KR102364003B1 - Yttrium oxyfluoride sprayed coating and method for producing the same, and sprayed member - Google Patents

Abstract

(Project) To provide a yttrium oxyfluoride thermal sprayed coating capable of suppressing the generation of microcracks and particles, and a thermal sprayed coating containing yttrium oxyfluoride.
(Solution) In the diffraction spectrum obtained by X-ray diffraction with Y ₅ O ₄ F ₇ as a main component, when the sum of all peak intensities attributed to yttrium oxyfluoride is 100, yttrium fluoride and yttrium oxide are It is a yttrium oxyfluoride thermal sprayed coating characterized in that the sum of all the peak intensities attributed to it is less than 10. In addition, in the diffraction spectrum obtained by the X-ray diffraction method, when the sum of all peak intensities attributed to yttrium oxyfluoride and yttrium fluoride is 100, the sum of all peak intensities attributed to yttrium oxide is less than 1. It is a thermal sprayed coating containing yttrium oxyfluoride.

Description

Yttrium oxyfluoride thermal sprayed coating, manufacturing method thereof, and thermal spraying member

The present invention relates to a yttrium oxyfluoride thermal sprayed film that can be formed on a member such as a semiconductor manufacturing apparatus, a manufacturing method thereof, and a thermal sprayed member.

In semiconductor manufacturing apparatuses such as CVD apparatus, PVD apparatus, ion implantation apparatus, diffusion furnace, and etching apparatus, a highly corrosive gas or chemical is generally used. is exposed to For this reason, a particle may generate|occur|produce when the material which comprises each member corrodes. These particles adversely affect the semiconductor to be manufactured and cause a decrease in quality or a decrease in manufacturing yield. Therefore, the surface of each member is coated with a material resistant to gas or chemical as described above. Although various things are known as the material used for such a coating, a fluoride type material is proposed in recent years (for example, refer patent document 1, 2).

Patent Document 1 discloses a corrosion-resistant member comprising a substrate surface coated with a plurality of materials, the outermost surface of the coating layer being a rare-earth element fluoride, and having an oxide layer of a rare-earth element having a porosity of less than 5% below it. . Further, in Patent Document 2, a slurry obtained by dispersing a raw material powder containing an oxyfluoride of a rare earth element (Ln) in an organic solvent is used to thermally spray on the surface of a substrate, and oxyfluoride of the rare earth element (Ln) is obtained. A film-attached substrate is disclosed having a film containing fluoride, fluoride and oxide as main components. The corrosion-resistant member described in these patent documents 1 and 2 and the base material with a film all have a certain level or more plasma resistance.

As described above, fluoride or oxyfluoride such as yttrium has resistance to highly corrosive gases and chemicals, and therefore is useful as a coating material for a member of a semiconductor manufacturing apparatus.

Patent Document 1: Japanese Patent No. 4985928 Publication Patent Document 2: Japanese Patent Laid-Open No. 2016-89241

However, when thermal spraying is performed using only a raw material of yttrium fluoride, a raw material containing yttrium fluoride and yttrium oxyfluoride, there are the following problems. That is, in a thermal sprayed coating using only yttrium fluoride as a raw material, yttrium fluoride of an ideal (異phase: structure different from orthorhombic crystal) is generated in addition to orthorhombic yttrium fluoride. Yttrium fluoride above this is exposed to heat (for example, plasma heat) generated during the use of a semiconductor manufacturing apparatus, thereby changing the phase to orthorhombic yttrium fluoride, and volume expansion or volume contraction accompanying the phase change occurs. By doing so, microcracks may occur in the thermal sprayed coating, and further, there is a possibility that particles may be generated. In order to suppress the generation of abnormal yttrium fluoride due to thermal spraying, thermal spraying should be performed on the preheated substrate before thermal spraying, or heat treatment should be performed on the thermal sprayed film after thermal spraying.

Moreover, when thermal spraying with the raw material containing yttrium fluoride and yttrium oxyfluoride, a thermal spraying film containing yttrium fluoride and yttrium oxyfluoride or these in addition to yttrium oxide may be formed. Yttrium fluoride contained in this thermal sprayed coating has the same problems as described above. Moreover, about the yttrium oxide contained in this thermal spraying film, as a result of volume expansion or volume contraction by fluorination by the fluorine plasma used at the time of use of a semiconductor manufacturing apparatus generate|occur|produces, a particle may generate|occur|produce.

The present invention has been made in view of the above conventional problems, and an object thereof is to provide a yttrium oxyfluoride thermal sprayed coating capable of suppressing the generation of microcracks or particles, a manufacturing method thereof, and a thermal spraying member having the thermal sprayed coating.

In the diffraction spectrum obtained by the X-ray diffraction method of the yttrium oxyfluoride thermal sprayed coating of the present invention, when the sum of all peak intensities attributed to yttrium oxyfluoride is 100, all peak intensities attributed to yttrium fluoride and yttrium oxide It is characterized in that the sum of is less than 10.

In the yttrium oxyfluoride thermal sprayed coating of the present invention, it is a yttrium oxyfluoride thermal sprayed coating, that is, a single-phase thermal sprayed coating of yttrium oxyfluoride, and contains yttrium fluoride causing a phase change by heat and yttrium oxide fluorinated by fluorine plasma. Even if it is not included or is included, since it is a very trace amount, the stability against heating such as plasma heat is high, and the generation of cracks and particles can be suppressed. Furthermore, it can be used suitably as a thermal spraying film with respect to the member of a semiconductor manufacturing apparatus.

The thermal sprayed member of the present invention has a yttrium oxide thermal sprayed film and a yttrium oxyfluoride thermal sprayed film on a substrate in this order, and in the diffraction spectrum of the yttrium oxyfluoride thermal sprayed film obtained by X-ray diffraction, all properties belonging to yttrium oxyfluoride It is characterized in that the sum of all peak intensities attributed to yttrium fluoride and yttrium oxide is less than 10 when the sum of the peak intensities is 100.

That is, the thermal sprayed member of the present invention is a member in which a yttrium oxide thermal sprayed coating and the yttrium oxyfluoride thermal sprayed coating of the present invention are laminated in this order on a substrate. The yttrium oxide thermal sprayed coating contributes to the improvement of the adhesion between the substrate and the yttrium oxyfluoride thermal sprayed coating. Therefore, the thermal spraying member of the present invention is formed by forming a yttrium oxyfluoride thermally sprayed film with high stability against heating such as plasma heat on the substrate while having high adhesion. Furthermore, it can be used suitably as a thermal spraying member in a semiconductor manufacturing apparatus.

