JP2013231208A - Bubble generating apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bubble generating apparatus which can stably generate a microbubble in a liquid.SOLUTION: A bubble generating apparatus 10 includes: a means that includes a plurality of electrodes different in polarity, at least parts of the electrodes being immersed into a liquid 20, and electrolyzes the liquid 20 to gasify the liquid; and a means for applying vibration to at least one of the electrodes. In the bubble generating apparatus, a nanostructure is provided at at least one of the surfaces of the plurality of electrodes to take a microbubble generated by the plurality of electrodes inside or outside the liquid 20 by the vibration that is applied to at least one of the plurality of electrodes by the means for applying vibration.

Description

 The present invention relates to a bubble generator.

 Usually, bubbles contained in water rise toward the water surface and burst, and cannot exist in water. However, bubbles (microbubbles) having a diameter of 50 μm or less contained in water shrink and disappear while rising toward the water surface, or become microbubbles (nanobubbles) having a diameter of 100 nm or less. Can be stably dispersed and present.

Such nanobubbles stimulate cells, promote the blood flow and growth of the organism, increase the dissolved oxygen concentration in the water, prevent the oxygen deficiency of the organism that ingested water containing oxygen in its high concentration, It is known to have an effect of activating the action of microorganisms.
In addition, since nanobubbles have a negative potential, they are expected to have an effect of attaching and removing dirt and the like.
Furthermore, it is known that nanobubbles are excellent in dispersibility, diffusibility, and aggregation.
From these characteristics, nanobubbles are expected to exert a great effect on water, the environment, health, and the like.

 As a nanobubble generating device, for example, an apparatus having an anode for electrolysis provided on the entire bottom surface of a rectangular tube and a cathode provided in a hydrogen discharge pipe communicating with the rectangular tube is known. (For example, refer to Patent Document 1). Note that Patent Document 1 does not disclose a detailed configuration of the electrode.

 However, in order to generate nanobubbles accurately, it is necessary to control the surface shape of the electrode. In addition, it has been reported that a fine nano shape triggers the generation of nano bubbles (see, for example, Non-Patent Document 1).

Japanese Patent No. 4016099

“Observation of Nanobubble on Carbon Nanotubes”, Applied Physics Express 3,065103, 2010

 This invention is made | formed in view of the said situation, Comprising: It aims at providing the bubble generator which can generate | occur | produce stably a microbubble in a liquid.

 The bubble generator of the present invention has a plurality of electrodes of different polarities at least partially immersed in a liquid, and electrolyzes and gasifies the liquid, and vibrates at least one of the electrodes. And a means for applying the vibration to the microbubbles generated at the plurality of electrodes, the nanostructure being provided on at least one surface of the plurality of electrodes. In this case, the liquid is taken out into or out of the liquid by vibration applied to at least one of the plurality of electrodes.

 In the bubble generating apparatus of the present invention, the means for applying the vibration may be a means for applying an ultrasonic wave.

 The bubble generator of the present invention has a plurality of electrodes of different polarities at least partially immersed in a liquid, and includes means for electrolyzing and gasifying the liquid, and means for stirring the liquid. The bubble generating apparatus includes a nanostructure provided on at least one surface of the plurality of electrodes, and microbubbles generated at the plurality of electrodes are contained in the liquid or by the means for stirring the liquid. It is characterized by being taken out of the liquid.

 In the bubble generating apparatus of the present invention, an electrode that is not provided with the nanostructure may be disposed so as to surround the electrode that is provided with the nanostructure among the plurality of electrodes. .

 In the bubble generating device of the present invention, an electrode provided with a nanostructure among the plurality of electrodes may be disposed so as to surround an electrode provided with no nanostructure among the plurality of electrodes. .

 In the bubble generator of the present invention, at least one of the plurality of electrodes may be provided on an insulating substrate.

 In the bubble generating device of the present invention, the nanostructure may be provided on the surface of the conductive film.

 In the bubble generator of the present invention, the electrode provided with the nanostructure among the plurality of electrodes may have a positive potential.

