Hydrophilic aluminum surface body having hybrid nanostructure and manufacturing method thereof
10870256 ยท 2020-12-22
Assignee
Inventors
- Myoung Woon Moon (Seoul, KR)
- Sun Mi Yoon (Seoul, KR)
- Kwang Ryeol Lee (Seoul, KR)
- Hye Bin Lee (Seoul, KR)
- Young A Lee (Seoul, KR)
Cpc classification
B32B15/20
PERFORMING OPERATIONS; TRANSPORTING
B32B5/16
PERFORMING OPERATIONS; TRANSPORTING
International classification
B32B5/16
PERFORMING OPERATIONS; TRANSPORTING
B32B15/20
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Provided are a hydrophilic aluminum surface body having a hybrid nanostructure and a manufacturing method thereof. The hydrophilic aluminum surface body includes an aluminum substrate; and a nanopattern including a hybrid nanostructure formed on a surface of the aluminum substrate, wherein the hybrid nanostructure includes nanoparticles and a plurality of nanoflakes around the nanoparticles. According to the manufacturing method of the hydrophilic aluminum surface body, hydrophobic aluminum may be artificially prepared as hydrophilic or superhydrophilic aluminum due to a small contact angle, and large-area and mass production is possible and the method is eco-friendly.
Claims
1. A hydrophilic aluminum surface body comprising: an aluminum substrate; and a nanopattern including a hybrid nanostructure formed directly or indirectly on a surface of the aluminum substrate, wherein the hybrid nanostructure includes nanoparticles and a plurality of nanoflakes around the nanoparticles, wherein each of the nanoparticles include at least one selected from the group consisting of metals, metal oxides, carbon nanotubes, and graphene, and wherein the metals include at least one selected from the group consisting of Ti, Au, Ag, Pt, Cr, Fe, Co, Ni, Cu, Si, and alloys thereof, and the metal oxides are oxides of the metals except for boehmite (AlO(OH))), aluminum oxide (Al2O3), or a combination thereof.
2. The hydrophilic aluminum surface body of claim 1, wherein each of the nanoflakes has a plate shape, a needle shape, or a combined shape thereof, and the nanoflakes are formed around the nanoparticles and on the aluminum substrate and grown in an upper direction of the surface of the aluminum substrate.
3. The hydrophilic aluminum surface body of claim 1, wherein each of the nanoflakes has a height of 10 nm to 300 nm.
4. The hydrophilic aluminum surface body of claim 1, wherein each of the nanoflakes includes boehmite (AlO(OH)), aluminum oxide (Al.sub.2O.sub.3), or a combination thereof.
5. The hydrophilic aluminum surface body of claim 1, wherein a plurality of nanoparticles are aggregated to form a nanocluster.
6. The hydrophilic aluminum surface body of claim 1, wherein an average diameter of the nanoparticles is about 1 nm to about 1000 nm.
7. The hydrophilic aluminum surface body of claim 1, wherein the aluminum substrate has a plate or mesh shape.
8. The hydrophilic aluminum surface body of claim 1, further comprising: an aluminum oxide film including boehmite (AlO(OH)), aluminum oxide (Al.sub.2O.sub.3), or a combination thereof between the nanopattern and the surface of the aluminum substrate.
9. The hydrophilic aluminum surface body of claim 1, wherein the aluminum surface body has a contact angle of 10 or less using purified water.
10. An oil-water separation apparatus comprising the hydrophilic aluminum surface body of claim 1.
11. A manufacturing method of the hydrophilic aluminum surface body of claim 1, the method comprising: preparing a hydrophilic aluminum surface by oxidizing nanoparticles and an aluminum substrate to form a hybrid nanostructure including nanoparticles on a part or the whole of the surface of the aluminum substrate and a plurality of nanoflakes around the nanoparticles.
12. The manufacturing method of claim 11, wherein oxidation in the preparing of the hydrophilic aluminum surface is performed by bringing a reaction liquid including water or a vapor thereof into contact with the nanoparticles and the aluminum substrate.
13. The manufacturing method of claim 11, wherein oxidation in the preparing of the hydrophilic aluminum surface is performed by bringing a reaction liquid including water at about 70 C. to about 150 C. or a vapor thereof into contact with the nanoparticles and the aluminum substrate.
14. The manufacturing method of claim 11, wherein oxidation in the preparing of the hydrophilic aluminum surface is performed for about 1 minute to 100 minutes.
15. The manufacturing method of claim 11, wherein each of the nanoparticles includes at least one selected from the group consisting of metals, metal oxides, carbon nanotubes, and graphene.
