KR102084426B1 - Ceramic Thick Film Prepared by Aerosol Deposition and Preparation Method Thereof - Google Patents

Abstract

The present invention relates to a ceramic thick film manufactured by using an aerosol deposition method and a manufacturing method thereof, and more specifically, to a method for manufacturing a ceramic thick film by using an aerosol deposition method and a ceramic thick film manufactured thereby. In particular, a base coating layer on a base material, which is formed through aerosol deposition, undergoes heat treatment under a predetermined condition such that a coating binding force of an interlayer between the base material and the base coating layer can be increased. In addition, aerosol deposition is performed on the base coating layer to manufacture a ceramic thick film. Therefore, adhesion strength between the ceramic thick film and the base material can be increased for a thicker and denser ceramic thick film to be manufactured.

Description

Ceramic Thick Film Prepared by Aerosol Deposition and Its Preparation Method {Ceramic Thick Film Prepared by Aerosol Deposition and Preparation Method Thereof}

The present invention relates to a ceramic thick film and a method for forming the same, and more particularly, an aerosol capable of forming a thicker and dense ceramic thick film while improving the adhesive strength between the ceramic thick film and the substrate using an aerosol deposition method. A method for producing a ceramic thick film using a vapor deposition method, and a ceramic thick film produced by the manufacturing method.

Magnesium or magnesium alloys, aluminum or aluminum alloys, carbon steel, stainless steel, alumina and the like are the most widely used substrates in the modern industrial field. On the other hand, in order for these substrates to be applied to actual products or special applications, it is required to increase the corrosion resistance by coating the surface thereof. Among various surface treatment methods, ceramic coatings having a high corrosion resistance on these substrate surfaces are known to be very effective in improving the corrosion resistance of materials.

Ceramic coating technology currently used for thin film coating includes chemical vapor deposition (CVD), physical vapor deposition (PVD), abrasion resistance of mechanical parts, and thermal spray coating, which are widely used in semiconductor and display fields. However, the coating layer by a thin film coating process, such as CVD or PVD, is not suitable for requiring a certain thickness or more for corrosion resistance when cracking or peeling occurs when the thickness is several micrometers or more. On the other hand, the spraying process that is frequently used for the corrosion-resistant coating can be coated a thickness of more than a few hundred micrometers at high speed, there is a problem such as pores, cracks, etc. of the coating layer is difficult to control the thickness and the surface is very rough.

On the other hand, as a ceramic coating technique which has been studied a lot recently, there is an aerosol deposition method. The aerosol deposition process enables high-speed coating, forms a dense and crack-free coating layer at room temperature, forms a coating layer of a wide range of thicknesses, easily controls the composition and stoichiometric ratio of the coating layer, and can use various substrates. Due to its advantages, it is being used and researched in various fields at high speed. In particular, the interest in research to improve the corrosion resistance of the substrate is increasing in that a dense ceramic coating is performed at room temperature.

However, since the raw powder used in the aerosol deposition method generally uses fine powders of several hundred nm to several μm in size, it is easy to cause agglomeration of the powder during the coating process. It is difficult to obtain a strong bonding force between the coating layer, there was a problem that it is difficult to make a dense thick film of 60 ㎛ or more when deposited using a rare earth metal compound.

Thus, in Korean Patent Application Publication No. 2016-0084510, in order to improve the surface roughness due to agglomeration of aerosol deposition, the coating layer is prepared by aerosol deposition, and then a coating layer is further formed by a chemical solution deposition method such as a sol-gel method. A thick film coating method for improving the surface flatness is proposed, and Korean Patent No. 0941472 mixes the conductive oxide raw material powder by milling and then calcines to obtain a conductive oxide by re-milling the conductive oxide, which is prepared on a substrate. Although a method of manufacturing a conductive thick film deposited by aerosol deposition has been proposed, these also constitute a coating layer having different substrates and components, and the added coating layer is also difficult to obtain a strong adhesive strength between the substrate and the coating layer because the substrate and components are different. Thick film thickness of 50 μm or less, dense thick film of 60 μm or more Prepared to have been limited.