It is preferable that the thermal sprayed member of the present invention further has a thermal sprayed film comprising yttrium oxide and yttrium oxyfluoride between the yttrium oxide thermal sprayed film and the yttrium oxyfluoride thermal sprayed film.

Since the thermal sprayed film containing yttrium oxide and yttrium oxyfluoride has a linear expansion coefficient intermediate between the yttrium oxide thermal sprayed film and the yttrium oxyfluoride thermal sprayed film, each thermal sprayed film by having a thermal sprayed film containing yttrium oxide and yttrium oxyfluoride Thermal stress applied to the interface can be relieved.

The method for producing a yttrium oxyfluoride thermal sprayed coating of the present invention is characterized by including a step of plasma spraying using a powder (granule) raw material containing yttrium oxyfluoride and having an oxygen content of 7.0 to 11.5 mass%.

The yttrium oxyfluoride thermal sprayed film of the present invention can be manufactured by the manufacturing method of the present invention.

The thermal sprayed coating containing yttrium oxyfluoride of the present invention is attributed to yttrium oxide when the sum of all peak intensities attributed to yttrium oxyfluoride and yttrium fluoride in the diffraction spectrum obtained by the X-ray diffraction method is 100 It is characterized in that the sum of all peak intensities is less than 1.

Here, "it contains yttrium oxyfluoride" means that components other than yttrium oxyfluoride may be included, for example, yttrium fluoride may be included.

Since the thermal sprayed coating containing yttrium oxyfluoride of the present invention does not contain yttrium oxide or even contains yttrium oxide, it has a very small amount, so it has high thermal stability, so cracks do not occur, and generation of particles can be suppressed. Therefore, it can be used suitably as a thermal spraying film with respect to the member used for a semiconductor manufacturing apparatus.

The thermal sprayed member of the present invention has a yttrium oxide thermal sprayed film and a thermal sprayed film containing yttrium oxyfluoride in this order on a substrate, and in the diffraction spectrum obtained by the X-ray diffraction method, the thermal sprayed film containing the yttrium oxyfluoride, When the sum total of all peak intensities attributed to yttrium fluoride and yttrium fluoride is 100, it is characterized in that the sum of all peak intensities attributed to yttrium oxide is less than 1.

That is, the thermal sprayed member of the present invention is a member in which a yttrium oxide thermal sprayed coating and a thermal sprayed coating containing the yttrium oxyfluoride of the present invention are laminated in this order on a substrate. The yttrium oxide thermal sprayed coating contributes to the improvement of the adhesion between the substrate and the yttrium oxyfluoride thermal sprayed coating. Therefore, the thermal spraying member of the present invention is formed by forming a yttrium oxyfluoride thermally sprayed film with high stability against heating such as plasma heat on the substrate while having high adhesion. Furthermore, it can be used suitably as a thermal spraying member in a semiconductor manufacturing apparatus.

The method for producing a thermal sprayed coating containing yttrium oxyfluoride of the present invention uses a slurry raw material prepared from a powder raw material containing at least one of yttrium oxyfluoride or yttrium fluoride and having an oxygen content of 0 to 6.0 mass%, using HVOF ( High Velocity Oxygen Fuel) It is characterized in that it includes a thermal spraying process.

Another method for producing a thermal sprayed coating containing yttrium oxyfluoride of the present invention is a powder raw material containing at least one of yttrium oxyfluoride or yttrium fluoride and having an oxygen content of 0 to 6.0 mass%, or a slurry raw material adjusted from the powder raw material. It is characterized in that it includes a step of high-speed plasma thermal spraying using hydrogen gas as a working gas.

By this manufacturing method, it is possible to manufacture the thermal sprayed film containing the yttrium oxyfluoride of the present invention.

1 is an X-ray diffraction spectrum of a raw material (A), a yttrium oxyfluoride thermal sprayed film (B), and an annealed yttrium oxyfluoride thermal sprayed film (C) used in Example 1. FIG.
Fig. 2 is an X-ray diffraction spectrum of a raw material (A) used in Example 5, a thermal sprayed film containing yttrium oxyfluoride (B), and an annealed thermal sprayed film containing yttrium oxyfluoride (C).
Fig. 3 is an X-ray diffraction spectrum of the raw material (A) used in Example 10, the thermal sprayed film containing yttrium oxyfluoride (B), and the thermal sprayed film containing yttrium oxyfluoride after annealing (C).

<Yttrium oxyfluoride thermal sprayed film>

In the diffraction spectrum obtained by the X-ray diffraction method of the yttrium oxyfluoride thermal sprayed coating of the present invention, when the sum of all peak intensities attributed to yttrium oxyfluoride is 100, all peak intensities attributed to yttrium fluoride and yttrium oxide It is characterized in that the sum of is less than 10.

In the yttrium oxyfluoride thermal sprayed coating of the present invention, YOF, Y ₇ O ₆ F ₉ , and Y ₆ O ₅ F ₈ are mentioned as components other than Y ₅ O ₄ F ₇ .

Further, in the yttrium oxyfluoride thermal sprayed coating of the present invention, when the sum of all peak intensities attributed to yttrium oxyfluoride is 100, the sum of all peak intensities attributed to yttrium fluoride and yttrium oxide is less than 10, which is It means that it does not contain yttrium and yttrium oxide, or that it contains trace amounts. As described above, since yttrium fluoride and yttrium oxide are adversely affected by plasma heat or the like, the sum of the peak intensities of the yttrium fluoride and yttrium oxide is preferably 0 with respect to the sum of the peak intensities of yttrium oxyfluoride. That is, it is preferable that it is a complete single-phase yttrium oxyfluoride thermal sprayed film.

From the above points, as described above, in the yttrium oxyfluoride thermal sprayed coating of the present invention, it is a yttrium oxyfluoride single-phase thermal sprayed coating. In other words, since yttrium fluoride, which causes a phase change by plasma heat, and yttrium oxide, which is fluorinated by fluorine plasma, are not included or are included in a very small amount, the stability to heating such as plasma heat is high, and the generation of cracks and particles can be suppressed. there is. Furthermore, it can be used suitably as a thermal spraying film with respect to the member of a semiconductor manufacturing apparatus.

