KR20180023500A - Coating layer for improving delamination, method of fabricating the same, and plating equipment using the same - Google Patents

Abstract

The present invention relates to a coating layer having a delamination property, a heat-resisting property, and an erosion-resisting property, a method of fabricating the same, and plating equipment using the same. According to the present invention, the coating layer having a delamination property, a heat-resisting property, and an erosion-resisting property is applied to at least a surface of an object to be treated, and comprises a magnesium oxide.

Description

TECHNICAL FIELD [0001] The present invention relates to a coating layer, a plating layer,

The present invention relates to a molten metal plating technique, and more particularly, to a coating layer having peelability, heat resistance, and corrosion resistance, a method of manufacturing the same, and a plating apparatus using the same.

The plated steel sheet can be produced by immersing the plated steel sheet in a plating solution (for example, molten zinc, molten aluminum) in a plating bath as a non-limiting example of the plating apparatus. At this time, at least a part or the whole of the plating apparatus can be immersed in the plating liquid in the plating bath together with the steel plate. The plating bath generally consists of steel castings and refractory bricks, which may include a snout of stainless steel, a sink roll, and a support roll .

As such, during the plating operation, parts or parts of the plating apparatus such as Snout, sink roll and support roll operate continuously for a long time at a temperature of 400 ° C to 700 ° C in a state immersed in the plating bath. The plating liquid is easily adhered to a part of the plating apparatus immersed during the plating operation and heating and cooling are repeated during the continuous process so that the plating apparatus can be oxidized and / or eroded by the plating liquid. As a result, cleanliness and stable supply of the plating liquid may become difficult during the plating operation.

Therefore, in order to reduce such deterioration, additional operations such as repairing the plating bath, adjusting the plating solution concentration, replacing the plating apparatus, or removing the plating solution attached to the plating apparatus need to be repeatedly performed.

However, since the plating operation is interrupted by such additional work, productivity and work efficiency of the plated steel sheet may be deteriorated. In order to improve the productivity and work efficiency of such a coated steel sheet, the plating apparatus has a peelability that the attached plating liquid easily peels off from the plating apparatus, and has heat resistance and / or corrosion resistance (or corrosion resistance ).

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a coating layer having peelability, heat resistance, and / or erosion resistance in order to increase productivity and work efficiency of a coated steel sheet.

Another technical problem to be solved by the present invention is to provide a method of manufacturing a coating layer having the above-described advantages.

Another object of the present invention is to provide a plating apparatus using a coating layer having the above-described advantages.

According to one aspect of the present invention, a coating layer having a peelable property, a heat resistance property and a corrosion resistance property, which is applied to at least a part of the surface of the object to be treated, includes magnesium oxide.

The coating layer may further include at least one of a different metal oxide of aluminum oxide, molybdenum oxide, and manganese oxide.

In one embodiment, when the coating layer is pure magnesium oxide, the content of magnesium (Mg) is in the range of 40 wt% to 50 wt% with respect to the total weight of the coating layer.

In another embodiment, when the coating layer further comprises a dissimilar metal oxide only of aluminum oxide, the content of magnesium (Mg) is in the range of 30 wt% to 40 wt% with respect to the total weight of the coating layer, ) Is in the range of 2 wt% to 10 wt%.

In another embodiment, when the coating layer further comprises a molybdenum oxide-only dissimilar metal oxide, the content of magnesium (Mg) in the coating layer is in the range of 5 wt% to 15 wt%, and molybdenum (Mo) Is in the range of 25 wt% to 35 wt%.

In another embodiment, when the coating layer further comprises a manganese oxide-only dissimilar metal oxide, the content of magnesium (Mg) in the coating layer is in the range of 10 wt% to 20 wt% Is in the range of 20 wt% to 30 wt%.

Wherein the coating thickness of the coating layer is in the range of 2.1 to 5.2 m, the average center roughness of the coating layer is in the range of 2.3 to 4.0 m, and the contact angle of the coating layer is in the range of 400 to 700 < 150 < / RTI > In some embodiments, the coating amount of the coating layer may be in the range of 0.1% to 5.0% of the total weight of the coating layer and the object to be treated.

The surface of the hot dip galvanizing apparatus is made of stainless steel such as stainless steel SUS201, SUS02, SUS301 to SUS303, SUS303Se, SUS304, SUS304L, SUS304N1, SUS304N2, SUS304LN, SUS304J3, SUS305, SUS309S, SUS310S, SUS316, SUS316L, SUS316J1L, SUS316Ti, SUS317, SUS317L, SUS317LN, SUS317J1, SUS317J4-L, SUS317J5-L, SUS312, SUS347, SUS329J1, SUS329J4-L, SUS405, SUS410L, SUS430, SUS430F, SUS434, SUS444, SUS447J1, SUS403, And may include any one of SUS410, SUS410J1, SUS410F2, SUS416, SUS420J1, SUS420J2, SUS420F, SUS420F2, SUS431, SUS440A, SUS440B, SUS440C, SUS440F, SUS630 and SUS631.

The object to be processed may include a plating apparatus which is immersed in a plating liquid or at least one component constituting the plating apparatus.

According to another aspect of the present invention, a method of manufacturing a coating layer comprises the steps of: preparing a component of a hot-dip coating apparatus; And sputtering at least one metal target material to form a coating layer having releasability, heat resistance and erosion resistance on the surface of the part, wherein the coating layer may comprise magnesium oxide.

In one embodiment, the sputtering may satisfy at least one of the following conditions:

Output power range for sputtering: 50 W to 150 W

Argon (Ar) for the sputtering: oxygen (O ₂₎ gas flow rate (SCCM) ratio range from 15: 0 to 30:10

Substrate temperature range: 200 캜 to 300 캜

Process pressure range: 2.0 mTorr to 10.0 mTorr

The coating layer may further include any one of aluminum (Al), molybdenum (Mo), and manganese (Mn).

In one embodiment, the component of the hot dip apparatus may be immersed by a plating solution comprising either zinc or aluminum.

In one embodiment, the reactivity of the magnesium oxide may be greater than the reactivity of the plating liquid adhered to the hot dip coating apparatus.