16. The manufacturing method of claim 11, wherein each of the nanoparticles include at least one selected from the group consisting of Ti, Au, Ag, Pt, Cr, Fe, Co, Ni, Cu, Al, Si, alloys thereof and oxides thereof.
17. The manufacturing method of claim 11, wherein each of the nanoflakes has a plate shape, a needle shape, or a combined shape thereof, and the nanoflakes are formed around the nanoparticles and on the aluminum substrate and grown in an upper direction of a surface of the aluminum substrate to form a hybrid nanostructure.
18. The manufacturing method of claim 11, wherein each of the nanoflakes includes boehmite (AlO(OH)), aluminum oxide (Al.sub.2O.sub.3), or a combination thereof.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings in which:
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DETAILED DESCRIPTION
(16) Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the figures, to explain aspects of the present description. Expressions such as at least one of, when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
(17) Meanwhile, the terminology used in the following description is used only to describe specific embodiments and is not intended to limit the present disclosure. An expression in the singular includes an expression in the plural unless the content clearly indicates otherwise. In the following description, it should be understood that terms, such as include and have, are used to indicate the presence of stated features, numbers, steps, operations, elements, parts, components, materials, or a combination thereof described in the specification without excluding in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, elements, parts, components, materials, or combinations thereof.
(18) Hereinafter, a hydrophilic aluminum surface body according to an embodiment and a manufacturing method thereof will be described in detail with reference to the accompanying drawings.
(19)
(20) As shown in
(21) The hydrophilic aluminum surface body is formed with a nanopattern of a hybrid nanostructure including nanoparticles and nanoflakes on a part or the whole of the surface of the aluminum substrate and has a small contact angle with purified water (water), and the small contact angle may have durability without affecting the aging effect.
(22) The aluminum substrate means a substrate made of aluminum, regardless of its shape, thickness, and bonding with other materials, and is not limited to a material made of pure aluminum. The aluminum substrate may be in the form of a plate or mesh.
(23) The aluminum substrate may further include an aluminum oxide film including boehmite (AlO(OH)), aluminum oxide (Al.sub.2O.sub.3) or a combination thereof on the surface of the aluminum substrate as shown in
(24) The nanopattern formed on the surface of the aluminum substrate includes a hybrid nanostructure formed by hybridizing nanoparticles and nanoflakes, and the nanoflakes may have shapes of needles, plates, or combinations thereof. The hybrid nanostructure has a shape in which the nanoparticles are hybridized with the nanoflakes so that the nanoparticles are formed alone or in a cluster therein and the nanoflakes are formed on the outside of the nanoparticles.
(25) The size of the nanoparticle may be several nm to several hundreds nm. For example, the nanoparticles may have an average diameter in the range of about 1 nm to about 1000 nm, for example, about 20 nm to about 600 nm, and about 50 nm to about 500 nm. In the range, while the nanoflakes are grown around the nanoparticles, a hybrid nanostructure having a shape capable of imparting hydrophilicity to the aluminum substrate may be obtained.
(26) The nanoparticles sustain hydrophilicity of the aluminum surface body, and may serve as a nucleus that forms a central point in growing the nanoflakes through oxidation of the aluminum substrate and may form a hydrophilic aluminum substrate having a unique characteristic of the nanoparticles.
(27) The nanoparticles are generally spherical in shape, but may be in the form of a plate or a tube, and may include at least one selected from the group consisting of metals, metal oxides, carbon nanotubes, and graphenes. The nanoparticles may include at least one selected from the group consisting of Ti, Au, Ag, Pt, Cr, Fe, Co, Ni, Cu, Al, Si, alloys thereof and oxides thereof. For example, TiO.sub.2, SiO.sub.2, Au, Pt, Ag, carbon nanotube, graphene, and the like may be used. Depending on the type of nanoparticles used, application fields may also be varied considering the functionality of the material.
(28) The nanoparticles may be present singly or a plurality of nanoparticles may be aggregated to form a nanocluster, and the nanoparticles may be present in a combined form.
(29) Each of the nanoflakes has a plate, needle or dot shape and may include boehmite (AlO(OH)), aluminum oxide (Al.sub.2O.sub.3) or a combination thereof. The nanoflakes are formed around the nanoparticles. For example, a plurality of nanoflakes may have a structure which is formed around the nanoparticles and on the aluminum substrate and grown toward the top of the surface of the aluminum substrate.