<The thermal spray coating containing yttrium oxyfluoride>

The thermal sprayed coating containing yttrium oxyfluoride of the present invention is attributed to yttrium oxide when the sum of all peak intensities attributed to yttrium oxyfluoride and yttrium fluoride in the diffraction spectrum obtained by the X-ray diffraction method is 100 It is characterized in that the sum of all peak intensities is less than 1.

_In the _thermal sprayed coating containing yttrium _oxyfluoride of this invention, _Y7O6F9 , _Y6O5F8 , _YOF , _{and YF3} are mentioned as components other _{than Y5O4F7} .

Further, in the thermal sprayed coating containing yttrium oxyfluoride of the present invention, when the sum of all peak intensities attributed to yttrium oxyfluoride and yttrium fluoride is 100, the sum of all peak intensities attributed to yttrium oxide is less than 1. , this means that yttrium oxide is not included or is in a very small amount even if it is included. As described above, since yttrium oxide is adversely affected by plasma heat or the like, the peak intensity of the yttrium oxide is preferably zero for all peak intensities attributed to yttrium oxyfluoride. That is, it is preferable that it is a thermal sprayed film containing yttrium oxyfluoride which does not contain yttrium oxide.

From the above points, in the thermal sprayed coating containing yttrium oxyfluoride of this invention, it is a mixed thermal sprayed coating of yttrium oxyfluoride and yttrium fluoride. That is, since yttrium fluoride is not included or even if it is included in a very trace amount, it is possible to suppress the generation of cracks and particles due to high stability against heating such as plasma heat. Furthermore, it can be used suitably as a thermal spraying film with respect to the member of a semiconductor manufacturing apparatus.

The thickness of the yttrium oxyfluoride thermal sprayed film and the thermal sprayed film containing yttrium oxyfluoride of this invention can be 10-1000 micrometers, when it is set as the coating film of the member of a semiconductor manufacturing apparatus, for example.

The yttrium oxyfluoride thermal sprayed coating of the present invention and the thermal sprayed coating containing yttrium oxyfluoride can be manufactured by the manufacturing method described below.

<Method for producing yttrium oxyfluoride thermal sprayed coating>

The manufacturing method of the yttrium oxyfluoride thermal sprayed coating of this invention is characterized by including the process of plasma spraying using the powder raw material which contains yttrium oxyfluoride and has an oxygen content of 7.0-11.5 mass %.

In the manufacturing method of the present invention, there is no limitation in particular as a member on which the thermal sprayed film is formed, but from the viewpoint that the thermal sprayed film formed as described above can suppress the generation of particles, a member of the semiconductor manufacturing apparatus is targeted. It is very suitable to Hereinafter, the manufacturing method of the present invention will be described in detail.

In the present invention, in order to form a single-phase yttrium oxyfluoride thermal sprayed film, plasma thermal spraying is performed under predetermined conditions using a powder (granule) raw material containing yttrium oxyfluoride and having an oxygen content of 7.0 to 11.5 mass%. do.

In the present invention, the oxygen content in the raw material containing yttrium oxyfluoride is 7.0 to 11.5 mass%. If it is less than 7.0 mass%, yttrium fluoride is generated in the yttrium oxyfluoride thermal sprayed film, and if it exceeds 11.5 mass%, the yttrium oxyfluoride thermal sprayed film During the process, a crystalline phase of yttrium oxide is formed. 7.5-9.5 mass % is preferable and, as for the said oxygen content, 8.0-9.0 mass % is more preferable. In addition, the oxygen content in the raw material can be obtained by an inert gas melting-IR method.

The manufacturing method of the present invention employs a plasma spraying method, which is a thermal spraying method using a plasma flame as a heat source for softening and melting the raw material to be sprayed. When an inert gas is flowed between the electrodes to discharge, it is ionized and a high-temperature, high-speed plasma is generated. In general, when an arc is generated between electrodes using an inert gas such as argon as a working gas, the working gas is converted into a plasma by the arc, which is ejected as a high-temperature and high-speed plasma jet from the nozzle. A thermal sprayed coating is obtained by injecting a powder raw material into this plasma jet, heating and accelerating it, and spraying it on a substrate to adhere it. In the manufacturing method of this invention, the raw material containing yttrium oxyfluoride may be supplied in a powder state with respect to a plasma spraying apparatus at the time of plasma spraying, or may be supplied in a slurry state.

As conditions for plasma thermal spraying, it is preferable to make a thermal spraying speed into 150-330 m/s. Moreover, as a spraying distance (distance from the nozzle tip of a plasma spraying apparatus to a base material), it can set between 20-250 mm, for example, and 50-150 mm is preferable. Moreover, as for the kind of working gas, the combination _of Ar and O2 is preferable. The gas amount is preferably 40 to 140 L/min in total of Ar and O ₂ . Moreover, 80-110A of electric current, 240-280V of voltage, and 19-31kW of electric power are preferable. Moreover, as for a scan speed|rate, 100-1000 mm/s is preferable.

The average particle diameter (D50) of yttrium oxyfluoride can use the thing of 1-50 micrometers. The form of the particles may be only granules or primary particles. If it is less than 1 μm, the weight of the molten particles is small and does not adhere to the substrate, and if it exceeds 50 μm, the unmelted particles tend to adhere to the substrate, making it difficult to form a thermal sprayed film. The raw material containing yttrium oxyfluoride contains at least ₁ sort(s) of _YOF and _Y5O4F7 as yttrium oxyfluoride, and may contain YF3 other _than the said yttrium oxyfluoride. For example, a raw material with a high oxygen content contains a relatively large amount of YOF, and a raw material with a low oxygen content contains a relatively large amount of YF ₃ . Therefore, the oxygen content in the raw material can be adjusted by adjusting the composition ratio of each compound (YOF, Y ₅ O ₄ F ₇ and YF ₃ ) contained in the raw material. In addition, the raw material of yttrium oxyfluoride may contain trace amounts of Y ₇ O ₆ F ₉ and Y ₆ O ₅ F ₈ .

Moreover, although the thermal spraying film in after thermal spraying can be used in the state as it is, it is preferable to perform annealing treatment as needed. Residual stress can be released by performing annealing treatment. The annealing treatment temperature is preferably 200 to 500°C, and the annealing time is preferably 10 minutes to 600 minutes.