Korean Laid-Open Patent No. 2016-0084510 (published: 2016.07.14) Korean Registered Patent No.0941472 (Published: 2009.06.18)

The main object of the present invention is to solve the above-mentioned problems, the base coating layer on the substrate formed by aerosol deposition through the heat treatment of a specific condition to enhance the coating bonding strength of the interface between the substrate and the base coating layer, the substrate and the bonding strength is enhanced By forming a coating layer by performing aerosol deposition on the base coating layer to prepare a ceramic thick film, it is possible to improve the adhesion strength between the ceramic thick film and the substrate, and to form a thicker and dense ceramic thick film, using the aerosol deposition method. To provide a ceramic thick film production method and a ceramic thick film produced thereby.

In order to achieve the above object, an embodiment of the present invention comprises the steps of (a) forming a base coating layer by aerosol deposition of rare earth metal powder on a substrate; (b) first heat treating the formed base coating layer; And (c) aerosol deposition of the rare earth metal powder on the first heat-treated base coating layer to form a coating layer.

In a preferred embodiment of the present invention, the first heat treatment of the step (b) may be performed for 1 to 20 hours at 750 ℃ or more in Ar, He, O2, Air or vacuum atmosphere.

In a preferred embodiment of the present invention, the crystallite of the base coating layer after the step (b) may be characterized in that 1.5 to 3 times larger than the crystallite of the base coating layer of step (a).

In a preferred embodiment of the present invention, step (c) may be characterized in that it is carried out at least once or more times.

In a preferred embodiment of the present invention, the rare earth metal powder is one or more selected from the group consisting of Y ₂ O ₃ , Dy ₂ O ₃ , Er ₂ O ₃ , Sm ₂ O ₃ , YAG, YF ₃ and YOF It can be characterized.

In a preferred embodiment of the present invention, the base coating layer may be characterized in that the thickness is 0.5 ㎛ ~ 30 ㎛.

In a preferred embodiment of the present invention, the coating layer may be characterized in that the thickness of 1 ㎛ ~ 200 ㎛.

In a preferred embodiment of the present invention, the method of manufacturing a ceramic thick film may further comprise a step (d) after the second heat treatment after step (c).

In a preferred embodiment of the present invention, the secondary heat treatment may be performed for 1 to 20 hours at 750 ℃ or more in Ar, He, O ₂ , Air or vacuum atmosphere.

In a preferred embodiment of the present invention, the crystallite of the coating layer after the secondary heat treatment may be characterized in that 1.5 to 3 times larger than the crystallite crystal of the step (c).

In a preferred embodiment of the present invention, the method of manufacturing a ceramic thick film may be characterized by repeating step (c) and step (d) one or more times sequentially.

In a preferred embodiment of the present invention, the method of manufacturing the ceramic thick film may be characterized in that the step (c) is further performed only on the last coating layer repeatedly performed (c) and (d).

Another embodiment of the present invention provides a ceramic thick film formed by the above method.

In the method of manufacturing a ceramic thick film according to the present invention, the base coating layer on the substrate formed by aerosol deposition is subjected to heat treatment under a specific condition to enhance the coating adhesion of the interface between the substrate and the base coating layer, By coating to form a coating layer to form a ceramic thick film, the adhesive strength between the ceramic thick film and the substrate can be improved, thereby preventing the coating interface layer from being easily peeled off by external impact, and at the same time, a thicker and denser ceramic thick film. Since it can be prepared by the fusion-resistant corrosion-resistant member of various properties has the effect that can be implemented.

1 is a vertical sectional schematic view of a ceramic thick film according to the present invention.
2 is an image obtained by measuring the vertical cross section of the ceramic thick film prepared in Example 7 of the present invention by FE SEM.
3 is an image measured by the FE SEM of the vertical section of the ceramic thick film according to an embodiment of the present invention, (a-1) is an image of the base coating layer of the ceramic thick film prepared in Comparative Example 1, (a-2 ) Is an image of the interface between the base coating layer and the substrate of the ceramic thick film prepared in Comparative Example 1, (b-1) is an image of the base coating layer of the ceramic thick film prepared in Example 2, (b-2) is an example It is an image of the interface of the base coating layer and the base material of the ceramic thick film manufactured in 2.
4 is an image obtained by measuring FE SEM of a vertical cross section of a ceramic thick film according to an embodiment of the present invention, (a) is a ceramic thick film image of Comparative Example 2, and (b) is a ceramic thick film image of Example 1 (c) is the ceramic thick film image of Example 2, and (d) is the ceramic thick film image of Example 3.
5 is an image obtained by measuring the vertical cross section of the ceramic thick film prepared in Example 8 of the present invention by FE SEM.
6 is an image obtained by measuring the vertical cross section of the ceramic thick film prepared in Example 9 of the present invention by FE SEM.
7 is an image of the chemical resistance of the ceramic thick film prepared in Example 2 and Comparative Example 1 of the present invention by 3D Laser Scanning.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

