KR20190041747A - SURFACE MODIFICATION METHOD FOR TiO2 SiO2 HYBRID COATING BY ION BEAM MIXING AND LAMINATE STRUCTURE MANUFACTURED BY USING SAME - Google Patents

Abstract

The present invention relates to a surface modification method by heavy ion irradiation. More specifically, the surface modification method for TiO_2-SiO_2 hybrid coating includes: a step of preparing a base metal; a step of coating the surface of the base metal with a coating material containing a TiO_2 sol solution or a TiO_2-SiO_2 hybrid sol solution; a step of exposing the coated surface of the base metal to a heavy ion beam generated by a heavy ion beam irradiation device; and a step of coating the surface of the coated base metal radiating the heavy ion beam with a second coating material. A level of energy of the heavy ion beam is equal to or greater than 1 MeV. According to the present invention, the surface modification method for TiO_2 coating or TiO_2-SiO_2 hybrid coating by heavy ion irradiation can improve heat stress at high temperature, corrosion resistance, and adhesion performance of coating.

Description

TECHNICAL FIELD The present invention relates to a surface modification method of a TiO 2 SiO 2 hybrid coating by a heavy ion beam irradiation and a laminate prepared by using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface modification method for a TiO 2 SiO 2 hybrid coating,

The present invention relates to a surface modification method of a TiO ₂ coating or a TiO ₂ -SiO ₂ hybrid coating by irradiation with a heavy ion beam and a laminate manufactured using the same, more preferably a step of preparing a base material; Coating a coating material comprising a TiO ₂ sol solution or a TiO ₂ -SiO ₂ hybrid sol solution on the surface of the base material; And exposing the coated base material surface to a heavy ion beam generated from the heavy ion beam irradiator, wherein the energy of the heavy ion beam is TiO ₂ coating or TiO ₂ -SiO ₂ hybrid coating by heavy ion beam irradiation of 1 MeV or more To a method for modifying the surface of a substrate.

Pre-oxidation technology, Pt / TiO ₂ coating technology, ceramic chemical vapor deposition (CVD), and plasma spray technology are used as technologies to prevent material deterioration by forming a protective coating on reactor structure and system surface. However, the adhesion to base metal was insufficient and there was no significant progress.

Ion beam mixing is a technology to improve the bondability of the coating by forming a homogeneous intermediate coating layer in which a coating material and a metal base material are mixed by utilizing an ion beam. The use of this technology is expected to improve coating cracking and corrosion resistance due to thermal expansion.

However, in the prior art, ion beam mixing was induced by irradiating an ion beam of 50 to 500 keV, but in this case, it was difficult to obtain a large mixing effect.

Therefore, the inventors of the present invention have developed a technology to combine a new concept of sol-gel TiO ₂ coating and a hybrid TiO ₂ -SiO ₂ coating material with an ion mixing surface modification technique through ion beam irradiation, And has reached the present invention in which prevention of corrosion deterioration of the surface of a nuclear power plant is expected.

Korean Patent No. 1052036 (Registration date: July 20, 2011)

It is an object of the present invention to provide a laminate having improved thermal stress, corrosion resistance and coating adhesion at high temperatures.

Another object of the present invention is to provide a method for surface modification of a TiO ₂ -coated or TiO ₂ -SiO ₂ hybrid coating by a heavy ion beam irradiation which can more effectively produce such a laminate.

A TiO ₂ -coated or TiO ₂ -SiO ₂ hybrid-coated surface modification method according to a preferred embodiment of the present invention comprises: preparing a base material; Coating a coating material comprising a TiO ₂ sol solution or a TiO ₂ -SiO ₂ hybrid sol solution on the surface of the base material; And exposing the coated base material surface to a heavy ion beam generated from the heavy ion beam irradiator, wherein the energy level of the heavy ion beam is 500 KeV or more, preferably 1 MeV or more, more preferably 2 to 40 MeV .

The elements used in the heavy ion beam irradiating apparatus include iron (Fe), iodine (I), tungsten (W), copper (Cu), silicon (Si), argon (Ar), gold (Au) Titanium (Ti), and a mixture of one or more thereof.

The dose of the heavy ion beam may be from 50 uC to 10,000 uC, the current applied to the heavy ion beam irradiator may be from 0.01 μA to 1 μA, and the exposure time of the heavy ion beam may be from 1 minute to 2 hours.