(30) When each of the nanoflakes has a needle shape, the longitudinal direction thereof is substantially vertical to the surface of the aluminum substrate, one end in the longitudinal direction is chemically bonded to the surface of the aluminum substrate, and the other end forms the surface of the hydrophilic aluminum surface body to contact the air. Further, when each of the nanoflakes has a plate shape, one end in a height direction substantially vertical to the surface of the aluminum substrate is chemically bonded to aluminum and the other end has a structure which forms the surface of the hydrophilized aluminum surface body to contact the air, and the plate-shaped nanoflakes form a hybrid nanostructure having a leave or petal-like shape around the nanoparticles. The plate-like nanoflakes may have a sawtooth shape at the end portion in contact with air.
(31) Each of the nanoflakes may have a height of about 10 nm to about 300 nm in the case of the needle shape and a height of about 10 nm to about 30 nm and a width of about 10 nm to about 300 nm in the case of the plate shape. In the range, the hybrid nanostructure for imparting hydrophilicity to the aluminum surface body may be formed.
(32) When the nanopattern formed of the hybrid nanostructure including the nanoparticles and the nanoflakes is formed on the surface of the aluminum substrate, the hydrophobic aluminum surface may be changed to hydrophilic due to the fine nanopattern. In addition, the nanopattern is excellent in durability and chemically stable, so that hydrophilicity may be maintained for a long time.
(33) The hydrophilic aluminum surface body may exhibit a hydrophilic property with a contact angle of 20 or less using purified water, and may exhibit a superhydrophilic property with a contact angle of 10 or less. Such hydrophilic to superhydrophilic properties are strong in persistence enough to maintain hydrophilic to superhydrophilic properties even though the hydrophilic aluminum surface body is exposed to the atmosphere for 60 days or more.
(34) Since the hydrophilic aluminum surface body includes nanoparticles having persistent hydrophilicity and is hydrophilized by a technique for controlling the microstructure of the aluminum surface, the hydrophilic or superhydrophilic property may be maintained for a much longer time than simple coating or surface activation treatment. In addition, hydrophilicity may be imparted by a nanopattern including the hybrid nanostructure chemically bonded to the surface of aluminum. Such a nanopattern is stable in energy and the durability of the hydrophilic aluminum surface body is excellent.
(35) Such a hydrophilic aluminum surface body may be effectively applied to an oil-water separating apparatus.
(36) In addition, the hydrophilic aluminum surface body may be applied to various products depending on the functionality of the nanoparticles. The hydrophilic aluminum surface body may be applied to all or a part of components, and may be applied to, for example, industrial or household dehumidifiers; Sanitary piping; mirrors or glasses that are not glazed; and various heat exchangers such as air conditioners, refrigerators, freezers, and the like.
(37) Hereinafter, a manufacturing method of a hydrophilic aluminum surface body according to one embodiment will be described.
(38) The manufacturing method of a hydrophilic aluminum surface body according to one embodiment includes: preparing a hydrophilic aluminum surface by oxidizing nanoparticles and an aluminum substrate to form a hybrid nanostructure including nanoparticles on a part or the whole of the surface of the aluminum substrate and a plurality of nanoflakes around the nanoparticles.
(39) The hybrid nanostructure in which nanoparticles and nanoflakes are hybridized on the surface of the aluminum substrate may be formed by the manufacturing method.
(40) The oxidation in the preparing of the hydrophilic aluminum surface may be performed by bringing a reaction liquid including water or a vapor thereof into contact with the nanoparticles and the aluminum substrate. The water may be distilled water, deionized water, or a combination thereof, and the reaction liquid may be made of water, or made of an acid, a salt including Cl, and a combination thereof with water. As the salt including Cl, for example, sodium chloride (NaCl) may be applied.
(41) The oxidation in the preparing of the hydrophilic aluminum surface may performed by contact with the reaction liquid at about 70 C. to about 150 C. or its vapor. The oxidation in the preparing of the hydrophilic aluminum surface may performed by contact with a reaction liquid at about 80 C. to about 130 C., a reaction liquid at about 90 C. to about 100 C., or its vapor. In addition, the oxidation may be performed, for example, for about 1 minute to about 100 minutes. In the range, the surface of the aluminum substrate may be rapidly oxidized to form a nanopattern in which a double nanostructure of nanoparticles and nanoflakes is hybridized on a part or the whole of the surface of the aluminum substrate, thereby manufacturing an aluminum surface with improved hydrophilicity.
