CN108699718B - Metal oxide film and method for producing same - Google Patents
Metal oxide film and method for producing same Download PDFInfo
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- CN108699718B CN108699718B CN201780005711.XA CN201780005711A CN108699718B CN 108699718 B CN108699718 B CN 108699718B CN 201780005711 A CN201780005711 A CN 201780005711A CN 108699718 B CN108699718 B CN 108699718B
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Abstract
A metal oxide film which comprises a metal oxide represented by the following formula (1) or a ZnO-containing metal oxide and has a porous structure in which a plurality of needle-like or plate-like crystals are arranged in a mesh or a sword-like shape. MxL3‑xO4(1) (in the formula, M is not equal to L, M is selected from the group consisting of Mg, Fe, Zn, Mn, Cu, Co, Cr and Ni, L is selected from the group consisting of Co, Al, Fe and Cr, and x is not less than 0 and not more than 1).
Description
Technical Field
The present invention relates to a metal oxide film and a method for producing the same.
Background
Conventionally, a film is formed on the surface of a substrate for the purpose of imparting desired surface characteristics to the substrate, and the like. The metal oxide film has advantages such as high heat resistance and good adhesion to a metal substrate, and the use of the metal oxide film may be used instead of a conventional film to solve the technical problem of the conventional film.
For example, as conventional water repellent materials, there can be exemplified: a water repellent material described in patent document 1 in which an organic compound is formed on the surface of a metal substrate having a large number of micropores formed therein, and a water repellent material described in patent document 2 in which a silica film having irregularities is formed on the surface of a glass substrate. The organic compound film of patent document 1 has low heat resistance, and therefore, substitution with a metal oxide film is expected to improve heat resistance. In addition, the silica film of patent document 2 has low adhesion to a metal substrate, and thus substitution with a metal oxide film is expected to improve adhesion to the substrate. The silica film is insulating and is difficult to be used for electronic components and the like in which generation of static electricity is a problem, but the metal oxide film can be suitably used for electronic components and the like.
As a conventional light absorbing material, for example, as described in patent document 3, there is exemplified a light absorbing material formed in a film shape by selecting ferroferric oxide as a substance that efficiently absorbs light in a wide wavelength range from visible light to infrared light, and thermally spraying a powder thereof on a surface of a metal or ceramic substrate. However, in patent document 3, since a film is formed by thermal spraying of ferroferric oxide as an inorganic material, a light absorbing material having excellent durability can be obtained, but it is difficult to form a fine uneven structure on the surface thereof, and the light absorption property cannot be sufficiently improved. In patent documents 4 and 5, in order to improve the light absorption of the light absorbing material, a fine uneven structure is formed by forming the surface of the light absorbing material by a nanoimprint method or a pressing method. The method of forming a fine uneven structure by molding or processing can be applied to a resin or a soft inorganic material, but is difficult to apply to a hard inorganic material having high durability such as a metal oxide film described in patent document 3. There is a demand for development of a metal oxide film which is excellent in light absorption and durability and can be produced inexpensively with a small number of steps.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-207123
Patent document 2: japanese patent laid-open No. 2000-144116
Patent document 3: japanese laid-open patent publication No. 7-325212
Patent document 4: japanese patent laid-open No. 2008-70448
Patent document 5: japanese patent laid-open publication No. 2013-32594
Disclosure of Invention
Problems to be solved by the invention
There is a demand for development of a metal oxide film suitable for use as a water repellent material, instead of an organic compound film or a silicon oxide film. In general, metal oxides have low water repellency (a small true contact angle) compared with organic compounds and silicon dioxide, and therefore it is necessary to improve water repellency by an operation such as appropriately forming a porous structure on a film surface. In addition, when a metal oxide film is used as the light absorbing material, it is preferable to improve the light absorption property by an operation such as forming a fine porous structure on the surface thereof. Further, the metal oxide film having a porous structure formed on the surface thereof is preferably manufactured inexpensively with a small number of steps.
In view of the above problems, an object of the present invention is to provide a metal oxide film having a porous structure on the surface thereof and a method for producing the metal oxide film with less man-hours and at low cost.
Means for solving the problems
As a result of intensive studies, the present inventors have succeeded in producing a metal oxide film having a porous structure in which a plurality of needle-like or plate-like crystal grains are arranged in a mesh shape or a sword-like shape on the surface thereof at low cost with few man-hours. The present inventors have also paid attention to the fact that the metal oxide film is a film material excellent in water repellency or light absorbency, and finally completed the present invention.
The 1 st metal oxide film provided by the present invention contains a metal oxide represented by the following formula (1), and has a porous structure in which a plurality of needle-like or plate-like crystals are arranged in a mesh or a sword-like shape.
MxL3-xO4 (1)
In the formula, M is not equal to L, M is selected from the group consisting of Mg, Fe, Zn, Mn, Cu, Co, Cr and Ni, L is selected from the group consisting of Co, Al, Fe and Cr, and x satisfies 0-1.
The 2 nd metal oxide film provided by the present invention contains a metal oxide containing ZnO and has a porous structure in which a plurality of needle-like or plate-like crystals are arranged in a mesh shape or a sword-like shape.
The 1 st or 2 nd metal oxide film has a porous structure in which a plurality of needle-like or plate-like crystal bodies are arranged in a mesh shape or a sword-like shape. High water repellency or light absorbency can be obtained by utilizing this porous structure. Thus, the metal oxide film according to the present invention can be suitably used as a water repellent material or a light absorbing material. Further, since the metal oxide film is used, it has high heat resistance and can be favorably adhered to a metal base material. This makes it possible to suitably apply the composition to applications such as machine parts and electronic parts, and to improve the heat transfer property between the base material and the metal oxide film. Further, the resin composition can be produced inexpensively with a small number of steps according to a production method described later.
