KR20220027426A - Ceramic composition for coating and coating method using the same - Google Patents

Abstract

Disclosed are a ceramic composition for coating that includes an anionic solvent to enable in-situ reaction with a solute and a coating method for coating by suspension plasma spray using the ceramic composition for coating. The coating method according to the present invention includes a step (a) of preparing a ceramic composition for coating; and a step (b) of coating a base substrate with the ceramic composition for coating using suspension plasma spray, wherein the step of preparing the ceramic composition for coating includes a step (a1) of mixing oxide particles with an anion-containing solvent, a surface reaction layer containing anions is formed on the surface of the oxide particles during the mixing, and a ceramic coating layer having a different composition according to the thickness of the surface reaction layer is formed in the coating step.

Description

Ceramic composition for coating and coating method using the same

The present invention relates to a ceramic composition for coating containing an anionic solvent and a coating method for coating by suspension plasma spray using the ceramic composition for coating.

Materials applied to the defense industry, aerospace and high-tech industries are those that are exposed to extreme environments such as ultra-high temperature, high pressure, and chemical degradation.

For example, the materials include chambers for semiconductor manufacturing, engineering ceramic components, turbine components, and the like.

The materials require heat resistance, light weight and corrosion resistance. And the materials require physical properties that can maintain and protect the properties of the material.

In order to exhibit these properties, the materials are made of a ceramic material that withstands high temperature or plasma atmosphere.

Recently, in order to improve the corrosion resistance or thermal stability of the material, research on forming a coating film on the surface of the material is being conducted.

When a coating film is formed on the surface of the material, it is possible to produce a high-functional material exhibiting abrasion resistance, corrosion resistance, heat resistance, oxidation resistance, friction characteristics and mechanical characteristics.

Accordingly, there is also a need for a method capable of easily coating a large area object in a short time.

It is an object of the present invention to provide a ceramic composition for coating for in-situ reaction with a solute.

It is also an object of the present invention to provide a coating method using a ceramic composition for coating in order to improve not only plasma resistance, abrasion resistance, but also mechanical properties.

The objects of the present invention are not limited to the objects mentioned above, and other objects and advantages of the present invention not mentioned may be understood by the following description, and will be more clearly understood by the examples of the present invention. Further, it will be readily apparent that the objects and advantages of the present invention may be realized by the means and combinations thereof indicated in the claims.

The ceramic composition for coating according to the present invention comprises: a solvent containing an anion; and oxide particles dispersed in the solvent, wherein the oxide particles include a surface reaction layer including the anion.

The coating method according to the present invention comprises the steps of (a) providing a ceramic composition for coating; And (b) using the suspension plasma spray, coating the ceramic composition for coating on the base substrate; including, wherein the step of preparing the ceramic composition for coating includes (a1) mixing a solvent containing an anion and oxide particles and, during the mixing, a surface reaction layer containing the anion is formed on the surface of the oxide particle, and in the coating step, a ceramic coating film having a different composition according to the concentration of the anion is formed.

In the present invention, by using an anionic solvent, an in-situ reaction with the solute is possible when coating with suspension plasma spray.

In addition, in the present invention, it is possible to change the composition of the finally formed ceramic coating film according to the concentration of anions, thereby exhibiting the effect of resistance to external chemical deterioration conditions.

In addition, in the present invention, there is an effect of improving the mechanical properties as well as the plasma resistance and abrasion resistance.

In addition to the above-described effects, the specific effects of the present invention will be described together while describing specific details for carrying out the invention below.

1 shows a ceramic composition for coating of the present invention.
2 and 3 show the core-shell structure of the oxide particle of the present invention.
4 is a flowchart of the coating method of the present invention.
5 is a schematic diagram of the coating method of the present invention.
6 is a cross-sectional view of a structure in which a ceramic coating film is disposed on a base substrate using the coating method of the present invention.

The above-described objects, features and advantages will be described below in detail with reference to the accompanying drawings, and accordingly, those of ordinary skill in the art to which the present invention pertains will be able to easily implement the technical idea of the present invention. In describing the present invention, if it is determined that a detailed description of a known technology related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to indicate the same or similar components.

In the following, that an arbitrary component is disposed on the "upper (or lower)" of a component or "above (or below)" of a component means that any component is disposed in contact with the upper surface (or lower surface) of the component. Furthermore, it may mean that other components may be interposed between the component and any component disposed on (or under) the component.

