KR20180000309A - Yttrium oxyfluoride sprayed coating and method for producing the same, and sprayed member - Google Patents

Abstract

The present invention provides an yttrium oxyfluoride sprayed film capable of suppressing generation of micro cracks or particles, and a sprayed film containing yttrium oxyfluoride. The yttrium oxyfluoride sprayed film contains Y_5O_4F_7 as a main component. When the total intensity of all peaks attributable to yttrium oxyfluoride in a diffraction spectrum obtained by X-ray diffractometry is assumed to be 100, the total intensity of all peaks attributable to yttrium fluoride and yttrium oxide is less than 10. Also, when the total intensity of all peaks attributable to yttrium oxyfluoride and yttrium fluoride in a diffraction spectrum obtained by X-ray diffractometry is assumed to be 100, the total intensity of all peaks attributable to yttrium oxide is less than 1.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a yttrium fluoride yttrium fluoride coating film, a yttrium fluoride yttrium fluoride coating film,

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

In a semiconductor manufacturing apparatus such as a CVD apparatus, a PVD apparatus, an ion implanting apparatus, a diffusion furnace, and an etching apparatus, generally, a highly corrosive gas or a chemical agent is used, and each member such as a chuck, Lt; / RTI > For this reason, particles may be generated due to corrosion of the material constituting each member. These particles adversely affect the semiconductor to be produced, which causes deterioration of the quality and deterioration of the production yield. Therefore, the surface of each member is coated with a gas or a material resistant to chemicals as described above. A variety of materials are known to be used for such coatings. In recent years, fluoride-based materials have been proposed (see, for example, Patent Documents 1 and 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 fluoride of a rare earth element, and an oxide layer of a rare earth element having a porosity of less than 5% . 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 spray the surface of the base material, and oxygen of the rare earth element (Ln) And a coating film containing fluoride, fluoride, and oxide as a main component. The corrosion-resistant member and the coating-adhered base described in Patent Documents 1 and 2 all have a plasma resistance of a certain level or more.

As described above, fluoride or oxyfluoride such as yttrium is useful as a coating material for a member of a semiconductor manufacturing apparatus because it has resistance to a corrosive gas or a chemical agent.

Patent Document 1: Japanese Patent No. 4985928 Patent Document 2: JP-A-2016-89241

However, when the raw material containing yttrium fluoride alone, yttrium fluoride and yttrium oxyfluoride is used for spraying, there are the following problems. In other words, yttrium fluoride is formed in a yttrium fluoride solvent only in addition to yttrium fluoride in orthorhombic form. The yttrium fluoride is phase-changed into yttrium-stabilized yttrium by exposure to heat (for example, plasma heat) generated at the time of using the semiconductor manufacturing apparatus, and volume expansion or volumetric shrinkage There is a possibility that micro-cracks are formed in the thermal sprayed coating, and further, particles are generated. In order to inhibit the formation of yttrium fluoride by thermal spraying, the base material preheated before spraying should be sprayed or the thermal sprayed film should be heat treated.

In addition, when spraying with a raw material containing yttrium fluoride and yttrium oxyfluoride, a thermal sprayed film containing yttrium fluoride and yttrium oxyfluoride or yttria in addition to them may be formed. There is a problem as described above with respect to yttrium fluoride contained in this thermal sprayed coating. Furthermore, as for yttrium oxide contained in this thermal sprayed film, volume expansion or volumetric shrinkage due to fluorination by the fluorine plasma used at the time of use of the semiconductor manufacturing apparatus occurs, and particles may be generated.

The present invention has been made in view of the above problems, and an object thereof is to provide a yttria-yttrium fluoride thermal sprayed film capable of suppressing the generation of micro cracks and particles, a method for producing the same, and a sprayed member having the thermal sprayed film.

The yttrium oxyfire yttrium sprayed coating of the present invention is characterized in that when the sum of all peak intensities attributed to yttrium oxyfluoride in the diffraction spectrum obtained by the X ray diffraction method is taken as 100 and all the peak intensities attributed to yttrium fluoride and yttrium Is less than 10.

The yttria yttrium fluoride coating film of the present invention is a yttrium fluoride yttrium fluoride film, that is, a single phase yttrium fluoride film, and contains yttrium fluoride which causes phase change by heat and yttrium oxide which is fluorinated by fluorine plasma Since it is in a very small amount even if it is not included or contained, stability against heating such as plasma heat is high, and generation of cracks and particles can be suppressed. Furthermore, it can be suitably used as a thermal barrier film for a member of a semiconductor manufacturing apparatus.

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

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

It is preferable that the sprayed member of the present invention further has a sprayed film containing yttrium oxide and yttrium oxyfluoride between the yttria-yttrium oxide film and the yttria-yttrium fluoride 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 yttria yttrium fluoride thermal sprayed film, by having a thermal sprayed film containing yttrium oxide and yttrium oxyfluoride, The thermal stress applied to the interface can be relaxed.

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

The yttrium oxyfluoride sprayed film of the present invention can be produced by the production method of the present invention.

When the total peak intensity attributed to yttrium oxyfluoride and yttrium fluoride in the diffraction spectrum obtained by the X-ray diffraction method is taken as 100, it is preferable that the yttrium oxyfluoride- And the sum of all peak intensities is less than 1.

