KR101511734B1 - Surface modification method of ceramic materials - Google Patents

Abstract

The present invention relates to a method for modifying surfaces on ceramic materials, comprising a step of radiating 2x10^15 ions/cm^2 to 1x10^20 ions/cm^2 radiation to a ceramic substrate including at least one compound selected from a group consisting of a positive electrode aluminum oxide and aluminum hydroxide and having a three-dimensional nanostructure on a surface.

Description

TECHNICAL FIELD [0001] The present invention relates to a surface modification method for a ceramic material,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for modifying a surface of a ceramic material. More particularly, the present invention relates to a ceramic material surface modification method capable of easily fabricating a ceramic material having a large functionality, greatly changing the surface characteristics of the ceramic material through a simple physical method, and maintaining the surface characteristics changed over time .

Generally, the surface of a solid such as a metal, a ceramic, or a polymer has an inherent surface energy, and when the liquid such as water or oil is buried on the surface, the surface energy is reflected as a contact angle between the solid surface and the liquid. When the contact angle is 90 DEG or less, the liquid exhibits hydrophilicity and excellent wettability that spreads on the surface thereof and makes the surface wet with the liquid. When the contact angle is 90 DEG or more, spherical liquid droplets do not wet the solid surface, Which is a hydrophobic property.

If the surface of a specific material has a super-hydrophobic property, the material can have properties of excellent transparency, resistance to seizure, and self-cleansing, and thus various studies for producing an artificial superhydrophobic surface have been made.

For example, there has been proposed a method of coating a metal on a metal surface, but this method has a limitation in that the wettability of the surface depends only on the chemical properties, so that the durability and durability are remarkably reduced over time.

In order to solve such a problem, a method of manufacturing a hydrophobic material by forming a nano / microstructure on the surface of a metal to increase the contact angle has been proposed. Specifically, as the surface of a solid has a microstructural concavo-convex structure and the surface becomes microscopically rough, air is trapped in the microstructure to reduce the contact area between the liquid and the solid surface, thereby reducing both the hydrophilic surface and the hydrophobic surface The contact angle is increased. The correlation between the contact angle and the geometrical structure of the surface can be confirmed by the following equation (1), which is a mixed equation of the Cassie-Baxter model and the Wenzel model.

[Equation 1]

cosθr ^c = rfcosθ + f - 1

In Equation 1, r is perpendicular to the solid surface projected - to the contact area between the droplet, the droplet-except the contact area with the air, the actual solid surface and the contact area between the droplet ratio, θr ^c is Where f is the solid surface fraction, ie the total contact area of the liquid droplet, excluding the contact area with air, the total contact area of the area actually in contact with the solid surface, It is the ratio to the area.

However, in the case of metal materials, wet etching and electroless plating are mainly used for the reason that surface nano pores are not easily formed. However, wet etching and plating methods cause many environmental problems, And the like. Accordingly, a method of patterning the metal surface by a method such as laser etching [Anne-Marie Kietzig, Savvas G. Hatzikiriakos and Peter Englezos, Langmuir 25 (8), (2009) 4821-4827] There is a problem that production is difficult.

Accordingly, there is a demand for a new surface control method of a ceramic material that can proceed in a simpler and more secure manner, while maintaining the surface properties even over time.

The present invention relates to a ceramic material surface modifying method capable of easily fabricating a ceramics material having a large area and greatly changing the surface characteristics of the ceramic material through a simple physical method, .

In this specification, a surface modification method of a ceramic material is provided.

Hereinafter, a surface modification method of a ceramic material according to a specific embodiment of the present invention will be described in detail.

According to one embodiment of the present invention, there is provided a ceramic substrate having a nanostructure formed on a surface thereof and containing at least one compound selected from the group consisting of anodized aluminum and aluminum hydroxide, and having a density of 2 x 10 < ¹⁵ > ^And irradiating the substrate with radiation of ²⁰ ions / cm < 2 >.