In the 1 st metal oxide film, in the metal oxide, L in the formula (1) is preferably Fe. In addition, the metal oxide particularly preferably contains ZnO. This makes it possible to obtain a metal oxide film having higher water repellency or light absorbency.
In the 1 st or 2 nd metal oxide film described above, the distance of adjacent crystals in the porous structure in a direction parallel to the surface of the metal oxide film is preferably 10 μm or less.
In the 1 st or 2 nd metal oxide film of the present invention, the crystal body of the porous structure is preferably elongated toward the surface side of the metal oxide film at an angle α of 45 ° to 90 ° formed by an angle α formed by a line connecting the top end of the crystal body and the center of the bottom surface of the crystal body in the short side direction with respect to the bottom surface. A metal oxide film having higher water repellency or light absorption can be obtained.
The present invention provides a water repellent material, wherein the 1 st or 2 nd metal oxide film is formed on the surface thereof. The metal oxide film 1 or 2 has high water repellency even when a metal oxide known as a material having a general water repellency lower than that of the water repellent material described in patent document 1 or the like is used, and can be used in place of a conventionally used water repellent material such as an organic compound film or a silica film. The present invention can provide a water repellent material which has high heat resistance, can adhere well to a metal base material, and can be suitably used for applications such as machine parts and electronic parts.
Further, there is provided a light absorbing material having the 1 st or 2 nd metal oxide film formed on the surface thereof. According to the 1 st or 2 nd metal oxide film, since the film is formed using a material having high absorptivity with respect to light having a wide range of wavelengths and has a porous structure in which a plurality of needle-like or plate-like crystal bodies are arranged in a mesh shape or a sword-like shape, more excellent light absorption can be obtained based on both effects of the material and the structure. The present invention can provide a light absorbing material which is excellent in light absorption and durability and can be produced inexpensively with a small number of steps. The light absorbing material of the present invention can be produced inexpensively with a small number of steps, and therefore, is not limited to the use as a fine component of an optical device or the like, and can be practically used as a relatively large-sized member such as a light absorbing portion for solar power generation, a solar absorbing plate, a light absorbing heat exchanger, a heater, or the like. In addition, the metal oxide represented by the above formula (1) can be favorably adhered to a metal base material, and thus the heat transfer property between the base material and the light absorbing material can be improved, and thus the metal oxide can contribute to improvement in the thermal efficiency of the light absorbing portion, the solar absorbing plate, the light absorbing heat exchanger, the heater, and the like of solar power generation.
The present invention also provides a method for producing the metal oxide film. The manufacturing method comprises the following steps: a deposition step of depositing a metal or a metal compound containing one or more elements selected from Fe, Zn, Cu, Co, Cr, Ni, Mg and Al on the surface of the base material, and a heat treatment step of heat-treating the substrate after the deposition step. According to the above-described production method, the porous structure of the metal oxide film is formed only by the deposition step and the heat treatment step without performing forming, processing, or the like. That is, the metal oxide film can be produced inexpensively with a small number of steps.
In the production method of the present invention, the deposition step is preferably carried out by electrodeposition in an electrodeposition bath containing an organic acid and one or more elements selected from Fe, Zn, Cu, Co, Cr, Ni, Mg, and Al. The organic acid forms a complex with the metal element, and carbon and oxygen are introduced into the metal compound obtained by film formation, whereby the crystal structure of the crystal after heat treatment can be controlled.
In the production method of the present invention, the precipitation step preferably precipitates one or more elements selected from Fe, Zn, Cu, Co, Cr, Ni, Mg, and Al in one or more layers.
In the production method of the present invention, the heat treatment step is preferably performed at 200 ℃ or higher for 1 minute or more and 10 hours or less.
Drawings
Fig. 1 is a schematic diagram illustrating a metal oxide film according to an embodiment.
Fig. 2 is a schematic view illustrating the water repellency of the metal oxide film according to the embodiment.
Fig. 3 is a schematic diagram illustrating the light absorption of the metal oxide film according to the embodiment.
Fig. 4 is a schematic diagram illustrating the angles of the crystals constituting the metal oxide film according to the embodiment.
Fig. 5 shows an SEM image of the surface of the metal oxide film of example 1.
Fig. 6 is an enlarged SEM image of a part of fig. 5.
Fig. 7 is a graph showing the results of X-ray diffraction of the metal oxide film of example 1.
Fig. 8 shows a TEM image of the metal oxide film of example 1.
Fig. 9 is a graph showing the results of electron beam diffraction of the metal oxide film of example 1.
Fig. 10 is an SEM image showing a cross section of the metal oxide film of example 1.
Fig. 11 is an enlarged SEM image of a part of fig. 10.
Fig. 12 is an image of the metal oxide film of example 1 with water droplets dropped on the surface.
Fig. 13 is a diagram showing the light absorption properties of the metal oxide film of example 8.
Fig. 14 shows an SEM image of the surface of the metal oxide film of example 8.
Fig. 15 is a graph showing the results of X-ray diffraction of the metal oxide film of example 8.