Here, " including yttrium oxyfluoride " means that it may contain a component other than yttrium oxyfluoride, for example, yttrium fluoride may be included.

Since the yttrium oxyfluoride-containing coating film of the present invention does not contain yttrium oxide or has a very small amount even if yttrium oxide is contained therein, the thermal stability against heat is high, cracks do not occur, and generation of particles can be suppressed. Therefore, it can be suitably used as a thermal barrier film for a member used in a semiconductor manufacturing apparatus.

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

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

A method for producing a yttrium fluoride-containing yttrium fluoride according to the present invention is a method for producing a yttria yttrium fluoride (HVOF) containing at least one of yttrium oxyfluoride and yttrium fluoride by using a raw material slurry prepared from a powdery raw material having an oxygen content of 0 to 6.0 mass% High Velocity Oxygen Fuel) spraying process.

Another process for producing a yttrium fluoride-containing yttrium fluoride according to the present invention is a process for producing yttrium fluoride from a powdery raw material containing at least one of yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 0 to 6.0 mass% And a step of high-speed plasma spraying using hydrogen gas as an operating gas.

By this manufacturing method, a sprayed film containing yttrium oxyfluoride of the present invention can be produced.

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

<Yttrium oxyfluoride desert>

The yttrium oxyfire yttrium sprayed coating of the present invention is characterized in that when the sum of all peak intensities attributed to yttrium oxyfluoride in the diffraction spectrum obtained by the X ray diffraction method is taken as 100 and all the peak intensities attributed to yttrium fluoride and yttrium Is less than 10.

Oxy yttrium fluoride sprayed coating of the present invention, there may be mentioned Y ₅ O ₄ F As the components other than the _{7 YOF, Y 7 O 6 F} 9, Y 6 O 5 F 8.

When the sum of all the peak intensities attributed to yttrium oxyfluoride in the yttrium fluoride yttrium fluoride film of the present invention is 100, the sum of all the peak intensities attributed to yttrium fluoride and yttrium is less than 10, Yttrium &quot; and &quot; yttrium oxide &quot;. Since yttrium fluoride and yttrium oxide are adversely affected by plasma heat and the like as described above, the sum of the peak intensities of yttrium fluoride and yttrium oxide is preferably 0 relative to the sum of the peak intensities of yttrium oxyfluoride. That is, it is desirably a completely single-phase yttrium oxyfluoride coating film.

In view of the above, as described above, the yttrium oxyfluoride coating film of the present invention is a yttrium oxyfluoride single phase coating film. That is, since yttrium fluoride which causes phase change by plasma heat and yttrium oxide which is fluorinated by fluorine plasma or does not contain yttrium oxide are extremely small in quantity, stability against heating such as plasma heat is high and generation of cracks and particles can be suppressed have. And furthermore can be suitably used as a thermal barrier film for members of a semiconductor manufacturing apparatus.

<Explosive film containing yttrium oxyfluoride>

When the total peak intensity attributed to yttrium oxyfluoride and yttrium fluoride in the diffraction spectrum obtained by the X-ray diffraction method is taken as 100, it is preferable that the yttrium oxyfluoride- And the sum of all peak intensities is less than 1.

As the components other than Y ₅ O ₄ F ₇ , Y ₇ O ₆ F ₉ , Y ₆ O ₅ F ₈ , YOF and YF ₃ of the thermal sprayed film containing yttrium oxyfluoride of the present invention can be mentioned.

When the sum of all the peak intensities attributed to yttrium oxyfluoride and yttrium fluoride in the thermal sprayed film containing yttrium oxyfluoride of the present invention is 100, the sum of all the peak intensities attributed to yttrium oxide is less than 1 , Which means that it does not contain or includes trace amounts of yttria. As described above, since yttrium oxide is adversely influenced by plasma heat or the like, it is preferable that the peak intensity of yttria is 0 relative to all peak intensities attributed to yttrium oxyfluoride. That is, it is preferably a thermal sprayed film containing yttrium oxyfluoride not containing yttria.

In view of the above, in the thermal sprayed film containing yttrium oxyfluoride of the present invention, it is a desiccant for mixing yttrium oxyfluoride and yttrium fluoride. That is, since yttrium oxide is not contained or contained in a very small amount even if fluorinated yttrium oxide is included, stability against heating such as plasma heat is high, and generation of cracks and particles can be suppressed. And furthermore can be suitably used as a thermal barrier film for members of a semiconductor manufacturing apparatus.

The thickness of the thermal sprayed coating containing yttria yttrium fluoride and yttrium oxyfluoride of the present invention may be 10 to 1000 占 퐉 when it is used as a coating film of a member of a semiconductor manufacturing apparatus, for example.

The above-described yttria yttrium fluoride thermal sprayed coating and yttrium oxyfluoride-containing thermal sprayed coating of the present invention can be produced by the following production method.

&Lt; Process for producing yttrium oxyfluoride coating film &

The method for producing a yttria yttrium fluoride thermal spraying film according to the present invention is characterized by comprising plasma spraying using a powdery raw material containing yttrium oxyfluoride and having an oxygen content of 7.0 to 11.5 mass%.