The inventors have formed the nano three-dimensional structure on the surface, on a ceramic substrate comprising at least one compound selected from the group consisting of anode aluminum hydroxide and aluminum oxide of 2 x 10 ¹⁵ ions / ㎠ to 1 x 10 ²⁰ ions / ㎠ The surface modification method of the ceramic material including the step of irradiating the radiation can be performed in a large area while the surface can have a functionality as a nanostructure and can be manufactured in a large area, The surface characteristics of the material can be changed drastically and the surface characteristics of the changed ceramic material can be maintained over time.

Specifically, a nanostructure may be formed on a surface of a ceramic substrate including at least one compound selected from the group consisting of anodized aluminum and aluminum hydroxide. The ceramics refers to a compound generally referred to as various silicates or oxides, carbides, borides, emulsions, nitrides of metals, and may include anodized aluminum or aluminum hydroxide. In addition, the nanostructure is a three-dimensional structure, which means a structure satisfying the size of a nanometer unit. Examples of the nanostructure include, but are not limited to, a nanoporous structure, a nanowire structure, a nanomicro-concave-convex structure, and the like.

The ceramic substrate may be irradiated with radiation of 2 x 10 ¹⁵ ions / cm 2 to 1 x 10 ²⁰ ions / cm 2, or 3 x 10 ¹⁵ ions / cm 2 to 1 x 10 ¹⁷ ions / cm 2. The irradiation amount of the radiation means the number of electrically charged particles reaching a unit area of the ceramic substrate to which the radiation is irradiated. When the irradiation amount of the radiation is less than 2 x 10 ¹⁵ ions / cm 2, The number of electrically charged particles becomes too small, and the number of electrically charged particles injected into the surface of the ceramic substrate becomes small, so that the effect of modifying the surface of the ceramic substrate can be reduced. On the other hand, if the dose of the radiation is more than 1 x 10 ²⁰ ions / cm 2, further surface modification may not proceed after a certain level of surface modification.

The radiation may have a intensity of 100 keV to 200 keV, or 120 keV to 180 keV, or 140 keV to 160 keV. The radiation can accelerate the electrostatically charged particles in the electric field by electrostatic attraction and change the intensity according to the accelerated velocity. When the radiation is irradiated on the ceramic substrate as the radiation has an intensity of 100 to 200 keV, the electrically charged particles present in the radiation are injected into the surface of the ceramic substrate to cause a change in the microstructure on the surface . If the intensity of the radiation is less than 100 keV, the intensity of the radiation is weakened so that the electrically charged particles can not enter the surface of the ceramic substrate. On the other hand, if the intensity of the radiation exceeds 200 keV, the intensity of the radiation becomes excessively large, and may not be so large as to modify the ceramic substrate, but may become too large to cause a secondary reaction.

The radiation may have a current density of 0.1 μA / cm 2 to 5 μA / cm 2, or 0.5 μA / cm 2 to 4 μA / cm 2 and 0.7 μA / cm 2 to 3 μA / cm 2. The current density is a value obtained by dividing the current flowing through the radiation by the cross-sectional area of the radiation. When the current density of the radiation is less than 0.1 μA / cm 2, the flow of the electrically charged particles inside the radiation is small, The amount of irradiation may not be sufficient enough to modify the surface of the ceramic substrate. On the other hand, if the current density of the radiation exceeds 5 A / cm < 2 >, the flow of the electrically charged particles inside the radiation is large, and the energy and irradiation amount of the radiation not only modifies the surface of the ceramic substrate, . ≪ / RTI >

A nanoporous structure may be formed on the surface of the ceramic substrate including the anodized aluminum. The nanoporous structure may include pores uniformly distributed on the surface of the ceramic substrate, as shown in FIG. As the nanoporous structure is formed on the surface of the ceramic substrate, the ceramic substrate may exhibit functionality.

The nanoporous structure may have pores having a diameter of 3 nm to 500 nm, or 5 nm to 400 nm. If the diameter of the pores is less than 3 nm, the surface area of the ceramic substrate may be excessively small. On the other hand, if the diameter of the pores is more than 50 nm, the porous structure of the surface of the ceramic substrate can not be formed at a microscopic level, so that the contact angle of the ceramic substrate may not be increased to an appropriate level.