When a part in the present specification is said to "include" a certain component, this means that it may further include other components, except to exclude other components unless specifically stated otherwise.

The present invention comprises the steps of (a) aerosol deposition of rare earth metal powder on a substrate to form a base coating layer; (b) first heat treating the formed base coating layer; And (c) aerosol-depositing rare earth metal powder on the first heat-treated base coating layer to form a coating layer, and a ceramic thick film prepared by the method.

More specifically, the method for manufacturing a ceramic thick film according to the present invention is to strengthen the coating bonding strength of the interface between the substrate and the base coating layer through the heat treatment of the base coating layer on the substrate formed by aerosol deposition in a specific condition, the base and the bonding strength is enhanced base By repeating aerosol deposition on the coating layer to form a coating layer to prepare a ceramic thick film, the ceramic using aerosol deposition method that can improve the adhesion strength between the ceramic thick film and the substrate, and at the same time can form a thicker and dense ceramic thick film A thick film production method and a ceramic thick film produced thereby.

Hereinafter, with reference to the accompanying drawings of the present invention will be described in more detail.

1 is a vertical cross-sectional schematic diagram of a ceramic thick film according to the present invention, Figure 2 is a FE SEM image of the vertical cross section of the ceramic thick film according to an embodiment of the present invention, the method of manufacturing a ceramic thick film according to the present invention In addition, the rare earth metal powder is aerosol deposited on the substrate 100 to form the base coating layer 110 (step (a)).

The base material 100 is a base material for forming the ceramic thick film 130 of the present invention. If the base material requires corrosion resistance, the base material 100 may be applied without limitation to an electrostatic chuck applied to the inside of the plasma apparatus, It may be a plasma device component such as a heater, a chamber liner, a shower head, a CVD boat, a focus ring, a wall liner, and the base material may be iron, magnesium, Metals such as aluminum and alloys thereof; Ceramics such as SiO ₂ , MgO, CaCO ₃ , Y ₂ O ₃ , quartz and alumina; It may be a polymer such as polyethylene terephthalate, polyethylene naphthalate, polypropylene adipate, polyisocyanate and the like, but preferably selected from any one of SiO ₂ , MgO, CaCO ₃ , Y ₂ O ₃ , quartz, alumina. Can be.

In addition, although there are various kinds of rare earth metal powders, the rare earth metal powders to be applied to the present invention include Y ₂ O ₃ , Dy ₂ O ₃ , Er ₂ O ₃ , Sm ₂ O ₃ , YAG, YF ₃ and YOF. It may be at least one selected from. In particular, Y ₂ O ₃ has the advantage of providing additional functionality in addition to the corrosion properties, because in addition to improving the corrosion resistance, the material itself has very good properties and economics and various applications to various industries.

In this case, the average particle diameter of the rare earth metal powder may be applied without limitation as long as it is a particle size that can be applied to conventional aerosol deposition, preferably 0.5 μm to 50 μm, and the aerosol deposition conditions according to the particle diameter change of the rare earth metal powder It can be easily changed and applied.

The rare earth metal powder is aerosol deposited to form the base coating layer 110. The aerosol deposition is performed by preparing a rare earth metal powder according to a known method, followed by aerosol deposition.

For example, aerosol deposition is a carrier gas (Ar, He) is introduced into the aerosol chamber containing the rare earth metal powder (MFC), the aerosolized rare earth metal powder floating in the aerosol chamber They are sprayed through a nozzle to a substrate in a deposition chamber under vacuum. The substrate is mounted on an X-Y-Z stage, a positioner or a robot to move in the X and Y axes by the movement of the stage. In the deposition chamber, the degree of vacuum is controlled by a mechanical booster pump.