The step of exposing to the heavy ion beam can be carried out one or more times, and when the step of exposing to the heavy ion beam is performed twice or more, the step of exposing the coated base material surface to the heavy ion beam, And coating a second coating material on the surface of the base material.

The second coating may be a TiO ₂ sol solution or a TiO ₂ -SiO ₂ hybrid sol solution.

The base material may be any of metals selected from 304 stainless steel, Alloy 800H, Alloy 690, Hastelloy X, Hayness 230, Hayness 556, CX2002U, Alloy X750, Alloy 718, Sanicro28 and composites thereof.

Further, according to another preferred embodiment of the present invention, the metal base material; A mixed interface layer including a metal component of a metal base material and a TiO ₂ component or a TiO ₂ -SiO ₂ hybrid component; And a TiO ₂ coating layer or a TiO ₂ -SiO ₂ hybrid coating layer laminated on the mixed interface layer.

The mixed interfacial layer may be formed of at least one of Fe, I, W, Cu, Si, Ar, Au, Al, Oxygen (O), and one or more elements selected from the group consisting of a mixture of one or more of these elements, and may have a thickness of 1 to 200 nm.

The surface modification method of TiO ₂ coating or TiO ₂ -SiO ₂ hybrid coating by heavy ion beam irradiation of the present invention can improve the thermal stress, corrosion resistance and bonding property at high temperature of the coating.

1 is a flowchart of a surface modification method of TiO ₂ coating or TiO ₂ -SiO ₂ hybrid coating by heavy ion beam irradiation of the present invention.
2 is a photograph of the heavy ion beam irradiating apparatus of the present invention.
FIG. 3 is a SRIM (Stopping and Range of Ions in Materials) program for analyzing the results of surface modification of a TiO ₂ coating or a TiO ₂ -SiO ₂ hybrid coating by heavy ion beam irradiation of the present invention.
4 is a graph showing the content distribution of Fe, O, and Ti elements according to the distance from the surface formed inside and outside the boundary of the 100 nm mixed interface layer formed on the iron substrate with respect to the laminate of Example 7 as in Experimental Example 1 of the present invention to be.
5 is a photograph of the surface of Examples 1 to 3 as in Experimental Example 2 of the present invention.
6 is a photograph (magnification of 100 times) showing the uniformity of the coating surface before and after irradiation with the heavy ion beam of Example 7 as in Experimental Example 3 of the present invention.
7 is a photograph (magnification of 100 times) showing the uniformity of the coating surface before and after irradiation with the heavy ion beam of Example 1 as in Experimental Example 3 of the present invention.
8 is a photograph (magnified 100 to 5,000 times) of SEM observation of the surface uniformity of the coating interface after heavy ion irradiation and secondary coating of Examples 1 to 3 as in Experimental Example 3 of the present invention, (6,500 times to 100,000 times magnification).

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. It is to be understood that the term " comprises " or " having " in the present invention is intended to specify the presence of stated features, integers, steps, operations, elements, parts, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, parts, or combinations thereof.

As shown in the schematic view of FIG. 1, a method for surface modification of a TiO ₂ coating or a TiO ₂ -SiO ₂ hybrid coating by heavy ion beam irradiation according to a preferred embodiment of the present invention includes: preparing a base material 10; (a) coating (20) a coating material comprising a TiO ₂ sol solution or a TiO ₂ -SiO ₂ hybrid sol solution on the surface of the base material (10); And (b) exposing the surface of the coated base material (10, 20) to a heavy ion beam (31) originating from the heavy ion beam irradiator, wherein the energy of the heavy ion beam is at least 500 KeV, MeV, more preferably 2 to 40 MeV.

The coating material 20 may be a TiO ₂ sol solution or a TiO ₂ -SiO ₂ hybrid sol solution, more preferably a TiO ₂ -SiO ₂ hybrid sol solution.

The coating step using the sol solution corresponding to step (a) of FIG. 1 can be carried out by any of coating methods using a commonly used sol-gel method, and the coating conditions can also be selected depending on the kind of the base material 10 and the coating material 20 To < / RTI > use conventional coating conditions.