(42) The surface of the aluminum substrate becomes a state in which the surface is easily oxidized by a hot reaction liquid. The surface of the aluminum substrate forms a nanopattern in which needle-like nanoflakes are hybridized with the nanoparticles on the surface thereof by contact with the reaction liquid including water or its vapor. The oxidation reaction occurs when the aluminum surface comes into contact with water or water vapor included in the reaction liquid or the vapor thereof. The needle-like nanoflakes may be grown on the surface of the nanoparticles, and while the nanoflakes are grown in other areas, the nanopattern having a hybrid structure in which the plate-like nanoflakes are densely formed may be formed.
(43) According to one embodiment, as shown in
(44) The hydrophilic aluminum surface body manufactured by the manufacturing method may exhibit a hydrophilic property with a contact angle of 20 C. or less using purified water and may exhibit a superhydrophilic property with a contact angle of 10 C. or less.
(45) According to the manufacturing method of the hydrophilic aluminum surface body, hydrophobic aluminum may be artificially prepared as hydrophilic or superhydrophilic aluminum without forming a coating film coated with a separate adduct such as a hydrophilic polymer or the like. The hydrophilic or superhydrophilic aluminum treated above has an improved dehumidification function and may be used for water harvesting, anti-fog, magnetic cleaning, anti-bacteria or growing cells. In addition, the hydrophilic aluminum treated by the manufacturing method hardly exhibits an aging effect, maintains a hydrophilic property for a long time, and may obtain a hydrophilic surface without using a hydrophilic coating agent. For example, an aluminum surface with a hybrid nanostructure including TiO.sub.2 nanoparticles or Ag nanoparticles has hydrophilic persistence and an antimicrobial property. Furthermore, the method is a method that may be applied to large-area aluminum and may perform a large-scale oxidation process, and an eco-friendly method by minimizing the use of a toxic substance such as an acidic solution, thereby providing hydrophilic hybrid nanostructured aluminum.
(46) Hereinafter, one or more embodiments will be described in more detail with reference to Examples.
(47) The morphology structures of surfaces prepared in the following Examples and Comparative Examples were examined by a scanning electron microscope (SEM, FEI, Nova NanoSEM 200, USA). A contact angle (CA) for water was measured with a contact angle meter (Goniometer, Rame-Hart, USA). The volume of each droplet used at a static contact angle was 8 l. The average CA values were measured at five different locations for the same sample.
Example 1
(48) A plate material (thickness of 0.3 mm) having a purity of 99.9% was used as an aluminum substrate, and TiO.sub.2 nanoparticles (average particle diameter of 30 nm) and the aluminum substrate were immersed in boiling water, maintained for 10 minutes and then removed from water to form an aluminum surface with a hybrid nanostructure.
Comparative Example 1
(49) The aluminum substrate (pristine) used in Example 1 in a water-untreated state was regarded as Comparative Example 1.
Comparative Example 2
(50) Instead of using TiO.sub.2 nanoparticles, only the aluminum substrate used in Example 1 was immersed in boiling water, maintained for 10 minutes, and then removed from the water to prepare aluminum having a nanopatterned surface.
Evaluation Example 1: SEM Analysis and Evaluation of Water Contact Angle
(51) A scanning electron microscope (SEM) was used to examine the morphology of the aluminum surface according to Example 1, and the results are shown in
(52) For comparison with Comparative Examples 1 and 2, SEM photographs of aluminum surfaces according to Comparative Examples 1 and 2 and Example 1 and contact angle images of purified water on each surface are shown in
(53) In contact angle images of purified water at the lower portion of
Evaluation Example 2: SEM Image According to Water Treatment Time
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Evaluation Example 3: TEM Analysis
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Evaluation Example 4: Change in Water Contact Angle with Time
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(57) As shown in
Examples 2 to 5
(58) In the present Examples, in order to develop an oil-water separation filter excellent in mechanical durability using an aluminum surface with the hybrid nanostructure, a water treatment method was used.
(59) In Examples 2 to 5, aluminum meshes with purity of 99.9% were used as aluminum substrates. The aluminum substrates used in Examples 2 to 5 were represented by Al #1 (a diameter of about 50 m and a hole size of about 7,600 m2), Al #2 (a diameter of about 90 m and a hole size of about 16,000 m2), Al #3 (a diameter of about 230 m and a hole size of about 90,000 m2), and Al #4 (a diameter of about 250 m and a hole size of about 164,000 m2) depending on a mesh size, respectively.
(60) TiO.sub.2 nanoparticles (an average particle diameter of 30 nm) and the aluminum mesh was immersed in boiling water, maintained for 10 minutes, and then removed from the water to form a hybrid nanostructure on the surface of the aluminum mesh. The aluminum meshes formed with the hybrid nanostructures in Examples 2 to 5 may be represented by water and TiO.sub.2 treated Al #1, Al #2, Al #3, and Al #4.