In the aerosol deposition, other deposition conditions are not particularly limited, and the nozzle size of the aerosol deposition is 2 mm to 50 mm, and the flow rate is preferably 1 L / min to 60 L / min.

The thickness of the base coating layer 110 is controlled by adjusting the transfer speed of the substrate, the thickness of the base coating layer may be 0.5 ㎛ to 30 ㎛. If the thickness of the base coating layer 110 is less than 0.5 μm, the thickness is too thin to cause thickness nonuniformity. If the thickness of the base coating layer 110 is greater than 30 μm, the adhesion between the base material and the base coating layer is degraded and the base coating layer is easily peeled from the base material. Problems may arise.

As described above, when the base coating layer 110 is formed on the substrate 100, the formed base coating layer 110 is subjected to a first heat treatment (step (b)).

The first heat treatment induces necking phenomenon between the interface of the substrate 100 and the base coating layer 110 or the base coating layer to improve the adhesive strength between the substrate and the base coating layer, such as Ar, He, O ₂ , Air and vacuum atmosphere. In an atmosphere selected from the above, it may be performed at 750 ° C. or more for 1 hour to 20 hours, preferably at 800 ° C. to 1500 ° C. for 3 hours to 10 hours.

When the heat treatment is performed at a first heat treatment temperature of less than 750 ° C. or less than 1 hour, the necking phenomenon between the substrate and the base coating layer interface and the base coating layer particles does not occur, so that the contact strength between the substrate and the base coating layer may be reduced. When the heat treatment is performed for more than 20 hours, there is no meaningful necking phenomenon that can improve the strength and so on.

In this case, the primary heat treatment is heat treatment using a conventional furnace, furnace annealing (FA), rapid thermal annealing (RTA), excimer laser annealing (ELA), spark annealing (spark annealing) ), Plasma annealing, or the like, but is not limited thereto.

The heat treatment of the base coating layer as described above causes necking between the interface of the substrate 100 and the base coating layer 110 and the crystal, and the crystallite size is increased 1.5 to 3 times larger than the crystallite size of the base coating layer before heat treatment. Increasing the bonding strength of the grain boundary to improve the physicochemical properties such as hardness and chemical resistance of the coating layer, and at the same time to strengthen the coating bonding strength of the interface between the substrate and the base coating layer to obtain a high adhesive strength between the substrate and the base coating layer. . In this case, the crystallite size of the base coating layer may be calculated through the Scherrer equation using XRD Peak.

If the base coating layer crystallite after the heat treatment is 1 times or less in size than the base coating layer crystallite before the heat treatment, densification and bonding force between the interface and the crystal are hardly increased.

Subsequently, the primary heat-treated base coating layer 110 forms a coating layer 120 by aerosol deposition of rare earth metal powder on the primary heat-treated base coating layer 110 to form a ceramic thick film 130 [( c) step].

Aerosol deposition on the primary heat-treated base coating layer may also prepare a rare earth metal powder and then perform an aerosol deposition process in accordance with known methods, and may be performed under the same or different conditions as the aerosol deposition described above.

According to the present invention, in order to form the ceramic thick film 130 having high corrosion resistance on the substrate, a certain thickness is required in order to obtain somewhat stable characteristics. That is, when the thickness of the coating layer 120 is thin, the thickness nonuniformity is large, and if the surface irregularities are generated, the characteristics are likely to be poor. Therefore, in order to solve the thickness and thickness non-uniformity of the desired coating layer 120, by controlling the substrate transfer rate and the number of coatings to form a coating layer.

On the other hand, in the case of the thin coating layer 120, it is possible to obtain a desired thickness by increasing the number of aerosol deposition. The thickness of the coating layer increases with aerosol deposition. However, at a certain thickness or more, since the adhesiveness is lowered due to internal stress, the number of coatings is adjusted in consideration of this. In the case of the thickness and thickness non-uniformity of the coating layer will vary slightly depending on the type of substrate and the type of spray powder, but the transport speed (stage moving speed) of the substrate is within the range of 1 mm / s to 200 mm / s, aerosol deposition The number of times the coating is repeated one or more times, preferably in the range of 2 to 10 times.