The elements used in the heavy ion beam irradiating apparatus for providing the heavy ion beam 31 corresponding to the step (b) of FIG. 1 include iron (Fe), iodine (I), tungsten (W), copper (Si), argon (Ar), gold (Au), aluminum (Al), titanium (Ti), argon (Ar) and one or more of these.

The injection amount of the heavy ion beam 31 is 50 uC to 10,000 uC, the current applied to the heavy ion beam irradiator is 0.01 μA to 1 μA, and the exposure time of the heavy ion beam is 1 to 2 hours. When the preferred range of the heavy ion beam dose, the current range applied to the heavy ion beam irradiator, and the heavy ion beam exposure time range of the present invention is exceeded, there is a problem that effective ion beam mixing does not occur.

1 (b) can be performed once or twice or more, and when the step of exposing to the heavy ion beam 31 is performed twice or more, (b) the coating (C) coating the second coating material (40) on the surface of the coated base material (10, 30) irradiated with the heavy ion beam after the step of exposing the surface of the base material (10, 30) to the heavy ion beam (31) You may.

The second coating 40 may be a TiO ₂ sol solution or a TiO ₂ -SiO ₂ hybrid sol solution. Thus, the first coating after coating the coating material 10 and exposed to the heavy ion beam (31) by performing a second coating (40) - TiO ₂ coated with a second coating coated -TiO _2, TiO ₂ coating - TiO ₂ -SiO ₂ coating, metal base material and TiO ₂ hybrid coating -TiO ₂ coating, metal base material and TiO ₂ hybrid coating -TiO ₂ -SiO ₂ coating, TiO ₂ -SiO ₂ coating -TiO ₂ coating, TiO ₂ -SiO ₂ nose -TiO ₂ -SiO ₂ coating, a metal base material and TiO ₂ -SiO ₂ -TiO ₂ coating a hybrid coating, a metal base material and TiO ₂ -SiO ₂ -TiO ₂ -SiO hybrid coating and _second coating may be formed, and more preferably TiO ₂ -SiO ₂ coating -TiO ₂ coating, TiO ₂ -SiO ₂ coating -TiO ₂ -SiO ₂ coating, TiO ₂ -SiO ₂ hybrid coating -TiO ₂ coating or metal base material and TiO ₂ -SiO ₂ hybrid coating -TiO ₂ -SiO ₂ coating has to be formed.

The base material 10 may be any metal selected from 304 stainless steel, Alloy 800H, Alloy 690, Hastelloy X, Hayness 230, Hayness 556, CX2002U, Alloy X750, Alloy 718, Sanicro28 and composites thereof.

TiO ₂ sol solution or TiO ₂ SiO ₂ ?? hybrid sol solution is used as the coating 20 or second coating 40 may be to include a titanium alkoxide, a silicon alkoxide, an acid or base catalyst and a solvent.

The titanium alkoxide may be selected from the group consisting of titanium isopropoxide (TIP), titanium tetraethoxide (TTE), titanium tetraisopropoxide (TTIP), titanium tetrabutoxide (TTB) , Tetrabutyl orthotitanate (TBOT), and mixtures thereof. More preferably, the titanium alkoxide may be one using TBOT.

The silicon alkoxide is selected from the group consisting of tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthosilicate (TPOS), tetrn-butylorthosilicate (TBOS) ), Gamma-methacryloxypropyltrimethoxysilane (MAPTS, γ-methacryloxy propyltrimethoxysilane), and mixtures thereof. More preferably, the silicon alkoxide may be a MAPTS.

The organic / inorganic hybrid (TiO ₂ -SiO ₂ hybrid) sol solution may contain 0.40 mol or more of silicon alkoxide per mol of the titanium alkoxide. Preferably 0.40 to 13.5 moles of silicon alkoxide per mole of titanium alkoxide, and still more preferably 8 to 13.5 moles of silicon alkoxide per mole of titanium alkoxide. If the silicon alkoxide is contained in an amount of less than 0.40 mol based on 1 mol of the titanium alkoxide, the uniformity of the coating and the bonding effect due to the formation of the TBOT-MAPTS network structure may be weakened.

