KR101341592B1 - Method for coating on the basic material, basic material coated by the same - Google Patents

Abstract

An object of the present invention is to provide a method for coating the inner surface of the base material and thus the base material coated therein.
To this end, the present invention is to obtain a coating source material of reduced density from the coating source material (step 1); And
A step of subliming the coating source material having a reduced density obtained in step 1 and coating the base material by reaching the base material (step 2);
It provides an internal surface coating method of the base material comprising a.
According to the present invention, it is possible to coat the invisible part including the inner wall of the cylindrical or spherical material, which was not possible with the conventional coating method, and the inner wall of the cylindrical part among the components of the thermochemical plant for nuclear hydrogen production and It can be applied to cylindrical inner walls and joint parts of weapons including cannons or rifles, which can greatly improve wear resistance and corrosion resistance, and give lubricity and ultimately increase the service life.

Description

Method for coating the inner surface of the base material and the base material coated thereon {Method for coating on the basic material, basic material coated by the same}

The present invention relates to a method for coating the inner surface of the base material and thus the base material coated therein.

The method of coating the surface of the material may be classified into physical vapor deposition (PVD), chemical vapor deposition (CVD), electrolytic and electroless deposition (Electro- and Electoless-Deposition).

Among them, physical vapor deposition includes sputtering, electron-beam evaporation, thermal evaporation, laser molecular beam epitaxy, and pulsed laser deposition. These methods vaporize the coating source material in a vacuum environment and coat the material surface. Specifically, the method comprises vaporizing the coating source material, bringing the vaporized material to the material surface, and growing the coating layer. In the deposition process by physical vapor deposition, in order for the vaporized coating source material to reach the material surface, the vaporized coating source materials must have kinetic energy and the reaction chamber must always be kept in a high vacuum state. If the degree of vacuum is poor and many other gases are present in the vacuum chamber, vaporized coating source materials may interfere with the other gases and prevent them from reaching the material surface. In addition, if the kinetic energy of the coating source materials is increased to increase the coating speed, the coating source materials tend to reach the surface of the material and the coating rate increases, but as the kinetic energy increases, the linear motion of the coating source materials also increases, resulting in a curved portion. Coating of parts not visible to the naked eye becomes difficult.

Chemical vapor deposition is a method in which a gaseous precursor reacts chemically on a surface of a substrate to form a solid coating layer. Since the chemical vapor deposition method uses the principle of coating the coating source material that reaches the surface through the heating of the coating source material by applying the motility to the coating source material uniformity of somewhat curved or invisible parts compared to the physical vapor deposition method Known as an advantageous method for coating. However, chemical vapor deposition also has a problem that it does not uniformly coat the curved portion evenly.

As a conventional technique, Japanese Patent Laid-Open No. 10-2008-063618 provides a vacuum deposition apparatus and a vacuum deposition method. Specifically, under a reduced pressure atmosphere, a support member having a deposition source disposed on an inner circumferential side of a substrate having an inner circumferential surface of the curved surface is charged, the reciprocating movement of the deposition source in an axial direction, and the substrate is rotated about an axis. It includes a rotating means, and the method of heating the deposition source on the inner peripheral surface of the rotating substrate, and coating the inner peripheral surface of the substrate having an inner peripheral surface with a curved surface by using a vacuum deposition apparatus equipped with the heating means deposited do. When coating the inner circumferential surface of the substrate according to the above manufacturing method is useful for coating the inner circumferential surface, but the conventional technique has a problem in that the high temperature is maintained for deposition because the bulk deposition source is used as it is during the coating process. However, the present invention has a difference in that coating can be performed even at a low temperature of less than 1000 ℃ by lowering the density of the deposition source.

In addition, the Republic of Korea Patent Publication 10-2007-0111078 provides a method for coating a nano-material using electron beam irradiation. Specifically, (a) forming a first layer containing an inorganic salt on the substrate; And (b) irradiating an electron beam on the coated substrate obtained in step (a). In the case of coating according to the above coating method, it is possible to produce nano-materials of various sizes and shapes and to coat them in thin film or island form.However, coating method using electron beam irradiation and uniformity in the case of curved or hidden parts There is a problem that is not coated.