Comparative Examples 3 to 6
(61) Aluminum meshes (pristine Al #1, Al #2, Al #3, and Al #4) in the water-untreated state used in Examples 2 to 5 were regarded as Comparative Examples 3 to 6, respectively.
Comparative Examples 7 to 10
(62) Instead of using TiO.sub.2 nanoparticles, the aluminum meshes used in Examples 2 to 5 were immersed in boiling water, maintained for 10 minutes, and then removed from water to prepare aluminum meshes (water treated Al #1, Al #2, Al #3, and Al #4) having surfaces with nanopatterns and the prepared aluminum meshes were regarded as Comparative Examples 7 to 10.
Evaluation Example 5: SEM Analysis and Evaluation of Water Contact Angle
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(64) The water contact angle of the aluminum mesh according to Example 2 was measured, and as a result, it was confirmed that the contact angle was less than about 5.
Evaluation Example 6: Oil-Water Separation Experiment
(65) An experiment for separating crude oil from water was performed by applying aluminum meshes according to Comparative Examples 3 and 7 and Example 2, the oil was separated and removed from water, and then the aluminum mesh surface was washed with water, and thereafter, the aluminum mesh surface was analyzed by an optical microscope and an electron microscope.
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(67) As shown in
(68) The aluminum mesh according to Comparative Example 7 had more oil-water separation performance than water treatment, but it was confirmed that the separation rate of the oil and the sample was slow during water washing, and oil residues covered the nanostructures on the surface when observed by an electron microscope. Therefore, it is expected that the aluminum mesh according to Comparative Example 7 will have difficulty in maintaining hydrophilicity and reuse.
(69) The aluminum mesh according to Example 2, in which the hybrid nanostructure was formed on the surface, was excellent in separability of the oil and the sample during washing, and it was difficult to find the oil except for a part where the meshes overlapped with each other on the optical micrographs. In addition, even with an electron microscope, the oil does not cover the nanostructure, so its shape was confirmed and its reusability was confirmed.
Evaluation Example 7: Measurement of Oil Permeation Pressure
(70) In order to compare a size of an aluminum mesh and oil treatment pressure according to treatment,
(71) As shown in
Evaluation Example 8: Measurement of Water Contact Angle
(72) In order to confirm hydrophilicity and underwater oleophobicity of aluminum meshes according to Comparative Examples 3 to 5 (pristine Al #1, Al #2, and Al #3), Comparative Examples 7 to 9 (water treated Al #1, Al #2, and Al #3) and Examples 2 to 4 (water and TiO.sub.2 treated Al #1, Al #2, and Al #3), a water contact angle for crude oil was measured and analyzed, and the result thereof was shown in
(73) As shown in
(74) In addition, a result of measuring water sliding angles of aluminum meshes according to Comparative Examples 3 to 5 (pristine), Comparative Examples 7 to 9 (water treated Al) and Examples 2 to 4 (water and TiO.sub.2 treated Al) was shown in
(75) SEM images of water contact angles and water sliding angles of aluminum meshes according to Comparative Example 3, Comparative Example 7, and Example 2 are shown in
Example 6
(76) A plate material (thickness of 0.3 mm) having purity of 99.9% was used as an aluminum substrate, and Pt nanoparticles (average particle diameter of 30 nm) and the aluminum substrate were immersed in boiling water, maintained for 10 minutes and then removed from water to form an aluminum surface with a hybrid nanostructure.
Evaluation Example 9: SEM Analysis
(77) An SEM was used to confirm the morphology of a hybrid nanostructure formed on the aluminum surface according to Example 6, and the results are shown in
(78) As shown in
(79) As described above, according to one or more embodiments, the hydrophilic aluminum surface body is excellent in hydrophilicity, does almost not exhibit an aging effect, and may maintain hydrophilicity for a long time. According to the manufacturing method of the hydrophilic aluminum surface body, it is possible to prepare hydrophobic aluminum artificially as hydrophilic or superhydrophilic aluminum due to a small contact angle, and to provide an aluminum surface body which does almost not exhibit an aging effect and maintains hydrophilicity for a long time. In addition, it is possible to impart excellent hydrophilicity to the aluminum surface without using a hydrophilic coating agent. The manufacturing method is a method which may be applied to large-area aluminum and may be processed under low vacuum or atmospheric pressure to make a mass production, and an eco-friendly method by minimizing the use of toxic substances such as an acidic solution.
(80) It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments.
(81) While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure as defined by the following claims.