The thickness of the ceramic substrate including the anodized aluminum may be 50 nm to 50,000 nm, or 100 nm to 30,000 nm. Since the anodic oxidation process is performed only by the primary anodization process without the general anodization, etching, and secondary anodization processes, it is not necessary to undergo a separate etching process, and the thickness of the ceramic substrate is relatively reduced So that the ceramic substrate can have excellent flexibility. If the thickness of the ceramic substrate is excessively large, the flexibility of the ceramic substrate may be reduced.

On the surface of the ceramic substrate including the aluminum hydroxide, a nano stereoscopic projection in the form of a plate may be formed. The plate-like shape is a structure in which the plate is arranged in a relatively thin plate-like shape in a horizontal plane, and each of the projections is a structure in which a part of the projection is protruded or bulged. As shown in FIG. 2, a plate-shaped nano-prism structure having various sizes can be formed on the substrate. As the nano solid protrusions are formed on the surface of the ceramic substrate, the ceramic substrate may exhibit functionality.

Specifically, the platelet-like nano-dimensional protrusions may have a width of 5 nm to 20 nm, a line length of 50 nm to 500 nm, and a height of 100 nm to 500 nm. The line length means the length of the plate-like nano-spherical protrusion defined or confirmed in the plan view of the substrate.

For example, the nano solid protrusions may be straight lines in the form of polygonal columns, semi cylinders, or the like, or they may be curved in the form of polygonal columns or semi-cylinders It may be warped. In addition, the plate-like nano-cubic protrusions may be in a state of intersecting with each other, or may be in a state of being in parallel with each other and not meeting with each other even when the plate-shaped nano- It may not be crossed or parallel, but it may be in a state where it can cross if extended.

The angle formed between the plate-like nano-scale projection and the substrate may be more than 0 DEG and less than 90 DEG. Wherein an angle between the plate-like nano-scale protrusion and the substrate is such that when the plate-like nano-scale protrusion and a straight line are drawn on the surface of the substrate so as to include the plate- It can mean the smaller of the angles of the straight line. When the angle formed by the two straight lines is equal to 90 °, the angle formed between the plate-like nano-scale protrusion and the substrate is 90 °, which means that the plate-shaped nano-scale protrusions are formed vertically on the substrate have.

On the other hand, the surface modification method of the ceramic material is a method in which a hydrogen cations And irradiating ion beam radiation. The hydrogen cation (H ⁺ ) The ion beam radiation can be appropriately utilized for the surface modification of the ceramic substrate through the use of hydrogen cations, that is, protons, which are present in the above-mentioned radiation, through the properties of protons which are distorted in a magnetic field and are hardly permeable to substances.

The hydrogen cations After ion beam irradiation, the ceramic substrate comprising the anodized aluminum may have a contact angle of 70 to 80 degrees, or 72 to 80 degrees. The contact angle means an angle formed by the fluid and the solid when the liquid equilibrates thermodynamically on the solid surface. As described above, when the contact angle is 90 DEG or less, the liquid spreads over the surface to make the surface wet with the liquid And exhibits excellent hydrophilicity and excellent wettability. When the contact angle is 90 DEG or more, spherical liquid droplets exhibit hydrophobicity that keeps the spherical surface without wetting the solid surface.

The hydrogen cations The contact angle change rate of the ceramic substrate including the anodized aluminum before and after the irradiation with the ion beam may be 60% to 110%, or 62% to 108%, or 64% to 106%. The hydrogen cations The contact angle change rate of the ceramic substrate including the anodized aluminum before and after the irradiation with the ion beam can be obtained by the following equation (2).

&Quot; (2) "

Change in contact angle (%) = (contact angle after modification - initial contact angle) / initial contact angle X 100

In the above formula (2), the initial contact angle is the hydrogen cations Refers to the contact angle of the ceramic substrate including the anodized aluminum before irradiating the ion beam radiation, and the contact angle after the modification means the hydrogen cation Refers to the contact angle of the ceramic substrate including the anodized aluminum after irradiation with ion beam radiation.

