchor portion cannot hold the stress acting during solidification, resulting in a phenomenon in which a sprayed film cannot be formed on the substrate.

The present invention is not limited to the above-described embodiment, and it goes without saying that it covers various modifications and equivalents that fall within the spirit and scope of the present invention. Furthermore, the structure, shape, number, position, size, etc. of the components shown in each drawing are for convenience of explanation and may be changed as appropriate.

1 Ceramic sintered body substrate 2 Ceramic thermal spray coating 10 Surface to be thermally sprayed

Claims (11)

A method for producing a thermal sprayed film-coated member, comprising the steps of:
an adjusting step of adjusting the spatial volume Vvv (μm ³ /μm ² ) of the sprayed surface of the ceramic sintered body substrate made of a sintered body containing SiC, AlN, or Al ₂ O ₃ to a predetermined range;
a coating step of coating the surface to be sprayed of the substrate by plasma spraying a slurry made of water and a ceramic raw material powder having an average particle size D50 in the range of 0.5 μm to 6 μm,
The adjustment step is performed with respect to the spatial volume Vvv and the average particle diameter D50,
0.001≦(Vvv/(D50) ³ )≦0.40
The method for producing a thermal sprayed film-coated member, comprising adjusting the temperature so that the temperature is within the range of 2. The method for producing a thermal sprayed film-coated member according to claim 1, wherein the ceramic sintered body substrate is made of a SiC sintered body. The method for producing a thermal sprayed film coated member according to claim 1, wherein the ceramic sintered body base material is made of _{an Al2O3} sintered body. The method for manufacturing a thermal sprayed film-coated member according to claim 1, characterized in that the ceramic sintered body substrate is made of an AlN sintered body. The method for manufacturing a sprayed film-coated member according to any one of claims 1 to 4, characterized in that the plasma spraying uses a non-oxidizing gas. The method for manufacturing a thermal sprayed film-coated member according to any one of claims 1 to 5, characterized in that the ceramic raw material powder is a powder of alumina, yttria, zirconia, titania, chromia, yttrium aluminum garnet, or any mixture of these powders. The method for manufacturing a thermal sprayed film-coated member according to any one of claims 1 to 6, characterized in that the spatial volume Vvv is 0.01 or more and 0.30 or less. A thermal sprayed film-coated member comprising a ceramic sintered body substrate and a thermal sprayed film provided on a surface to be thermally sprayed of the ceramic sintered body substrate,
With respect to the spatial volume Vvv (μm ³ /μm ² ) of the surface to be sprayed of the ceramic sintered body substrate and the average particle diameter D50 (μm) of the ceramic forming the sprayed film,
0.001≦(Vvv/(D50) ³ )≦0.40
Fulfilling
The ceramic sintered body base material is a sintered body containing SiC, AlN, or Al ₂ O ₃ ,
A thermal sprayed film-coated member, characterized in that no chemical bond exists between the elements constituting the ceramic sintered body substrate and the thermal sprayed film. A thermal sprayed film-coated member comprising a ceramic sintered body substrate and a thermal sprayed film provided on a surface to be thermally sprayed of the ceramic sintered body substrate,
With respect to the spatial volume Vvv (μm ³ /μm ² ) of the surface to be sprayed of the ceramic sintered body substrate and the average particle diameter D50 (μm) of the ceramic forming the sprayed film,
0.002≦(Vvv/(D50) ³ )≦0.40
Fulfilling
The thermal sprayed film-coated member, wherein the ceramic sintered body substrate is a SiC sintered body, an AlN sintered body, or _{an Al2O3} sintered body having a purity of 99.5% or more. The ceramic sintered body substrate is a SiC sintered body, an Al ₂ O ₃ sintered body, or an AlN sintered body,
9. The member coated with a thermal spray film according to claim 8, wherein the thermal spray film is made of one or a combination of two or more of alumina, yttria, zirconia, titania, chromia, and yttrium aluminum garnet. The sprayed film-coated member according to claim 9, characterized in that the sprayed film is made of one or a combination of two or more of alumina, yttria, zirconia, titania, chromia, and yttrium aluminum garnet.