Accordingly, the inventors of the present invention, while conducting research to solve the problem of maintaining a high temperature environment in the method of subliming the deposition source and the problem of not uniformly coating the curved portion in the ion beam irradiation method, the density of the deposition source When the coating is performed by sublimation in a lowered state, it was confirmed that uniform coating is possible at low temperature, and the present invention was completed.

An object of the present invention is to provide a method for coating the inner surface of the base material.

Another object of the present invention to provide a base material coated with the interior according to the method.

The present invention to achieve the above object,

Obtaining a coating source material having a reduced density from the coating source material (step 1); And

A step of subliming the coating source material having a reduced density obtained in step 1 and coating the base material by reaching the base material (step 2);

It provides an internal surface coating method of the base material comprising a.

The present invention also provides a base material coated with an inner surface coated according to the above method.

According to the present invention, the method of coating the inner surface of the base material enables the coating of the invisible part including the inner wall of the cylindrical or spherical material, which was not possible with the conventional coating method, and thus the coating of the thermochemical plant for nuclear hydrogen production. It can be applied to the inner wall of cylindrical parts and cylindrical inner walls and joint parts of weapons including cannons or rifles, which greatly improves the wear resistance and corrosion resistance, and gives lubricity to ultimately increase the service life. have.

1 is a schematic diagram showing a method for coating the inner surface of the base material according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing the inner surface coating method of the base material according to Example 1 of the present invention.
3 is a photograph taken of the coating source material of Example 1 with a scanning electron microscope (SEM). (a) is a photograph taken with a scanning electron microscope of a low density silicon carbide coating source material deposited on a Hastelloy X substrate by physical vapor deposition method, and (b) is a coating source material at 5 × 10 ^-5 Torr and 925 ℃ Scanning electron microscope (c) is a photograph taken with a scanning electron microscope of the surface of the alumina boat before coating, (d) is a particle of the coating source material coated on the alumina boat after the coating is completed It is a photograph.
Figure 4 is a graph showing the weight loss rate of the low density silicon carbide coating source material (Example 1) on the substrate according to the vacuum chamber temperature.
FIG. 5 is a graph obtained by analyzing the coating source material of Hastelloy X substrate and the coating source material of alumina boat in Example 1 by X-ray photoelectron spectroscopy (XPS).

The present invention provides a method of coating the inner surface of a base material.

Hereinafter, the present invention will be described in detail.

The present invention comprises the steps of obtaining a coating source material of reduced density from the coating source material (step 1); And

A step of subliming the coating source material having a reduced density obtained in step 1 and coating the base material by reaching the base material (step 2);

It provides an internal surface coating method of the base material comprising a.

Hereinafter, the method for coating the inner surface of the base material according to the present invention will be described in more detail step by step.

First, in the present invention, the step 1 is to obtain a coating source material having a reduced density from the coating source material, it is possible to prepare a low density coating source material film by depositing the coating source material on the substrate using a vapor deposition method. .

By performing step 1, a low density coating source material film is prepared, and thus it is possible to perform a deposition process even at a lower temperature than a conventional deposition temperature.

The method of manufacturing a coating source material having a reduced density may be performed using a vapor deposition method, and as the vapor deposition method, a physical vapor deposition method (PVD) or a chemical vapor deposition method (CVD) may be used. Specifically, sputtering, electron beam evaporation, thermal evaporation, laser molecular beam evaporation and pulse laser evaporation may be used as the physical vapor deposition method, and as a chemical vapor deposition method, an organic metal chemical vapor deposition method (Metal-Organic Chemical Vapor Deposition) may be used. , MOCVD), Hydrogen Vapor Phase Epitaxy (HVPE) and Plasma Enhanced Chemical Vapor Deposition (PECVD) may be used, but electron beam deposition is preferred.