The hydrogen cations If the rate of change of the contact angle of the ceramic substrate including the anodized aluminum before and after the irradiation with the ion beam is too small, the surface modification effect of the ceramic substrate due to the irradiation of the ion beam may not be sufficient.

The hydrogen cations The ceramic substrate comprising anodized aluminum after ion beam irradiation may have a surface roughness of 5.0 nm or less, or 1.0 to 4.7 nm, or 2.0 to 4.6 nm. The surface roughness refers to the degree of fine irregularities occurring on the surface of the material. The method of measuring the surface roughness is not limited to a specific one. For example, a cantilever having a sharp probe at its end passes through the surface of the sample using a tubular piezoelectric ceramic scanner, and the degree of bending of the probe on the curved surface measuring can be determined to achieve a certain curve, through the Rq (Root mean squre average roughness) indicated by the average of the absolute values of both the height of the center line r _ms indicated by the square mean value from the average value of the curve.

As the surface roughness decreases, the surface energy of the ceramic substrate decreases and the contact angle increases. If the surface roughness of the ceramic substrate exceeds 5.0 nm, even if the ceramic substrate is irradiated with the ion beam, the etching by the ion beam is insufficient, and the change of the surface characteristics of the ceramic substrate can be reduced.

On the other hand, on the ceramic substrate containing the anodized aluminum, hydrogen cations Prior to the step of irradiating the ion beam radiation, an aluminum substrate may be anodized to form a ceramic substrate including an aluminum oxide layer having a nanoporous structure formed on the surface thereof.

The step of anodizing the aluminum substrate to form a ceramic substrate including an aluminum oxide layer having a nanoporous structure on the surface thereof may be performed by using the aluminum substrate as an anode in an alumite treatment tank at a temperature of 10 ° C to 20 ° C and a constant And electrolyzing 0.1 to 0.5M aqueous oxalic acid solution for 10 to 14 hours at a voltage.

On the other hand, the surface modification method of the ceramic material is a method in which a ceramic substrate containing aluminum hydroxide And irradiating ion beam radiation. The xenon cation (Xe ⁺ ) ion beam radiation can accelerate the xenon cations as electrically charged particles present in the radiation and impinge on the surface of the ceramic substrate to transfer the momentum of the xenon cations . The bonding energy of the ceramic substrate is smaller than the momentum of the xenon cation so that the surface materials of the ceramic substrate are etched away from the surface with a momentum corresponding to the extra energy, Can be utilized.

After the xenon cation irradiation, the ceramic substrate comprising the aluminum hydroxide may have a contact angle of 40 [deg.] To 130 [deg.], 45 [deg.] To 125 [deg.], Or 48 [ After the xenon cation irradiation, the ceramic substrate containing aluminum hydroxide has a contact angle of at most 100 degrees, and thus can exhibit super-hydrophobic characteristics. The xenon cation Since the contact angle of the ceramic substrate containing aluminum hydroxide is maintained at 300 ° C or higher even after 3 months of holding the aluminum hydroxide after irradiation, the superhydrophobic characteristic can be maintained over a certain level even after a lapse of time

The contact angle change rate of the ceramic substrate including the aluminum hydroxide before and after irradiation with the xenon cation beam may be 3,000% or more, or 4,000% to 12,000%. The rate of change of the contact angle of the ceramic substrate including the aluminum hydroxide before and after irradiation with the xenon cation beam can be obtained by the following equation (3).

&Quot; (3) "

Change in contact angle (%) = (contact angle after modification - initial contact angle) / initial contact angle X 100

In the formula (3), the initial contact angle refers to the contact angle of the ceramic substrate including aluminum hydroxide before irradiation with the xenon cation ion beam radiation, and the contact angle after modification is determined by irradiating the xenon cation ion beam radiation, Means the contact angle of the substrate.