The thickness of the coating layer 120 is controlled by adjusting the transfer rate and the number of deposition of the base material 100 on which the base coating layer 110 is formed, the thickness of the coating layer may be 1 ㎛ to 200 ㎛.

If the thickness of the coating layer is less than 1 μm, the thickness thereof is too thin to make a thick film of a desired thickness. If the thickness of the coating layer is more than 200 μm, the adhesion between the coating layers may be degraded and the coating layer may be easily separated.

The ceramic thick film 130 manufactured as described above has a necking phenomenon between the substrate 100 and the base coating layer 110 to improve adhesive strength between the substrate and the interface of the base coating layer. The phenomenon that a layer peels can be prevented.

On the other hand, the method of manufacturing a ceramic thick film according to the present invention further comprises the step of performing a secondary heat treatment after forming the coating layer (step (c)) to improve the compaction, adhesion between the base coating layer and the coating layer or repeatedly deposited coating layer. [Step (d)].

The secondary heat treatment may be performed for 1 to 20 hours at 750 ° C. or higher in Ar, He, O ₂ , Air, or a vacuum atmosphere, and may be performed under the same or different conditions as the above-described primary heat treatment conditions.

If the second heat treatment temperature is less than 750 ° C. or less than one hour, the necking phenomenon between the base coating layer, the coating layer and the coating layer particles does not occur, which may cause a problem that the contact strength between the substrate and the base coating layer is lowered. have.

At this time, the secondary heat treatment may be performed under the same or different conditions as the above-described primary heat treatment method, heat treatment using a conventional heating furnace, furnace annealing (FA), rapid thermal annealing (RTA) Excimer laser annealing (ELA), spark annealing (spark annealing), plasma annealing (plasma annealing), etc. may be performed using, but is not limited thereto.

As described above, the heat-treated coating layer induces necking phenomenon between the interface between the base coating layer and the coating layer and the crystals of the coating layer, and as the crystallite size increases 1.5 to 3 times larger than the crystallite size before the heat treatment, the grain boundary of the grain boundary (grain boundary) is increased. By increasing the bonding strength to improve the physical and chemical properties such as hardness, chemical resistance, etc. of the coating layer, it is possible to enhance the coating bonding strength of the interface between the coating layer to obtain a high adhesive strength between the coating layer.

In addition, the secondary heat treatment may be performed by selectively adjusting the number of aerosol deposition coating. For example, when the coating is performed five times by aerosol deposition on the first heat-treated base coating layer 110, the second heat treatment is performed five times for each coating, or the second heat treatment is performed twice for each coating. Alternatively, the second heat treatment may be performed once after the last coating.

The ceramic thick film 130 prepared as described above has a necking phenomenon between the substrate 100 and the base coating layer 120 to improve adhesive strength between the interface of the substrate and the base coating layer. The phenomenon that a layer peels can be prevented.

In addition, the method for producing a ceramic thick film according to the present invention is to repeat step (c) and step (d) one or more times, preferably 2 to 10 times in sequence, or (c) and (d) On the last coating layer performed repeatedly by repeating the step (c) by additionally performing only the addition of the necking phenomenon between the coating layer to improve the adhesive strength can form a dense and thick coating layer.

The ceramic thick film prepared by the method according to the present invention includes a heat-treated base coating layer 110 and a coating layer 120, the heat treatment of the base coating layer is a necking phenomenon between the interface and the crystal of the substrate and the base coating layer is generated As the crystallite size is increased 1.5 to 3 times larger than the size of the base coating layer before heat treatment, it is dense and thick and can prevent the coating interface layer from being easily peeled off due to external impact. There is a possible effect.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are merely examples to help understanding of the present invention, but the scope of the present invention is not limited thereto.

< Example  1>

One- 1: primary Heat-treated  Base coating layer formation

In the aerosol chamber, yttria (Y ₂ O ₃ ) was aerosolized using a powder vibration vibrator, and then the aerosolized yttria powder was flowed together with argon gas using the pressure difference between the aerosol chamber and the deposition chamber. Physical impact on the alumina (Al ₂ O ₃ ) plate at L / min to form a base coating layer having a thickness of 3 ㎛. The alumina plate on which the base coating layer was formed was placed in a heating furnace, and then subjected to a first heat treatment at 800 ° C. for 3 hours in an air atmosphere.