When the electron beam deposition method is used in the step 1, the electron beam irradiation energy is 1 to 30 keV, and the electron beam current is preferably adjusted to 100 mA to 500 mA. If the electron beam irradiation energy is less than 1 keV, a problem may occur that the coating source material film is not formed, and when the electron beam irradiation energy is more than 30 keV, a problem may occur that the physical properties of the coating source material are modified. In addition, if the electron beam current is less than 100 mA, the coating source material may not be melted and the deposition may not be performed. When the electron beam current is irradiated over 500 mA, the coating source material may contain the coating source material. Melting may occur due to the crucible.

In the present invention, the coating source material is preferably used silicon carbide (SiC), tungsten carbide (WC), silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ) and aluminum oxide (Al ₂ O ₃ ). The coating source material generally has a property of decreasing density during deposition, and the degree of decrease in density may vary according to a deposition method. For example, the coating source material has a lower density when the electron beam deposition method is used than the sputtering method because the kinetic energy of the deposited particles is larger than the electron beam deposition method when the sputtering method is used.

In addition, in the present invention, the substrate used in the vapor deposition method is a coating source material can be sublimed well from the substrate when coating the inner surface of the base material, it is preferable to use a metal material having excellent heat resistance even at 700 ℃ ~ 1000 ℃. . Specifically, it is preferable to use Alloy 800H, Alloy 690, Hastelloy X, Hayness230, Hayness556, CX2002U composite, Alloy X750, Alloy 718, Sanicro28, stainless steel, and the like, and more preferably Hastelloy X.

As the step 1 is performed, the density of the coating source material deposited on the substrate is reduced by 20 to 40% from the original density by physical vapor deposition to form a low density coating source material. The low-density coating source material as described above can be coated by vaporizing the material at a relatively low temperature of 1000 ° C. or less than when using a conventional bulk coating source material and is visible to the naked eye including the inner wall of a cylindrical or spherical material. It is possible to effectively coat hidden parts that cannot be counted.

Next, the step 2 is a step of coating the base material by sublimation of the coating source material having a reduced density obtained in the step 1 to reach the base material. Figure 1 illustrates an apparatus for coating the base material inner wall used in the present invention. As shown in FIG. 1, step 2 may be performed by loading a substrate on which a low density coating source material is deposited into a base material mounted in a vacuum chamber.

By carrying out the step 2, it is possible to coat the invisible part including the inner wall of the cylindrical or spherical material such as the bent part of the base material.

In the present invention, the sublimation of step 2 is carried out by sublimation by charging the coating source material obtained in step 1 into the vacuum chamber and heating it, specifically increasing the temperature inside the vacuum chamber and applying a vacuum to the substrate. The coating process is performed by reaching the inner surface of the base material to be coated.

In step 2, the vacuum treatment is preferably controlled to a pressure of 1 × 10 ^-7 Torr ~ 1 × 10 ^-4 Torr. If the vacuum is 1 × 10 ^-4 If Torr is exceeded, a problem may arise that the temperature must be further increased to sublime, and the physical property of the metal material to be coated may change due to the temperature rise.

In addition, the sublimation of step 2 is preferably carried out at a temperature of 700 ℃ to 1000 ℃. If the temperature of the chamber is less than 700 ℃, the sublimation does not occur sufficiently, it is difficult to effectively coat the inside of the base material, if it exceeds 1000 ℃, such as melting, decomposition of low-density coating source material Changes in physical properties may occur. Therefore, it is preferable to perform by adjusting the degree of vacuum so that sublimation may occur at a temperature in the range of 700 ℃ to 1000 ℃.

The sublimation of step 2 is controlled by the temperature and the degree of vacuum, the temperature and the vacuum treatment conditions of the vacuum chamber can be changed within the given range to form the optimum coating conditions, depending on the type and density of the coating source material. Specifically, the heating in the chamber can be controlled low in high vacuum and high in low vacuum to control the sublimation rate of the coating source material.

In another aspect, the present invention provides a base material coated with the interior produced by the above method.

The base material coated with the inner surface coated according to the present invention enables coating of the invisible part including the inner wall of cylindrical or spherical material, which was not possible with the conventional coating method, and thus, wear resistance and corrosion resistance. It can be greatly improved and gives lubricity, which can ultimately increase the service life.