In the manufacturing method of the present invention, the member to be the target of the formation of the thermal sprayed film is not particularly limited, but from the viewpoint that the thermal sprayed film formed as described above can suppress the generation of particles, . Hereinafter, the production method of the present invention will be described in detail.

In the present invention, in order to form a single-phase yttrium oxyfluoride sprayed film, plasma spraying is performed under a predetermined condition using a powder (granular) 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 produced in the yttrium fluoride yttrium sprayed film. If it exceeds 11.5 mass% A crystalline phase of yttrium oxide is produced. The oxygen content is preferably 7.5 to 9.5 mass%, more preferably 8.0 to 9.0 mass%. The oxygen content in the raw material can be obtained by the inert gas melting-IR method.

In the manufacturing method of the present invention, the plasma spraying method is employed, and the plasma spraying method is a spraying method using a plasma flame as a heat source for softening and melting raw materials to be sprayed. When an inert gas flows between the electrodes and is discharged, the plasma is ionized and a high-temperature, high-speed plasma is generated. Generally, when an inert gas such as argon is used as an operating gas to generate an arc between the electrodes, the working gas is plasmaized by the arc, and the plasma jet is ejected from the nozzle at high temperature and high speed. A powdery raw material is charged into the plasma jet and heated and accelerated to be sprayed onto a substrate to obtain a thermal sprayed film. In the production method of the present invention, the raw material containing yttrium oxyfluoride may be supplied to the plasma spraying apparatus in the form of powder or plasma in the slurry state at the time of plasma spraying.

As the condition of the plasma spraying, the spraying speed is preferably 150 to 330 m / s. The spraying distance (the distance from the nozzle tip of the plasma spraying apparatus to the substrate) can be set, for example, between 20 and 250 mm, and is preferably 50 to 150 mm. The operating gas is preferably a combination of Ar and O ₂ . The gas amount is preferably 40 to 140 L / min in total of Ar and O ₂ . The current is preferably 80 to 110 A, the voltage is preferably 240 to 280 V, and the power is preferably 19 to 31 kW. The scan speed is preferably 100 to 1000 mm / s.

The average particle diameter (D50) of yttrium oxyfluoride is 1 to 50 mu m. The shape of the particles may be only granules or primary particles. If it is less than 1 mu m, the weight of the molten particles is small, and the fine particles do not adhere to the substrate. When the thickness exceeds 50 mu m, unmelted particles adhere to the base material, making it difficult to form a sprayed film. The raw material containing yttrium oxyfluoride contains at least one of YOF and Y ₅ O ₄ F ₇ as yttrium oxyfluoride and may contain YF ₃ in addition to yttrium oxyfluoride. For example, a raw material having a high oxygen content contains a relatively large amount of YOF, and a raw material having a low oxygen content contains a relatively large amount of YF ₃ . Therefore, the oxygen content in the raw material can be controlled 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, yttrium oxyfluoride may contain a trace amount of Y ₇ O ₆ F ₉ and Y ₆ O ₅ F ₈ as raw materials.

The thermal sprayed film after spraying can be used as it is, but it is preferable to carry out annealing as required. The residual stress can be released by annealing. The annealing temperature is preferably 200 to 500 占 폚, and the annealing time is preferably 10 to 600 minutes.

&Lt; Process for producing yttrium fluoride-containing thermal sprayed coating &gt;

The method for producing a yttrium fluoride-containing yttrium fluoride according to the present invention is a method for producing a yttria yttrium fluoride film by spraying HVOF with a slurry raw material adjusted from a powdery raw material containing at least one of yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 0 to 6.0 mass% And a high-speed plasma spraying step.

In the present manufacturing method, there is no particular limitation on a member to be a target for forming a thermal sprayed film, but from the viewpoint that the thermal sprayed film formed as described above can suppress the generation of particles, It is very suitable. Hereinafter, the production method of the present invention will be described.

In the present production method, in order to form a sprayed film containing yttrium oxyfluoride, a slurry raw material adjusted from a powdery raw material containing at least one of yttrium oxyfluoride and yttrium fluoride and having an oxygen content adjusted to 0 to 6.0 mass% To perform HVOF spraying under predetermined conditions.

In the present manufacturing method, the oxygen content in the raw material containing at least one of yttrium oxyfluoride and yttrium fluoride is 0 to 6.0% by mass, and when it exceeds 6.0% by mass, a crystalline phase of yttrium oxide is produced in the yttria yttrium fluoride coating film to be. The oxygen content is preferably 0 to 6.0% by mass.

In the present manufacturing method, the HVOF spraying method is adopted, and the HVOF spraying method is a spraying method using the heat of combustion of fuel as a heat source for melting the slurry raw material. In general, 0 ₂ , kerosene or the like is used as fuel, and the nozzle is sprayed with a high-temperature high-speed flame. A slurry raw material is charged into the flame and heated and accelerated to be sprayed onto a substrate to obtain a thermal sprayed film.

As a condition of the HVOF spraying, the spraying speed is preferably 200 to 1000 m / s. The spraying distance (distance from the nozzle of the plasma spraying apparatus to the substrate) is preferably set to be, for example, 50 to 130 mm. In addition, a combination of 0 ₂ and kerosene for fuel is preferable. The scan speed is preferably 100 to 1000 mm / s.