If the rate of change of the contact angle of the ceramic substrate containing aluminum hydroxide before and after irradiation with the xenon cation ion beam is too small, the effect of modifying the surface of the ceramic substrate due to the ion beam irradiation may not be sufficient.

On the other hand, on the ceramic substrate containing aluminum hydroxide, The step of irradiating the ion beam radiation may further comprise a step of alkali-treating the aluminum substrate to form a ceramic substrate including an aluminum hydroxide layer formed with nano-scale projections in the form of a plate. It is possible to form a ceramic substrate including an aluminum hydroxide layer formed with nano-scale projections in a plate-like form by simply treating the aluminum substrate with alkali.

The aluminum substrate contains pure aluminum metal in an amount of 99 wt% or more, and the size of the aluminum substrate is not limited. However, due to limitations of the equipment for irradiating radiation, for example, To 60 mm, and a thickness of 0.5 to 1.5 mm.

The alkali refers to a compound in which the aqueous solution exhibits basicity, and may mainly include a hydroxide of an alkali metal and an alkaline earth metal element or a carbonate of an alkali metal, ammonia, an amine and the like, preferably sodium hydroxide (NaOH) Aqueous solution may be used.

The sodium hydroxide aqueous solution may have a concentration of 0.01 M to 0.1 M and a temperature of 70 to 90 ° C. Further, the aluminum substrate may be subjected to alkali treatment for 5 minutes to 20 minutes. By appropriately maintaining the concentration, the temperature and the reaction time of the sodium hydroxide aqueous solution, a plate-like nano solid protrusion having the specific width, line length and height as described above can be formed on the aluminum substrate.

According to the present invention, there is provided a surface modification method of a ceramic material in which a functional ceramic material is easily manufactured in a large area, a surface property of the ceramic material is greatly changed by a simple physical method, Can be provided.

Figure 1 shows a SEM image of a surface of a ceramic substrate comprising anodized aluminum.
Figure 2 shows a SEM image of a surface of a ceramic substrate comprising aluminum hydroxide.
FIG. 3 is a SEM image of an anodized aluminum ceramic substrate fabricated to a thickness of 5 μm after irradiating an ion beam.
FIG. 4 is an AFM image after an ion beam is irradiated on an anodized aluminum ceramic substrate manufactured to a thickness of 5 μm.
5 shows an SEM image of an ion beam irradiated onto a ceramic substrate containing aluminum hydroxide.

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

Ⅰ. Nano-porous structure Anodic oxidation  Surface modification of aluminum

< Example  1 to 4: Surface Modification Method of Ceramic Material>

(1) Preparation of anodic aluminum oxide with nanoporous structure.

(HClO ₄ ) and ethanol are mixed at a ratio of 1: 1 in order to remove irregular surface portions of the object to be processed. In the case of using an aluminum alloy containing 99.999% by weight of aluminum, 4 at a constant temperature of 7 ° C and a constant voltage of 20V. An aqueous solution of 0.3 M oxalic acid ((COOH) ₂ .2H ₂ O) and the above-mentioned material were placed in an alumite treatment tank and subjected to an anodic oxidation treatment at a constant voltage of 15 V and a constant voltage of 40 V for 12 hours, , An anodized aluminum having a pore size of 32 nm and a nano-porous structure with a space of 100 nm in space was produced.

(2) Hydrogen cation Ion beam irradiation

The hydrogen cation ion beam radiation having a current density of 1 mu A / cm &lt; ² &gt; and an energy of 150 keV was examined on the anodized aluminum of the nanoporous structure so as to satisfy the radiation dose shown in Table 1 below.

< Comparative Example  1 to 2: Surface Modification Method of Ceramic Material>

As shown in Table 1 below, hydrogen cations The anodized aluminum of the nanoporous structure was prepared in the same manner as in Example 1, except that the ion beam was not irradiated.

< Comparative Example  3 to 4: Surface Modification Method of Ceramic Material>

The anodic aluminum oxide thickness of the nanoporous structure of Table 1 and hydrogen cations The anodized aluminum of the nanoporous structure was prepared in the same manner as in Example 1 except that the irradiation amount of the ion beam was irradiated.