<Method for producing thermal sprayed coating containing yttrium oxyfluoride>

The method for producing a thermal sprayed coating containing yttrium oxyfluoride according to the present invention comprises at least one of yttrium oxyfluoride or yttrium fluoride and contains at least one of yttrium oxyfluoride or yttrium fluoride, and has an oxygen content of 0 to 6.0 mass%. It is characterized in that it includes a process of high-speed plasma thermal spraying.

In this manufacturing method, although there is no restriction|limiting in particular as a member as a target for forming a thermal sprayed film, From a viewpoint that the thermal spraying film formed as mentioned above can suppress the generation|occurrence|production of a particle, it is preferable to target the member of a semiconductor manufacturing apparatus very suitable Hereinafter, the manufacturing method of this invention is demonstrated.

In this manufacturing method, in order to form a thermal sprayed film containing yttrium oxyfluoride, a slurry raw material adjusted from a powder raw material containing at least one of yttrium oxyfluoride or yttrium fluoride and having an oxygen content adjusted to 0 to 6.0 mass% HVOF thermal spraying is performed under predetermined conditions using

In this manufacturing method, the oxygen content in the raw material containing at least either yttrium oxyfluoride or yttrium fluoride is 0 to 6.0 mass%, but when it exceeds 6.0 mass%, a crystalline phase of yttrium oxide is generated in the yttrium oxyfluoride thermal sprayed film. am. As for the said oxygen content, 0-6.0 mass % is preferable.

In this manufacturing method, the HVOF thermal spraying method is employ|adopted, The HVOF thermal spraying method is a thermal spraying method using fuel combustion heat as a heat source for melting a slurry raw material. In general, 0 ₂ , kerosene, etc. as fuel, is ejected as a high-temperature and high-speed flame from the nozzle. A thermal sprayed coating is obtained by injecting a slurry raw material into this flame, heating and accelerating it, and spraying it to a base material.

As a condition of HVOF thermal spraying, it is preferable that a thermal spraying speed shall be 200-1000 m/s. Moreover, as a spraying distance (distance from the nozzle of a plasma spraying apparatus to a base material), it is preferable to set between 50-130 mm, for example. Moreover, as for a fuel, the combination of 0 ₂ and kerosene is preferable. Moreover, as for a scan speed|rate, 100-1000 mm/s is preferable.

As for the average particle diameter of the slurry raw material containing at least either one of yttrium oxyfluoride or yttrium fluoride, the thing of 0.1-8 micrometers can be used. If it is less than 0.1 μm, the weight of the molten particles is too small to adhere to the substrate, and if it is less than 1 μm, the weight of the molten particles is small and difficult to adhere to the substrate. On the other hand, when it exceeds 8 μm, it becomes difficult to form a slurry, which impairs the supply of raw materials.

As for the slurry raw material containing at least either one of yttrium oxyfluoride or yttrium fluoride, for example, a raw material with much oxygen content contains relatively much _YOF , and a raw material with little oxygen content contains relatively much YF3. Therefore, oxygen content in a raw material can be adjusted by adjusting the structural ratio of _each compound ( _YOF , _Y5O4F7 , and _YF3 ) contained in a raw material.

Moreover, it is preferable to implement similarly to the case of plasma thermal spraying also about the annealing process after thermal spraying.

Moreover, as another manufacturing method of the thermal sprayed coating containing yttrium oxyfluoride of this invention, in order to form the thermal sprayed film containing yttrium oxyfluoride, it contains at least either one of yttrium oxyfluoride or yttrium fluoride, and oxygen content is 0-11.5 High-speed plasma thermal spraying is performed under predetermined conditions using the powder raw material adjusted to mass %.

In this manufacturing method, the oxygen content in the raw material containing at least either yttrium oxyfluoride or yttrium fluoride is 0 to 11.5 mass%, but when it exceeds 11.5 mass%, a crystalline phase of yttrium oxide is generated in the yttrium oxyfluoride thermal sprayed film. am. As for the said oxygen content, 0-9.5 mass % is preferable.

Another method for producing a thermal sprayed coating containing yttrium oxyfluoride of the present invention, using a slurry raw material prepared from a powder raw material containing at least one of yttrium oxyfluoride or yttrium fluoride and having an oxygen content of 0 to 6.0 mass% High-speed plasma spraying is performed under predetermined conditions. In this case, the oxygen content is 0 to 6.0 mass%, but when the oxygen content exceeds 6.0 mass%, a yttrium oxide crystal phase is formed in the yttrium oxyfluoride thermal sprayed coating.

This manufacturing method employs a high-speed plasma spraying method, which is a thermal spraying method using a plasma flame as a heat source for softening and melting the raw material to be sprayed. When an arc is generated between the electrodes using an inert gas as a working gas, the working gas is converted into plasma by the arc, which is ejected as a high-temperature and high-speed plasma jet from the nozzle. A thermal sprayed coating is obtained by injecting a powder raw material into this plasma jet, heating and accelerating it, and spraying it on a substrate to adhere it. In the manufacturing method of the present invention, the raw material containing yttrium oxyfluoride may be supplied in a powder state to the plasma thermal spraying apparatus during plasma thermal spraying, or may be supplied in a slurry state.

As conditions for high-speed plasma thermal spraying, it is preferable that a thermal spraying speed shall be 600-700 m/s. Moreover, as a spraying distance (distance from the nozzle front-end|tip of a plasma spraying apparatus to a base material), it can set between 20-250 mm, for example, and 90-130 mm is preferable. In addition, a combination of Ar, N ₂ , and H ₂ is preferable as the type of the working gas. The amount of gas is preferably 40 to 350 L/min in total of Ar and N ₂ . As for H2, _0-70L /min is preferable. More preferably, H ₂ is 0 to 10 L/min.

When the flow rate of H ₂ is too large, the reaction of YOF+H ₂ →Y ₂ O ₃ +HF proceeds to generate Y ₂ O ₃ . In addition, when the flow rate of H ₂ increases, the amount of heat generated by the plasma increases, and it is assumed that the chemical reaction rate in the reaction is increased to promote the generation of Y ₂ O ₃ . Therefore, it is preferable to make the flow _volume of H2 into less than a fixed value. Moreover, 200-400A of electric current, 180-280V of voltage, and 40-105 kW of electric power are preferable. Moreover, as for a scan speed, 100-200 mm/s is preferable.

In addition, the properties of the raw material are the same as in the case of plasma thermal spraying and HVOF thermal spraying.