Detailed Description
The 1 st or 2 nd metal oxide film of the present invention is formed on the substrate as a needle-like or plate-like crystal. When the surface of the metal oxide film is observed, a plurality of needle-like or plate-like crystals are arranged in an irregular mesh or a sword-like shape, thereby forming a porous structure. The plurality of needle-like crystal grains may be needle-like crystal grains that cross each other in a state where the crystal grains extend in the longitudinal direction substantially parallel to the surface of the metal oxide film and form a mesh structure as a whole, or needle-like crystal grains that stand like a sword-mountain forest. The plurality of plate-shaped crystals may be: the metal oxide film is elongated in a wall shape with a certain width in the thickness direction of the metal oxide film and is randomly elongated in the surface direction of the metal oxide film to form plate-like crystals having a mesh structure as a whole. The water repellency of the water repellent material is increased by the gas present in the space in the porous structure. In addition, the porous structure makes the light absorption of the light absorbing material high.
Such a porous structure is easily formed in the case where the metal oxide film contains the metal oxide represented by the above formula (1) or the case where the metal oxide film contains a metal oxide containing ZnO. In order to obtain high water repellency or high light absorption, the metal oxide film preferably contains a metal oxide represented by the above formula (1) or a ZnO-containing metal oxide as a main component. The metal oxide of the metal oxide film of the present invention is preferably a spinel-type metal oxide, and particularly preferably a spinel-type metal oxide containing Zn and Fe. When the metal oxide film of the present invention is analyzed by X-ray diffraction, it is preferable that 3 or more peaks of the metal oxide represented by the above formula (1) are observed.
The metal oxide film will be described by referring to fig. 1 as a specific example. The metal oxide film 10 includes a plurality of crystal bodies 12 extending from the surface of a metal substrate 16. The crystal body 12 is a plate-like crystal body including the metal oxide according to the present invention. Although fig. 1 schematically shows a cross section of the plate-like crystal bodies 12, when the metal oxide film 10 is viewed from the front surface side, the plurality of plate-like crystal bodies 12 randomly extend in the planar direction of the metal oxide film 10 to form a mesh-like porous structure. The crystal body 12 is a plate-like crystal having a cross-sectional shape of a long and narrow triangular shape, and the width of the top 14 of the crystal body 12 is the narrowest. When water droplets or the like adhere to the surface of the metal oxide film 10, the crystals 12 come into contact with the water droplets, and air present in the spaces within the porous structure formed by the crystals 12 also comes into contact with the water droplets. Since the real contact angle of air is larger than that of the crystal body 12, the water repellency of the metal oxide film becomes high by bringing the air inside the crystal body 12 into contact with the water droplet.
The water repellency of the metal oxide film 10 will be described in more detail with reference to fig. 2. Fig. 2 shows a state in which water droplets 1 are attached to the surface of the water repellent material 10. Water droplets 1 contact the tips 14 of crystals 12 and also contact the air present between adjacent crystals 12. When the area of the contact surface between the water droplet 1 and the crystal body 12 is a1 and the area of the contact surface between the water droplet 1 and the crystal body 12 is a2, the ratio a of the contact surface of the crystal body 12 to the contact surface between the water droplet 1 and the metal oxide film 10 is represented by a1/(a1+ a 2). Using this ratio A, the contact angle φ of the water droplet 1 shown in FIG. 2 is represented by Cassie's formula shown in the following formula (2), which is described in "Transactions of the Faraday Society" 40, 546-551 (1944).
cosφ＝Acosφ1+(1-A)cosφ2 (2)
Here, Φ 1 is a real contact angle of the metal oxide constituting the crystalline body 12, and Φ 2 is a real contact angle of air. For example, Fe is ferroferric oxide in the crystalline body 123O4In the case of (2), the true contact angle of the crystal body 12 is about 70 °, the true contact angle of air is 180 °, and the smaller a, the larger the contact angle, and the higher the water repellency of the metal oxide film 10.
The 1 st or 2 nd metal oxide film is formed by using a material having high absorptivity with respect to light having a wide range of wavelengths, and has a porous structure in which a plurality of needle-like or plate-like crystal bodies are arranged in a mesh shape or a sword-like shape, and therefore, more excellent light absorption can be obtained based on both effects of the material and the structure. This porous structure can be naturally formed in the process of manufacturing the light absorbing material of the present invention, and thus a metal oxide film having high durability can be manufactured without performing molding, processing, or the like. That is, according to the 1 st or 2 nd metal oxide film, a metal oxide film which is excellent in light absorption and durability and can be manufactured inexpensively with a small number of steps can be provided. The metal oxide film of the present invention can be produced at low cost with a small number of steps, has excellent mass productivity, and therefore can be practically used as a relatively large-sized light absorbing material such as a light absorbing portion for solar power generation, a solar absorbing plate, a light absorbing heat exchanger, and a heater, without being limited to the use as a fine component of an optical device or the like.
The light absorption of the metal oxide film 10 will be specifically described with reference to fig. 3 schematically showing the form of the 1 st or 2 nd metal oxide film. The metal oxide film 10 has a porous structure formed by crystals 12 extending from the surface of a substrate 16. Since the metal oxide film 10 is formed of a material having a high light absorptivity, every time the light 101 is irradiated to the metal oxide film 10, it is absorbed so that its reflected light is greatly attenuated. The attenuated reflected light further strikes crystalline bodies 12 in the pores of the porous structure (i.e., the spaces between adjacent crystalline bodies 12), and is further absorbed and attenuated. In the metal oxide film 10, light is absorbed and attenuated in the pores of the porous structure, and reflected light reflected to the outside of the porous structure can be greatly reduced, so that higher light absorption can be obtained.