Also, when it is described that a component is "connected", "coupled" or "connected" to another component, the components may be directly connected or connected to each other, but other components are "interposed" between each component. It is to be understood that “or, each component may be “connected,” “coupled,” or “connected,” through another component.

Hereinafter, a ceramic composition for coating according to some embodiments of the present invention and a coating method using the same will be described.

The present invention provides a ceramic composition for coating capable of forming a composite anionic ceramic coating film using an anionic solvent for in-situ reaction with a solute and using a suspension plasma spray, and a coating method using the same want to

1 shows a ceramic composition for coating of the present invention.

As shown in FIG. 1 , the ceramic composition 100 for coating of the present invention includes a solvent 10 containing an anion and oxide particles 20 dispersed in the solvent 10 .

In the present invention, the solvent 10 containing an anion has a function to prevent a phenomenon in which fine coating particles are not coated due to excessive plasma energy and evaporated into the atmosphere, like an alcohol-based solvent or distilled water solvent used in the prior art. .

In addition, the main feature is that the solvent 10 containing an anion has a surface reaction layer 22 having a complex anion composition on the surface of the oxide particle 20 and has a function of changing the composition of the final ceramic coating film 300 .

When the oxide is in chemical contact with fluoride, chloride, etc., chemical deterioration of the coating film may occur such as decomposition of the oxide. In order to suppress this chemical deterioration, the effect of the passive layer can be expected by forming a complex anionic composition similar to the external chemical composition on the surface reaction layer.

In this regard, it is preferable that the solvent 10 containing the anion excludes the solvent in which the oxide particles 20 are decomposed. It is also desirable to exclude solvents that are not sufficiently usable for suspension plasma spray applications.

The anion includes at least one of fluorine (F), chlorine (Cl), nitrogen (N) and sulfur (S).

The anion also includes anionic salts such as NO ₃ ^-nitrate , NO ₂ ^-nitrite .

For example, the solvent 10 containing the anion is HSO ₄ ^- , SO ₃ ² - , H ₂ PO ₄ ^- , Cl ^- , NO ₃ ^- , NO ₂ ^- , ClO ₄ ^- , F ^- , S ² - , HS ^- may include one or more of.

Preferably, the solvent 10 containing the anion may include a fluorine-containing salt.

In the present invention, the concentration of the anion is an important factor.

In the solvent 10 containing anions, the composition of the ceramic coating film 300 is changed according to the concentration of the anions. The change in the composition of the ceramic coating film 300 means that the chemical composition of the surface itself (surface reaction layer) of the oxide particles 20 constituting the ceramic coating film 300 is changed.

In the present invention, the surface of the oxide particles 20 is decomposed and reacted by plasma energy to form a complex anion.

In the surface reaction layer 22 including anions, the element composition and element ratio present in the surface reaction layer are changed by high temperature together with plasma. The ratio of these elements depends on the suspension plasma conditions and the concentration of anions in the solvent.

Under the assumption that the anion is completely dissolved in the solvent, the concentration of the anion can be used up to the maximum amount. It is preferable that the salt is also completely dissolved in the solvent.

When the conversion ratio of anions dissolved in a solvent to a complex anionic compound in the surface reaction layer is 100% or the maximum conversion is aimed at, the anions may be added to the solvent up to the maximum solubility limit.

With respect to the solvent, the concentration of the anion may be 5 ppm (weight/weight) or more.

When the concentration of the anions is less than 5 ppm, when the surface reaction layer 22 is formed on the surface of the oxide particles 20, the conversion to the compound of the complex anionic composition may be very insignificant, so in the suspension plasma spraying process, the ceramic coating film 300 It can be difficult to change the composition of

The oxide particles 20 are dispersed in the solvent 10 containing anions as a solute.

The oxide particles 20 include a surface reaction layer 22 containing the anions.

A surface reaction layer 22 containing anions is formed on the surface of the oxide particles 20 through a mechanical action and a thermal action in the mixing process of the solvent 10 containing anions and the oxide particles 20 .

Here, the mechanical action and the thermal action may be friction and pulverization by mixing and stirring.

The oxide particles 20 may include at least one of group 3-13 metal oxides, silicon dioxide, and rare earth oxides.