Moreover, it is preferable to implement similarly to the case of plasma thermal spraying also about the annealing process after thermal spraying.

<Brave member>

The thermal sprayed member of the present invention has a yttrium oxide thermal sprayed film and a yttrium oxyfluoride thermal sprayed film on a substrate in this order, and in the diffraction spectrum of the yttrium oxyfluoride thermal sprayed film obtained by X-ray diffraction, all properties belonging to yttrium oxyfluoride It is characterized in that the sum of all peak intensities attributed to yttrium fluoride and yttrium oxide is less than 10 when the sum of the peak intensities is 100. In addition to aluminum, metals such as aluminum alloy and stainless steel, ceramics such as quartz glass and alumina, etc. can be used as the material constituting the base material.

Another thermal sprayed member of the present invention has a yttrium oxide thermal sprayed film and a yttrium oxyfluoride thermal sprayed film not containing yttrium oxide on a substrate in this order, and in the diffraction spectrum obtained by the yttrium oxyfluoride thermal sprayed film by X-ray diffraction method, When the sum of all peak intensities attributed to yttrium oxyfluoride and yttrium fluoride is 100, it is characterized in that all peak intensities attributed to yttrium oxide are less than 1. In addition to aluminum, metals such as aluminum alloy and stainless steel, ceramics such as quartz glass and alumina, etc. can be used as the material constituting the base material.

In the thermal sprayed member of the present invention or the second invention, a yttrium oxide thermal sprayed film is provided on an aluminum substrate, and the yttrium oxyfluoride thermal sprayed film of the present invention or a thermal sprayed film containing yttrium oxyfluoride is provided thereon. In this way, by interposing the yttrium oxide thermal sprayed film between the aluminum substrate and the yttrium oxyfluoride thermal sprayed film or the thermal sprayed film containing yttrium oxyfluoride of the present invention, the yttrium oxyfluoride thermal sprayed film or yttrium oxyfluoride of the present invention is applied on the aluminum substrate. The adhesion is increased compared to the case in which the included thermal sprayed coating is directly formed. The reason why the adhesion is increased in this way is because, in particular, when the substrate is made of a metal (aluminum, titanium, etc.), yttrium oxide has superior chemical wettability to the substrate than yttrium oxyfluoride.

In the thermal sprayed member of the present invention, the thickness of the yttrium oxyfluoride thermal sprayed film or the thermal sprayed film containing yttrium oxyfluoride may be 10 to 200 μm, and in this case, in order to secure sufficient adhesion, the thickness of the yttrium oxide thermal sprayed film is 10 It is preferable to set it as -200 micrometers.

Further, in the thermal sprayed member of the present invention, it is preferable to further have a thermal sprayed film containing yttrium oxide and yttrium oxyfluoride between the yttrium oxide thermal sprayed film and the yttrium oxyfluoride thermal sprayed film or the thermal sprayed film containing yttrium oxyfluoride of the present invention. Do. Since the thermal sprayed coating containing yttrium oxide and yttrium oxyfluoride has an intermediate linear expansion coefficient between the yttrium oxide thermal sprayed film and the yttrium oxyfluoride thermal sprayed film of the present invention or the thermal sprayed coating containing yttrium oxyfluoride, each thermal sprayed film interface It is possible to relieve the thermal stress applied to the

Yttrium oxide (X) and oxyfluoride in the thermal sprayed coating containing yttrium oxide and yttrium oxyfluoride formed between the yttrium oxide thermal sprayed coating and the yttrium oxyfluoride thermal sprayed film or the thermal sprayed coating containing yttrium oxyfluoride of the present invention The mass ratio (X/Y) of the total (Y) of yttrium and yttrium fluoride is preferably 0.3 to 0.7 from the viewpoint of relaxation of thermal expansion. Moreover, it is preferable to set it as 10-200 micrometers as thickness of the said thermal sprayed film.

Each thermal sprayed film in the thermal spraying member of this invention can be formed by plasma thermal spraying. The conditions of the plasma thermal spraying of each thermal spraying film are the same as the conditions of the plasma thermal spraying in the yttrium oxyfluoride thermal spraying film mentioned above.

The thermal spraying film containing each yttrium oxyfluoride in the thermal spraying member of this invention can be formed by HVOF thermal spraying or high-speed plasma thermal spraying. The thermal spray conditions of these thermal sprayed coatings are the same as the conditions of the HVOF thermal spraying and high-speed plasma thermal spraying in the thermal spraying film mentioned above.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

[Example 1]

A powder raw material (particle diameter: 25 μm) containing yttrium oxyfluoride and having an oxygen content of 8.5 mass% was prepared, and for this raw material, an X-ray diffraction apparatus (manufactured by Rigaku Co., Ltd., MultiFlex) was used under the conditions shown below. X-ray diffraction spectrum was measured. The obtained X-ray diffraction spectrum is shown in FIG. 1(A).

X-ray light source: Cu-Kα ray (wavelength: 1.54060 Å)

Scan step: 0.02˚

Scan axis: 2θ

Scanning range: 10-80˚

Then, the raw material was plasma-sprayed with respect to the substrate (aluminum alloy: A6061) to form a yttrium oxyfluoride thermal sprayed film having a thickness of 200 μm. The conditions for Plasma Heroes are as follows.

Plasma thermal sprayer: Aeroplasma product APS-7100

Working gas: Ar, O ₂

Scanning speed: 100-1000mm/s

Spray distance: 80mm

Thermal spraying speed: 150-330 m/s

Current: 80~110A

Voltage: 240-280V

Power: 19~31kW

The X-ray diffraction spectrum was measured for the formed thermal sprayed coating in the same manner as the above-mentioned raw material. The obtained X-ray diffraction spectrum is shown in FIG. 1(B). It turns out that the crystal phase of _Y5O4F7 and _YOF is included in the formed thermal _sprayed film from FIG.1(B).

Further, the formed thermal sprayed coating was annealed at 300°C for 2 hours using an atmospheric furnace. And the X-ray diffraction spectrum was measured similarly to the raw material mentioned above about the thermal sprayed film after annealing. The obtained X-ray diffraction spectrum is shown in FIG. 1(C). In (B) and (C) of FIG. 1, a difference was not recognized in a diffraction spectrum, but it turns out that the thermal spraying film after plasma thermal spraying is stable. Table 1 also shows the crystal phases contained in the raw material, each step after thermal spraying and after annealing.