In the case of using a metal oxide as the water repellent material, the distance of adjacent crystals (crystals 12 schematically shown in fig. 2) in the porous structure in the direction parallel to the surface of the metal oxide film is preferably 10 μm or less, and particularly preferably 5 μm or less. The porous structure of the metal oxide film can retain gas, and exchange of water droplets and the like with the gas can be suppressed, and high water repellency can be obtained.
In the case of using a metal oxide as the water repellent material, the distance of adjacent crystals (crystals 12 schematically shown in fig. 3) in the porous structure in the direction parallel to the surface of the metal oxide film is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The effect of absorbing light can be further improved in the porous structure of the metal oxide film, and high light absorption can be obtained. In order to secure the space between crystals of the porous structure, the distance between crystals in the direction parallel to the surface is preferably 0.02 μm or more, and more preferably 0.1 μm or more.
As shown in fig. 4, an angle α formed by the plate-shaped crystal body 12 with respect to the surface of the substrate 16 can be expressed as: an angle α formed by a line connecting the top end 14 of the crystal body 12 and the center of the bottom surface of the crystal body 12 in the short side direction (coinciding with the surface of the base 16 in fig. 3) with respect to the bottom surface of the crystal body 12. When the angle α is too small, water droplets become easy to enter the space within the porous structure along the side surface of the inclined crystal body 12, and thus the angle α is preferably large. In addition, when the angle α is too small, it becomes difficult to obtain the effect of absorbing light in the porous structure of the metal oxide film, and therefore the angle α is preferably large. The angle α is preferably in the range of 45 ° to 90 °, and particularly preferably about 90 ° (maximum value of the angle α).
The 1 st and 2 nd metal oxide films may further include a material having liquid repellency or light absorbency on the surface or in the pores of the porous structure. For example, by using a liquid repellent material to impart liquid repellency to the surface or in the pores of the porous structure, it is possible to prevent the liquid from adhering to the metal oxide film and impairing the surface properties such as light absorption. In addition, for example, by attaching a light-absorbing material to the surface or in the pores of the porous structure, the wavelength or the absorption rate of light absorbed by the metal oxide film can be adjusted. Specifically, for the metal oxide film, a liquid repellent material such as silicone, a black material such as carbon powder or carbon nanotubes having high light absorption, a pigment, a dye, or the like can be preferably used. The material having liquid repellency or light absorbency may be a particulate material, or a film-like or gel-like material. The material having liquid repellency or light absorbency may be coated or painted, chemically or physically bonded to the surface of the metal oxide film, or synthesized from a raw material on the surface of the metal oxide film.
The metal oxide film of the present invention can be favorably adhered to a metal substrate. The metal oxide film of the present invention can be formed by depositing 1 or more layers of metal or metal compound on a substrate by electrodeposition or vapor deposition, and performing heat treatment. When a metal oxide film is formed on a metal substrate, the substrate is preferably used as a cathode, and electrodeposition is preferably performed using an electrodeposition solution containing a component metal element (for example, metal element M, L shown in formula (1)) constituting a metal oxide that is a main component of the metal oxide film. The metal oxide film and the substrate can be favorably adhered to each other, and the composition of the metal oxide contained in the metal oxide film can be easily controlled by controlling the composition of the electrodeposition liquid. The electrodeposition method is not limited to a substrate made of a conductive material such as a metal, and can be applied to a substrate having a surface subjected to a conductive treatment.
The bath preferably contains the constituent metal elements in the form of sulfates, sulfamates, chlorides. Further, the electrodeposition liquid preferably contains 1 or more organic acids selected from the group consisting of L-ascorbic acid, citric acid and fumaric acid. In order to effectively promote electrodeposition, the total concentration of the organic acid and the salt of the organic acid contained in the electrodeposition liquid is preferably 0.1g/L or more, and more preferably 0.5g/L or more. The electrodeposition is preferably carried out at a current density of 0.1A/dm2～30A/dm2The temperature of the electrodeposition liquid is 0-90 ℃, and the electrodeposition time is 0.01-60 minutes.
In the method for producing the 1 st or 2 nd metal oxide film of the present invention, the precipitation step may precipitate one or more elements selected from Fe, Zn, Cu, Co, Cr, Ni, Mg, and Al in one or more layers.
It is preferable that the compound containing the component metal element is precipitated on the surface of the base material, and then heat treatment is performed using a gas such as air as an atmospheric gas. The heat treatment temperature is preferably 200 ℃ or higher, and the treatment temperature is particularly preferably 200 to 600 ℃. The heat treatment time is preferably 1 minute to 10 hours, more preferably 10 minutes to 5 hours, and particularly preferably 0.5 hours to 3 hours.
Examples
In the examples and comparative examples, a 2cm square plate-shaped metal plate was used as a base material, and a metal oxide film was formed on the surface of the metal base material, and the structure and properties thereof were analyzed. Some of the production conditions, the analysis results, and the like are shown in table 1 or table 2.
(example 1)
(method for producing Metal oxide film)
(electrodeposition step)
A base material made of SUS440C (JIS G4304) was prepared as a stainless steel material. Prepared to contain FeSO4(concentration: 100g/L), ZnSO4(concentration: 5.5g/L), citric acid (concentration: 1g/L), and L-ascorbic acid (concentration: 3g/L) as an aqueous solutionAnd (4) electrodepositing liquid. Immersing the iron electrode as an anode and the base material as a cathode in an electrodeposition solution at a current density of 5A/dm2And electrodeposition was carried out at 50 ℃ for 10 minutes. As a result, a metal film having a thickness of about 10 μm can be deposited on the substrate.