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

Example 1 Coating of Alumina Boat with Silicon Carbide

As a coating source material, 12g of silicon carbide (SiC) in powder form was prepared as a low density coating source material using an electron beam. Specifically, the low density silicon carbide having an electron beam irradiation energy of 6.5 keV and an electron beam current of 200 mA was deposited on the Hastelloy X substrate by irradiating the coating source material on the substrate, and the density was reduced by about 30% than the powdered silicon carbide on the substrate. A film was formed.

The substrate was transferred to an alumina boat and the alumina boat was mounted inside a vacuum chamber. Thereafter, the inside of the vacuum chamber was sealed, and the pressure was reduced to 5 × 10 ⁻⁵ Torr with a rotary pump and gradually heated up to 650 ° C., 750 ° C., 850 ° C. and 925 ° C. using an electric force of 10 kW, and then 925 ° C. The temperature was maintained for 5 hours at, and the coating was performed while observing the change of the inner wall of the alumina boat.

The low density silicon carbide coated source material deposited on the Hastelloy X substrate was transferred to the inner wall of the alumina boat according to the sublimation principle, and due to the characteristics of the low density coated source material, the curved surface and the corner portion of the alumina boat were also It was observed that the coating film was formed uniformly.

Experimental Example 1 Shape Analysis of the Silicon Carbide Coating Source Material Coated on the Alumina Boat

In Example 1, the silicon carbide coated source material coated on the alumina boat was photographed with a scanning electron microscope to obtain a photo as shown in FIG. 3.

3 is a photograph taken with a scanning electron microscope of the silicon carbide coating source material according to Example 1. Figure 3 (a) is a photograph taken with a scanning electron microscope of a low density silicon carbide coating source material deposited on a Hastelloy X substrate using a physical vapor deposition method.

From (a) of FIG. 3, it can be seen that the low density coating source material deposited on the substrate has small amorphous particles of 5 μm or less uniformly dispersed on the substrate as compared with the existing bulk coating source material.

Figure 3 (b) is a photograph taken with a scanning electron microscope of the coating source material at 5 × 10 ^-5 Torr and 925 ℃. As shown in (b) of Figure 3, the heating and vacuum treatment of the coating source material was compared with the shape of (a), it was confirmed that the change to the crystalline particles by the heat, the coating source material as a whole uniform size It was observed that it was maintained.

Figure 3 (c) is a photograph taken with a scanning electron microscope of the surface of the alumina boat before coating. The surface of the alumina boat before coating showed a nonuniform particle distribution.

3 (d) is a photograph of the particles of the coating source material coated on the alumina boat after the coating is completed according to the above method. As shown in (d) of FIG. 3, after the coating was completed, the surface of the alumina boat was confirmed to be evenly coated by the coating source material, and the coating source material was relatively uniform with a size of 1 to 2 μm on average. It was observed that the particles were distributed.

In addition, in Example 1, the silicon carbide coating source material was observed to change to a different color according to the experimental step. Specifically, the low density silicon carbide coating source material on the Hastelloy X substrate changed from yellow to gray as reacted under conditions of 5 × 10 ⁻⁵ Torr and 925 ° C. The reason for the above can be explained by the fact that the silicon carbide, which had an amorphous structure, changed to a crystalline structure as the vacuum and heating processes were performed. In addition, it was confirmed that the coating source material appeared green after the coating was completed on the alumina boat, because the sublimed silicon carbide coating source material was again adhered.

Experimental Example 2 Coating Change of Silicon Carbide Coating Source Material with Temperature Change

In Example 1, when the temperature of the vacuum chamber is gradually heated to 1.5 ° C., 750 ° C., 850 ° C. and 925 ° C. at 1.5 × 10 ⁻⁵ Torr, and heated for 5 hours, the low density silicon carbide coated source material on the Hastelloy X substrate The degree of sublimation of was analyzed by measuring the weight loss.