1-2: coating layer formation

The first heat-treated base coating layer of Example 1-1 was placed in an aerosol chamber, and yttria (Y ₂ O ₃ ) was aerosolized using a powder vibrating vibrator in the aerosol chamber, and then between the aerosol chamber and the deposition chamber. Using the pressure difference, the aerosolized yttria powder was physically collided with the argon gas at a flow rate of 30 L / min on the base coating layer to form a coating layer, thereby preparing a ceramic thick film having a total thickness of about 20 μm.

< Example  2>

A ceramic thick film was prepared in the same manner as in Example 1, but the first thick heat treatment was performed at 1,000 ° C. for 3 hours in an air atmosphere to prepare a ceramic thick film having a total thickness of about 20 μm.

< Example  3>

A ceramic thick film was prepared in the same manner as in Example 1, but the first heat treatment was performed at 1,000 ° C. for 6 hours in an air atmosphere to prepare a ceramic thick film having a total thickness of about 20 μm.

< Example  4>

A ceramic thick film was prepared in the same manner as in Example 1, but the first thick heat treatment was performed at 1,200 ° C. for 3 hours in an air atmosphere to prepare a ceramic thick film having a total thickness of about 20 μm.

< Example  5>

A ceramic thick film was prepared in the same manner as in Example 1, but the first heat treatment was performed at 1,500 ° C. for 3 hours in an air atmosphere to prepare a ceramic thick film having a total thickness of about 20 μm.

< Example  6>

A ceramic thick film was prepared in the same manner as in Example 1, but the first thick heat treatment was performed at 1,800 ° C. for 3 hours in an air atmosphere to prepare a ceramic thick film having a total thickness of about 20 μm.

< Example  7>

After forming the first heat-treated base coating layer in the same manner as in Example 2, the base coating layer was placed in an aerosol chamber, and the yttria (Y ₂ O ₃ ) was aerosolized using a powder vibration vibrator in the aerosol chamber. Then, using the pressure difference between the aerosol chamber and the deposition chamber, the aerosolized yttria powder was physically collided with argon gas at a flow rate of 30 L / min to form a coating layer having a thickness of 10 μm. The formed coating layer was subjected to secondary heat treatment at 1,000 ° C. for 3 hours, and then the secondary heat-treated coating layer was repeatedly performed once more in the same manner to prepare a ceramic thick film having a total thickness of about 20 μm.

< Example  8>

After the base heat-treated base coating layer was formed in the same manner as in Example 2, the base coating layer was placed in an aerosol chamber, and yttria (Y ₂ O ₃ ) was aerosolized using a powder vibration vibrator in the aerosol chamber. Then, using the pressure difference between the aerosol chamber and the deposition chamber, the aerosolized yttria powder was physically collided with argon gas at a flow rate of 30 L / min to form a coating layer having a thickness of 10 μm. The formed coating layer was subjected to secondary heat treatment at 1,000 ° C. for 3 hours, and then the secondary heat treated coating layer was repeatedly performed six times in the same manner to prepare a ceramic thick film having a total thickness of about 70 μm.

< Example  9>

9- 1: primary Heat-treated  Base coating layer formation

In the aerosol chamber, yttria (Y ₂ O ₃ ) was aerosolized using a powder vibration vibrator, and then the aerosolized yttria powder was flowed together with argon gas using the pressure difference between the aerosol chamber and the deposition chamber. Physical impact on the alumina (Al ₂ O ₃ ) plate at L / min to form a base coating layer having a thickness of 13 ㎛. The alumina plate formed with the base coating layer was placed in a heating furnace, and then subjected to a primary heat treatment at 1000 ° C. for 3 hours in an air atmosphere.

9-2: Coating Layer Formation

The first heat-treated base coating layer of Example 9-1 was placed in an aerosol chamber, and yttria (Y ₂ O ₃ ) was aerosolized using a powder vibrating vibrator in the aerosol chamber, and then between the aerosol chamber and the deposition chamber. Using the pressure difference, the aerosolized yttria powder was physically collided with argon gas at a flow rate of 30 L / min to form a coating layer having a thickness of 40 μm. The formed coating layer was subjected to secondary heat treatment at 1,000 ° C. for 3 hours, and then the secondary heat treated coating layer was repeatedly performed four times in the same manner to prepare a ceramic thick film having a total thickness of about 200 μm.