 In the bubble generating device of the present invention, the nanostructure may be composed of a porous film formed by anodizing aluminum or an aluminum alloy.

 In the bubble generating device of the present invention, the nanostructure may include at least one selected from the group consisting of nanotubes and nanoparticles.

 In the bubble generator of the present invention, the electrode provided with the nanostructure among the plurality of electrodes may be composed of an indium tin oxide film (ITO) or an indium zinc oxide film (IZO).

 The bubble generator of the present invention may include means for exhausting at least one of the gases generated by the electrolysis of the liquid.

 According to the bubble generator of the present invention, microbubbles having a diameter of 1000 nm or less can be stably generated at the anode or the cathode by electrolysis of liquid. Further, microbubbles generated at the anode or the cathode can be taken out into the liquid by means for applying ultrasonic waves or means for stirring the liquid.

It is a schematic perspective view which shows 1st embodiment of a bubble generator. It is a SEM image of an anodized alumina film. It is a schematic diagram of an anodized alumina film. It is a SEM image of the nanostructure consisting of a carbon nanotube. It is a SEM image of the nanostructure consisting of nanoparticles of aluminum nitride. It is a SEM image of the nanostructure which consists of a petal-like alumina nanoparticle. It is a SEM image of the nanostructure which consists of a nanoparticle of copper oxide. It is an AFM (atomic force microscope) image of an indium tin oxide film having an arithmetic average roughness (Ra) of 1.0 nm. It is a schematic perspective view which shows 2nd embodiment of a bubble generator. It is a schematic perspective view which shows 3rd embodiment of a bubble generator. It is a schematic perspective view which shows 4th embodiment of a bubble generator. It is a schematic perspective view which shows 5th embodiment of a bubble generator. It is a schematic perspective view which shows 6th embodiment of a bubble generator. It is a schematic perspective view which shows 7th embodiment of a bubble generator. It is a schematic perspective view which shows 8th embodiment of a bubble generator. It is a schematic perspective view which shows 9th embodiment of a bubble generator. 4 is a graph showing measurement results of particle diameters of bubbles generated by the bubble generator of Example 1. 6 is a graph showing the measurement result of the particle size of bubbles generated by the bubble generator of Comparative Example 1. It is a graph which shows the measurement result of the particle size of the bubble produced | generated by the bubble generator of Example 2. FIG.

Hereinafter, an embodiment of a bubble generator according to the present invention will be described with reference to the drawings.
The following embodiments are specifically described for better understanding of the gist of the invention, and do not limit the present invention unless otherwise specified.
In addition, in the drawings used in the following description, in order to make the features of the present invention easier to understand, there is a case where a main part is shown in an enlarged manner for convenience, and the dimensional ratio of each component is the same as the actual one. Not necessarily.

(1) First Embodiment FIG. 1 is a schematic perspective view showing a first embodiment of a bubble generator.
The bubble generator 10 of this embodiment includes a pair of an anode 11 and a cathode 12 arranged at a predetermined interval, an ultrasonic vibrator 13 that applies ultrasonic waves to the anode 11, and a space between the anode 11 and the cathode 12. And a power source 14 for energizing the current.
In the bubble generator 10, the anode 11 and the cathode 12 are used by at least partly immersing them in the liquid 20.

 The anode 11 is provided with an electrode substrate and a nanostructure provided on the surface thereof. A nanostructure is a structure having a nano-order level size. The “surface of the electrode base material” here refers to the electrode surface in contact with the liquid 20. In this embodiment, the nanostructure may be provided on a surface other than the electrode substrate in the solution.

 As an electrode base material, a base material made of a metal such as aluminum, aluminum alloy, platinum or gold, a base material made of the above metal on a carbon electrode, or an insulating base material made of glass, ceramics, plastic, or the like. Layered ones are used.