Specifically, metal oxides of Group 3-13 include zinc oxide, titanium oxide, aluminum oxide, zirconium oxide, chromium oxide, copper oxide, vanadium oxide, cobalt oxide, hafnium oxide, iron oxide, niobium oxide, tantalum oxide, tungsten oxide, and the like. include

The rare earth oxide refers to an oxide of a lanthanide element corresponding to atomic numbers 57 to 71 and an element including scandium (No. 21) and yttrium (39). Rare earth oxides include, for example, yttrium oxide, lanthanum oxide, gadolinium oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, ruthenium oxide, and the like.

The average particle size d ₁ of the oxide particles 20 may be 0.1 to 100 μm. When this range is satisfied, the density of the ceramic coating film 300 can be ensured, and a uniform thickness can be formed.

When the average particle size (d ₁ ) of the oxide particles 20 is less than 0.1 μm, the particle size (d ₁ ) is too small to cause agglomeration of the oxide particles 20 . In addition, the effect of improving hardness and strength, which is a function of the oxide particles 20 , may be insufficient.

Conversely, when the average particle size (d ₁ ) of the oxide particles 20 exceeds 100 μm, it is difficult to sufficiently secure the strength and hardness of the ceramic coating film 300 , and there is a problem in that the performance of the ceramic coating film 300 itself is lowered.

The ceramic composition for coating 100 may include 5 to 70 parts by weight of the oxide particles 20 based on 100 parts by weight of the solvent 10 containing an anion.

When the content of the oxide particles 20 is out of 5 to 70 parts by weight, it may be difficult to secure the mechanical properties, thermal stability, and density of the ceramic coating film 300 .

2 and 3 show the core-shell structure of the oxide particle of the present invention.

2 and 3 , the oxide particle 20 has a core-shell structure by an in-situ reaction. The part corresponding to the core is the oxide particle 20 , and the part corresponding to the shell is the surface reaction layer 22 .

The surface reaction layer 22 includes a single anion or includes two or more complex anions.

The surface reaction layer 22 including anions has a structure disposed on the surface of the oxide particles 20 . And the surface reaction layer 22 may have a structure in which one or more layers are stacked.

For example, when using a fluorine-based anionic solvent and yttria (Y ₂ O ₃ ) as the oxide particles 20 in the state of the ceramic composition for coating, the surface of the oxide particles 20 may be converted into YOF or the like by plasma energy. there is.

The ratio of O and F in the surface reaction layer 22 may be affected by the conditions of the suspension plasma and the influence of the concentration of anions in the solvent.

Furthermore, in the process of coating with suspension plasma spray, the ceramic composition for coating 100 reacts with plasma by high temperature while the element of the oxide particle 20 and the element of the surface reaction layer 22 are connected or combined with each other can be

That is, after coating with suspension plasma spray, the in-situ compound may have a structure in which a solute element and an anion element are connected or combined with each other.

By high temperature with plasma, the elements of the oxide particles 20 may be connected or combined with an anion element present in the solvent, so that the surface of the oxide particles 20 may be formed of complex elements.

Accordingly, the composition of the surface reaction layer 22 may include an anion element or an element of the oxide particle 20 together.

The thickness d ₂ of the surface reaction layer 22 may be adjusted according to the concentration of the anion.

For example, as shown in FIG. 2 , as the concentration of the anion approaches about 5 ppm, the thickness d ₂ of the surface reaction layer 22 tends to decrease.

It can be seen that the conversion of the surface of the oxide particles 20 to the compound of the complex anionic composition is very insignificant.

Comparing the particle size (d ₁ ) of the oxide particles 20 and the thickness (d ₂ ) of the surface reaction layer 22 , the particle size (d ₁ ) is greater than the thickness (d ₂ ), as d ₁ ≥ d ₂ , or the particle size (d ₁ ) and thickness (d ₂ ) may be the same.

4 is a flowchart of the coating method of the present invention. 5 is a schematic diagram of the coating method of the present invention.

4 and 5 , the coating method of the present invention includes a step of preparing a ceramic composition for coating (S110) and coating the ceramic composition for coating on a base substrate using a suspension plasma spray (S120) do.

The step of preparing the ceramic composition 100 for coating includes mixing the solvent 10 containing anions and the oxide particles 20 .

In the process of mixing the solvent 10 containing anions and the oxide particles 20 , the oxide particles 20 are smoothly stirred in the solvent 10 .

The surface reaction layer 22 containing anions is formed on the surface of the oxide particles 20 while friction and pulverization are applied by the stirring.

The mixing may be performed at about 25 to 100° C., but is not limited thereto.