In one embodiment, the sputtering can be DC planar diode sputtering, Triode sputtering, Magnetron sputtering, RF sputtering, Ion beam sputtering, and RF magnetron sputtering.

According to another aspect of the present invention, a hot dip coating apparatus includes a coating layer having the releasability, heat resistance and erosion resistance on the surface of the component body or component.

In one embodiment, the component body or component may be a snout, a sink roll, a support roll, a snorkel, a sink roll frame, A metal pump frame, and a brick cover.

According to an embodiment of the present invention, by including magnesium oxide, a coating layer having peelability, heat resistance, and / or erosion resistance can be provided.

Further, according to another embodiment of the present invention, a method of manufacturing a coating layer having the above-described advantages can be provided.

Further, according to another embodiment of the present invention, a plating apparatus using a coating layer having the above-described advantage can be provided.

1A to 1B are coating layers formed on the object to be processed, which have peelability, heat resistance and erosion resistance.
Fig. 2 is a flow chart for explaining a method for producing a coating layer having peelability, heat resistance and erosion resistance.
3A to 3H are measurement results of a hot contact angle based on a temperature change according to an embodiment of the present invention.
4A to 4H are views showing the surface state, peelability and erosion resistance of a sample according to an embodiment of the present invention.
5A to 5H are views showing the surface state of a sample from which foreign substances have been removed after immersion according to an embodiment of the present invention.
6 is a graph showing X-ray diffraction (XRD) analysis results of a sample according to an embodiment of the present invention.
7 is a view showing a plating apparatus using a coating layer according to an embodiment of the present invention.

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

The embodiments of the present invention are described in order to more fully explain the present invention to those skilled in the art, and the following embodiments may be modified into various other forms, It is not limited to the embodiment. Rather, these embodiments are provided so that this disclosure will be more faithful and complete, and will fully convey the scope of the invention to those skilled in the art.

Like numbers refer to like elements in the drawings. Also, as used herein, the term "and / or" includes any and all combinations of any of the listed items.

The terms used herein are used to illustrate the embodiments and are not intended to limit the scope of the invention. Also, although described in the singular, unless the context clearly indicates a singular form, the singular forms may include plural forms. Also, the terms "comprise" and / or "comprising" used herein should be interpreted as referring to the presence of stated shapes, numbers, steps, operations, elements, elements and / And does not exclude the presence or addition of other features, numbers, operations, elements, elements, and / or groups.

Reference herein to a layer formed "on" a substrate or other layer refers to a layer formed directly on top of the substrate or other layer, or may be formed on intermediate or intermediate layers formed on the substrate or other layer Layer. ≪ / RTI > It will also be appreciated by those skilled in the art that structures or shapes that are "adjacent" to other features may have portions that overlap or are disposed below the adjacent features.

As used herein, the terms "below," "above," "upper," "lower," "horizontal," or " May be used to describe the relationship of one constituent member, layer or regions with other constituent members, layers or regions, as shown in the Figures. It is to be understood that these terms encompass not only the directions indicated in the Figures but also the other directions of the devices.

As used herein, the term "plating apparatus" or "plating apparatus" as used herein refers to a mechanical apparatus or a mechanical apparatus for producing a metal plating or a coated steel sheet by immersing a metal or steel sheet to be plated in a plating bath in a plating bath, Refers to an aqueous solution of metal salts used for plating.

In the following, embodiments of the present invention will be described with reference to cross-sectional views schematically illustrating ideal embodiments (and intermediate structures) of the present invention. In these figures, for example, the size and shape of the members may be exaggerated for convenience and clarity of explanation, and in actual implementation, variations of the illustrated shape may be expected. Accordingly, embodiments of the present invention should not be construed as limited to any particular shape of the regions shown herein. In addition, reference numerals of members in the drawings refer to the same members throughout the drawings.

A sink roll, and a support roll, a snorkel, a sink roll frame, a metal pump frame, a brick cover, cover are generally cast from stainless steel (SUS), and at least some of the above-mentioned plating equipment parts can be immersed in the plating solution in the plating bath during the plating operation. Therefore, in the embodiment of the present invention, oxidation and / or erosion of the plating equipment component by the plating solution is reduced, and the plating solution attached to the plating equipment component is easily peeled off. A coating layer having releasability, heat resistance and erosion resistance is formed on the surface of an object such as stainless steel, and a method of manufacturing a coating layer based on optimal deposition conditions of the coating layer can be provided.

1A to 1B are sectional views of an object to be treated 10 including a coating layer 20 having peelability, heat resistance and erosion resistance.

Referring to FIG. 1A, a coating layer 20 having peelability, heat resistance and erosion resistance can be formed on at least a part of the surface of the object to be treated 10. The object to be processed 10 may be any of various materials such as a snout, a sink roll and a support roll of a plating apparatus or a plating facility, a snorkel, a sink roll frame, a metal pump frame, a brick cover, and the like. However, the object to be treated 10 is not limited thereto, and may be a device or a part which is immersed in molten metal or an electrolytic solution in connection with various other plating processes.

The coating layer 20 may include magnesium oxide so as to have peelability, heat resistance and corrosion resistance. In some embodiments of the present invention, the coating layer 20 may further comprise at least one of a different metal oxide of aluminum oxide, molybdenum oxide, and manganese oxide.

In the case where the coating layer 20 is pure magnesium oxide, the magnesium content of the coating layer 20 is in the range of 40 wt% to 50 wt%, and the coating layer 20 is composed of the aluminum oxide- The content of magnesium (Mg) in the coating layer 20 is in the range of 30 wt% to 40 wt%, the content of aluminum (Al) is in the range of 2 wt% to 10 wt% When the coating layer 20 further comprises a molybdenum oxide-only dissimilar metal oxide, the content of magnesium (Mg) in the coating layer 20 is in the range of 5 wt% to 15 wt%, and the content of molybdenum (Mo) (Mg) in the coating layer 20 is in the range of 25 wt% to 35 wt%, and when the coating layer 20 further comprises a manganese oxide-only dissimilar metal oxide, the content of magnesium (Mg) % And the content of manganese (Mn) is in the range of 20 wt% to 30 wt%.