 Examples of the nanostructure include those made of a porous film formed by anodizing an electrode base material made of aluminum or an aluminum alloy in an oxalic acid aqueous solution or dilute sulfuric acid. Specifically, as shown in FIGS. 2 and 3, this porous film is an anode formed on the surface of the aluminum substrate 31 by anodizing the aluminum substrate 31 in an oxalic acid aqueous solution or dilute sulfuric acid. This is an alumina oxide film (alumite film) 40. The anodized alumina film 40 is an aggregate of hexagonal columnar cells 43 having a barrier layer 41 and fine holes 42. A fine hole 42 exists in the center of each cell 43, and the fine hole 42 leads to the barrier layer 41 formed at the interface between the aluminum substrate 31 and the anodized alumina film 40.

 The diameter of the opening of the fine hole 42 is preferably 1000 nm or less, and more preferably 1 to 300 nm. If the diameter of the opening of the fine hole 42 exceeds 1000 nm, the diameter of the gas generated by electrolysis of the liquid 20 may not be 1000 nm or less.

Moreover, as a nanostructure, what contains at least 1 sort (s) selected from the group which consists of a nanotube and a nanoparticle, for example is mentioned. That is, in the nanostructure of this example, an aggregate composed of at least one selected from the group consisting of nanotubes and nanoparticles formed a nano-level (1000 nm or less) uneven structure on a part of the surface of the electrode substrate. Is.
Further, when the nanostructure is an aggregate composed of a large number of nanoparticles, a large number of nanoparticles are deposited on the surface of the electrode substrate, and a minute gap is formed between the nanoparticles.

Examples of the nanotube include carbon nanotubes, boron nitride-based nanotubes, silicon nanotubes, metal complex-type organic nanotubes, and titania nanotubes.
The diameter of the nanotube is preferably 1000 nm or less. When the diameter of the nanotube exceeds _1000 nm, a fine nano level uneven structure cannot be formed on the surface of the electrode substrate, and the diameter of the gas generated by electrolysis of the liquid 20 may not be reduced to 1000 nm or less. .
Among these, the nanostructure made of carbon nanotubes is an aggregate of a large number of carbon nanotubes provided so that one end thereof is in contact with the surface of the electrode base material, for example, as in the SEM image shown in FIG. As can be seen from the SEM image shown in FIG. 4, the nanostructure made of carbon nanotubes constitutes a porous film.

Examples of the nanoparticles include aluminum nitride nanoparticles, petal-like alumina nanoparticles, copper oxide nanoparticles, nickel nanoparticles, and the like.
The average particle diameter of the nanoparticles is preferably 1000 nm or less. If the average particle diameter of the nanoparticles exceeds 1000 nm, a fine nano-level uneven structure cannot be formed on the surface of the electrode substrate, and the diameter of the gas generated by electrolysis of the liquid 20 cannot be reduced to 1000 nm or less. Sometimes.
The nanostructure made of aluminum nitride nanoparticles is an aggregate of a large number of aluminum nitride nanoparticles deposited on the surface of the electrode substrate, for example, as shown in the SEM image shown in FIG. As can be seen from the SEM image shown in FIG. 5, the nanostructure made of aluminum nitride nanoparticles constitutes a porous film.
The nanostructure composed of petal-like alumina nanoparticles is an aggregate of a large number of petal-like alumina nanoparticles deposited on the surface of the electrode substrate, for example, as shown in the SEM image shown in FIG. As can be seen from the SEM image shown in FIG. 6, the nanostructure composed of petal-like alumina nanoparticles constitutes a porous film.
The nanostructure composed of copper oxide nanoparticles is an aggregate of a large number of copper oxide nanoparticles deposited on the surface of the electrode substrate, for example, as shown in the SEM image shown in FIG. As can be seen from the SEM image shown in FIG. 7, the nanostructure made of copper oxide nanoparticles constitutes a porous film.

 Nanostructures include a combination of a conductor and an insulator, a combination of an inorganic substance and an organic substance, a structure in which a large number of polymer nanoparticles such as styrene are deposited on the surface of an electrode substrate, A polymer porous membrane or the like is also used.