1A to 1C, in order to facilitate comparison of the respective X-ray diffraction spectra, they are sequentially stacked from the lower side to the upper side in the vertical axis direction. Therefore, the intensity of the vertical axis does not represent absolute intensity, but is relative.

[Example 2]

A powder raw material (particle diameter: 25 μm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 7.0 mass% was prepared, and the raw material was subjected to the same procedure as in Example 1, and the raw material was plasma sprayed to 200 A yttrium oxyfluoride thermal sprayed film having a thickness of μm was formed and annealed. Table 1 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing treatment.

[Example 3]

A powder raw material (particle diameter: 25 µm) containing yttrium oxyfluoride and having an oxygen content of 11.5 mass% was prepared, and the raw material was subjected to the same procedure as in Example 1, and the raw material was plasma-sprayed to the base material to a thickness of 200 µm. A yttrium oxyfluoride thermal sprayed film was formed and annealed. Table 1 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing treatment.

In all of the above Examples 2 and 3, similarly to Example 1, the formed thermal sprayed coating contains Y ₅ O ₄ F ₇ and YOF crystal phases, and no difference is seen before and after the annealing treatment, so that the thermal sprayed coating is stable.

[Example 4]

A yttrium oxide thermal sprayed film of 100 μm is formed by plasma thermal spraying on an aluminum substrate (thickness: 5 mm), and a raw material containing yttrium oxyfluoride and having an oxygen content of 8.5% by mass was subjected to plasma thermal spraying under the same thermal spraying conditions as in Example 1. Thus, a 50 μm yttrium oxyfluoride thermal sprayed film was formed. In addition, the conditions of plasma thermal spraying at the time of formation of a yttrium oxide thermal sprayed film are the same as that of the plasma thermal spraying of the yttrium oxyfluoride thermal sprayed film shown in Example 1.

And, the adhesion force of the yttrium oxyfluoride thermal sprayed coating of this Example and Example 1 was measured by a tensile tester. Rather than directly forming the yttrium oxyfluoride thermal sprayed film on the aluminum substrate, the yttrium oxide thermal sprayed film on the aluminum substrate, The result was obtained that the adhesion between the base material and the thermal sprayed coating was increased in the direction in which the yttrium fluoride thermal sprayed film was formed.

[Comparative Example 1]

A powder raw material (particle diameter: 25 μm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 6.4 mass% was prepared. A yttrium oxyfluoride thermal sprayed film having a thickness of μm was formed and annealed. Table 1 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing treatment. From the X-ray diffraction spectrum, the raw material contains crystal phases of Y ₅ O ₄ F ₇ and YF ₃ (orthorhombic), and the formed thermal sprayed film has crystal phases of Y ₅ O ₄ F ₇ and YF ₃ (ideal). and Y ₅ O ₄ F ₇ and YF ₃ (orthorhombic) crystal phase after the annealing treatment, it can be seen that stability is lacking.

[Comparative Example 2]

Prepare a powder raw material (particle diameter: 25 µm) containing yttrium oxyfluoride and having an oxygen content of 12.0 mass%, and the same as in Example 1 for this raw material, plasma spraying the raw material on the substrate to a thickness of 200 µm A yttrium oxyfluoride thermal sprayed film was formed and annealed. Table 1 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing treatment. The X-ray diffraction spectrum shows that the raw material is a YOF single phase, but since it becomes a crystal phase of YOF and Y ₂ O ₃ after the formed thermal spraying film and annealing treatment, stability is insufficient.

crystalline phase Y ₂ O ₃
YOF
Y ₅ O ₄ F ₇
YF ₃ stability
orthogonal More than
Example 1
Raw material - - ○ - - - after plasma spray - ○ ○ - - ○
after annealing - ○ ○ - -
Example 2
Raw material - - ○ ○ - - after plasma spray - ○ ○ - - ○
after annealing - ○ ○ - -
Example 3
Raw material - - ○ - - - after plasma spray - ○ ○ - - ○
after annealing - ○ ○ - -
Comparative Example 1
Raw material - - ○ ○ - - after plasma spray - - ○ - ○ △
after annealing - - ○ ○ -
Comparative Example 2
Raw material - ○ - - - - after plasma spray ○ ○ - - - △
after annealing ○ ○ - - -

In the evaluation of stability, a case in which no difference was seen in the crystal phase before and after the annealing treatment was denoted as ○, and a case in which a change was observed was denoted by Δ.

An X-ray diffraction apparatus (manufactured by Rigaku Co., Ltd., MultiFlex) was used to identify the crystalline phase, but if accurate measurement cannot be performed due to the influence of the underlying thermal sprayed coating to be measured, a thin film is required as needed. X-ray diffraction (In-plane XRD), ESCA, TEM (transmission electron microscope) can be substituted.

[Example 5]

A slurry raw material (particle diameter: 2 µm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 5.6 mass% was prepared.

Then, with respect to the substrate (aluminum alloy: A6061), the raw material was HVOF thermally sprayed to form a yttrium oxyfluoride thermal sprayed film having a thickness of 200 μm. The conditions for HVOF warriors are as follows.

O ₂ flow: 480 L/min

Kerosene flow rate: 180mL/min

Scan speed: 1000mm/s

Spray distance: 100mm

Thermal spraying speed: 450m/s

An X-ray diffraction spectrum was measured in the same manner as in Example 1 for the formed thermal sprayed coating. The obtained X-ray diffraction spectrum is shown in FIG.2(B). It turns out that although the crystal phase of _Y5O4F7 , _YF3 , and _YOF is included in _the formed thermal spraying film from _FIG.2 (B), Y2O3 is not included _. In addition, (A) of FIG. 2 is a diffraction spectrum of a thermal spraying raw material.

Further, the formed thermal sprayed coating was annealed at 300° C. for 2 hours using an atmospheric furnace. And the X-ray diffraction spectrum was measured similarly to the raw material mentioned above about the thermal sprayed film after annealing. The obtained X-ray diffraction spectrum is shown in FIG.2(C). In comparison of the diffraction spectra of Fig. 2(B) and (C), loss of YF ₃ (ideal phase) is recognized. As a result, it turns out that the thermal spraying film after HVOF thermal spraying is stable. Table 2 also shows the crystal phases contained in the raw material, each step after thermal spraying and after annealing.

In addition, in Fig. 2, in order to facilitate comparison of the respective X-ray diffraction spectra, the graphs are sequentially stacked from the lower side to the upper side in the vertical axis direction. Therefore, the intensity of the vertical axis does not represent absolute intensity, but is relative.