The solvent is any one selected from the group consisting of C _1-10 alcohols, water, and mixtures thereof. More preferably, the solvent may be any one selected from the group consisting of ethanol, methanol, propanol, butanol, water, and mixtures thereof. The solvent may be contained in an amount of 1 to 20 moles per mole of titanium contained in the titanium alkoxide, more preferably 13 to 18 moles per mole of titanium. When the solvent is contained in an amount of less than 1 mole per mole of titanium, the solution may not be stably dissolved. When the solvent is contained in excess of 20 mole per mole of titanium, the density of the solution is lowered and the amount of catalyst required to stably disperse the particles constituting the sol solution May be lacking.

The acid catalyst may include hydrochloric acid (HCl), acetic acid, and a mixed acid containing at least one thereof, preferably 0.1 to 2 moles of acid catalyst per 1 mole of titanium constituting the titanium alkoxide, 6 < / RTI > When the acid catalyst is contained at less than 0.1 mole per mole of titanium or when the pH of the sol solution is more than 6, the sol solution may not be formed smoothly due to insufficient amount of catalyst. In addition, if the acid catalyst contains more than 2 mol of titanium per mole of titanium, or if the pH of the sol solution is less than 2, a rapid gelling reaction proceeds and the sol solution may not be stably maintained.

Base catalyst may be one containing ethanolamine may comprise (Ethanolamine, ETA), titanium alkoxide per mole of the basic catalyst 1x10 ^-6 to 2x10 ^-6 mol. When the base catalyst is contained at less than 1 x 10 < ^-6 > mol per mol of titanium alkoxide, the formation rate of Ti fine particles or Ti-Si hybrid fine particles becomes very slow due to the insufficient amount of catalyst, If it is contained in an amount exceeding 2 x 10 < ^-6 > mol per mol of the titanium alkoxide, a rapid gelation reaction may proceed and the sol solution may not be stably maintained.

According to another preferred embodiment of the present invention, as shown in FIG. 1 (c), a metal base material 10; A mixed interface layer (30) comprising a metal component of a metal base material and a TiO ₂ component or a metal component of a metal base material and a TiO ₂ --SiO ₂ hybrid component; And a TiO ₂ coating layer 40 or a TiO ₂ -SiO ₂ hybrid coating layer 40 laminated on the mixed interface layer 30.

The mixed interfacial layer 30 may be formed of at least one selected from the group consisting of Fe, Iodine, W, Cu, Si, Ar, Au, (Ti), oxygen (O), and an element group in which one or more of these elements are present, and has a thickness of 1 to 200 nm, preferably a thickness of 1 to 100 nm, And may have a thickness of 50 nm.

In addition, the coating layer 40 laminated on the mixed interface layer 30 forms a uniformly bonded interface between the boundaries of the coating, and may include a single coating layer without cracks. Compared to a coating layer not subjected to ion beam mixing, a laminate including a mixed interface layer and a coating layer has a uniform coating thickness and an effect of increasing thickness.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[Example 1]

2.86 ml of TBOT (tetrabutyl orthotitanate, molecular weight: 340.32 g / mol, supplied by Aldrich), which is a titanium alkoxide, was added to 100 ml of ethanol, and the silicone alkoxide MAPTS was added so that 1 mole of Si was contained per mole of Ti contained in the TBOT γ-methacryloxy propyltrimethoxysilane, molecular weight: 240.32 g / mol, Aldrich) to prepare a first mixed solution.

A second mixed solution containing acetic acid and ethyl acetoacetate (EAcAc, molecular weight: 130.14 g / mol, supplied by Aldrich) in a molar ratio of TBOT: acetic acid: EAcAc of 1: 0.5: 0.65 was prepared, 1 mixed solution for 30 minutes, followed by stirring for 2 hours to prepare a TiO ₂ -SiO ₂ hybrid sol solution.

A 304 stainless steel base metal was prepared as a base material and a TiO ₂ -SiO ₂ hybrid sol solution was first dip-coated to prepare a hybrid coating specimen. The base material was precisely polished to a particle size of # 100 to # 2000 using 1.0 μm alumina (Al ₂ O ₃ ) powder and pretreated by ultrasonic washing in an acetone solution for 30 minutes to remove residual impurities after polishing. The descending-rising speed of the dip coating was 3.36 mm / sec. The base material was dipped in the solution for 15 minutes, then coated up by drying, and then dried at 50 ° C for 15 minutes. This procedure was repeated three times and the coated base material was heat treated at 200 ° C for 1 hour.