 In addition, as a method of forming the nanostructure, a method of depositing (adhering) metal nanoparticles on the surface of the electrode substrate by plating, a nanoimprint using the above-described resist containing nanotubes and nanoparticles, and electrode A method of forming a porous film containing a resist containing nanotubes and nanoparticles on the surface of the substrate, a method of spray-coating the above-mentioned nanoparticles on the surface of the electrode substrate, and a nano-order formed on the surface of the electrode substrate A method of forming an electrode on an uneven shape having a level size is also used.

The anode 11 may be composed of an indium tin oxide (ITO) film. In this example, an indium tin oxide (ITO) film forms an electrode substrate and a nanostructure provided on the surface thereof, and an indium tin oxide (ITO) film is provided on the surface of the electrode substrate. And a case of forming a nanostructure.
The indium tin oxide film having an arithmetic average roughness (Ra) of 1.0 nm has fine nano level unevenness, for example, as shown in FIG.
The surface roughness of the indium tin oxide film constituting the anode 11 is preferably 1.0 nm or less in terms of arithmetic average roughness (Ra).

 As the cathode 12, a base material made of a metal such as aluminum, an aluminum alloy, platinum, or gold, or a base material made of the above metal is laminated on an insulating base material made of a carbon electrode, glass, ceramics, plastic, or the like. Used.

 The ultrasonic transducer 13 is provided on the upper end side of the anode 11 (on the side opposite to the side immersed in the liquid 20) so as to be in contact with at least a part of the anode 11. Is applied. Thereby, oxygen microbubbles (nanobubbles) 21 generated at the anode 11 can be taken out into the liquid 20.

As the ultrasonic vibrator 13, a piezoelectric ceramic element, a piezoelectric polymer film vibrator, a piezoelectric thin film vibrator, or the like is used.
Piezoelectric ceramics are composed of polycrystalline ceramics obtained by baking high-temperature powders such as titanium oxide and barium oxide at high temperatures. By applying polarization treatment to the polycrystalline ceramic, piezoelectricity is generated.
The piezoelectric polymer film can be obtained by subjecting a polymer solution or a film prepared from a solution to polarization treatment.
The piezoelectric thin film is obtained by depositing zinc oxide (ZnO) on a medium such as quartz or sapphire by a sputtering method. Piezoelectricity is produced by orienting zinc oxide (ZnO) in a C-axis orientation in a medium such as quartz or sapphire.

 The power supply 14 is not particularly limited.

 The liquid 20 electrolyzed by the bubble generator 10 is not particularly limited as long as it is gasified by electrolysis, that is, a gas is generated by electrolysis. When the liquid 20 generates oxygen and hydrogen by electrolysis, examples of the liquid 20 include water, a solution in which various solutes are dissolved using water as a solvent, and a dispersion in which various substances are dispersed using water as a dispersion medium. Liquid and the like.

 In addition, although the case where a pair of anode 11 and cathode 12 was used is illustrated in FIG. 1, the number of electrodes is not limited to this, and a plurality of cathodes for one anode or one cathode A plurality of electrodes can also be used.

Next, a bubble generation method using the bubble generator 10 will be described with reference to FIG.
Here, the case where water is used as the liquid 20 is illustrated.
The anode 11 and the cathode 12 arranged at a predetermined interval are immersed in the liquid 20, and a direct current or a direct current is pulsed between the anode 11 and the cathode 12 from the power source 14. By doing so, the liquid 20 is electrolyzed.
At this time, at least a part of the anode 11 and the cathode 12 is immersed in the liquid 20.
Further, when a direct current is applied between the anode 11 and the cathode 12, an ultrasonic wave is applied to the anode 11 by the ultrasonic vibrator 13.

At this time, the cathode 12 undergoes a chemical reaction represented by the following chemical reaction formula (1) to generate hydrogen.
2H ₂ O + 2e ⁻ → H ₂ + 2OH ⁻ (1)
On the other hand, at the anode 11, a chemical reaction represented by the following chemical reaction formula (2) occurs to generate oxygen.
2OH ⁻ → H ₂ O + 1 / 2O ₂ + 2e ⁻ (2)

The current density applied between the anode 11 and the cathode 12 immersed in the liquid 20 is preferably 100 to 10,000 mA / cm ² .