(Heat treatment Process)
The substrate after the electrodeposition step was placed in an electric furnace heated to 580 ℃ and heat-treated in an atmospheric atmosphere for 1 hour, and then the substrate was taken out from the electric furnace. The substrate taken out of the electric furnace was immediately placed in a vacuum drier and allowed to cool for 24 hours, thereby producing a metal oxide film of example 1.
(surface observation)
Fig. 5 and 6 show images obtained by observing the surface of the metal oxide film of example 1 with a Scanning Electron Microscope (SEM). As shown in fig. 5 and 6, there are a plurality of plate-like crystals extending from the surface of the substrate. When the plurality of plate-like crystals are viewed from the surface side of the metal oxide film in plan, the plurality of plate-like crystals extend in the thickness direction of the metal oxide film in a wall shape having a certain width and randomly extend in the surface direction of the metal oxide film, and thus have a complex mesh-like porous structure as a whole. The interval between adjacent crystal bodies was measured using the SEM image of fig. 5 and using a tangent method (a method of measuring the interval between adjacent crystal bodies along a straight line drawn at equal intervals in the up-down direction and the left-right direction of the SEM image). SEM images of the surface of the metal oxide film of example 1 were taken at 5 sites including fig. 5, and the interval between adjacent crystals was measured by the tangent method in the same manner, and the upper limit value thereof is shown in table 1. It is understood that the distance of the adjacent crystals in the metal oxide film of example 1 in the direction parallel to the surface of the metal oxide film is 0.9 μm or less.
(structural analysis)
Fig. 7 shows the results of X-ray diffraction of the metal oxide film of example 1. As shown in fig. 6, in the metal oxide film of example 1, spinel-type metal oxide (Fe) was observed3O4Or ZnFe2O4) A peak of (d) (a peak marked by a black triangle) and a peak of ZnO (a peak marked by a white circle). More than 3 spinel type metal oxide peaks are observed. As shown in fig. 7, the metal oxide film of example 1 contains a spinel-type metal oxide as a main component, and a part thereof contains ZnO. In addition, the metal oxide film of example 1 was analyzed by a Transmission Electron Microscope (TEM). The results are shown in fig. 8 and 9. Fig. 9 shows the result of electron beam diffraction of the portion surrounded by a circle in fig. 8. As shown in fig. 9, it is apparent that ZnFe is contained in the spinel-type metal oxide2O4。
(section observation)
Fig. 10 and 11 show images obtained by SEM observation of a cross section obtained by cutting the metal oxide film of example 1 in the thickness direction thereof. Fig. 11 is an enlarged view of a portion surrounded by a dotted quadrangle in fig. 10. The frame shown by the dotted line in fig. 11 indicates a portion where the metal oxide film is formed. As shown in fig. 10 and 11, a plurality of plate-like crystal bodies extending from the surface of the substrate are provided, and the crystal bodies are arranged so as to be separated from each other, and a space is formed between the crystal bodies. From fig. 10, an angle α formed by a line connecting the top end of the plate-like crystal body and the center in the short side direction of the bottom surface of the crystal body with respect to the bottom surface was measured. SEM images of the cross section of the metal oxide film of example 1 were taken at 3 positions including fig. 10, and the angle α was measured in the same manner, and the lower limit value thereof is shown in table 1. In the metal oxide film of example 1, α ≧ 67.
(contact Angle measurement)
The contact angle was measured by the liquid drop method (sessile drop method). With 9 intersections of 3 × 3 straight lines obtained by dividing a 2cm square metal oxide film into 4 × 4 squares as measurement points, 1 μ L of water droplets was dropped onto each of the 9 measurement points, and the average values of the measured contact angles are shown in table 1. Fig. 12 is an image of the metal oxide film 10 of example 1 with water droplets 1 dropped on the surface. In the metal oxide film of example 1, the average value of the contact angle Φ was 153 °. By using a metal oxide film as a material of the water repellent material, a water repellent material having water repellency larger than a contact angle (about 80 °) of a general water repellent material can be realized.
(example 2)
In the metal oxide film of example 2, as shown in table 1, in the electrodeposition process, a nickel electrode was used as an anode, and ZnSO was contained4(concentration: 4g/L), Ni (NH)2SO3)2(concentration: 300g/L), citric acid (concentration: 0.5g/L), and L-ascorbic acid (concentration: 5g/L) as an electrodeposition solution. In the heat treatment step, heat treatment was performed for 0.5 hour. Other production conditions are the same as in example 1, and therefore, the description thereof is omitted. The metal oxide film of example 2 was also subjected to surface observation, structural analysis, and cross-sectional analysis in the same manner as in example 1, and the results are shown in table 1.
(example 3)
In the metal oxide film of example 3, as shown in table 1, the material of the base material was stainless steel SUS304(JIS G4304). In addition, in the electrodeposition process, FeSO is used4(concentration: 160g/L), ZnSO4(concentration: 5g/L) as an electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 500 ℃ and heat-treated in an atmospheric atmosphere for 1 hour. Other production conditions are the same as in example 1, and therefore, the description thereof is omitted. The metal oxide film in example 3 was also subjected to surface observation, structural analysis, and cross-sectional analysis in the same manner as in example 1, and the results are shown in table 1.
(example 4)
In the metal oxide film of example 4, the material of the substrate was steel SPC270(JIS G3141) as shown in table 1. In addition, in the electrodeposition process, FeSO is used4(concentration: 180g/L), Ni (NH)2SO3)2An aqueous solution of (concentration: 150g/L), citric acid (concentration: 2g/L) and L-ascorbic acid (concentration: 4g/L) was used as the electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step is charged into an electric furnace heated to 600 ℃The heat treatment was performed for 0.4 hour in an atmospheric atmosphere. Other production conditions are the same as in example 1, and therefore, the description thereof is omitted. The metal oxide film of example 4 was also subjected to surface observation, structural analysis, and cross-sectional analysis in the same manner as in example 1, and the results are shown in table 1.