[Example 6]

Prepare a slurry raw material (particle diameter: 2 μm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 2.2% by mass, in the same manner as in Example 5 for this raw material, and HVOF thermal spraying the raw material for the substrate 200 A yttrium oxyfluoride thermal sprayed film having a thickness of μm was formed and annealed. Table 2 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing treatment.

[Example 7]

Prepare a slurry raw material (particle diameter: 2 µm) of yttrium fluoride (oxygen content is 0 mass%), and the raw material is the same as in Example 5, and the raw material is HVOF sprayed to the substrate to oxyfluoride 200 µm thick. A yttrium thermal sprayed film was formed and annealed. Table 2 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing treatment.

[Example 8]

Prepare a slurry raw material (particle diameter: 2 μm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 6.0 mass %, in the same manner as in Example 5 for this raw material, and HVOF thermal spraying the raw material for the substrate 200 A yttrium oxyfluoride thermal sprayed film having a thickness of μm was formed and annealed. Table 2 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing treatment.

In Examples 6 to 8 above, similarly to Example 5, the formed thermal sprayed film did not contain Y ₂ O ₃ , but contained Y ₅ O ₄ F ₇ and YF ₃ or a crystalline phase of YOF in them, and YF after annealing. ₃ (phase) is lost, so the thermal sprayed coating is stable.

[Example 9]

A yttrium oxide thermal sprayed film of 100 μm is formed on an aluminum substrate (thickness: 5 mm) by plasma thermal spraying, and a slurry raw material containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 5.6 mass % is sprayed thereon as in Example 5. By HVOF thermal spraying under the conditions, a thermal sprayed film containing yttrium oxyfluoride of 50 μm was formed. In addition, the conditions of plasma thermal spraying at the time of formation of a yttrium oxide thermal sprayed film are the same as that of the plasma thermal sprayed film of the yttrium oxyfluoride thermal sprayed film shown in Example 1.

And, the adhesion force of the thermal sprayed coating containing yttrium oxyfluoride of Examples 9 and 5 was measured using a tensile tester, and a yttrium oxide thermal sprayed film on an aluminum substrate and a thermal sprayed film containing yttrium oxyfluoride thereon were formed. As a result, the adhesion between the substrate and the thermal sprayed coating was increased.

[Comparative Example 3]

Prepare a slurry raw material (particle diameter: 2 μm) containing yttrium oxyfluoride and having an oxygen content of 8.4% by mass, in the same manner as in Example 5 for this raw material, and HVOF thermal spraying the raw material to a substrate having a thickness of 200 μm A yttrium oxyfluoride thermal sprayed film was formed and annealed. Table 2 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing treatment. From the X-ray diffraction spectrum, it can be seen that the crystal phase of Y ₂ O ₃ appears and lacks stability after the raw material, the formed thermal sprayed film, and the annealing treatment.

crystalline phase Y ₂ O ₃
YOF
Y ₅ O ₄ F ₇
YF ₃ safety
orthogonal More than Example 5
(5.6wt%)
Raw material - - ○ ○ - - After HVOF Champion - ○ ○ ○ ○ ○
after annealing - ○ ○ ○ - Example 6
(2.2wt%)
Raw material - - ○ ○ - - After HVOF Champion - - ○ ○ ○ ○
after annealing - - ○ ○ - Example 7
(0wt%)
Raw material - - - ○ - - After HVOF Champion - - ○ ○ ○ ○
after annealing - - ○ ○ - Example 8
(6.0wt%)
Raw material - - ○ ○ - - After HVOF Champion - ○ ○ ○ ○ ○
after annealing - ○ ○ ○ - Comparative Example 3
(8.4wt%)
Raw material - - ○ - - - After HVOF Champion ○ ○ ○ - - △
after annealing ○ ○ ○ - -

[Example 10]

A powder raw material (particle diameter: 25 µm) containing yttrium oxyfluoride and having an oxygen content of 8.4% by mass was prepared.

Then, the powder raw material was subjected to high-speed plasma spraying of the base material (aluminum alloy: A6061) to form a yttrium oxyfluoride thermal sprayed film having a thickness of 200 μm. The conditions for high-speed plasma spraying are as follows. In addition, the powder raw material is in a granular state.

Working gases: Ar, N ₂ , H ₂

H ₂ gas flow rate: 5L/min

Scan speed: 850mm/s

Spray distance: 90mm

Thermal spraying speed: 600~700m/s

Current: 400A

Voltage: 260V

Power: 104kW

An X-ray diffraction spectrum was measured in the same manner as in Example 1 for the formed thermal sprayed coating. The obtained X-ray diffraction spectrum is shown in FIG.3(B). It turns out that although the crystal phase _{of Y5O4F7} and _YOF is included in the formed thermal _sprayed film from _FIG.3 (B), Y2O3 is not included. 3A is a diffraction spectrum of a thermal spraying raw material.

Further, the formed thermal sprayed coating was annealed at 300°C for 2 hours using an atmospheric furnace. And the X-ray diffraction spectrum was measured similarly to the raw material mentioned above about the thermal sprayed film after annealing. The obtained X-ray diffraction spectrum is shown in FIG.3(C). In comparison of the diffraction spectra of Fig.3 (B) and (C), a difference was not recognized, but it turns out that the thermal spraying film after high-speed plasma thermal spraying is stable. Table 3 also shows the crystal phases contained in the raw material, each step after thermal spraying and after annealing.

Also, in Fig. 3, in order to facilitate comparison of the respective X-ray diffraction spectra, the graphs are sequentially stacked from the lower side to the upper side in the vertical axis direction. Therefore, the intensity of the vertical axis does not represent absolute intensity, but is relative.

[Example 11]

A powder raw material (particle diameter: 25 µm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 4.6 mass% was prepared. Thus, a 200 μm thick yttrium oxyfluoride thermal sprayed film was formed, and annealing was performed. Table 3 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing treatment.

[Example 12]

A yttrium oxide thermal sprayed film of 100 μm is formed by plasma spraying on an aluminum substrate (thickness: 5 mm), and a powder raw material (particle diameter: 25 μm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 5.6 mass% (particle diameter: 25 μm) High-speed plasma spraying was performed under the same spraying conditions as in Example 10 to form a thermal sprayed film containing yttrium oxyfluoride of 50 μm. In addition, the conditions of plasma thermal spraying at the time of formation of a yttrium oxide thermal sprayed film are the same as that of the plasma thermal sprayed film of the yttrium oxyfluoride thermal sprayed film shown in Example 1.