 The frequency of the vibrator applied to the anode 11 by the ultrasonic vibrator 13 is preferably 100 Hz to 100 kHz, and more preferably 10 kHz to 100 kHz.

According to the bubble generator 10 of the present embodiment, the microbubbles (nanobubbles) 21 having a diameter of 100 nm or less can be stably generated in the anode 11 by electrolysis of the liquid 20. The ultrasonic vibrator 13 can take out oxygen microbubbles (nanobubbles) 21 generated in the anode 11 into the liquid 20. Accordingly, the microbubbles (nanobubbles) 21 of oxygen are stably dispersed, and the existing liquid 20 can be obtained.
On the other hand, hydrogen bubbles 22 are generated in the cathode 12, but the liquid bubbles 20 are vibrated by the ultrasonic waves applied to the anode 11 by the ultrasonic vibrator 13, so that the hydrogen bubbles 22 are discharged out of the liquid 20. .

(2) Second Embodiment FIG. 9 is a schematic perspective view showing a second embodiment of the bubble generator.
The bubble generator 50 of the present embodiment includes a cylindrical cathode 51, an anode 52 disposed in the center of the cathode 51 in the cathode 51, an ultrasonic transducer 53 that applies ultrasonic waves to the anode 52, and a cathode A power source 54 for passing a current between 51 and the anode 52 and an exhaust port 55 for exhausting a gas generated by the electrolysis of the liquid 60 are schematically configured.
That is, in the bubble generator 50, the cylindrical cathode 51 is provided so as to surround the anode 52. And the anode 52 arrange | positioned in the center and the cathode 51 surrounding it are arrange | positioned at predetermined intervals.
In the bubble generating apparatus 50, at least a part of the cathode 51 and the anode 52 is immersed in the liquid 60 and used.

 The cathode 51 has a cylindrical shape in which the upper end 51a side is closed to form an upper surface (a surface opposite to the side immersed in the liquid 60) 51b and the lower end 51c side is opened. . Therefore, when the lower end 51 c side of the cathode 51 is immersed in the liquid 60, the liquid 60 enters the inside of the cathode 51. As a result, the cathode 51 and the anode 52 disposed in the cathode 51 are in contact with the liquid 60.

 The surface area of the anode 52 with respect to the cathode 51 is not particularly limited, but in order to perform an electrolysis reaction efficiently or to increase the current density of the anode 52 in the liquid 60, the surface area of the cathode is larger. Is preferred.

As the cathode 51, the thing similar to the cathode 12 in the above-mentioned first embodiment is used.
As the anode 52, the thing similar to the anode 11 in the above-mentioned first embodiment is used.

The ultrasonic transducer 53 is provided on the upper surface 51 b of the cathode 51 so as to be in contact with at least a part of the anode 52, and applies ultrasonic waves directly to the anode 52. Thereby, oxygen microbubbles (nanobubbles) 61 generated at the anode 52 can be taken out into the liquid 60.
As the ultrasonic transducer 53, the same transducer as the ultrasonic transducer 13 in the first embodiment described above is used.

The exhaust port 55 is provided in the vicinity of the inner surface 51 d of the cathode 51 on the upper surface 51 b of the cathode 51. Thereby, hydrogen generated in the cathode 51 can be efficiently discharged to the outside of the cathode 51.
The exhaust port 55 is made of a stable material that is not damaged by a gas such as hydrogen. Examples of the material of the exhaust port 55 include polyethylene, polystyrene, polycarbonate, polyethylene terephthalate, methacrylic resin, and silicon resin.

 Examples of the liquid 60 that is subjected to potential decomposition by the bubble generating device 50 include the same liquid 20 as in the first embodiment.