Ⅱ. Plate  Surface Modification of Aluminum Hydroxide in the Form of Nanosubstrates

< Example  5 to 6: Surface Modification Method of Ceramic Material>

(1) Production of aluminum hydroxide in which plate-shaped nano-cubic projections are formed

A plate-shaped article having a width of 50 mm, a length of 40 mm, and a height of 1 mm was prepared using an aluminum alloy containing 99.5% by weight of aluminum. The article to be treated was immersed in a 0.05M sodium hydroxide (NaOH) Aqueous solution and reacted for 10 minutes. After 10 minutes, the surface of the object to be treated was put into deionized water at a temperature of 100 ° C to stabilize the surface, thereby preparing aluminum hydroxide having a plate-like nano-cubic protrusion.

(2) Xenon cation Ion beam irradiation

Xanon cation ion beam radiation having a current density of 1 mu A / cm &lt; ² &gt; and an energy of 150 keV was irradiated to the aluminum hydroxide in which the plate-shaped nano-cubic projections were formed so as to satisfy the irradiation dose shown in Table 2 below.

< Example  7 to 8: Surface Modification Method of Ceramic Material>

The aluminum hydroxide in which the plate-shaped nano-cubic protrusions prepared in Examples 5 to 6 were formed was kept for 3 months from the production.

< Comparative Example  5: Surface modification method of ceramic material>

As shown in Table 2 below, Except that the ion beam was not irradiated, aluminum hydroxide in which the plate-like nano-cubic protrusion was formed was prepared in the same manner as in Example 5 above.

< Comparative Example  6 to 7: Surface Modification Method of Ceramic Material>

The xenon cations of Table 2 Aluminum hydroxide in which the plate-shaped nano-cubic protrusions were formed was prepared in the same manner as in Example 5, except that irradiation was performed so as to satisfy the ion beam irradiation dose.

< Comparative Example  8 to 9: Surface Modification Method of Ceramic Material>

The aluminum hydroxide in which the plate-shaped nano-cubic protrusions prepared in Comparative Examples 6 to 7 were formed was kept for 3 months from the production.

< Experimental Example  : Example  And In the comparative example  Measurement of Physical Properties of the Ceramic Material Obtained>

The physical properties of the ceramic materials obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2, respectively.

1. Surface structure

1-1. SEM

The surface structure of the ceramic materials obtained in the above Examples and Comparative Examples was confirmed by field-emission scanning electron microscopy (FE-SEM; LEO SUPRA 55, Carl Zeiss).

1-2. AFM

The surface structures of the ceramic materials obtained in the above Examples and Comparative Examples were confirmed by non-contact method using an atomic force microscopy (AFM; XE150, PSIA) apparatus.

2. Surface properties

2-1. Surface Roughness

The surface roughness of the ceramic materials obtained in the above Examples and Comparative Examples was measured by a non-contact method using an atomic force microscopy (AFM; XE150, PSIA) apparatus in a room condition.

2-2. Contact angle

The contact angles of the ceramic materials obtained in the above Examples and Comparative Examples were measured by a static method using a camera under room conditions.

3. Thickness

The thicknesses of the ceramic materials obtained in the above Examples and Comparative Examples were measured by Cross Section method using field-emission scanning electron microscopy (FE-SEM; LEO SUPRA 55, Carl Zeiss) at room temperature.

The surface modification conditions and results of the experimental examples of the above examples are shown in Tables 1 and 2 below.