Referring to the evaluation results of releasability and erosion resistance to be described later, the peeling property of the magnesium-based coating film is the most excellent among various thin films. It is considered that the thin film of magnesium oxide component is excellent in peelability against molten Zn due to high reactivity of Mg than Zn. Therefore, when the content of the element to be deposited is the most important for the peelability effect, and additionally the content of the magnesium and magnesium and the other element is deposited in the above-mentioned content range, coating films of other components (for example, SiC, ZnO, SiO ₂ , Si ₃ N ₄ Thin film).

Regarding the properties of peelability, heat resistance and erosion resistance of the coating layer 20, the coating thickness of the coating layer 20 is in the range of 2.1 탆 to 5.2 탆, and the average center roughness of the coating layer 20 is in the range of 2.3 탆 And the contact angle of the coating layer 20 is in the range of 100 ° to 150 ° within a temperature range of 400 ° C to 700 ° C and the coating layer 20 has a length of 100 mm, a width of 50 mm, a thickness of 2 mm Is in the range of 0.1% to 5.0% of the weight of the object to be treated (10).

In an embodiment of the present invention, the deposition thickness and the change in the average center roughness may occur in accordance with the deposition time, the substrate temperature, the gas partial pressure, and the RF power variation, which will be described later. If the thickness and surface roughness of the coating film change due to the change of the deposition conditions, the density, porosity and crystallinity of the coating film may be affected. For example, as the surface roughness is increased and the thickness of the coating film is increased, the contact angle is increased to improve the peelability and / or erosion resistance. Further, as the thickness of the deposition increases, the thermal conductivity of the oxide thin film is lower than that of the metal thin film, do. However, when a large coating film having a large thermal expansion coefficient difference from the substrate is deposited, there is a high possibility that the coating film is separated from the substrate. Therefore, in the embodiment of the present invention, in consideration of the desorption phenomenon of the coating film depending on the deposition thickness, the deposition thickness of the coating layer 20 is in the range of 2.1 탆 to 5.2 탆, and the average center roughness is in the range of 2.3 탆 to 4.0 탆 .

As described above, the factor that has the greatest influence on the peelability, heat resistance and erosion resistance of the thin film against molten zinc is the element component of the coating film. For example, the contact angle is most affected by the reactivity of the coating film to zinc and the surface tension of the coating film. Therefore, in the case of a magnesium-based coating film that has excellent releasability, a magnesium-based oxide film having excellent high-temperature peeling property and a higher reactivity than zinc is formed together with the hetero-element oxide film, and when the molten zinc is adhered to the MgO oxide film coated with SUS, Magnesium is more reactive than molten zinc, which can reduce the rate of reaction to oxidation or erosion of zinc. Therefore, in order to improve the peelability, the heat resistance and the erosion resistance, parameters such as the composition of the coating film and the deposition thickness and surface roughness of the coating film depending on the deposition conditions can be considered.

The coating layer 20 is formed of zinc oxide which is excellent in peeling property at a high temperature and is a magnesium-based oxide which is more reactive than aluminum (Al) used as a plating solution, Even if it is adhered (or adhered) to the coating layer 20, the magnesium-based oxide is more reactive than molten zinc or molten aluminum, so that the rate of oxidation and erosion reaction due to zinc or aluminum can be reduced.

The surface of the object to be processed 10 is made of stainless steel and the stainless steel is made of stainless steel such as SUS201, SUS02, SUS301 to SUS303, SUS303Se, SUS304, SUS304L, SUS304N1, SUS304N2, SUS304LN, SUS304J3, SUS305, SUS309S, SUS310S , SUS316, SUS316L, SUS316J1L, SUS316Ti, SUS317, SUS317L, SUS317LN, SUS317J1, SUS317J4-L, SUS317J5-L, SUS312, SUS347, SUS329J1, SUS329J4-L, SUS405, SUS410L, SUS430, SUS430F, SUS434, SUS444, SUS447J1, , SUS410, SUS410J1, SUS410F2, SUS416, SUS420J1, SUS420J2, SUS420F, SUS420F2, SUS431, SUS440A, SUS440B, SUS440C, SUS440F, SUS630 and SUS631. However, the surface of the object to be treated 10 is not limited to stainless steel. For example, the surface of the workpiece 10 may be carbon steel or alloy steel.

1A shows a coating layer 20 having peelability, heat resistance and erosion resistance which is formed only on the first surface of the object to be treated 10. However, as shown in Fig. 1B, not only the first surface of the object to be treated 10, A coating layer 30 may be further formed on the second surface opposite to the first surface. Since the coating layer 20 and the coating layer 30 have the same characteristics, the description of the coating layer 30 can be referred to the description of the coating layer 20. [ Although the first surface and the second surface are shown to be opposed to each other in Fig. 1B, depending on the type and / or shape of the workpiece 10 (i.e., depending on the part type of the plating apparatus) Two or more surfaces may be included, and two or more coating layers 20 corresponding thereto may be formed on the object to be treated 10. For example, a coating layer may further be formed on the first surface or the third surface and / or the fourth surface perpendicular to the second surface of the object to be treated 10.

As described above, according to the embodiment of the present invention, by forming the coating layer 20 containing the magnesium-based oxide in the thickness range of 2.1 탆 to 5.1 탆 on both sides of the plating apparatus in which the plating bath is immersed in the plating bath, A coating layer having peelability, heat resistance and erosion resistance can be provided. According to the embodiment of the present invention, the coating layer 20 having the peelability, heat resistance and erosion resistance is formed on the material 10 of the plating apparatus to prevent deformation and erosion of the plating apparatus or the plating apparatus by the plating liquid , The delay of the plating process due to the replacement of the plating apparatus or the parts of the plating facility or the additional operation such as removal of the plating liquid attached to the plating apparatus or parts of the plating facility can be minimized. In addition, the problems of peeling, thermal deformation, and component dilution between the coating layer 20 and the object to be treated 10 are reduced based on the optimum conditions of the deposition for the coating layer 20 having peelability, heat resistance and erosion resistance, The maintenance cost of the equipment can be reduced, and the loss caused by the stoppage of the production line can be reduced.