Next, a bubble generation method using the bubble generator 50 will be described with reference to FIG.
Here, the case where water is used as the liquid 60 is illustrated.
A cathode 51 and an anode 52 arranged at a predetermined interval are immersed in the liquid 60, and a direct current or a direct current is pulsed between the cathode 51 and the anode 52 from the power source 54. By doing so, the liquid 60 is electrolyzed.
At this time, at least a part of the cathode 51 and the anode 52 is immersed in the liquid 60.
Further, when a direct current is applied between the cathode 51 and the anode 52, ultrasonic waves are applied to the anode 52 by the ultrasonic vibrator 53.

According to the bubble generator 50 of this embodiment, oxygen microbubbles (nanobubbles) 61 having a diameter of 100 nm or less can be stably generated at the anode 52 by electrolysis of the liquid 60. The ultrasonic vibrator 53 can take out oxygen microbubbles (nanobubbles) 61 generated in the anode 52 into the liquid 60. Therefore, oxygen microbubbles (nanobubbles) 61 are stably dispersed, and the existing liquid 60 can be obtained.
On the other hand, since the hydrogen bubbles 62 generated in the cathode 51 can be efficiently discharged to the outside of the cathode 51 through the exhaust port 55, the oxygen microbubbles (nanobubbles) 61 are highly purified and stable. Dispersed and the liquid 60 present can be obtained.

(3) Third Embodiment FIG. 10 is a schematic perspective view showing a third embodiment of the bubble generator.
The bubble generator 70 of this embodiment includes a cylindrical anode 71, a cathode 72 disposed in the center of the anode 71 in the anode 71, an ultrasonic vibrator 73 that applies ultrasonic waves to the cathode 72, and an anode The power source 74 is used to pass a current between 71 and the cathode 72, and the exhaust port 75 is used to exhaust gas generated by electrolysis of the liquid 80.
That is, in the bubble generator 70, the cylindrical anode 71 is provided so as to surround the cathode 72. And the cathode 72 arrange | positioned in the center and the anode 71 surrounding it are arrange | positioned at predetermined intervals.
In the bubble generating device 70, at least a part of the anode 71 and the cathode 72 is immersed in the liquid 80 and used.

 The anode 71 has a cylindrical shape in which the upper end 71a side is closed to form an upper surface (a surface opposite to the side immersed in the liquid 80) 71b and the lower end 71c side is opened. . Therefore, when the lower end 71 c side of the anode 71 is immersed in the liquid 80, the liquid 80 enters the inside of the anode 71. As a result, the anode 71 and the cathode 72 disposed in the anode 71 are in contact with the liquid 80.

 The length and surface area of the cathode 72 with respect to the anode 71 are not particularly limited.

As the anode 71, the thing similar to the anode 11 in the above-mentioned 1st embodiment is used.
As the cathode 72, the thing similar to the cathode 12 in the above-mentioned first embodiment is used.

The ultrasonic transducer 73 is provided on the upper surface 71 b of the anode 71 so as to be in contact with at least a part of the cathode 72, and directly applies ultrasonic waves to the cathode 72. Thereby, the hydrogen bubbles 82 generated at the cathode 72 can be taken out (discharged) out of the liquid 80.
As the ultrasonic vibrator 73, the same ultrasonic vibrator 13 as in the first embodiment described above is used.

The exhaust port 75 is provided in the vicinity of the inner surface 71 d of the anode 71 on the upper surface 71 b of the anode 71. Thereby, hydrogen generated in the anode 71 can be efficiently discharged to the outside of the anode 71.
As the exhaust port 75, the thing similar to the exhaust port 55 in the above-mentioned 2nd embodiment is used.

 Examples of the liquid 80 that is potential-decomposed by the bubble generator 70 include the same liquid 20 as that in the first embodiment.

