Method for obtaining mixed-phase Y2O3 coating based on atmospheric plasma spraying

Abstract

The invention belongs to the field of ceramic coatings, and particularly discloses a method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying, which comprises the following steps: S1, putting Y2O3 powder and absolute ethyl alcohol into a planetary ball mill for mechanical ball milling; s2, drying the first mixed slurry, adding deionized water, a dispersing agent and an adhesive, and mechanically stirring; s3, carrying out spray granulation on the second mixed slurry to obtain spherical Y2O3 powder; s4, the spherical Y2O3 powder is placed in a muffle furnace to be subjected to pressureless calcination under the air atmosphere; by controlling the calcining temperature and the cold quenching process, a coating structure with coexistence of a cubic phase and a monoclinic phase is obtained, the high hardness of the monoclinic phase is combined with the toughness of the cubic phase, so that the plasma etching resistance rate of the coating is reduced compared with that of a pure cubic phase coating, after spray granulation powder is calcined, the particle porosity is reduced, the sprayed coating has relatively high density, and the coating has relatively high hardness and toughness. And plasma permeation is effectively blocked.

Description

Technical Field

[0001] The present invention belongs to the field of ceramic coatings, and particularly relates to a method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying. Background Art

[0002] A chip is a carrier of information intelligence, and it contains increasingly complex integrated circuits inside. Plasma etching is one of the core process flows in the integrated circuit manufacturing industry. Currently, integrated circuits are developing towards higher integration and smaller feature sizes, which also places higher and higher requirements on the components of the equipment. The plasma etching-resistant material was initially to deposit a hard anodic protective layer on an aluminum substrate, and later a thermal spraying method was used to prepare an alumina coating on the surface of the part. In recent years, yttrium oxide has been used instead of alumina as the thermal spraying raw material because the etching resistance of yttrium oxide is higher than that of alumina. However, with the continuous improvement of the equipment, the etching resistance of the ordinary cubic-phase yttrium oxide coating can no longer meet the requirements, so it is necessary to develop a more corrosion-resistant coating.

[0003] Chinese Patent with Publication No. CN 112210741A discloses a method for preparing a ceramic layer applied to the integrated circuit industry. This method uses yttrium oxyfluoride to obtain a coating with better etching resistance than yttrium oxide through atmospheric plasma spraying. However, this material has higher costs compared to yttrium oxide, and fluorine will also escape at high temperatures, etc. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying, so as to solve the problem of the low density of the traditional plasma-sprayed cubic-phase yttrium oxide coating proposed in the above background art.

[0005] To achieve the above purpose, the present invention provides the following technical solutions:

[0006] A method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying, including:

[0007] S1. Put Y2O3 powder and absolute ethanol into a planetary ball mill for mechanical ball milling to obtain a first mixed slurry;

[0008] S2. Dry the first mixed slurry, and after drying, add deionized water, a dispersant, and a binder for mechanical stirring to obtain a second mixed slurry;

[0009] S3. Spray granulate the second mixed slurry to obtain spherical Y2O3 powder;

[0010] S4. Place the spherical Y2O3 powder in a muffle furnace for pressureless calcination in an air atmosphere;

[0011] S5. Spray the calcined spherical Y2O3 powder onto the part to be sprayed using atmospheric plasma spraying to obtain a mixed-phase Y2O3 coating;

[0012] S6. Gas-cool quench the mixed-phase Y2O3 coating using an argon gas flow.

[0013] Preferably, the mixed-phase Y2O3 coating includes a cubic phase and a monoclinic phase.

[0014] Preferably, in step S1, the mass ratio of the absolute ethanol to the Y2O3 powder is 3 - 4:1, the D50 of the Y2O3 powder is 10 μm, the planetary ball mill uses zirconia ball mills with a diameter range of 5 - 15 mm, and the mechanical ball milling time is 20 - 24 h until the D50 of the Y2O3 powder is 1.2 - 1.5 μm.

[0015] Preferably, in step S2, the Y2O3 fine powder and deionized water are mechanically stirred and mixed in advance, after stirring for 3 - 8 minutes, a dispersant is added and mechanical stirring continues, and a binder is added at the end.

[0016] Preferably, in step S3, the second mixed slurry is spray granulated using a spray dryer. The inlet temperature of the spray dryer is 150 - 260 °C, the outlet temperature is 50 - 260 °C, the atomizer rotation speed of the spray dryer is 30 - 50 Hz, and the D50 of the spherical Y2O3 powder is 20 - 60 μm.