Fig. 2 is a flow chart for explaining a method for producing a coating layer having peelability, heat resistance and erosion resistance.

Referring to FIG. 2, the manufacturing method includes preparing a part to be dipped in a plating apparatus (S10), and sputtering at least one metal target material to form a coating layer having peelability, heat resistance, and erosion resistance on the surface of the part (S20). The coating layer may comprise magnesium oxide. In addition, the coating layer may further include any one of aluminum (Al), molybdenum (Mo), and manganese (Mn). In one embodiment of the present invention, a first coating layer is formed on the basis of magnesium oxide through a first sputtering, and then a second coating layer is formed by sputtering either one of aluminum (Al), molybdenum (Mo), and manganese A second coating layer may be formed on the first coating layer. In another embodiment of the present invention, any one of aluminum (Al) oxide, molybdenum (Mo) oxide, manganese (Mn) oxide and aluminum oxide (Al), molybdenum (Mo), manganese ) And a single coating layer containing magnesium can be formed.

The sputtering may be one of DC planar diode sputtering, Triode sputtering, Magnetron sputtering, RF sputtering, Ion beam sputtering, and RF magnetron sputtering. However, the present invention is not limited thereto, and other deposition techniques capable of forming a homogenized film can be used.

In the embodiment of the present invention, the sputtering can satisfy the following at least one condition range in order that the coating layer 20 has excellent peelability, heat resistance and erosion resistance and is homogenized and deposited on the workpiece 10. The output power for the target is in the range of 50 W to 150 W. For example, if the metal target is magnesium (Mg), the output power is 100 W or 150 W, and the metal target is aluminum (Al), molybdenum (Mo) or manganese (Mn) When the output power is 150 W or more, the deposition rate of the coating film increases and the thickness of the final coating film increases. At this time, the metal content in the coating film increases and the density and crystallinity of the final coating layer can be determined. This is because an increase in the metal content of the coating film may deteriorate performance against peelability, heat resistance, and erosion resistance, and may cause a desorption phenomenon of the coating film when the deposition thickness is large. Further, when the output power is reduced to 50 W or less, the deposition rate of the coating film is decreased and the deposition thickness is decreased. Therefore, as the output power decreases, the density and crystallinity of the metal components contained in the coating film due to the O ₂ gas flow are reduced. Therefore, if the output power is 50 W or less, the thickness and density can be reduced, and the peelability, heat resistance and erosion resistance can be reduced.

Argon (Ar): the proportion of oxygen (O ₂₎ gas flow rate (unit: sccm Im) is 15: may be in the range of 10: 0-30. The argon (Ar) is an inert gas and can be used to activate the chamber in a plasma state to deposit a target element of the material to be deposited to the substrate. In an embodiment of the present invention, the inert gas is not limited to argon and other inert gases may be utilized. For example, the inert gas may be any one of neon, krypton, and helium. Further, as the argon gas supply is increased, the working pressure in the vacuum chamber increases and the deposition rate is improved. In addition, Ar: O ₂ In the gas flow rate ratio, the oxygen (O ₂ ) flow rate greatly affects the crystallinity of the coating film, and as the O ₂ gas flow rate increases, the crystallinity decreases, the density decreases, and the pore increases. Therefore, Ar: O ₂ The physical properties of the coating film vary depending on the gas flow rate. As the flow rate of the O ₂ gas increases, the density decreases and the pore increases, which is advantageous in heat resistance. However, as the porosity increases, the surface roughness increases and the specific surface area increases. Accordingly, when the molten zinc is in contact with the coating film, the contact area increases, and the erosion resistance and peelability may decrease.

The substrate temperature ranges from 200 캜 to 300 캜, and the operating pressure ranges from 2 mTorr to 10 mTorr. The temperature of the substrate affects the degree of crystallization of the thin film, and as the temperature increases, the density and crystallinity may increase. And, the working pressure increases the pressure in the chamber, and the pressure parameter together with the temperature parameter is related to the deposition rate of the coating film. Also, as the operating pressure increases, the thickness and surface roughness of the coating film increase. As the thickness of the coating film increases, the heat resistance increases. When the surface roughness increases, the contact angle increases and the peelability and erosion resistance increase. However, if the operating pressure increases beyond the above-mentioned range, the deposition element may not reach the substrate and the deposition rate may be rather reduced, thereby possibly changing the coating film component content. Therefore, an optimum operating pressure condition is required, and if the temperature is outside the range of the above-mentioned substrate temperature and operating pressure, the properties of peelability, heat resistance and erosion resistance can be deteriorated.

In an embodiment of the present invention, the parts of the plating apparatus may be immersed in a plating solution containing either zinc or aluminum. However, the present invention is not limited thereto, and the parts of the plating apparatus may be immersed in a plating solution containing brass, copper, or silver.

By satisfying the above-mentioned at least one conditional range, a coating layer having the effects of excellent peelability, heat resistance and corrosion resistance with the plating solution can be formed. In addition, the coating layer 20 of the present invention has a uniform shape on the surface 10 of the component to be dipped in a large-area plating apparatus and has a characteristic of a high melting point, but can be made thin at a relatively low temperature.

In the embodiment of the present invention, in order to reduce the zinc plating liquid adhered to the plating apparatus or the plating apparatus immersed in the plating bath, excellent releasability to molten zinc at an operating temperature range of 450 캜 to 530 캜 of the plating facility is required. For this purpose, the surface tension of the coating layer 20 must be high. Here, the surface tension is proportional to the contact angle, and the higher the surface tension, the higher the contact angle between the coating layer 20 and the zinc plating liquid. In addition, the difference in thermal expansion coefficient between the object to be processed 10 and the coating layer 20 should be small to prevent the coating layer 20 from being desorbed, so that excellent heat resistance and resistance to erosion resistance to the plating liquid can be maintained.