The prepared coating base material specimen was mounted on a heavy ion irradiation equipment (Tendem) shown in FIG. 2, and a 2 MeV Si ²⁺ ion beam was irradiated for 0.5 hour at 0.5 uA for a total of 7,000 uC.

The TiO ₂ -SiO ₂ hybrid sol solution used in the first dip coating was dip-coated on the coated base material sample after the ion beam mixing was completed to prepare a laminate sample.

[Examples 2 to 3]

(Example 3) irradiated with a total of 70 uC by irradiating a total of 700 uC (Example 2) and 0.05 uA for 6 minutes by irradiating a medium ion beam at 0.05 uA for 1 hour under the conditions of Example 1, , A laminate specimen was prepared in the same manner as in Example 1. The results are shown in Table 1. < tb > < TABLE >

[Examples 4 to 6]

Same as Examples 1 to 3 except that a TiO ₂ -SiO ₂ hybrid sol solution in which MAPTS was added so that 4 moles of Si was contained per 1 mole of Ti contained in the TBOT under the conditions of Examples 1 to 3 To prepare a laminate specimen.

[Example 7]

A laminate specimen was prepared in the same manner as in Example 1, except that a TiO ₂ sol solution containing no MAPTS was prepared under the conditions of Example 1.

[Comparative Example 1]

A laminate specimen was prepared in the same manner as in Example 1 except that a 500 keV ion beam was irradiated under the conditions of Example 1.

[Experimental Example 1] Analysis of SRIM irradiation

FIG. 3 is a flow chart of a SRIM (Stopping and Range of Ions in Materials) program for analyzing the results of coating surface modification by heavy ion beam irradiation, and FIG. (B) oxygen (O) and (c) titanium (Ti) ions according to the depth of the titanium oxide layer.

As shown in FIGS. 4 (a) to 4 (c), the content distribution of Fe, O, and Ti elements in the layered product of Example 7 according to the distance from the surface was analyzed. As a result, TiO ₂ coating, it is confirmed that there exists a region where Fe, O, Ti, etc. are mixed with each other in the depth 10 nm of the specimen based on the coating layer boundary. Therefore, it can be seen from this SRIM analysis that a mixed interface layer formed by mixing the interface between the metal base material and the oxide coating layer by the ion beam irradiation is formed.

[Experimental Example 2] Surface analysis (color) after irradiation with a heavy ion beam

Fig. 5 is a photograph of the surface of the examples 1 to 3 (Test 1 to 3) of the present invention after irradiation with a heavy ion beam.

As compared with Example 3, the heavy ion beam irradiation amount of Example 2 was increased by 10 times, Example 1 had 10 times as many ion irradiation amount as that of Example 2, and as a result of observation of FIG. 5, The surface color change was more clear.

The degree of mixing of the ion beam of the TiO ₂ -SiO ₂ hybrid coating film and the metal matrix of Example 1 was remarkable compared to that of Example 2 or 3 through the apparent pattern of the surface color change of the laminate after the irradiation with the heavy ion beam, It can be concluded that the ion mixing by the ionic liquid is substantially occurred.

[Experimental Example 3] Surface analysis (uniformity) after irradiation with a heavy ion beam

6 to 7 are photographs (100 times magnification) showing the uniformity of the coating interface surface after the heavy ion beam irradiation according to Example 7 or Example 1 of the present invention, and FIG. 8 is a photograph (100 to 5,000 times magnification) and a coating thickness SEM (magnification of 6,500 to 100,000 times) of the surface uniformity of the coating interface after the beam irradiation and the secondary coating.

6 (a) is a photograph of the surface (section and plane) of a specimen before irradiation with a heavy ion beam after primary coating in Example 7 of the present invention, (b) (Section and plane) of the specimen. As can be seen from the results of FIG. 6, it was confirmed that a uniform coating layer was formed without cracking by ion mixing effect by ion beam irradiation.

FIG. 7A is a photograph of a surface (cross-section and plane) of a specimen before irradiation with a heavy ion beam after primary coating in Embodiment 1 of the present invention, FIG. 7B is a photograph of a surface of a hybrid interface layer (Section and plane) of the specimen. As can be seen from the results of FIG. 7, it was confirmed that even when the hybrid coating was irradiated with a heavy ion beam, a uniform coating layer without cracking was formed by ion mixing similarly to the result of FIG.