[0017] Preferably, in step S4, the heating rate of the pressureless calcination in an air atmosphere is 2 - 5 °C / min, the calcination temperature range is 1500 - 1600 °C, and the high-temperature holding time is 3 - 5 h.

[0018] Preferably, in step S5, before using atmospheric plasma spraying, the part to be sprayed is sandblasted until the surface roughness of the template coating is obtained.

[0019] Preferably, in step S5, the current of the atmospheric plasma spraying is 200 - 220 A, the spraying distance is 150 - 175 mm, the argon gas flow rate used is 180 - 210 LPM, the helium gas flow rate used is 40 - 60 LPM, and the thickness of the mixed-phase Y2O3 coating is 150 - 250 μm.

[0020] Preferably, in step S6, the argon gas flow rate of the argon gas flow is 180 - 210 LPM.

[0021] Compared with the prior art, the beneficial effects of the present invention are:

[0022] By controlling the calcination temperature and the cold quenching process, the present invention obtains a coating structure in which the cubic phase and the monoclinic phase coexist. The combination of the high hardness of the monoclinic phase and the toughness of the cubic phase reduces the plasma etching rate of the coating compared with that of a pure cubic phase coating. After the spray granulated powder is calcined, the particle porosity is reduced, and the coating after spraying has a high density, effectively blocking the penetration of the plasma.

[0023] By using conventional Y2O3 raw materials, the present invention avoids the use of fluorides, reduces the raw material cost, and has no risk of fluorine escape, meeting the environmental protection requirements. The combination of sandblasting pretreatment and argon cold quenching process results in a high bonding strength between the coating and the substrate. The method is compatible with different substrates and can be applied on a large scale to key components such as the reaction chamber and focusing ring of an etching machine, extending the equipment maintenance cycle. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings. Among them:

[0025] Figure 1 It is the scanning electron microscope image of the yttrium oxide powder obtained in the first embodiment of the present invention;

[0026] Figure 2 It is the X-ray diffraction pattern of the yttrium oxide coating obtained in the first embodiment of the present invention;

[0027] Figure 3 It is the scanning electron microscope image of the yttrium oxide powder obtained in the second embodiment of the present invention;

[0028] Figure 4 It is the X-ray diffraction pattern of the yttrium oxide coating obtained in the second embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0029] To make the above objects, features, and advantages of the present invention more obvious and understandable, the following will give a detailed description of the specific embodiments of the present invention with reference to the drawings of the specification.

[0030] Many specific details are set forth in the following description to facilitate a thorough understanding of the present invention. However, the present invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar extensions without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0031] Second, the "one embodiment" or "embodiment" referred to herein means a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor is it an individual or alternative embodiment that is mutually exclusive with other embodiments.

[0032] As shown in the attached Figure 1 to the attached Figure 4 figures:

[0033] Embodiment 1: This embodiment provides a method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying, including:

[0034] S1. Put Y2O3 powder and absolute ethanol into a planetary ball mill for mechanical ball milling to obtain a first mixed slurry;

[0035] The mass ratio of absolute ethanol to Y2O3 powder is 3-4:1, the D50 of the Y2O3 powder is 10 μm, the planetary ball mill uses zirconia ball mills with a diameter range of 5-15 mm, and the mechanical ball milling time is 20 until the D50 of the Y2O3 powder is 1.2-1.5 μm.

[0036] S2. Dry the first mixed slurry, and after drying, add deionized water, a dispersant, and a binder for mechanical stirring to obtain a second mixed slurry;

[0037] Dry through an oven at 80°C and sieve to obtain refined Y2O3 fine powder. Based on the total amount of the slurry, pre-mix it mechanically with 50 wt% deionized water, continue mechanical stirring for 3-8 minutes after adding the dispersant, and add the binder at the end to obtain a precursor slurry for spray granulation.

[0038] The dispersant uses 1 wt% polyvinyl butyral, and the binder uses 0.4 wt% polyvinyl alcohol.

[0039] S3. Spray granulate the second mixed slurry to obtain spherical Y2O3 powder with D50 = 40 μm;

[0040] In step S3, spray granulating the second mixed slurry is carried out using a spray dryer. The inlet temperature of the spray dryer is 260°C, the outlet temperature is 110°C, and the atomizer rotation speed of the spray dryer is 46 Hz.