The slurry raw material containing at least one of yttrium oxyfluoride and yttrium fluoride may have an average particle diameter of 0.1 to 8 mu m. If it is less than 0.1 mu m, the weight of the molten particles is too small to adhere to the base material, and if it is less than 1 mu m, the weight of the molten particles is small and the base is hardly adhered to the base. On the other hand, if it exceeds 8 mu m, it becomes difficult to form a slurry, which hinders the supply of raw materials.

A slurry raw material containing at least one of yttrium oxyfluoride and yttrium fluoride has a relatively large amount of YOF in a raw material having a large oxygen content and a relatively large amount of YF _{3 in a} raw material having a small oxygen content. 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.

It is also preferable to carry out the annealing after spraying in the same manner as in the case of plasma spraying.

In order to form a thermal sprayed film containing yttrium fluoride, at least one of yttrium oxyfluoride and yttrium fluoride is contained and the oxygen content is adjusted to 0 to 11.5 The high-speed plasma spraying is performed under a predetermined condition using the powder raw material adjusted to the mass%.

In the present production method, the oxygen content in the raw material containing at least one of yttrium oxyfluoride and yttrium fluoride is 0 to 11.5 mass%, but when it exceeds 11.5 mass%, a yttrium oxide crystal phase is generated in the yttria yttrium fluoride coating film to be. The oxygen content is preferably 0 to 9.5 mass%.

Another method for producing a yttrium fluoride-containing yttrium fluoride according to the present invention is a method for producing a yttrium fluoride containing yttrium fluoride, High-speed plasma spraying is performed under a predetermined condition. In this case, the oxygen content is from 0 to 6.0% by mass, and if the oxygen content exceeds 6.0% by mass, a crystalline phase of yttrium oxide is formed in the yttria-yttrium fluoride coating film.

The high-speed plasma spraying method is a spraying method using a plasma flame as a heat source for softening and melting raw materials to be sprayed. When an inert gas is used as an operating gas and an arc is generated between the electrodes, the working gas is plasmaized by the arc, and is ejected from the nozzle as a high-temperature and high-speed plasma jet. A powdery raw material is charged into the plasma jet and heated and accelerated to be sprayed onto a substrate to obtain a thermal sprayed film. In the manufacturing method of the present invention, the raw material containing yttrium oxyfluoride may be supplied to the plasma spraying apparatus in the form of a powder or a slurry state in plasma spraying.

As a condition of the high-speed plasma spraying, the spraying speed is preferably 600 to 700 m / s. The spraying distance (distance from the nozzle tip of the plasma spraying apparatus to the substrate) can be set, for example, between 20 and 250 mm, and preferably 90 to 130 mm. The operating gas is preferably a combination of Ar, N ₂ , and H ₂ . The gas amount is preferably 40 to 350 L / min in total of Ar and N ₂ . H ₂ is preferably 0 to 70 L / min. More preferably, H ₂ is 0 to 10 L / min.

If the flow rate of H ₂ is too high, 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 is increased, the amount of heat generated by the plasma is increased and the chemical reaction rate is increased in the above-mentioned reaction, thereby promoting the generation of Y ₂ O ₃ . Therefore, it is preferable that the flow rate of H ₂ is made less than a predetermined value. The current is preferably 200 to 400 A, the voltage is preferably 180 to 280 V, and the electric power is preferably 40 to 105 kW. The scanning speed is preferably 100 to 200 mm / s.

The properties of the raw materials are the same as those of plasma spraying and HVOF spraying.

It is also preferable to carry out the annealing after spraying in the same manner as in the case of plasma spraying.

&Lt;

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

The other sprayed member of the present invention has a yttria yttrium oxide film and a yttrium oxyfluoride sprayed film not containing yttrium oxide in this order on the substrate, and in the diffraction spectrum obtained by the X-ray diffraction method of the yttria yttrium fluoride coating film, Wherein all the peak intensities attributed to yttrium oxide are less than 1 when the sum of all peak intensities attributed to yttrium oxyfluoride and yttrium fluoride is taken as 100. [ In addition to aluminum, metals such as aluminum alloy, stainless steel, ceramics such as quartz glass and alumina can be used for the material constituting the substrate.

The thermal spraying member of the present invention or the second invention has a thermal sprayed film of yttrium oxide on an aluminum substrate and a thermal sprayed film containing yttria yttrium fluoride coating or yttrium oxyfluoride of the present invention described above. As described above, by interposing the yttria yttrium oxide film between the aluminum substrate and the yttria yttrium fluoride coating film or the yttrium oxyfluoride-containing coating film of the present invention, the yttrium oxyfluoride coating film or the yttrium oxyfluoride film of the present invention The adhesion strength is higher than that in the case where the thermal sprayed coating containing the solvent is directly formed. This is because the yttria is chemically more wettable with respect to the substrate than yttrium oxyfluoride in the case where the substrate is made of metal (aluminum, titanium, or the like).