For example, the thermal expansion coefficient of the SUS 316L substrate is 17.2 x 10 < -6 > / K and the thermal expansion coefficient of the magnesium series coating film is in the range of 8 x 10-6 / K to 10 x 10-6 / K. Therefore, compared with general thermal expansion coefficients (SiO 2 (0.5 × 10 -6 / K), Si 3 N 4 (3.3 × 10 -6 / K) and SiC (4.0 × 10 -6 / K)) of the oxide, nitride and carbide coating films, The difference between the coefficient of thermal expansion of the series coating film and that of the SUS substrate is small, so that the separation of the coating film can be prevented even in long-term use. Therefore, the thermal expansion coefficient of the coating film may be at least 0.8 x 10 < -5 > / K to prevent the coating film from being desorbed for a long time.

In an embodiment of the present invention, the contact angle of the coating layer 20 to molten zinc may be at least 130 ° at 520 ° C, the facility operating temperature. The amount of zinc adhered to the coating layer 20 is within 3% of the weight of the object 10 including the coating layer 20. When the object 10 including the coating layer 20 is continuously used in the plating process, May be maintained within a range of 1% of the length of the object to be treated 10 including the coating layer 20 before use.

Experimental Example :

It is possible to form a thin film evenly on a large area in order to form the coating layer 20 on the object to be processed 10 and to make a material having a high melting point thinner at a low temperature and to make most materials such as ceramics, An RF magnetron sputter deposition method was used. Table 1 below shows the detailed deposition conditions of the coating layer 20 deposited on various substrates 10 based on RF magnetron sputtering and the deposition thickness and average center roughness of the coating layer 20 depending on the result. In Table 1, Example 1 and the SUS316L having a coating layer 20 containing the MgO, the second embodiment is SUS316L having a coating layer 20 containing the MgO and Mo ₃ O, the third embodiment is MgO and Al ₂ O, and Example 4 is SUS 316L having a coating layer 20 comprising MgO and MnO. Comparative Example 1 and pure SUS316L without a coating layer 20, and Comparative Example 2 is a SUS316L having a coating layer 20 including MnO, Comparative Example 3 is SUS316L having a coating layer 20 including the Si ₃ N ₄ And Comparative Example 4 is SUS316L having a coating layer 20 containing SiC.

Sample Type Output (W) of target 1 The output (W) of the target 2 Ar / O ₂ gas partial pressure (sccm) Substrate temperature
(° C) Working pressure
(mTorr) Deposition thickness
(μm) Average center roughness (nm) Comparative Example 1 SUS316L - - - - - - 22.3 Example 1 MgO Mg 100 - 24/6 250 7.0 2.1-3.1 2.3 Example 2 MgO: Mo ₃ O Mg 100 Mo 50 24/6 250 7.0 4.2-5.2 3.6 Example 3 MgO: Al ₂ O Mg 100 Al 50 24/6 250 7.0 4.1-5.1 3.8 Comparative Example 2 MnO Mn 150 - 24/6 250 7.0 3.2-4.1 4.7 Example 4 MgO: MnO Mg 100 Mn 50 24/6 250 7.0 4.1-5.2 4.0 Comparative Example 3 Si ₃ N ₄ Si 150 - 20/2 (N ₂ ) 200 2.5 1.2-3.5 1.4 Comparative Example 4 SiC SiC 100 - 24/0 200 2.0 1.2-3.6 1.8

Referring to Table 1, the detailed deposition conditions for the RF magnetron sputtering are as follows: the plasma output range for the first target is 100 W to 150 W; and the plasma output for the second target (e.g., Mo, Al, Mn) W, an argon (Ar): oxygen (O ₂₎ gas flow rate ratio of 24: 6 sccm, and the substrate temperature is from 250 ℃, operating pressure 7.0 mTorr having the coating layer 20 in this condition is the above the first surface 1 on the second surface opposite to the surface of the object to be treated 10 with a thickness of 1 m to 5 m. In addition, Si ₃ N ₄ and SiC evaluation of such a nitride or carbide films is also added to the coating layer formed on the Si ₃ N ₄ and SiC in order to proceed with, wherein an argon (Ar): oxygen (O ₂₎ gas flow rate ratio May be 20: 2 sccm or 24: 0 sccm.

The deposition thickness of the coating layer 20 was measured using a surface profiler (Alpha step 500, KLA Tencor). The surface roughness of the coating layer 20 was measured using an atomic force microscope (XE-BiO, Park system) was used to measure the average roughness average (Ra) in the range of 10 μm × 10 μm. In comparison 1, in the case of SUS316L which is the material of the general plating equipment or parts, the Ra value is 22.3 nm and the surface roughness is poor. On the other hand, in the case of the coating layer 20 deposited by vacuum equipment from at least 1.2 μm to a maximum of 5.2 μm, the average center roughness was 1.4 to 4.7 nm, and uniform surface roughness was secured. If the surface roughness value of the sample immersed in the molten plating solution is increased, the specific surface area at which the plating solution can contact the sample is increased, and the reactivity with the plating solution is increased to increase the erosion. Therefore, when the coating layer 20 is formed, based on the RF magnetron sputtering, a uniform surface state can be obtained, so that the reactivity with the plating liquid can be reduced.

3A to 3H are measurement results of a hot contact angle based on a temperature change according to an embodiment of the present invention. 3A to 3H show measurement results of the contact angle of the samples according to Examples 1 to 4 and Comparative Examples 1 to 4 of Table 1 described above. FIG. 3A shows a result of measurement of a high temperature contact angle of Comparative Example 1, FIG. 3B shows a result of measurement of a high temperature contact angle of Example 1 containing only magnesium oxide, FIG. 3C shows a result of measurement of a high temperature contact angle of Example 2 containing magnesium oxide and molybdenum oxide FIG. 3E shows the results of measurement of the contact angle at a high temperature of Comparative Example 2 containing only manganese oxide, FIG. 3F shows the results of measurement of the contact angle of magnesium oxide and manganese oxide FIG. 3G shows the results of the measurement of the hot contact angle of Comparative Example 3 containing Si ₃ N ₄ , and FIG. 3H shows the results of the hot contact angle measurement of Comparative Example ₄ containing SiC. In the present invention, the solid surface corresponds to the surface of the coating layer 20 formed on the workpiece 10 or the workpiece 10, and the surface of the liquid is in contact with the surface of the workpiece 10, And corresponds to the surface of the plating liquid adhered to the object to be processed 10. As the surface tension at the solid surface is larger, the liquid exists in a spherical shape and the contact angle becomes larger. As the surface tension becomes smaller, the liquid exists in a non-spherical shape, and the contact angle can be reduced.