FIG. 8 (a) is a SEM image of a coated surface on which a mixed interface layer is formed by irradiating a heavy ion beam after primary coating of Examples 1 to 3 by 100 to 5000 times. As can be seen from the results of FIG. 8 (a), it was confirmed that no crack occurred in the coating layer after ion mixing and a uniform surface layer was formed.

8B is an SEM image obtained by enlarging the cross section of the coating layer by 6,500 to 100,000 times when the _second interfacial TiO ₂ coating is performed after the formation of the mixed interfacial layer through ion beam mixing formed in (a) The average value of the coating thickness was calculated. As can be seen from the results of FIG. 8 (b), the average thickness of the secondary coating was 112.62 nm. As a result of ion mixing, the coating thickness of the re-coated specimen increased And the boundary of the coating forms a uniformly bonded interface and forms a single coating free from cracks.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

10: base material, 20: coating layer
30: mixed interface layer, 31: heavy ion (beam)
40: Second coating layer

Claims (10)

Preparing a base material;
Coating a coating material comprising a TiO ₂ sol solution or a TiO ₂ -SiO ₂ hybrid sol solution on the surface of the base material; And
Exposing the coated base material surface to a heavy ion beam generated from a heavy ion beam irradiating device,
Wherein the energy of the heavy ion beam is 1 MeV or more, and the TiO ₂ coating or the TiO ₂ -SiO ₂ hybrid coating is coated by a medium ion beam irradiation. The method according to claim 1,
Wherein the medium ion beam energy is in the range of 2 to 40 MeV, and the TiO ₂ coating or the TiO ₂ -SiO ₂ hybrid coating is coated by a heavy ion beam irradiation. The method according to claim 1,
The elements used in the heavy ion beam irradiating device include iron (Fe), iodine (I), tungsten (W), copper (Cu), silicon (Si), argon (Ar), gold (Au) , titanium (Ti) and a TiO ₂ coated by them in any of the heavy ion beam irradiation is selected from the group or a mixture of one or more of TiO ₂ -SiO ₂ surface modification method of a hybrid coating. The method according to claim 1,
The dose of the heavy ion beam is 50 uC to 10,000 uC,
The current applied to the heavy ion beam irradiating apparatus is 0.01 μA to 1 μA,
Wherein the exposure time of the heavy ion beam is from 1 minute to 2 hours.
Surface modification of TiO ₂ coating or TiO ₂ --SiO ₂ hybrid coating by heavy ion beam irradiation. The method according to claim 1,
Wherein the step of exposing to the heavy ion beam is a surface modification method of TiO ₂ coating or TiO ₂ -SiO ₂ hybrid coating by heavy ion beam irradiation performed once or twice or more. 6. The method of claim 5,
When the step of exposing to the heavy ion beam is performed twice or more,
Coating a second coating material on the surface of the coated base material irradiated with the heavy ion beam after the step of exposing the coated base material surface to the heavy ion beam, the TiO ₂ coating or the TiO ₂ -SiO ₂ hybrid A method of modifying the surface of a coating. The method according to claim 6,
Wherein the second coating material is a TiO ₂ sol solution or a TiO ₂ -SiO ₂ hybrid sol solution, wherein the second coating material is a TiO ₂ coating or a TiO ₂ -SiO ₂ hybrid coating by a heavy ion beam irradiation. The method according to claim 1,
The base material is a TiO ₂ coating by heavy ion beam irradiation, which is any metal selected from 304 stainless steel, Alloy 800H, Alloy 690, Hastelloy X, Hayness 230, Hayness 556, CX2002U, Alloy X750, Alloy 718, Sanicro28, Or a TiO ₂ -SiO ₂ hybrid coating. Metal base material;
A mixed interface layer comprising a metal component and a TiO ₂ component of the metal matrix or a metal component of the metal matrix and a TiO ₂ -SiO ₂ hybrid component; And
A TiO ₂ coating layer or a TiO ₂ -SiO ₂ hybrid coating layer laminated on the mixed interface layer;
≪ / RTI > 10. The method of claim 9,
The mixed interface layer may include at least one of iron (Fe), iodine (I), tungsten (W), copper (Cu), silicon (Si), argon (Ar), gold (Au), aluminum (Al) , Oxygen (O), and any element selected from the group consisting of at least one of these elements,
Wherein the mixed interface layer has a thickness of 1 to 200 nm.

Images