In the thermal spraying member of the present invention, the thickness of the thermal sprayed coating including the yttrium oxyfluoride coating film or the yttrium oxyfluoride coating film may be 10 to 200 mu m. In this case, the thickness of the yttrium oxide thermal coating film is preferably 10 To 200 mu m.

Further, in the sprayed member of the present invention, it is preferable to further include a thermal spray film containing yttria and yttrium oxyfluoride between the yttria yttria thermal sprayed coating and the thermal sprayed coating containing the yttria yttrium fluoride coating or yttrium oxyfluoride of the present invention Do. Since the thermal sprayed film containing the yttria and yttrium oxyfluoride has a linear expansion coefficient in the middle of the yttrium oxide thermal sprayed film and the thermal sprayed film containing the yttrium oxyfluoride thermal spraying film or yttrium oxyfluoride of the present invention, It is possible to alleviate the thermal stress applied to the substrate.

(X) and oxyfluoride (Y) in a thermal sprayed film containing yttria and yttrium oxyfluoride formed between a yttrium oxide thermal sprayed coating and a thermal sprayed coating containing yttria yttrium fluoride or yttrium oxyfluoride of the present invention, It is preferable that the mass ratio (X / Y) of the total amount (Y) of yttrium and yttrium fluoride is 0.3 to 0.7 from the viewpoint of thermal expansion relaxation. The thickness of the thermal sprayed coating is preferably 10 to 200 mu m.

Each thermal sprayed film in the thermal spraying member of the present invention can be formed by plasma spraying. The conditions of the plasma spraying in each of the thermal sprayed coatings are the same as those of the plasma spraying in the yttrium oxyfluoride thermal spray coating described above.

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

[Example]

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

[Example 1]

(Particle diameter: 25 mu m) containing yttrium oxyfluoride and having an oxygen content of 8.5 mass% was prepared, and the raw material was subjected to the following conditions using an X-ray diffraction apparatus (MultiFlex, Rigaku Co., Ltd.) X-ray diffraction spectrum was measured. The obtained X-ray diffraction spectrum is shown in Fig. 1 (A).

X-ray light source: Cu-K? Line (wavelength: 1.54060 Å)

Scan step: 0.02˚

Scanning axis: 2?

Scanning range: 10 ~ 80˚

Then, the raw material was plasma-sprayed on a substrate (aluminum alloy: A6061) to form a yttrium oxyfluoride sprayed film having a thickness of 200 mu m. The conditions of the plasma spray are as follows.

Plasma Spraying Equipment: Air Plasma Product APS-7100

Working gas: Ar, O ₂

Scanning speed: 100-1000 mm / s

Spray distance: 80㎜

Spraying speed: 150 ~ 330m / s

Current: 80 to 110A

Voltage: 240-280V

Power: 19 ~ 31kW

The X-ray diffraction spectrum of the formed thermal sprayed film was measured in the same manner as the above-mentioned raw materials. The obtained X-ray diffraction spectrum is shown in Fig. 1 (B). From FIG. 1 (B), it can be seen that Y ₅ O ₄ F ₇ and the crystalline phase of YOF are contained in the formed thermal sprayed film.

Further, the formed thermal sprayed film was annealed at 300 DEG C for 2 hours using an atmospheric-atmosphere furnace. The X-ray diffraction spectrum of the thermal sprayed film after the annealing treatment was measured in the same manner as the above-mentioned raw materials. The obtained X-ray diffraction spectrum is shown in Fig. 1 (C). 1 (B) and (C), no difference was observed in the diffraction spectrum, and it was found that the thermal sprayed film after the plasma spraying was stable. Table 1 also shows the crystal phases contained in each step after the raw material, after spraying and annealing.

1 (A) to 1 (C) are sequentially stacked from the lower side to the upper side in the vertical axis direction in order to facilitate comparison of X-ray diffraction spectra. Therefore, the strength of the vertical axis is relative to the strength, not the absolute strength.

[Example 2]

A powder raw material (particle diameter: 25 mu m) 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 process as in Example 1, A yttrium oxyfluoride sprayed film having a thickness of 탆 was formed and annealed. Table 1 shows the crystalline phases identified from the raw materials, the formed thermal sprayed coatings, and the X-ray diffraction spectra of the thermal sprayed coatings after the annealing treatment.

[Example 3]

A powder raw material (particle diameter: 25 탆) containing yttrium oxyfluoride and having an oxygen content of 11.5% by mass was prepared, and the raw material was subjected to the same process as in Example 1, A yttrium oxyfluoride sprayed film was formed and annealed. Table 1 shows the crystal phases identified from the raw material, the formed thermal sprayed coating, and the thermal sprayed film after the annealing treatment.

In both of Examples 2 and 3, as in Example 1, the formed thermal sprayed film contains a crystalline phase of Y ₅ O ₄ F ₇ and YOF, and no difference is observed before and after the annealing treatment, so that the thermal sprayed film is stable.

[Example 4]

A 100 占 퐉 yttrium oxide thermal sprayed film was formed on an aluminum substrate (thickness: 5 mm) by plasma spraying, and a raw material containing yttrium oxyfluoride and an oxygen content of 8.5 mass% was spray- Thereby forming a 50 占 퐉 yttrium oxyfluoride sprayed film. The conditions of the plasma spraying at the time of formation of the yttrium oxide thermal spray coating are the same as those of the plasma spraying of the yttrium oxyfluoride thermal spraying coating described in Example 1.