3A to 3H, the contact angles of molten zinc measured in the range of 472 to 520 ° C, which is the operating temperature of a plating component immersed in molten zinc in a plating bath, The contact angle of MgO: Mo ₃ O of Example 2 was 136 占 and the contact angle of MgO: Al (MgO: Al) of Example 3 was 89 °, ₂ O has a contact angle of 132 °, and the MgO: MnO 2 contact angle of Example 4 is 130 °. It can be seen that the peelability is improved due to the coating layer 20 formed on the samples of Examples 1 to 4 since the contact angles of Examples 1 to 4 are larger than the contact angle of Comparative Example 1. [ In particular, when the temperature is increased up to 700 ° C., the contact angle is reduced to 19 ° in the case of Comparative Example 1, but MgO and the different oxide elements (Mo ₃ O, Al ₂ O, MnO) The contact angle shows a small change in the contact angle within the range of 112 to 129 degrees. This means that the coating layer 20 has excellent heat resistance and / or erosion resistance as well as peelability.

 Table 2 below shows the hot contact angle of the samples according to temperature in Examples 1 to 4 and Comparative Examples 1 to 4.

Symbol of kind High contact angle 423 ° C 472 ° C 520 ° C 700 ° C SUS316L 128 ° 101 ° 89 ° 19 ° MgO 134 ° 133 ° 130 ° 112 ° MgO: Mo ₃ O 141 ° 139 ° 136 ° 129 ° MgO: Al ₂ O 139 ° 137 ° 132 ° 124 ° MnO 130 ° 111 ° 108 ° 101 ° MgO: MnO 135 ° 132 ° 130 ° 113 ° Si ₃ N ₄ 123 ° 122 ° 119 ° 105 ° SiC 129 ° 125 ° 120 ° 112 °

4A to 4H are views showing the surface state of the sample, the peelability and the erosion resistance against molten zinc according to the embodiment of the present invention. 4A is a view showing the surface state (A), the peelability (B) and the erosion resistance (C) of the SUS sample against molten zinc. FIG. 4B shows the surface state (A) (B), and a chart showing the abrasion resistance (C) of the molten zinc, Figure 4c Mgo + Mo ₃ O surface condition of the sample (a), including the coating layer, peeling resistance (B), abrasion resistance to the molten zinc (C) drawing and, Figure 4d is a schematic diagram showing an abrasion resistance (C) of the surface state (a), releasable (B), the molten zinc in the sample, including the Mgo + Al ₂ O coating layer, showing the Fig. 4E is a view showing the surface state (A), the peelability (B) and the erosion resistance (C) of the sample including the MnO coating layer and the erosion resistance (C) against the molten zinc. FIG. 4F shows the surface state of the sample including the Mgo + ), Peelability (B), and erosion resistance (C) against molten zinc. Fig. 4G is a graph showing Si ₃ N ₄ (A), the peelability (B), and the erosion resistance (C) against molten zinc. FIG. 4H is a graph showing the surface state (A), the peelability B), and erosion resistance (C) against molten zinc.

Figures 4a Referring to Figure 4h, embodiments of the result of the surface condition (A), releasable (B), abrasion resistance (C) of the molten zinc of samples Example 2 MgO of: Mo of ₃ O and Example 3 MgO : It can be seen that the sample state of the Al ₂ O coating layer is excellent.

The contact angle is a measure of the wettability of a solid surface. The higher the surface tension, the more the contact angle increases. The surface tension may vary depending on the elemental composition of the coating layer 20 and the surface condition. For example, the contact angle for the coating layer 20 comprising MgO and the heteroatom (Mo ₃ O, Al ₂ O) can be increased due to the high surface tension as compared to SUS 316 L of Comparison 1, which is associated with improved peelability .

In addition, the reactivity to the materials increases in the order of Mg> Zn> Al> Fe> Cu> SUS> Si> Pt. For example, the reactivity of Mg is larger than that of other elements, and the reactivity of Pt is smaller than that of other elements. Therefore, when zinc is used as the plating solution, when the reactivity of Zn is high and the Zn continuously reacts with stainless steel (SUS) in a molten state at high temperature, a Zn oxide film is formed, The volume of the Zn oxide film increases and molten Zn penetrates through the Zn oxide film to the interface of SUS to form a Zn alloy layer. Further, cracks are formed on the surface of the stainless steel (SUS) with the Zn alloy layer formed thereon, and the state of the stainless steel may become poor due to breakage and peeling of the Zn oxide film. This can be seen as a result of poor erosion resistance.

However, in an embodiment of the present invention. In the case of the coating layer 20 of MgO: Mo ₃ O and MgO: Al ₂ O having peelability, heat resistance and erosion resistance as shown in Figs. 4B to 4C, the coating layer 20 having excellent peeling property at a high temperature, Magnesium oxide is more reactive than molten zinc so that the rate of oxidation or erosion reaction by zinc can be reduced even if molten zinc (Zn) is deposited on the coating layer 20 containing SUS, MgO, have.

Conventionally, when a nitride or a carbide thin film is formed through spray coating, the surface condition is excellent, but the erosion resistance against molten zinc is confirmed to be poor. This is because the zinc penetrates into the SUS through the thin film which is less reactive than the molten zinc. In particular, the metal component which is easily formed by the coating of the nitride and the carbide thin film forms the alloy with the molten Zn to facilitate the diffusion of Zn, The surface state may become poor. Among various methods for increasing the peelability of the object to be treated 10 and molten zinc (Zn), a material having a high surface roughness and a high porosity exhibits a higher contact angle. However, as the porosity and pore size increase, the thin film peeling phenomenon also increases due to the increase in the SUS, and when the surface roughness increases, the contact area with the hot zinc plating solution increases and the thin film and zinc (Zn) There is a fear that the reactivity of the catalyst may increase.