< Comparative example  1>

A ceramic thick film was prepared in the same manner as in Example 1, except that a ceramic thick film having a total thickness of about 13 μm was prepared without first heat treatment.

< Comparative example  2>

A ceramic thick film was prepared in the same manner as in Example 1, but the first thick heat treatment was performed at 700 ° C. for 3 hours in an air atmosphere to prepare a ceramic thick film having a total thickness of about 20 μm.

[ Experimental Example  1]: ceramic Thick curtain  Structural shape measurement

Vertical sections of the ceramic thick films prepared in Examples and Comparative Examples were measured by FE SEM (JEM-2100F HR, JEOL LTD.). The results are shown in FIGS. 2 to 6.

3 is a vertical cross-sectional view of the ceramic thick film prepared in Comparative Example 1 and Example 2, Figure 3 (a-1) and (a-2) is a base coating layer of the ceramic thick film prepared in Comparative Example 1, respectively 3 (b-1) and (b-2) show the interface between the base coating layer, the base coating layer and the substrate of the ceramic thick film prepared in Example 2, respectively.

As shown in FIG. 3, in the case of the ceramic thick film manufactured in Comparative Example 1 (FIG. 3A-1), the necking phenomenon does not appear, whereas in the case of the ceramic thick film manufactured in Example 2 (FIG. 3B-1). In the base coating layer, it was confirmed that the coating bonding force was improved by the necking phenomenon. In the case of the ceramic thick film prepared in Comparative Example 1 (FIG. 3A-2), the interface between the base coating layer and the substrate was not completely bonded. In the case of the ceramic thick film prepared in 2 (FIG. 3B-2), it was confirmed that the base coating layer and the base were bonded without the interface boundary.

In addition, Figure 4 is a vertical cross section of the ceramic thick film prepared in Comparative Example 2 and Examples 1 to 3, (a) is a ceramic thick film image of Comparative Example 2, (b) is a ceramic thick film of Example 1 (C) is the ceramic thick film image of Example 2, and (d) is the ceramic thick film image of Example 3.

As shown in FIG. 4, in the case of the ceramic thick film of Comparative Example 2 (FIG. 4A), the necking phenomenon did not appear, whereas in the ceramic thick films of Examples 1 to 3, the necking phenomenon occurred. It was confirmed that it appeared.

On the other hand, Figure 2 is an image measuring the vertical cross section of the ceramic thick film prepared in Example 7, Figure 5 is an image measuring the vertical cross section of the ceramic thick film prepared in Example 8, Figure 6 is manufactured in Example 9 The vertical cross section of the ceramic thick film was measured.

As shown in Figures 2, 5 and 6, when the ceramic thick film was prepared without heat treatment as in Comparative Example 1 (Fig. 3 (a)), the thickness is about 13 ㎛, while there is a limit to the thicker thick film formation In FIGS. 2, 5 and 6, it was confirmed that a ceramic thick film having a thickness of 200 μm could be manufactured by heat treatment and repeated coating.

[ Experimental Example  2] ceramic Thick  Chemical resistance measurement

In order to measure the chemical resistance of the ceramic thick films prepared in Example 1 and Comparative Example 1, 8% HF, 12.5% HF, and 25% HF were dropped on the ceramic thick films, respectively, and held for 12 hours to generate spalling. Was measured by 3D Laser Scanning and is shown in FIG.

As shown in FIG. 7, in the ceramic thick film prepared in Comparative Example 1, spalling occurred in 12.5% HF and 25% HF after 12 hours, whereas in the ceramic thick film manufactured in Example 1, 12 hours after , 8% HF, 12.5% HF and 25% HF were all nonspecific.

[ Experimental Example  3] ceramic Thick  Determination Method

The crystallite size of the ceramic thick films prepared in Examples and Comparative Examples of the present invention was calculated by the following Equation 1 using XRD Peak and shown in Table 1 below.