As a result of measuring the adhesion of yttrium fluoride yttrium fluoride film of this example to Example 1 by a tensile tester, it was found that the yttrium fluoride thermal sprayed film was formed on the aluminum base material, It was found that the adhesion of the yttrium fluoride sprayed film to the base material and the thermal sprayed film was increased.

[Comparative Example 1]

A powder raw material (particle size: 25 탆) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 6.4% by mass was prepared and the raw material was subjected to the same process as in Example 1, A yttrium oxyfluoride sprayed film having a thickness of 탆 was formed and annealed. Table 1 shows the crystal phases identified from the raw material, the formed thermal sprayed coating, and the thermal sprayed film after the annealing treatment. From the X-ray diffraction spectrum, the raw material contains a crystal phase of Y ₅ O ₄ F ₇ and YF ₃ (orthorhombic), and the formed thermal sprayed film is a crystalline phase of Y ₅ O ₄ F ₇ and YF ₃ (different phase) and, after the annealing process, since a crystal phase of Y ₅ O ₄ F ₇ and YF ₃ (orthorhombic), it can be seen that the lack of stability.

[Comparative Example 2]

A powder raw material (particle diameter: 25 탆) containing yttrium oxyfluoride and having an oxygen content of 12.0% by mass was prepared, and the raw material was subjected to the same process as in Example 1, A yttrium oxyfluoride sprayed film was formed and annealed. Table 1 shows the crystal phases identified from the raw material, the formed thermal sprayed coating, and the thermal sprayed film after the annealing treatment. From the X-ray diffraction spectrum, it can be seen that the raw material is a single phase of YOF, but since it is a crystalline phase of YOF and Y ₂ O ₃ after the annealing treatment with the formed thermal sprayed film, stability is lacking.

Crystalline phase Y ₂ O ₃
YOF
Y ₅ O ₄ F ₇
YF ₃ stability
Everywhere More than
Example 1
Raw material - - ○ - - - After plasma spraying - ○ ○ - - ○
After annealing - ○ ○ - -
Example 2
Raw material - - ○ ○ - - After plasma spraying - ○ ○ - - ○
After annealing - ○ ○ - -
Example 3
Raw material - - ○ - - - After plasma spraying - ○ ○ - - ○
After annealing - ○ ○ - -
Comparative Example 1
Raw material - - ○ ○ - - After plasma spraying - - ○ - ○ △
After annealing - - ○ ○ -
Comparative Example 2
Raw material - ○ - - - - After plasma spraying ○ ○ - - - △
After annealing ○ ○ - - -

In the evaluation of the stability, a case in which no difference was observed in the crystal phase before and after the annealing treatment was evaluated as &amp; cir &amp;

When an X-ray diffraction apparatus (MultiFlex, product of Rigaku Co., Ltd.) was used for identification of the crystal phase but accurate measurement can not be performed due to the influence of the underlying layer of the thermal sprayed film to be measured, X-ray diffraction (In-plane XRD), ESCA, and TEM (transmission electron microscope) can be substituted.

[Example 5]

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

Then, the raw material was HVOF-sprayed on the base material (aluminum alloy: A6061) to form a 200 占 퐉 -thick yttrium oxyfluoride sprayed film. The conditions of the HVOF spray are as follows.

O ₂ flow rate: 480 L / min

Kerosene flow rate: 180 mL / min

Scan speed: 1000 mm / s

Spray distance: 100㎜

Spraying speed: 450m / s

The X-ray diffraction spectrum of the formed thermal sprayed film was measured in the same manner as in Example 1. The obtained X-ray diffraction spectrum is shown in Fig. 2 (B). From FIG. 2 (B), it can be seen that the formed thermal sprayed film contains the crystalline phase of Y ₅ O ₄ F ₇ , YF ₃ and YOF but does not contain Y ₂ O ₃ . 2 (A) is the diffraction spectrum of the spray raw material.

Further, the formed thermal sprayed film was subjected to an annealing treatment at 300 캜 for 2 hours by using an air atmosphere furnace. The X-ray diffraction spectrum of the thermal sprayed film after the annealing treatment was measured in the same manner as the above-mentioned raw materials. The obtained X-ray diffraction spectrum is shown in Fig. 2 (C). In the comparison of the diffraction spectrum of FIG. 2 (B) and FIG. 2 (C), disappearance of YF ₃ (different phase) is recognized. As a result, it can be seen that the thermal sprayed film after HVOF spraying is stable. Table 2 also shows the crystal phases contained in each step after the raw material, after spraying and annealing.

Also, in Fig. 2, in order to facilitate comparison of respective X-ray diffraction spectra, they are sequentially stacked from the lower side to the upper side in the vertical axis direction. Therefore, the strength of the vertical axis is relative to the strength, not the absolute strength.

[Example 6]

A slurry raw material (particle diameter: 2 mu m) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 2.2 mass% was prepared and the raw material was sprayed with HVOF to the substrate in the same manner as in Example 5 to obtain 200 A yttrium oxyfluoride sprayed film having a thickness of 탆 was formed and annealed. Table 2 shows the crystal phases identified from the raw material, the formed thermal sprayed coating, and the thermal sprayed film after the annealing treatment.