Surface Modification Conditions and Experimental Results of Anodized Aluminum of Nanoporous Structure Anodized aluminum thickness
(탆) Hydrogen cation Radiation dose
(ions / cm2) SEM AFM Surface roughness (nm) Contact angle Example 1 5 5 x 10 ¹⁵ 3 (c) 4 (c) 4.30 79˚ Example 2 5 1 x 10 ¹⁶ 3 (d) 4 (d) 4.53 80˚ Example 3 10 5 x 10 ¹⁵ - - - 75˚ Example 4 10 1 x 10 ¹⁶ - - - 76˚ Comparative Example 1 5 0 3 (a) 4 (a) 5.68 48˚ Comparative Example 2 10 0 - - - 37˚ Comparative Example 3 5 1 x 10 ¹⁵ 3 (b) 4 (b) 5.27 68˚ Comparative Example 4 10 1 x 10 ¹⁵ - - - 65˚

As shown in Table 1, in the case of the anodized aluminum of the nanoporous structure, SEM images of Examples 1 and 2 shown in Figs. 3 (c) and 3 (d) the AFM images of Examples 1 and 2 shown in Figs. 4 (c) and 4 (d) and the AFM images of Figs. 4 (a) and 4 Comparing the AFM images of Comparative Example 1 and Comparative Example 3 shown in FIG. 2 (b), there was no significant difference in surface morphology.

However, when the surface roughness (R _q ) is compared, the surface roughness values of Comparative Example 1 and Comparative Example 3 are 5.68 nm and 5.27 nm, respectively. However, The surface roughness values of Examples 1 and 2 irradiated with the ion beam were 4.30 and 4.53, respectively, and it was confirmed that the surface roughness was reduced compared to Comparative Examples 1 and 3.

In addition, as for the contact angle, the hydrogen cations In Examples 1 and 2 irradiated with ion beams, the contact angles were increased in comparison with Comparative Example 1 showing 48 ° or Comparative Example 3 showing 68 °, and Examples 3 and 4 also had contact angles greater than 70 ° The contact angle was increased as compared with Comparative Example 2 which showed 37 DEG or Comparative Example 4 which showed 65 DEG, so that the anodic aluminum oxide having a nanoporous structure had hydrogen cations It can be seen that the contact angle increases with irradiation of the ion beam.

As a result, the anodic aluminum oxide of the nanoporous structure has a hydrogen cations It can be confirmed that a considerable change occurs in the surface characteristics of the anodized aluminum of the nanoporous structure as the ion beam is irradiated.

Surface Modification Conditions of Aluminum Hydroxide with Plate-like Nano-Pellicular Projections and Experimental Results Xenon cation Radiation dose
(ions / cm2) SEM Contact angle Example 5 5 x 10 ¹⁵ 5 (c) 117˚ Example 6 1 x 10 ¹⁶ 5 (d) 75˚ Example 7 5 x 10 ¹⁵ - 100˚ Example 8 1 x 10 ¹⁶ - 50˚ Comparative Example 5 0 2 One Comparative Example 6 5 x 10 ¹⁴ 5 (a) 7˚ Comparative Example 7 1 x 10 ¹⁵ 5 (b) 8 Comparative Example 8 5 x 10 ¹⁴ - 4 Comparative Example 9 1 x 10 ¹⁵ - 5˚

On the other hand, as shown in Table 2, when SEM images of the aluminum hydroxide having the plate-like nano-scale protrusions shown in FIG. 2 and FIG. 5 were compared with each other, the aluminum hydroxide having the nano- Although the surface structure is not largely changed, it can be seen that as the irradiation dose increases, the density of the aluminum hydroxide in which the plate-shaped nano-cubic projections are formed decreases.

In addition, as for the contact angle, In all of Examples 5 to 6 irradiated with ion beams, the contact angle was greatly increased to 100 times or more as compared with Comparative Example 5, which had a contact angle of at most 117 degrees in Example 5, In the protruded aluminum hydroxide, a specific range of xenon cations It can be seen that a change in the surface characteristics in which the contact angle increases with irradiation of the ion beam occurs.

In Examples 7 to 8, even when the contact angle after 3 months was measured with respect to the aluminum hydroxide in which the plate-shaped nano-cubic projections of Examples 5 to 6 were formed, the contact angle of 40 DEG or more, And the contact angle was increased as compared with Comparative Example 5, It can be confirmed that the surface property of the aluminum hydroxide in which the plate-shaped nano-cubic protrusion changed according to the ion beam irradiation is maintained over time.