(example 5)
In the metal oxide film of example 5, the material of the substrate was oxygen-free copper as shown in table 1. In addition, in the electrodeposition process, FeSO is used4(concentration: 100g/L), ZnSO4An aqueous solution of (concentration: 6g/L), urea (concentration: 50g/L), citric acid (concentration: 1g/L) and L-ascorbic acid (concentration: 3g/L) was used as the electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 500 ℃ and heat-treated in an atmospheric atmosphere for 2 hours. Other production conditions are the same as in example 1, and therefore, the description thereof is omitted. The metal oxide film of example 5 was also subjected to surface observation, structural analysis, and cross-sectional analysis in the same manner as in example 1, and the results are shown in table 1.
(example 6)
In the metal oxide film of example 6, as shown in table 1, the material of the base material was aluminum material a3103(JIS Z3232). In addition, in the electrodeposition process, FeSO is used4(concentration: 200g/L) and L-ascorbic acid (concentration: 5g/L) as an electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 350 ℃ and heat-treated in an atmospheric atmosphere for 3 hours. Other production conditions are the same as in example 1, and therefore, the description thereof is omitted. The metal oxide film of example 6 was also subjected to surface observation, structural analysis, and cross-sectional analysis in the same manner as in example 1, and the results are shown in table 1.
(example 7)
In the metal oxide film of example 7, as shown in table 1, the material of the base material was aluminum material a6061(JIS Z3232). In addition, in the electrodeposition step, FeCl is used2(concentration: 80g/L), ZnSO4(concentration: 5.5g/L) and L-ascorbic acid (concentration: 5g/L) as an aqueous solutionIs an electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 350 ℃ and heat-treated in an atmospheric atmosphere for 0.8 hour. Other production conditions are the same as in example 1, and therefore, the description thereof is omitted. The metal oxide film of example 7 was also subjected to surface observation, structural analysis, and cross-sectional analysis in the same manner as in example 1, and the results are shown in table 1.
Comparative example
In comparative examples, as shown in table 1, in the electrodeposition process, a nickel electrode was used as an anode, and Ni (NH) was used2SO3)2(concentration: 300g/L), NiCl2(concentration: 5g/L), HBO3(concentration: 40g/L) and saccharin (concentration: 3g/L) as an aqueous solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 500 ℃ and heat-treated in an atmospheric atmosphere for 1 hour. Other production conditions are the same as in example 1, and therefore, the description thereof is omitted. In comparative examples, surface observation and structural analysis were also performed in the same manner as in example 1. The results are shown in Table 1. As a result of surface observation, a planar surface was observed, and no porous structure was observed.
TABLE 1
As shown in table 1, in the metal oxide films of examples 1 to 5, it was observed that a plurality of plate-like crystal bodies were elongated in a wall shape with a certain degree of width in the thickness direction of the metal oxide film and were randomly elongated in the surface direction of the metal oxide film, and a complex mesh-like porous structure was formed by the plurality of plate-like crystal bodies. In the metal oxide films of examples 6 and 7, it was observed that a plurality of needle-like crystals crossed each other in a state where the long direction thereof extended substantially parallel to the surface of the metal oxide film, and a mesh-like porous structure was formed by the plurality of needle-like crystals. In contrast, in the comparative example, the metal oxide film containing NiO formed on the surface of the substrate was planar, and no porous structure was observed. In addition, X-ray diffraction was performed on the metal oxide films of examples 1 and 3 to 7, and as a result, 3 or more peaks of the spinel-type metal oxide were observed in both of them.
As shown in table 1, in the metal oxide films of the comparative examples, the contact angle Φ was 10 ° or less and the water repellency was significantly low, whereas in the metal oxide films of the examples, the metal oxide films having the contact angle Φ of 90 ° or more and the water repellency was high were obtained. In the comparative example, the metal oxide film containing NiO formed on the surface of the substrate was planar and did not have a porous structure, and therefore, it was considered that air was not retained on the surface thereof, and the water repellency was low. On the other hand, in the metal oxide film of the example, the needle-like or plate-like crystal forms a porous structure, and air is held on the surface of the metal oxide film by the porous structure, and thus it is considered that high water repellency is obtained. In particular, the metal oxide films of examples 1 to 5 exhibited high water repellency with a contact angle φ of 100 ° or more. This is considered to be because the metal oxide films of examples 1 to 5 have smaller distances between adjacent crystals in a direction parallel to the surface of the metal oxide film than those of examples 6 and 7, and the angle α formed by the line connecting the top end of the crystal and the center of the bottom face of the crystal with respect to the bottom face is larger. Further, the water repellency is higher as the estimated angle θ is larger, but it is known that water repellency can be obtained if it is 45 ° or more as in example 7. It is understood that the metal oxide film may be a metal oxide film containing a spinel-type metal oxide represented by the above formula (1) as in examples 1, 3 to 7, or a metal oxide film containing ZnO even when not a spinel-type metal oxide as in example 2, in order to make the metal oxide film have a porous structure. The metal oxide film of the present example has high heat resistance, can be favorably used for applications such as machine parts and electronic parts, and can also be favorably adhered to a metal base material. In particular, the metal oxide film of example 1 has a contact angle Φ of 153 ° which is significantly large, and can be preferably used for applications as a super water repellent material.