5A to 5H are views showing the surface state of a sample from which foreign substances have been removed after immersion according to an embodiment of the present invention. Figure 5a is a SUS316L sample is immersed in molten zinc for one week, Fig. 5b is immersed in molten zinc for a sample that contains a SiC coating layer is immersed in molten zinc for a week, Figure 5c 1 shares Si ₃ N ₄ 5D is a sample containing a MgO coating layer immersed in molten zinc for 12 weeks or more, FIG. 5F is a sample containing a MnO coating layer immersed in molten zinc for 2 weeks, FIG. a and the MgO and the sample, including a coating layer containing the Mo ₃ O dipping, also 5g is a sample, including a coating layer containing the MgO and Al ₂ O immersed in more than 12 weeks the molten zinc, and Fig. 5h at least 8 weeks molten zinc And a coating layer containing MgO and MnO.

5A to 5H, the sample itself is eroded or cut by most of the molten zinc, and the surface state is mostly poor. Particularly, the sample including the MnO coating layer immersed in the molten zinc is cut by the diffusion of zinc (Zn) to a specific part, and the surface condition is poor. On the contrary, the MgO-based samples of FIGS. 5E to 5H maintain the shape over 12 weeks, and the zinc plating solution can be easily removed. Therefore, when samples (for example, Figs. 5E to 5H) including a MgO-based coating layer having a high contact angle at a high temperature and excellent corrosion resistance are applied to parts of a plating apparatus or a plating apparatus, oxidation and erosion of the plating liquid are prevented It is possible to maintain the cleanliness of the plating solution and securing the durability of the plating equipment to ensure the continuity of the plating process, thereby ensuring price competitiveness in the production of the coated steel sheet. In some embodiments, the coating layer is peeled off from the sample from which the zinc plating solution has been removed, and a new coating layer is re-formed on the sample and is usable again.

The following Table 3 shows the results obtained by immersing a sample of SUS (length 100 mm, width 50 mm, thickness 2 mm) containing the conventional SUS316L sample and the MgO-based coating layer having the peelability of the present invention in molten Zn in the plating bath, The coating amount of hot dip galvanizing was confirmed by the method of KS D 0201 (2011). The adhesion amount of zinc plating was confirmed by measuring the mass of zinc eluted with antimony trichloride solution. In the case of the SUS316L sample, the adhesion amount of the hot-dip galvanized coating was 11,568 g / m < ² > relative to the sample weight. On the other hand, in the case of the SUS sample including the MgO-based coating layer having the releasability of the present invention, ) Was 418 g / m < ² > and about 2.8% of the sample weight was adhered to confirm the peeling effect of the SUS sample including the MgO-based coating layer.

Sample Type Coating amount of hot dip galvanized (g / m ² ) SUS316L sample SUS samples containing MgO-based coating layers Total Area 11,568 (77.0%) 418 (2.8%) Immersion area 22,231 2,884

FIG. 6 is a diagram showing XRD (X-Ray Diffraction) analysis results of a sample according to an embodiment of the present invention. SUS316L Sample and MgO coating layer of a series of XRD analysis result _{(MgO, MgO: Mo 3 O} , MgO:: Al 2 O, MgO MnO).

Referring to FIG. 6, in the case of a sample coated with another oxide film containing a different element (for example, Mo ₃ O, Al ₂ O, MnO) together with the MgO oxide film, MgO, Mo ₃ O, Al ₂ O, or MnO < / RTI > It is also confirmed that MgO, Mo ₃ O, Al ₂ O, or MnO does not exist in the form of a metal in the coating layer, thereby preventing diffusion of Zn by alloying with molten Zn, thereby reducing reactivity of molten Zn and improving corrosion resistance I could. That is, when the coating layer is present in the form of a metal, the molten zinc and the metal of the coating layer are easily alloyed by the weak metal bond, and the molten zinc component diffuses into the substrate through the interface between the coating layer and the coating layer- There is a possibility that an alloy layer is formed due to an increase in reactivity and cracks are generated. However, when the coating layer is formed of a magnesium-based oxide thin film having a higher reactivity than molten zinc, when the zinc oxide is coated on the SUS coated MgO oxide, the magnesium is more reactive than the molten Zn to decrease the rate of oxidation and erosion reaction of Zn Erosion can be improved.

Table 4 below shows the dimensional changes (length, width, thickness) of SUS samples including the MgO-based coating layer at the working temperature of molten Zn and Al using a contact type three-dimensional measuring instrument (Duckin, VICTOR 121510N). It is confirmed that the dimensional change of the sample after continuous use at the working temperature is about 0.1% and the heat resistance at the working temperature is secured together with the peeling effect, so that it is applicable to the equipment immersed in the plating solution.

Symbol of kind Dimensional change Temperature (500 ° C) Variation Temperature (700 ° C) Variation Length 0.01 mm 0.01% 0.01 0.01% width 0.01 mm 0.02% 0.04 0.08% thickness 0.002 mm 0.1% 0.001 0.05%

7 is a view showing a plating apparatus using a coating layer according to an embodiment of the present invention.

Referring to Fig. 7, the plating apparatus or the plating apparatus may include a plating bath 1, a snout 4, a sink roll 6, a collect roll 7, and a stirrer roll 7. The plating bath 1 is filled with zinc or an aluminum plating solution 2 and the steel sheet 5 is immersed in the plating solution 2 through the Snart 4 during the plating process. Thereafter, a sink roll 6 is provided to change the direction of the steel strip 5, and a collect roll 7 and a stirrer roll 7 are provided on the upper side of the sink roll 6, (2). An air knife 8 may be provided on the upper part of the plating bath 1 and a heating device 3 may further be provided on the outer side wall of the plating bath 10. [ Here, the plating bath 1 is operated at a temperature condition of 400 to 700 ° C as required. In this case, there is no external interference due to heat loss on the wall surface of the plating bath 1 and heat loss on the surface of the plating liquid 2 The temperature of the plating bath 1 may be lowered. If the temperature of the plating bath 1 is lowered, there is a high risk that the top dross 9 will adhere to the steel sheet and the plating characteristics may be deteriorated. Therefore, in order to maintain proper plating conditions, 1) may be periodically heated.