4 is a graph showing the weight reduction rate of the low density silicon carbide coating source material on the substrate according to the vacuum chamber temperature. According to Figure 4, the weight loss rate of the low-density silicon carbide coating source material at 650 ° C was 0%, it was confirmed that the coating source material is not appropriate to perform the coating because the sublimation of the coating source material does not occur. Subsequently, sublimation occurred from about 700 ° C, and coating started. At 750 ° C, the weight loss was reduced by about 5%, and at 850 ° C, the weight of the coating source material was decreased by about 7%. From the above results, it can be inferred that the coating at 750 ° C. and 850 ° C. should increase the degree of vacuum or the reaction time. In addition, the coating source material showed a weight loss of 30% at 925 ° C. in which the coating reaction proceeded substantially. Based on the results, it was confirmed that 925 ° C. had an appropriate sublimation rate for performing a uniform coating.

Therefore, based on the above analysis results, it was possible to confirm the appropriate temperature to perform the coating in the vacuum chamber.

Experimental Example 3 Composition Analysis of Silicon Carbide Coating Source Material Coated on Alumina Boat

The low-density silicon carbide coating source material on the Hastelloy X substrate prepared in Example 1 and the silicon carbide coating source material coated on the alumina boat were analyzed by X-ray photoelectron spectroscopy to obtain a graph as shown in FIG. 5.

5 is a graph obtained by analyzing the coating source material of the Hastelloy X substrate and the alumina boat in Example 1 by X-ray photoelectron spectroscopy. Figure 5 (a) shows the spectrum of the coating source material coated on the alumina boat, Figure 5 (b) shows the spectrum of the low density silicon carbide coating source material on the Hastelloy X substrate. From FIG. 5, it was confirmed that the composition of the coating source material of the alumina boat had a silicon carbide component. From the results, it was confirmed that the coating source material on the Hastelloy X substrate and the coating source material of the alumina boat had the same composition.

Therefore, the coating source material coated on the surface of the alumina based on the above analysis results was confirmed that the coating source material on the Hastelloy X substrate is formed by sublimation.

Claims (14)

Coating source material selected from the group consisting of silicon carbide (SiC), tungsten carbide (WC), silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ) and aluminum oxide (Al ₂ O ₃ ) through the vapor deposition method Depositing onto a substrate to obtain a coating source material having reduced density (step 1); And
Sublimation by charging and heating the density of the coating source material obtained in step 1 in a vacuum chamber at a temperature of 700 ℃ to 1000 ℃ maintained in a vacuum in the range of 1 × 10 ^-7 Torr ~ 1 × 10 ^-4 Torr The method of claim 1, wherein the base material is coated by reaching the base material (step 2).
delete The method of claim 1, wherein the vapor deposition method is a physical vapor deposition method (PVD) or a chemical vapor deposition method (CVD).
4. The method of claim 3, wherein the physical vapor deposition method is selected from the group consisting of sputtering, electron beam deposition, thermal deposition, laser molecular beam deposition, and pulsed laser deposition.
The method of claim 3, wherein the chemical vapor deposition method is a metal-organic chemical vapor deposition (MOCVD), hydrogen vapor deposition (Hydride Vapor Phase Epitaxy, HVPE) and plasma enhanced chemical vapor deposition (Plasma Enhanced Chemical Vapor Deposition) PECVD), the inner surface coating method of the base material characterized in that it is selected from the group comprising.
The method of claim 4, wherein the physical vapor deposition is performed by an electron beam deposition method, the electron beam irradiation energy is 1 keV ~ 30 keV and the electron beam current is adjusted to 10 mA ~ 500 mA.
delete The method of claim 1, wherein the substrate used in the vapor deposition method is selected from the group consisting of Alloy 800H, Alloy 690, Hastelloy X, Hayness230, Hayness556, CX2002U composites, Alloy X750, Alloy 718, Sanicro28, and stainless steel. Internal surface coating method of the base material to be.
The method of claim 1, wherein the coating source material having a reduced density in step 1 is 20 to 40% less than the original density.
delete delete delete The method of claim 1, wherein the sublimation of step 2 is controlled by temperature and vacuum degree.
An interior coated base material, characterized in that the coating by the method of claim 1.

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