(example 8)
(method for producing light-absorbing Material)
(electrodeposition step)
A substrate made of SUS440C (JIS G4304) was prepared as a stainless steel material. Preparation of a catalyst containing FeSO4(concentration: 100g/L), ZnSO4(concentration: 5.5g/L), citric acid (concentration: 1g/L) and L-ascorbic acid (concentration: 3g/L) as an electrodeposition solution. Immersing the iron electrode as an anode and the base material as a cathode in an electrodeposition solution at a current density of 5A/dm2And the electrodeposition solution was allowed to stand at 50 ℃ for 15 minutes for electrodeposition. As a result, a metal film having a thickness of about 10 μm can be deposited on the substrate.
(Heat treatment Process)
The substrate after the electrodeposition step was charged into an electric furnace heated to 580 ℃, heat-treated in an atmospheric atmosphere for 1 hour, and then taken out of the electric furnace. The substrate taken out of the electric furnace was cooled to room temperature in the atmosphere, and the metal oxide film of example 8 was produced.
(optical Property analysis)
The results of measuring the light reflectance of the metal oxide film of example 8 using an ultraviolet-visible-near infrared spectrophotometer (UV-3600/ISR-3100) manufactured by Shimadzu corporation are shown in FIG. 3. As shown in fig. 13, the metal oxide films of example 8 all showed low reflectance (high light absorption) of less than 5% with respect to light in a wide wavelength range of 200nm to 1600 nm. In comparison with the case where the reflectance is about 10% in the light absorbing material of fig. 2 of patent document 3, the reflectance is reduced to about 1/2 in the metal oxide film of example 8, and the light absorption is high.
(surface observation)
Fig. 14 shows an image obtained by observing the surface of the metal oxide film of example 8 with a Scanning Electron Microscope (SEM). As shown in fig. 14, there are a plurality of plate-like crystalline bodies elongated from the surface of the substrate. When the plurality of plate-like crystal bodies are viewed from the front surface side of the light absorbing material in plan view, the plurality of plate-like crystal bodies extend in the thickness direction of the light absorbing material in a certain width wall shape and randomly extend in the surface direction of the light absorbing material, and thus have a complex mesh-like porous structure as a whole. The interval between adjacent crystal bodies was measured using the SEM image of fig. 14 and using a tangent method (a method of measuring the interval between adjacent crystal bodies along a straight line drawn at equal intervals in the up-down direction and the left-right direction of the SEM image). SEM images of the surface of the metal oxide film of example 8 were taken at 5 sites including fig. 14, and the interval between adjacent crystals was measured by the tangent method in the same manner, and the upper limit value thereof is shown in table 1. It is understood that in the metal oxide film of example 8, the distance between adjacent crystals in the direction parallel to the surface of the metal oxide film is 0.7 μm or less.
(structural analysis)
The results of X-ray diffraction of the light-absorbing material of example 8 are shown in fig. 15. As shown in fig. 15, in the metal oxide film of example 8, spinel-type metal oxide (Fe) was observed3O4Or ZnFe2O4) Peak of (d) (peak marked by black triangle). More than 3 spinel type metal oxide peaks are observed. As shown in fig. 15, the metal oxide film of example 8 contains a spinel-type metal oxide as a main component. Further, as a result of analyzing the metal oxide film of example 8 by a Transmission Electron Microscope (TEM), it is obvious that ZnFe is contained in the spinel-type metal oxide2O4。
(section observation)
SEM images were taken at 3 sites of the cross section obtained by cutting the metal oxide film of example 8 in the thickness direction thereof, and the measurement angle α was shown in table 2. In the metal oxide film of example 8, α.gtoreq.71 °.
(example 9)
In the metal oxide film of example 9, as shown in table 2, in the electrodeposition process, a nickel electrode was used as an anode, and ZnSO-containing was used4(concentration: 5g/L), Ni (NH)2SO3)2An aqueous solution of (concentration: 300g/L), citric acid (concentration: 0.5g/L), and L-ascorbic acid (concentration: 5g/L) was used as electricityAnd (4) depositing liquid. In the heat treatment step, heat treatment was performed for 0.5 hour. Other production conditions are the same as in example 8, and therefore, the description thereof is omitted. The results of surface observation, structural analysis, and cross-sectional analysis of the metal oxide film of example 9 are also shown in table 2 in the same manner as in example 8.
(example 10)
In the metal oxide film of example 10, as shown in table 2, the material of the base material was stainless steel SUS304(JIS G4304). In addition, in the electrodeposition process, FeSO is used4(concentration: 160g/L), ZnSO4(concentration: 5g/L) as an electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 500 ℃ and heat-treated in an atmospheric atmosphere for 1 hour. Other production conditions are the same as in example 8, and therefore, the description thereof is omitted. The results of surface observation, structural analysis, and cross-sectional analysis of the metal oxide film of example 10 are also shown in table 2 in the same manner as in example 8.
(example 11)
In the metal oxide film of example 11, the material of the substrate was steel SPC270(JIS G3141) as shown in table 2. In addition, in the electrodeposition process, FeSO is used4(concentration: 180g/L), Ni (NH)2SO3)2An aqueous solution of (concentration: 150g/L), citric acid (concentration: 2g/L) and L-ascorbic acid (concentration: 4g/L) was used as the electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 600 ℃ and heat-treated in an atmospheric atmosphere for 0.4 hour. Other production conditions are the same as in example 8, and therefore, the description thereof is omitted. The metal oxide film of example 11 was also subjected to surface observation, structural analysis, and cross-sectional analysis in the same manner as in example 8, and the results are shown in table 2.