With respect to 100 parts by weight of the solvent containing the anion, 5 to 70 parts by weight of the oxide particles may be mixed.

When the content of the oxide particles 20 is less than 5 parts by weight, it may be difficult to form the ceramic coating film 300, and it may be difficult to secure required mechanical properties, thermal stability, and density.

Conversely, when the content of the oxide particles 20 exceeds 70 parts by weight, the coating may not be performed smoothly due to sedimentation in the suspension. In addition, there is a disadvantage in that only the manufacturing cost increases without the effect of improving physical properties.

Since the solvent 10 and the oxide particles 20 containing anions are the same as those described above in the ceramic composition 100 for coating, they will be omitted.

Next, it is a step of coating the ceramic composition 100 for coating on the base substrate 200 by using the suspension plasma spray.

Suspension plasma spraying is a method similar to conventional plasma spraying, but a method using a suspension or slurry as a coating material.

Here, the suspension means that solid particles are dispersed in a liquid.

If suspension plasma spray is used, the molten particles are sprayed at high speed in the form of droplets (small droplets) by generating an ultra-high temperature of several thousand degrees or more, which is the central temperature of the plasma.

Specifically, the suspension plasma spray works as follows.

When plasma gas flows inside the plasma torch and generates an arc between the cathode and the anode, high heat is generated. As the plasma gas is dissociated by the high heat, a plasma jet is formed.

When the ceramic composition for coating 100 is injected into the flow of the plasma jet, the solvent is decomposed, and some of the anionic elements such as fluorine present in the solvent are removed from the surface of the oxide particles 20 by plasma energy in the reaction layer 22 is formed, and the melting of the oxide particles 20 is started simultaneously or sequentially, and while flying at the same time as a high-temperature flame, the melting continues and becomes droplets.

And ultimately, the oxide particles 20 including the converted oxide particles 20 collide with the surface of the base substrate 200, which is a material to be coated, and adhere to it, thereby forming the ceramic coating film 300. .

The plasma gas may be a mixture of an inert gas such as argon gas or helium gas, and at least one of oxygen gas, nitrogen gas, and hydrogen gas.

As such, using the suspension plasma spray, it is possible to secure a dense and high-density ceramic coating film 300 by the sprayed particles.

In addition, if the suspension plasma spray is used, it is advantageous to use the material properties of the ceramic coating film 300 to produce a high-functional material that exhibits abrasion resistance, corrosion resistance, heat resistance and thermal barrier, oxidation resistance, insulation, friction characteristics, and heat dissipation characteristics.

In addition, compared to other coating methods such as CVD or PVD, it has the advantage of being able to easily coat a large area object in-situ within a short time.

In the present invention, in the step of coating with suspension plasma spray, a ceramic coating film 300 having a different composition according to the thickness d ₂ of the surface reaction layer 22 is formed.

As described above, the composition of the ceramic coating film 300 may be changed according to the concentration of the anion.

For example, as shown in FIG. 3 , as the thickness d ₂ of the surface reaction layer 22 increases, the composition of the ceramic coating film 300 is converted with the initial oxide particles 20 and the content of the complex anions increases. develops in an increasing fashion. In addition, the ratio in which the converted complex negative ions exist in the structure of the ceramic coating film 300 also increases in the form of grain boundaries and interlayers. The grain boundary and interlayer are the interface between the oxide particles 20 including the surface reaction layer 22 and the particles, and the layer and the layer formed by the accumulation of droplets made by melting the oxide particles 20 including the surface reaction layer 22 points to

In addition, as the thickness d ₂ of the surface reaction layer 22 decreases, the composition of the ceramic coating film 300 decreases. The possibility that it exists only at the boundary of oxide particles increases, and the content ratio also tends to decrease.

As such, by changing the composition of the ceramic coating film 300 , it is possible to exhibit an effect of controlling resistance to external chemical deterioration.

By coating with suspension plasma spray, the ceramic coating film 300 may be formed with a uniform thickness d ₃ of 3 to 2000 μm.

If the thickness d ₃ of the ceramic coating film 300 is out of the range of 3 to 2000 μm, it may be difficult to properly represent the function of the ceramic coating film 300 .

The ceramic coating film 300 is a coating film having a porosity of 0.1 to 60 vol%, and is widely applicable from high density to porosity.

When the porosity exceeds 60 vol%, as the porosity increases, the density of the ceramic coating film 300 may be lowered and mechanical properties may be deteriorated.