[0041] S4. Place the spherical Y2O3 powder in a muffle furnace for pressureless calcination in an air atmosphere;

[0042] The heating rate for pressureless calcination in an air atmosphere is 2-5°C / min, the calcination temperature range is 1550°C, and the high-temperature holding time is 3 h to reduce the porosity of the particles and remove excess organic matter.

[0043] S5. Spray the calcined spherical Y2O3 powder onto the part to be sprayed by atmospheric plasma spraying to obtain a mixed-phase Y2O3 coating;

[0044] Before atmospheric plasma spraying, sandblasting treatment is carried out on the part to be sprayed. The abrasive used is alumina. The roughness of the part after sandblasting is about Ra = 6.4 μm until the surface roughness of the template coating is obtained.

[0045] Use atmospheric plasma spraying technology to spray yttrium oxide coating. The current of atmospheric plasma spraying is 220 A, the spraying distance is 150 mm, the argon gas flow rate used is 180 LPM, the helium gas flow rate used is 60 LPM, and the thickness of the mixed-phase Y2O3 coating is 200 μm.

[0046] S6. Use an argon gas flow with an argon gas flow rate of 180 LPM to perform gas cold quenching on the mixed-phase Y2O3 coating.

[0047] Example 2: This example provides a method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying, including:

[0048] S1. Put Y2O3 powder and absolute ethanol into a planetary ball mill for mechanical ball milling to obtain the first mixed slurry;

[0049] The mass ratio of absolute ethanol to Y2O3 powder is 3 - 4:1, the D50 of the Y2O3 powder is 10 μm, the grinding balls of the planetary ball mill use zirconia grinding balls with a diameter range of 5 - 15 mm, and the mechanical ball milling time is 24 until the D50 of the Y2O3 powder is 1.2 - 1.5 μm.

[0050] S2. Dry the first mixed slurry, and after drying, add deionized water, dispersant, and binder for mechanical stirring to obtain the second mixed slurry;

[0051] Dry through an oven at 80 °C and sieve to obtain refined Y2O3 fine powder. Based on the total amount of the slurry, pre-mix it with 50 wt% of deionized water by mechanical stirring. After stirring for 3 - 8 minutes, add the dispersant and continue mechanical stirring. At the end, add the binder to obtain the precursor slurry for spray granulation.

[0052] The dispersant uses 1.5 wt% ammonium citrate, and the binder uses 0.4 wt% polyvinyl alcohol.

[0053] S3. Perform spray granulation on the second mixed slurry to obtain spherical Y2O3 powder with D50 = 45 μm;

[0054] In step S3, the second mixed slurry is spray granulated using a spray dryer. The inlet temperature of the spray dryer is 220 °C, the outlet temperature is 130 °C, and the atomizer rotation speed of the spray dryer is 46 Hz.

[0055] S4. Place the spherical Y2O3 powder in a muffle furnace and calcine it under atmospheric pressure in an air atmosphere;

[0056] The heating rate for calcination under atmospheric pressure in an air atmosphere is 2 - 5 °C / min, the calcination temperature range is 1550 °C, and the high-temperature holding time is 3 h to reduce the porosity of the particles and remove excess organic matter.

[0057] S5. Spray the calcined spherical Y2O3 powder onto the part to be sprayed using atmospheric plasma spraying to obtain a mixed-phase Y2O3 coating;

[0058] Before atmospheric plasma spraying, the part to be sprayed is sandblasted. The abrasive used is quartz. After sandblasting, the surface roughness of the part is about Ra = 5 μm until the surface roughness of the template coating is obtained.

[0059] Use atmospheric plasma spraying technology to spray the yttrium oxide coating. The current of atmospheric plasma spraying is 220 A, the spraying distance is 150 mm, the flow rate of argon used is 180 LPM, the flow rate of helium used is 60 LPM, and the thickness of the mixed-phase Y2O3 coating is 200 μm.

[0060] S6. Gas-cool quench the mixed-phase Y2O3 coating using an argon gas flow with a flow rate of 180 LPM.