[Example 7]

A slurry raw material (particle diameter: 2 m) having yttrium fluoride (oxygen content of 0 mass%) was prepared, and the raw material was subjected to the same process as in Example 5, and the raw material was sprayed with HVOF to the substrate, A yttrium sprayed film was formed and annealed. Table 2 shows the crystal phases identified from the raw material, the formed thermal sprayed coating, and the thermal sprayed film after the annealing treatment.

[Example 8]

A slurry raw material (particle diameter: 2 mu m) containing yttrium oxyfluoride and yttrium fluoride having an oxygen content of 6.0 mass% was prepared, and the raw material was sprayed with HVOF to the substrate in the same manner as in Example 5 to obtain 200 A yttrium oxyfluoride sprayed film having a thickness of 탆 was formed and annealed. Table 2 shows the crystal phases identified from the raw material, the formed thermal sprayed coating, and the thermal sprayed film after the annealing treatment.

In Examples 6 to 8, the thermal sprayed film containing Y ₂ O ₃ does not contain Y ₅ O ₄ F ₇ and YF ₃ or the crystalline phase of YOF, and after the annealing treatment, YF ₃ (different phases) are lost, the thermal sprayed coating is stable.

[Example 9]

A 100 占 퐉 yttrium oxide thermal sprayed film was formed on an aluminum substrate (thickness: 5 mm) by plasma spraying, and a slurry raw material containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 5.6 mass% HVOF was sprayed to form a sprayed film containing yttrium oxyfluoride of 50 mu m. The conditions of the plasma spraying at the time of forming the yttrium oxide thermal spray coating are the same as those of the yttrium oxyfluoride thermal sprayed coating shown in Example 1.

The adhesion of the yttrium oxyfluoride-containing coating film of Example 9 and Example 5 was measured by using a tensile tester, and it was found that a yttria-yttrium-zirconia film was formed on the aluminum substrate, and a sprayed film containing yttrium fluoride was formed thereon The adhesion between the substrate and the solvent film was increased.

[Comparative Example 3]

A slurry raw material (particle diameter: 2 mu m) containing yttrium oxyfluoride and having an oxygen content of 8.4 mass% was prepared. The raw material was subjected to the same process as in Example 5, and the raw material was sprayed on the substrate by HVOF A yttrium oxyfluoride sprayed film was formed and annealed. Table 2 shows the crystal phases identified from the raw material, the formed thermal sprayed coating, and the thermal sprayed film after the annealing treatment. It can be seen from the X-ray diffraction spectrum that the raw material, the formed thermal sprayed film, and the crystalline phase of Y ₂ O ₃ appear after the annealing treatment, resulting in lack of stability.

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

[Example 10]

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

Then, the powdery material was sprayed on the base material (aluminum alloy: A6061) by high-speed plasma spraying to form a yttrium oxyfluoride sprayed film having a thickness of 200 mu m. The conditions of high-speed plasma spraying are as follows. The powder raw material is in a granulated state.

Working gas: Ar, N ₂ , H ₂

H ₂ gas flow rate: 5 L / min

Scan speed: 850 mm / s

Spray distance: 90㎜

Spraying speed: 600 to 700 m / s

Current: 400A

Voltage: 260V

Power: 104kW

The X-ray diffraction spectrum of the formed thermal sprayed film was measured in the same manner as in Example 1. The obtained X-ray diffraction spectrum is shown in Fig. 3 (B). From FIG. 3 (B), it can be seen that the formed thermal sprayed film contains a crystalline phase of Y ₅ O ₄ F ₇ and YOF but does not contain Y ₂ O ₃ . 3 (A) is the diffraction spectrum of the spray raw material.

Further, the formed thermal sprayed film was subjected to an annealing treatment at 300 캜 for 2 hours by using an air atmosphere furnace. The X-ray diffraction spectrum of the thermal sprayed film after the annealing treatment was measured in the same manner as the above-mentioned raw materials. The obtained X-ray diffraction spectrum is shown in Fig. 3 (C). No difference was observed in the comparison of the diffraction spectra between (B) and (C) in FIG. 3, and it was found that the thermal sprayed coating after the rapid plasma spraying was stable. Table 3 also shows the crystalline phases contained in each step after the raw material, after spraying and annealing.

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

[Example 11]

A powder raw material (particle size: 25 mu m) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 4.6 mass% was prepared, and the raw material was prepared in the same manner as in Example 10. The raw material powder was subjected to high- To form a yttrium oxyfluoride sprayed film having a thickness of 200 mu m, followed by annealing. Table 3 shows the crystal phases identified from the raw material, the formed thermal sprayed coating, and the X-ray diffraction spectrum of the thermal sprayed coating after the annealing treatment.

[Example 12]

A 100 占 퐉 yttrium oxide thermal sprayed film was formed on an aluminum substrate (thickness: 5 mm) by plasma spraying, and a powdery material (particle size: 25 占 퐉) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 5.6 mass% A high-speed plasma was sprayed under the same spraying conditions as in Example 10 to form a sprayed film containing yttrium oxyfluoride of 50 mu m. The conditions of the plasma spraying at the time of forming the yttrium oxide thermal spray coating are the same as those of the yttrium oxyfluoride thermal sprayed coating shown in Example 1.