And, when the adhesion of the thermal sprayed film containing yttrium oxyfluoride of Example 12 and Examples 10 and 11 was measured using a tensile tester, it was oxidized on the aluminum substrate rather than directly forming the yttrium oxyfluoride thermal sprayed film on the aluminum substrate. The result was obtained that the adhesion between the substrate and the thermal sprayed coating was increased by forming the yttrium thermal sprayed coating and the yttrium oxyfluoride thermal sprayed coating thereon.

[Example 13]

Prepare a slurry raw material (particle diameter: 2 μm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 4.6 mass%, the same as in Example 10 for this raw material, and high-speed plasma spraying of the slurry raw material for the substrate A yttrium oxyfluoride thermal sprayed film having a thickness of 200 μm was formed and annealed. From the X-ray diffraction spectrum, it was confirmed that the crystal phase of Y ₂ O ₃ did not occur in the thermal sprayed coating after the annealing treatment.

[Comparative Example 4]

A powder raw material (particle diameter: 25 μm) containing yttrium oxyfluoride and having an oxygen content of 8.4 mass% was prepared, and the H ₂ gas flow rate was increased to 70 L/min with respect to this raw material in the same manner as in Example 10, , a yttrium oxyfluoride thermal sprayed film having a thickness of 200 μm was formed by high-speed plasma spraying of the powder raw material on the substrate, followed by annealing. Table 3 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing. From the X-ray diffraction spectrum, it can be seen that the crystal phase of Y ₂ O ₃ appears in the thermal sprayed coating after the annealing treatment and lacks stability.

[Comparative Example 5]

A powder raw material (particle diameter: 25 µm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 4.6 mass% was prepared, and with respect to this raw material, the H ₂ gas flow rate was increased to 70 L/min. In the same manner, the powder raw material was subjected to high-speed plasma thermal spraying of the base material to form a yttrium oxyfluoride thermal sprayed film having a thickness of 200 µm, followed by annealing. Table 3 shows the crystal phases identified from the X-ray diffraction spectrum of the raw material, the formed thermal sprayed coating, and the thermal sprayed coating after annealing. From the X-ray diffraction spectrum, it can be seen that the crystal phase of Y ₂ O ₃ appears in the thermal sprayed coating after the annealing treatment and lacks stability.

[Comparative Example 6]

A slurry raw material (particle size: 2 µm) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 4.6 mass% was prepared, and the H ₂ gas flow rate was increased to 70 L/min with respect to this raw material as in Example 12. In the same manner, the slurry raw material was subjected to high-speed plasma thermal spraying of the substrate to form a yttrium oxyfluoride thermal sprayed film having a thickness of 200 µm, followed by annealing. From the X-ray diffraction spectrum, it can be seen that some generation of Y ₂ O ₃ is confirmed in the thermal sprayed coating after the annealing treatment, and thus lacks stability.

It can be seen that all of the thermal sprayed coatings of Examples 10 to 12 above are made of crystal phases of Y ₅ O ₄ F ₇ , YOF, and YF ₃ and do not contain the crystal phase of Y ₂ O ₃ , so that the thermal sprayed coating after annealing is stable. there was. On the other hand, generation of a crystal phase of Y ₂ O ₃ was confirmed in the thermal sprayed coatings prepared by the high-speed plasma thermal spraying of Comparative Examples 4 to 6 in which the H ₂ gas flow rate was increased, indicating that the thermal sprayed coating after annealing lacks stability. there was.

crystalline phase Y ₂ O ₃
YOF
Y ₅ O ₄ F ₇
YF ₃ stability
orthogonal More than Example 10
(8.4wt%)
(H ₂ flow rate: small) Raw material - - ○ - - - After high-speed plasma spraying - ○ ○ - - ○
after annealing - ○ ○ - - Example 11
(4.6wt%)
(H ₂ flow rate: small) Raw material - - ○ ○ - - After high-speed plasma spraying - ○ ○ ○ ○ ○
after annealing - ○ ○ ○ - Example 12
(4.6wt%)
(H ₂ flow rate: small) Raw material - - ○ ○ - - After high-speed plasma spraying - ○ ○ ○ ○ ○
after annealing - ○ ○ ○ - Comparative Example 4
(8.4wt%)
(H ₂ flow rate: large) Raw material - - ○ - - - After high-speed plasma spraying ○ ○ ○ - - △
after annealing ○ ○ ○ - - Comparative Example 5
(4.6wt%)
(H ₂ flow rate: large) Raw material - - ○ ○ - - After high-speed plasma spraying ○ ○ ○ ○ ○ △
after annealing ○ ○ ○ ○ - Comparative Example 6
(4.6wt%)
(H ₂ flow rate: large) Raw material - - ○ ○ - - After high-speed plasma spraying ○ ○ ○ ○ ○ △
after annealing ○ ○ ○ ○ -

Claims (9)

delete A yttrium oxide thermal sprayed film and a yttrium oxyfluoride thermal sprayed film are provided on the substrate in this order, and in the diffraction spectrum obtained by the yttrium oxyfluoride thermal sprayed film by X-ray diffraction, the sum of all peak intensities attributed to yttrium oxyfluoride is 100 When , the sum of all peak intensities attributed to yttrium fluoride and yttrium oxide is less than 10,
The thermal spraying member, characterized in that it further has a thermal sprayed film comprising yttrium oxide and yttrium oxyfluoride between the yttrium oxide thermal sprayed film and the yttrium oxyfluoride thermal sprayed film.
delete delete delete delete delete delete It has a yttrium oxide thermal sprayed film and a thermal sprayed film containing yttrium oxyfluoride on the substrate in this order, and in the diffraction spectrum obtained by the X-ray diffraction method, the thermal sprayed film containing the yttrium oxyfluoride belongs to yttrium oxyfluoride and yttrium fluoride When the sum of all the peak intensities used is 100, the sum of all the peak intensities attributed to yttrium oxide is less than 1,
A thermal spraying member, characterized in that it further includes a thermal sprayed film containing yttrium oxide and yttrium oxyfluoride between the yttrium oxide thermal sprayed film and the thermal sprayed film containing yttrium oxyfluoride.

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