Claims (23)

A radiation of 2 x 10 &lt; ¹⁵ &gt; to 1 x 10 &lt; ²⁰ &gt; ions / cm &lt; 2 &gt; is applied onto a ceramic substrate having a nano- Of the surface of the ceramic material.
The method according to claim 1,
Wherein the radiation has an intensity of 100 keV to 200 keV.
The method according to claim 1,
Wherein the radiation has a current density of 0.1 μA / cm 2 to 5 μA / cm 2.
The method according to claim 1,
Wherein a nanoporous structure is formed on the surface of the ceramic substrate including the anodized aluminum.
5. The method of claim 4,
Wherein the nanoporous structure has pores having a diameter of 3 nm to 500 nm distributed therein.
5. The method of claim 4,
Wherein the thickness of the ceramic substrate including the anodized aluminum is 50 nm to 50,000 nm.
5. The method of claim 4,
On the ceramic substrate containing the anodized aluminum, hydrogen cations A method of modifying a surface of a ceramic material, the method comprising: irradiating an ion beam radiation.
8. The method of claim 7,
Wherein the ceramic substrate comprising the anodized aluminum has a contact angle of 70 DEG to 80 DEG after the irradiation of radiation.
8. The method of claim 7,
Wherein the contact angle change rate of the ceramic substrate including the anodized aluminum before and after the irradiation with the radiation is 60% to 110%.
8. The method of claim 7,
After the irradiation of the radiation, the ceramic substrate comprising the anodized aluminum A surface modification method of a ceramic material having a surface roughness of 5.0 nm or less.
8. The method of claim 7,
On the ceramic substrate containing the anodized aluminum, hydrogen cations Prior to the step of irradiating the ion beam radiation,
Further comprising the step of anodizing the aluminum substrate to form a ceramic substrate including an aluminum oxide layer having a nanoporous structure formed on the surface thereof.
12. The method of claim 11,
Wherein the anodic oxidation step comprises electrolyzing an oxalic acid aqueous solution using the aluminum substrate as an anode.
13. The method of claim 12,
Wherein the electrolysis step comprises electrolyzing an oxalic acid aqueous solution at a constant voltage of 30 V to 50 V for 10 to 14 hours at a temperature of 10 to 20 占 폚.
The method according to claim 1,
Wherein a surface of the ceramic substrate including the aluminum hydroxide is formed with a plate-shaped nano solid protrusion.
15. The method of claim 14,
Wherein the plate-like nano-scale protrusions have a width of 5 nm to 20 nm, a line length of 50 nm to 500 nm, and a height of 100 nm to 500 nm.
15. The method of claim 14,
Wherein the angle between the plate-like nano-scale protrusion and the ceramic substrate is greater than 0 DEG and less than 90 DEG.
15. The method of claim 14,
And irradiating the ceramic substrate comprising the aluminum hydroxide with xenon cation ion beam radiation.
18. The method of claim 17,
Wherein the ceramic substrate comprising aluminum hydroxide has a contact angle of 40 [deg.] To 130 [deg.] After irradiation with the xenon cation ion beam radiation.
18. The method of claim 17,
The xenon cation Wherein the contact angle change rate of the ceramic substrate including aluminum hydroxide before and after irradiation with ion beam radiation is 3,000% or more.
18. The method of claim 17,
On the ceramic substrate containing aluminum hydroxide, a xenon cation Prior to the step of irradiating the ion beam radiation,
Further comprising a step of alkali-treating the aluminum substrate to form a ceramic substrate including an aluminum hydroxide layer on which nano-scale projections are formed in a plate-like shape.
21. The method of claim 20,
Wherein the alkali is an aqueous solution of sodium hydroxide.
22. The method of claim 21,
Wherein the temperature of the sodium hydroxide aqueous solution is 70 占 폚 to 90 占 폚.
21. The method of claim 20,
And the aluminum substrate is subjected to alkali treatment for 5 minutes to 20 minutes.

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