As described above, in the plating process, some parts of the plating apparatus or the plating apparatus 100, such as the swath 4, the sink roll 6, the collect roll 7 and the stabilizer roll 7, The plating solution 2 can be immersed in the plating solution 2 in the plating solution 2, so that some of the components can be plated with the plating solution 2 together with the steel sheet 5. However, some of these parts with the plating liquid 2 attached may be oxidized and / or eroded due to repeated heating and cooling during the continuous process. Also, the cleanliness and stable supply of the plating liquid 2 may become difficult during the plating operation. Therefore, in order to reduce such a performance deterioration, it is necessary to repair the plating bath 1, adjust the concentration of the plating solution 2, and control some parts such as the swath 4, the sink roll 6, the collect roll 7 and the stirrer roll 7 Such as the removal of the plating liquid 2 attached to some parts such as the swath 4, the sink roll 6, the collect roll 7 and the stirrer roll 7 need to be repeatedly performed .

The sink roll 4, the sink roll 6, the collect roll 7, and the conveyor roll 7 in order to improve the productivity and the work efficiency of the coated steel sheet in the embodiment of the present invention, based on FIGS. 1A, 1B, The plating solution 2 attached to the surface of some parts such as the surface layer 3 and the stabilizer roll 7 is easily peeled off from the parts and the heat resistance and / Coating layers 20 and 30 having corrosion resistance) are formed.

In the present invention, the plating process is based on a solution metal immersion plating in which a steel plate is put in a plating bath in which a metal to be attached to a surface is melted and a solution is adhered to the surface and then solidified by solidification. However, the present invention is not limited to dissolving metal immersion plating, but may also be applicable to spraying spray plating, electroplating, and deposition plating.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It will be clear to those who have knowledge.

10: 20, 30: Coating layer

Claims (20)

A coating layer having peelability, heat resistance and erosion resistance which is applied to at least a part of a surface of an object to be treated,
A coating layer comprising magnesium oxide. The method according to claim 1,
Wherein the coating layer comprises:
Wherein the coating layer further comprises at least one of a different metal oxide of aluminum oxide, molybdenum oxide, and manganese oxide. The method according to claim 1,
Wherein when the coating layer is pure magnesium oxide, the content of magnesium (Mg) is in the range of 40 wt% to 50 wt% with respect to the total weight of the coating layer. 3. The method of claim 2,
(Mg) in the coating layer is in the range of 30 wt% to 40 wt%, and the content of aluminum (Al) in the coating layer is in the range of 2 wt% to 10 wt%. 3. The method of claim 2,
The content of magnesium is in the range of 5 wt% to 15 wt%, the content of molybdenum (Mo) is less than 25 wt%, the content of magnesium is in the range of 5 wt% to 15 wt%, and the content of molybdenum (Mo) To 35 wt%. 3. The method of claim 2,
The content of manganese (Mn) is in the range of 10 wt% to 20 wt%, the content of manganese (Mn) is less than 20 wt%, and the content of manganese (Mn) To 30 wt%. The method according to claim 1,
Wherein the coating thickness of the coating layer is in the range of 2.1 占 퐉 to 5.2 占 퐉. The method according to claim 1,
Wherein the average center roughness of the coating layer is in the range of 2.3 탆 to 4.0 탆. The method according to claim 1,
Wherein the coating layer has a contact angle ranging from 100 DEG to 150 DEG within a temperature range of 400 DEG C to 700 DEG C. The method according to claim 1,
Wherein the coating amount of the coating layer is in a range of 0.1% to 5.0% of the total weight of the coating layer and the object to be treated. The method according to claim 1,
The surface of the hot dip coating apparatus is made of stainless steel (SUS)
The stainless steel may be selected from the group consisting of SUS201, SUS02, SUS301 to SUS303, SUS303Se, SUS304, SUS304L, SUS304N1, SUS304N2, SUS304LN, SUS304J3, SUS305, SUS309S, SUS310S, SUS316, SUS316L, SUS316J1L, SUS316Ti, SUS317, SUS317L, SUS317LN, SUS317J1, SUS317J5-L, SUS312J, SUS347, SUS329J1, , SUS440A, SUS440B, SUS440C, SUS440F, SUS630 and SUS631. The method according to claim 1,
Wherein the object to be processed comprises a plating apparatus immersed in a plating liquid or at least one component constituting the plating apparatus. Preparing a component of the hot dip coating apparatus; And
And sputtering at least one metal target material to form a coating layer having releasability, heat resistance and erosion resistance on the surface of the part,
Wherein the coating layer comprises magnesium oxide. 12. The method of claim 11,
In the sputtering,
Wherein the output power for the sputtering is within a first range of 50 W to 150 W,
The range of the gas flow rate (SCCM) ratio of argon (Ar): oxygen (O ₂ ) for the sputtering is within a _second range of 15: 0 to 30:10,
The substrate temperature is in the third range of 200 DEG C to 300 DEG C, and
Wherein the process pressure is performed within a range of at least one of the above ranges within a fourth range of 2.0 mTorr to 10.0 mTorr. 14. The method of claim 13,
Wherein the coating layer further comprises one of aluminum (Al), molybdenum (Mo), and manganese (Mn). 14. The method of claim 13,
Wherein the component of the hot dip coating apparatus is immersed by a plating liquid containing any one of zinc and aluminum. 14. The method of claim 13,
Wherein the reactivity of the magnesium oxide is greater than the reactivity of the plating liquid adhered to the hot dip coating apparatus. 14. The method of claim 13,
Wherein the sputtering is any one of DC planar diode sputtering, triode sputtering, magnetron sputtering, RF sputtering, ion beam sputtering, and RF magnetron sputtering. On the surface of the component body or part
A hot-dip coating apparatus comprising a coating layer having peelability, heat resistance and erosion resistance according to claim 1. 20. The method of claim 19,
The component body or part may comprise at least one of a snout, a sink roll, a support roll, a snorkel, a sink roll frame, a metal pump frame a metal pump frame, and a brick cover.

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