(example 12)
In the metal oxide film of example 12, the material of the substrate was oxygen-free copper as shown in table 2. In addition, in the electrodeposition process, FeSO is used4(concentration: 100g/L), ZnSO4(concentrated)Degree: 5g/L), urea (concentration: 50g/L), citric acid (concentration: 1g/L), L-ascorbic acid (concentration: 3g/L) of water solution as an electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 500 ℃ and heat-treated in an atmospheric atmosphere for 2 hours. Other production conditions are the same as in example 8, and therefore, the description thereof is omitted. The results of surface observation, structural analysis, and cross-sectional analysis of the metal oxide film of example 12 are also shown in table 2 in the same manner as in example 8.
(example 13)
In the metal oxide film of example 13, as shown in table 2, the material of the base material was aluminum material a3103(JIS Z3232). In addition, in the electrodeposition process, FeSO is used4(concentration: 200g/L) and L-ascorbic acid (concentration: 5g/L) as an electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 350 ℃ and heat-treated in an atmospheric atmosphere for 3 hours. Other production conditions are the same as in example 8, and therefore, the description thereof is omitted. The metal oxide film of example 13 was also subjected to surface observation, structural analysis, and cross-sectional analysis in the same manner as in example 8, and the results are shown in table 2.
(example 14)
In the metal oxide film of example 14, as shown in table 2, the material of the base material was aluminum material a6061(JIS Z3232). In addition, in the electrodeposition step, FeCl is used2(concentration: 80g/L), ZnSO4(concentration: 5g/L) and an aqueous solution of L-ascorbic acid (concentration: 5g/L) were used as the electrodeposition solution. In the heat treatment step, the substrate after the electrodeposition step was put into an electric furnace heated to 350 ℃ and heat-treated in an atmospheric atmosphere for 0.8 hour. Other production conditions are the same as in example 8, and therefore, the description thereof is omitted. The results of surface observation, structural analysis, and cross-sectional analysis of the metal oxide film of example 14 are also shown in table 2 in the same manner as in example 8.
TABLE 2
As shown in table 2, in the metal oxide films of examples 8 to 12, it was observed that a plurality of plate-like crystal bodies were elongated in the thickness direction of the metal oxide film in a wall shape with a certain width and were randomly elongated in the surface direction of the metal oxide film, and a complex mesh-like porous structure was formed by the plurality of plate-like crystal bodies. In the metal oxide films of examples 13 and 14, it was observed that the plurality of needle-like crystals crossed each other in a state where the long direction thereof extended substantially parallel to the surface of the metal oxide film, and a mesh-like porous structure was formed by the plurality of needle-like crystals. In addition, X-ray diffraction was performed on the metal oxide films of examples 8, 10 to 14, and 3 or more peaks of spinel-type metal oxide were observed in both of them.
As shown in table 2, in order to make the metal oxide film have a porous structure, the metal oxide film may be a metal oxide film containing a spinel-type metal oxide represented by the above formula (1) as shown in examples 8 and 10 to 14, or may be a metal oxide film containing ZnO even when the metal oxide film is not a spinel-type metal oxide as shown in example 9. The metal oxide film according to the embodiment is formed by using a material having high absorptivity with respect to light of a wide range of wavelengths, and has a porous structure in which a plurality of needle-like or plate-like crystal bodies are arranged in a mesh shape or a sword-mountain shape, and therefore, based on the effects of both the material and the structure, as shown in fig. 13, more excellent light absorptivity can be obtained.
Description of the symbols
10 metal oxide film
12 crystal
Top of 14 crystals
16 base material
Claims (10)
1. A metal oxide film comprising a metal oxide represented by the following formula (1) and having a porous structure in which a plurality of needle-like or plate-like crystal bodies are arranged in a mesh or a sword-like shape,
MxL3-xO4 (1)
in the above formula, M is Zn, L is Fe, x is 1,
the crystal body of the porous structure is elongated toward the surface side of the metal oxide film at an angle α of 45 ° to 90 ° relative to an angle α formed by a line connecting the top end of the crystal body and the center of the bottom surface in the short side direction of the crystal body with respect to the bottom surface.
2. The metal oxide film of claim 1, wherein the metal oxide further comprises ZnO.
3. The metal oxide film according to claim 1 or 2, wherein a distance of adjacent crystals in the porous structure in a direction parallel to a surface of the metal oxide film is 10 μm or less.
4. A water repellent material, wherein the metal oxide film according to any one of claims 1 to 3 is formed on a surface of the water repellent material.
5. A light absorbing material, wherein the metal oxide film according to any one of claims 1 to 3 is formed on a surface of the light absorbing material.
6. A method for producing a metal oxide film according to any one of claims 1 to 3, comprising:
a deposition step of depositing a metal or a metal compound containing Fe and Zn elements on the surface of the base material, and
and a heat treatment step of heat-treating the base material after the deposition step.
7. The method of claim 6, wherein the deposition step comprises performing electrodeposition in an electrodeposition bath containing Fe, Zn and an organic acid.
8. The method for producing a metal oxide film according to claim 6 or 7, wherein the precipitation step precipitates one or more layers of Fe and Zn elements.
9. The method for producing a metal oxide film according to claim 6 or 7, wherein the heat treatment step is performed at 200 ℃ or higher for 1 minute or more and 10 hours or less.
10. The method for producing a metal oxide film according to claim 8, wherein the heat treatment step is performed at 200 ℃ or higher for 1 minute or more and 10 hours or less.
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