When the adhesion of the yttrium oxyfluoride-containing coating film of Example 12 and Examples 10 and 11 was measured using a tensile tester, it was found that oxidation of yttrium fluoride on the aluminum base material The result of the yttrium sprayed coating forming the yttrium oxyfluoride sprayed coating on the yttrium coating increased the adhesion between the substrate and the sprayed coating.

[Example 13]

A slurry raw material (particle diameter: 2 mu m) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 4.6% by mass was prepared, and the raw material was prepared in the same manner as in Example 10. The slurry raw material was subjected to high- To form a yttrium oxyfluoride sprayed film having a thickness of 200 mu m, followed by annealing. From the X-ray diffraction spectrum, it was confirmed that no crystalline phase of Y ₂ O _{3 was formed in} the thermal sprayed film after annealing.

[Comparative Example 4]

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

[Comparative Example 5]

A powder raw material (particle size: 25 탆) containing yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 4.6% by 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, the substrate was subjected to high-speed plasma spraying of the powder raw material to form a yttrium oxyfluoride sprayed film having a thickness of 200 mu m, followed by annealing. Table 3 shows the crystal phases identified from the raw material, the formed thermal sprayed coating, and the X-ray diffraction spectrum of the thermal sprayed coating after the annealing treatment. From the X-ray diffraction spectrum, it can be seen that the crystalline phase of Y ₂ O ₃ appears in the thermal sprayed film after the annealing treatment and lacks stability.

[Comparative Example 6]

Except that a slurry raw material (particle diameter: 2 mu m) 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. In the same manner, the substrate was subjected to high-speed plasma spraying of the slurry raw material to form a yttrium oxyfluoride sprayed film having a thickness of 200 mu m, followed by annealing. From the X-ray diffraction spectrum, it can be seen that the generation of Y ₂ O ₃ is partially confirmed in the thermal sprayed film after the annealing treatment, and the stability is lacking.

All of the thermal sprayed films of Examples 10 to 12 were made of the crystalline phase of Y ₅ O ₄ F ₇ , YOF and YF ₃ , and did not contain the crystalline phase of Y ₂ O ₃ , indicating that the thermal sprayed film after the annealing treatment was stable there was. On the other hand, the formation of the crystal phase of Y ₂ O ₃ was confirmed in the thermal sprayed film produced by the high-speed plasma spraying of Comparative Examples 4 to 6 in which the flow rate of the H ₂ gas was increased and it was found that the thermal sprayed film after the annealing treatment lacked stability there was.

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

Claims (9)

Characterized in that the sum of all peak intensities attributed to yttrium fluoride and yttrium is less than 10 when the sum of all peak intensities attributed to yttrium oxyfluoride in the diffraction spectrum obtained by the X-ray diffraction method is 100, Yttrium fluoride desert.
A yttria yttrium fluoride thermal spraying film and a yttrium oxyfluoride thermal spraying film are formed on the substrate in this order and the yttrium oxyfire yttria coating film has a total of all the peak intensities attributed to yttrium oxyfluoride in a diffraction spectrum obtained by X- , The sum of all peak intensities attributed to yttrium fluoride and yttrium oxide is less than 10.
The method of claim 2,
Wherein the sprayed member further comprises a yttria film containing yttrium oxide and yttrium oxyfluoride between the yttria yttrium oxide film and the yttria yttrium fluoride thermal film.
A process for producing a yttria-yttrium fluoride thermal spraying film according to claim 1,
A process for producing a yttria yttrium fluoride thermal sprayed product, comprising the step of plasma-spraying using a powdery raw material containing yttrium oxyfluoride and having an oxygen content of 7.0 to 11.5 mass%.
Characterized in that the sum of all peak intensities attributed to yttrium is less than 1 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, A desiccant containing yttrium fluoride.
A process for producing a yttrium oxyfluoride-containing thermal sprayed film according to claim 5,
Characterized by comprising a step of spraying HVOF using a slurry raw material adjusted from a powder raw material containing at least one of yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 0 to 6.0 mass% Method of manufacturing desert.
A process for producing a yttrium oxyfluoride-containing thermal sprayed film according to claim 5,
Characterized by comprising a step of high-speed plasma spraying using a powder raw material containing at least one of yttrium oxyfluoride and yttrium fluoride and having an oxygen content of 0 to 6.0 mass% or a slurry raw material adjusted from the powder raw material, Yttrium-containing solvent.
The method of claim 7,
Wherein the hydrogen gas is supplied as an operating gas at a flow rate of less than 0 to 70 L / min in the high-speed plasma spraying step.
Wherein a yttria coating film and a yttrium oxyfluoride-containing thermal spray film are formed on the substrate in this order, and in the diffraction spectrum obtained by the X-ray diffraction method of the yttria yttrium fluoride-containing solvent film, yttrium oxyfluoride and yttrium fluoride Wherein the sum of all the peak intensities attributed to yttrium is less than 1, when the sum of all peak intensities to be added to the yttria is 100.

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