The base substrate 200 is a material used for a typical chamber component for semiconductor manufacturing, an engineering ceramic component, and a component for a turbine, and includes at least one of a metal, an alloy, and a ceramic.

The base substrate 200 may be a bulk material as a metal or a sintered body, or may be a material on which a coating film is formed.

The metal base substrate 200 may include a metallic substrate material including at least one of aluminum, anodized aluminum, iron-based alloys, iron-based alloys, non-ferrous metals, and non-ferrous alloys. For example, the metal material may include Ni, Co, Cr, Al, Y, a noble metal, and a rare metal.

For another example, the base substrate 200 may include silicon (Si), silicon carbide (SiC), titanium carbide (TiC), tungsten carbide (WC), chromium carbide (CrC), tantalum carbide (TaC), or zirconium carbide (ZrC). ), yttria (Y ₂ O ₃ ), Silica (SiO ₂ ), alumina (Al ₂ O ₃ ), chromium oxide (Cr ₂ O ₃ ), magnesium oxide (MgO), calcium oxide (CaO), iron oxide (FeO), tin oxide (SnO ₂ ), titanium dioxide ( TiO ₂ ), zirconia (ZrO ₂ ), hafnium oxide (HfO ₂ ), tantalum oxide (Ta ₂ O ₅ ), ruthenium oxide (RuO ₂ ), lead monoxide (PbO), zinc oxide (ZnO), strontium peroxide (SrO ₂ ) ), bismuth oxide (Bi ₂ O ₃ ), mullite (3Al ₂ O ₃ -2SiO ₂ ), and may include at least one of rare earth oxides.

6 is a cross-sectional view of a structure in which a ceramic coating film is disposed on a base substrate using the coating method of the present invention.

As shown in FIG. 6 , the ceramic coating film 300 may be formed on the base substrate 200 by using the suspension plasma spray coating method of the present invention.

The material on which the ceramic coating film 300 is formed on the base substrate 200 has excellent mechanical properties along with excellent plasma resistance, abrasion resistance, and corrosion resistance.

The material can be used for chamber walls, chamber liners, substrate supports, gas distribution plates, plasma confinement rings, nozzles, heating elements, plasma focus rings, etc. there is.

As described above, the present invention has been described with reference to the illustrated drawings, but the present invention is not limited by the embodiments and drawings disclosed in this specification, and various methods can be obtained by those skilled in the art within the scope of the technical spirit of the present invention. It is obvious that variations can be made. In addition, although the effects according to the configuration of the present invention have not been explicitly described and described while describing the embodiments of the present invention, it is natural that the effects predictable by the configuration should also be recognized.

10: solvent containing anion
20: oxide particles
22: surface reaction layer
100: ceramic composition for coating
200: base substrate
300: ceramic coating film

Claims (10)

a solvent containing an anion; and
Including; oxide particles dispersed in the solvent;
The oxide particle is a ceramic composition for coating comprising a surface reaction layer containing the anion.
The method of claim 1,
The anion is a ceramic composition for coating comprising at least one of fluorine (F), chlorine (Cl), nitrogen (N) and sulfur (S).
The method of claim 1,
The oxide particle is a ceramic composition for coating comprising at least one of a group 3-13 metal oxide, silicon dioxide, and a rare earth oxide.
According to claim 1,
With respect to the solvent, the concentration of the anion is 5 ppm or more of the ceramic composition for coating.
According to claim 1,
The average particle size of the oxide particles is a ceramic composition for coating of 0.1 to 100㎛.
(a) preparing a ceramic composition for coating; and
(b) using a suspension plasma spray, coating the ceramic composition for coating on the base substrate;
The step of preparing the ceramic composition for coating is
(a1) comprising the step of mixing a solvent containing an anion and oxide particles,
During the mixing, a surface reaction layer containing the anion is formed on the surface of the oxide particle,
In the coating step, a coating method for forming a ceramic coating film having a different composition depending on the concentration of the anion.
7. The method of claim 6,
A coating method of mixing 5 to 70 parts by weight of oxide particles with respect to 100 parts by weight of the solvent containing the anion.
7. The method of claim 6,
A coating method in which the thickness of the surface reaction layer is formed differently depending on the concentration of the anion.
7. The method of claim 6,
The thickness of the ceramic coating film is 3 ~ 2000㎛ coating method.
7. The method of claim 6,
The base substrate is a coating method comprising at least one of a metal, an alloy, and a ceramic.

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