[Equation 1]

d _XRD = size of the determinant calculated by Sherrer equation

λ: measured X-ray wavelength (λ _CuKa1 = 1.5406 Å)

B: half-width, broadening of diffraction lines, B = (2θ ₂ -2θ ₁ ) / 2 = θ ₂ -θ ₁

θ: diffraction angle

[ Experimental Example  5] ceramic Thick  Hardness measurement

Hardness (Hv) of the ceramic thick films prepared in Examples and Comparative Examples of the present invention was measured by Vickers hardness tester (KSB0811), the results are shown in Table 1 below.

division Crystalline size of ceramic thick film (nm) Hardness of Ceramic Thick Film (Hν) Example 1 27.49 450 Example 2 30.93 510 Example 3 32.90 550 Example 4 36.61 600 Example 5 38.48 620 Example 6 45.20 600 Comparative Example 1 18.32 320 Comparative Example 2 20.15 360

As shown in Table 1, in the case of the ceramic thick films prepared in Examples 1 to 6, it was confirmed that the crystallite size was 1.5 times larger than the crystallite size of the ceramic thick film prepared in Comparative Example 1. It was determined that the crystallite size increased due to the necking phenomenon of the ceramic thick film prepared in Examples 1 to 6 after the heat treatment.

In addition, in the case of the ceramic thick film prepared in Examples 1 to 5, it was confirmed that the coating bonding strength of the ceramic thick film is improved compared to Comparative Examples 1 and 2 in hardness, but in the case of the ceramic thick film prepared in Example 6 The high temperature of heat treatment caused the phase change of the thick film, and the hardness decreased.

Therefore, the manufacturing method of the ceramic thick film according to the present invention can improve the adhesive strength between the ceramic thick film and the substrate to prevent the coating interface layer from being easily peeled off by external impact and at the same time to produce a thicker and more dense ceramic thick film. Could confirm.

All simple modifications or changes of the present invention can be easily implemented by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

100: description
110: base coating layer
120: coating layer
130: ceramic thick film

Claims (13)

(a) aerosol deposition of at least one rare earth metal powder selected from the group consisting of Y ₂ O ₃ , Dy ₂ O ₃ , Er ₂ O ₃ , Sm ₂ O ₃ , YAG, YF ₃ and YOF Forming a base coating layer having a thickness of 0.5 μm to 30 μm;
(b) first heat treatment to increase the crystallite size of the formed base coating layer by 1.5 to 3 times, and to cause necking between the substrate and the base coating layer interface and the crystal; And
(c) aerosol deposition of rare earth metal powder on the first heat-treated base coating layer to form a coating layer.
The method of claim 1,
The primary heat treatment of step (b) is a method for producing a ceramic thick film, characterized in that performed for 1 to 20 hours at 750 ℃ or more in Ar, He, O ₂ , Air or vacuum atmosphere.
delete The method of claim 1,
Step (c) is a method for producing a ceramic thick film, characterized in that carried out repeatedly at least one or more times.
delete delete The method of claim 1,
The coating layer has a thickness of 1 ㎛ ~ 200 ㎛ characterized in that the manufacturing method of the ceramic thick film.
The method of claim 1,
The manufacturing method of the ceramic thick film is a method of manufacturing a ceramic thick film further comprising the step of (d), after the second heat treatment (d).
The method of claim 8,
The secondary heat treatment is a method for producing a ceramic thick film, characterized in that performed for 1 to 20 hours at 750 ℃ or more in Ar, He, O ₂ , Air or vacuum atmosphere.
The method of claim 8,
The crystallization of the coating layer after the second heat treatment method of manufacturing a ceramic thick film, characterized in that 1.5 to 3 times larger than the crystallization of the coating layer of step (c).
The method of claim 8,
The method of manufacturing a ceramic thick film is a method of manufacturing a ceramic thick film, characterized in that the steps (c) and (d) are repeated one or more times in sequence.
The method of claim 11,
The manufacturing method of the ceramic thick film is a method of manufacturing a ceramic thick film, characterized in that the step (c) additionally performed on the last coating layer performed by repeating steps (c) and (d).
The ceramic thick film formed by the manufacturing method of any one of Claims 1, 2, 4, and 7-12.

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