[0061] Importantly, it should be noted that the construction and arrangement of the present application shown in multiple different exemplary embodiments are merely illustrative. Although only a few embodiments are described in detail in this disclosure, those who refer to this disclosure should easily understand that many modifications are possible without substantially departing from the novel teachings and advantages of the subject matter described in this application (for example, the dimensions, scales, structures, shapes and proportions of various elements, and parameter values (such as temperature, pressure, etc.), installation arrangements, use of materials, changes in color, orientation, etc.). For example, an element shown as integrally formed may be composed of multiple parts or elements, the position of the element may be inverted or otherwise changed, and the nature, number or position of discrete elements may be altered or changed. Accordingly, all such modifications are intended to be included within the scope of the present invention. The order or sequence of any process or method steps may be changed or re-ordered according to alternative embodiments. In the claims, any "means-plus-function" clauses are intended to cover the structures that perform the recited functions herein, and not only structural equivalents but also equivalent structures. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the exemplary embodiments without departing from the scope of the present invention. Accordingly, the present invention is not limited to the specific embodiments, but extends to various modifications that still fall within the scope of the appended claims.

[0062] In addition, in order to provide a concise description of the exemplary embodiments, not all features of the actual embodiments may be described (i.e., those features that are not relevant to the currently contemplated best mode of carrying out the present invention or those features that are not relevant to implementing the present invention).

[0063] It should be understood that in the development of any actual implementation, as in any engineering or design project, numerous specific implementation decisions may be made. Such development efforts may be complex and time-consuming, but for those of ordinary skill in the art who benefit from this disclosure, without undue experimentation, such development efforts will be a routine task of design, fabrication and production.

[0064] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered by the scope of the claims of the present invention.

Claims

1. Method for obtaining a mixed-phase Y2O3 coating by atmospheric plasma spraying, characterized in that, Including: S1. Put Y2O3 powder and absolute ethanol into a planetary ball mill for mechanical ball milling to obtain a first mixed slurry; S2. Dry the first mixed slurry, and after drying, add deionized water, a dispersant, and a binder and conduct mechanical stirring to obtain a second mixed slurry; S3. Spray granulate the second mixed slurry to obtain spherical Y2O3 powder; S4. Place the spherical Y2O3 powder in a muffle furnace for pressureless calcination in an air atmosphere; S5. Use atmospheric plasma spraying to spray the calcined spherical Y2O3 powder onto the part to be sprayed to obtain a mixed-phase Y2O3 coating; S6. Use an argon gas flow to conduct gas quenching on the mixed-phase Y2O3 coating.

2. The method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying according to claim 1, characterized in that The mixed-phase Y2O3 coating includes a cubic phase and a monoclinic phase.

3. The method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying according to claim 1, characterized in that, In step S1, the mass ratio of the absolute ethanol to the Y2O3 powder is 3-4:1, the D50 of the Y2O3 powder is 10 μm, the planetary ball mill grinding media uses zirconia grinding media with a diameter range of 5-15 mm, and the mechanical ball milling time is 20-24 h until the D50 of the Y2O3 powder is 1.2-1.5 μm.

4. The method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying according to claim 1, characterized in that, In step S2, the Y2O3 fine powder and deionized water are pre-mechanically stirred and mixed, after stirring for 3-8 minutes, add a dispersant and continue mechanical stirring, and add a binder at the end.

5. The method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying according to claim 1, characterized in that, In step S3, spray granulating the second mixed slurry is carried out using a spray dryer for granulation. The inlet temperature of the spray dryer is 150-260 °C, the outlet temperature is 50-260 °C, the atomizer rotation speed of the spray dryer is 30-50 Hz, and the D50 of the spherical Y2O3 powder is 20-60 μm.

6. The method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying according to claim 1, characterized in that, In step S4, the heating rate of the pressureless calcination in an air atmosphere is 2-5 °C / min, the calcination temperature range is 1500-1600 °C, and the high-temperature holding time is 3-5 h.

7. The method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying according to claim 1, characterized in that, In step S5, before using atmospheric plasma spraying, the part to be sprayed is sandblasted until the surface roughness of the template coating is obtained.

8. The method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying according to claim 1, characterized in that, In step S5, the current of the atmospheric plasma spraying is 200-220 A, the spraying distance is 150-175 mm, the argon gas flow rate used is 180-210 LPM, the helium gas flow rate used is 40-60 LPM, and the thickness of the mixed-phase Y2O3 coating is 150-250 μm.

9. The method for obtaining a mixed-phase Y2O3 coating based on atmospheric plasma spraying according to claim 1, characterized in that, In step S6, the argon gas flow rate of the argon gas flow is 180-210 LPM.

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