Next, a bubble generation method using the bubble generation device 70 will be described with reference to FIG.
Here, the case where water is used as the liquid 80 is illustrated.
The anode 71 and the cathode 72 arranged at a predetermined interval are immersed in the liquid 80, and a direct current or a direct current is pulsed between the anode 71 and the cathode 72 from the power source 74. By doing so, the liquid 80 is electrolyzed.
At this time, at least a part of the anode 71 and the cathode 72 is immersed in the liquid 80.
Further, when a direct current is applied between the anode 71 and the cathode 72, ultrasonic waves are applied to the cathode 72 by the ultrasonic vibrator 73.

 According to the bubble generating device 70 of the present embodiment, oxygen microbubbles (nanobubbles) 81 having a diameter of 100 nm or less can be stably generated in the anode 71 by electrolysis of the liquid 80. In addition, the hydrogen bubble 82 generated at the cathode 72 can be taken out (discharged) out of the liquid 80 by the ultrasonic vibrator 73. As a result, only the oxygen microbubbles (nanobubbles) 81 generated in the anode 71 are extracted from the liquid 80, and the oxygen microbubbles (nanobubbles) 81 are stably dispersed to obtain the existing liquid 80. . Also, the hydrogen bubbles 82 generated at the cathode 72 can be efficiently discharged to the outside of the anode 71 through the exhaust port 75.

(4) Fourth Embodiment FIG. 11 is a schematic perspective view showing a fourth embodiment of the bubble generating device.
The bubble generator 90 of the present embodiment includes a pair of an anode 91 and a cathode 92 arranged at a predetermined interval, an ultrasonic vibrator 93 that applies ultrasonic waves to the anode 91, and between the anode 91 and the cathode 92. And a power source 94 for energizing the current.
In the bubble generator 90, at least a part of the anode 91 and the cathode 92 is immersed in the liquid 100 and used.

The anode 91 is provided on an insulating substrate 95 made of glass, ceramics, plastic, or the like.
As the anode 91, the thing similar to the anode 11 in the above-mentioned first embodiment is used.

The cathode 92 is provided on an insulating base 96 made of glass, ceramics, plastic, or the like.
As the cathode 92, the thing similar to the cathode 12 in the above-mentioned first embodiment is used.

The ultrasonic vibrator 93 is provided on the upper end side of the anode 91 (on the side opposite to the side immersed in the liquid 100) so as to contact at least a part of the anode 91 or the insulating base material 95. On the other hand, ultrasonic waves are applied directly or indirectly. Thereby, oxygen microbubbles (nanobubbles) 101 generated at the anode 91 can be taken out into the liquid 100.
As the ultrasonic transducer 93, the same ultrasonic transducer 13 as in the first embodiment described above is used.

Next, a bubble generation method using the bubble generation device 90 will be described with reference to FIG.
Here, the case where water is used as the liquid 100 is illustrated.
An anode 91 and a cathode 92 arranged at a predetermined interval in the liquid 100 are immersed, and a direct current or a direct current is pulsed from the power source 94 between the anode 91 and the cathode 92. By doing so, the liquid 100 is electrolyzed.
At this time, at least a part of the anode 91 and the cathode 92 is immersed in the liquid 100.
Further, when a direct current is applied between the anode 91 and the cathode 92, ultrasonic waves are applied to the anode 91 provided on the insulating base material 95 by the ultrasonic vibrator 93.

According to the bubble generator 90 of the present embodiment, oxygen microbubbles (nanobubbles) 101 having a diameter of 100 nm or less can be stably generated at the anode 91 by electrolysis of the liquid 100. The ultrasonic vibrator 93 can take out oxygen microbubbles (nanobubbles) 101 generated in the anode 91 into the liquid 100. Therefore, oxygen microbubbles (nanobubbles) 101 are stably dispersed, and the existing liquid 100 can be obtained.
On the other hand, although hydrogen bubbles 102 are generated at the cathode 92, the liquid bubbles 100 are oscillated by the ultrasonic wave applied to the anode 91 by the ultrasonic vibrator 93, so that the hydrogen bubbles 102 are discharged out of the liquid 100. .

(5) Fifth Embodiment FIG. 12 is a schematic perspective view showing a fifth embodiment of the bubble generator.
The bubble generator 110 of this embodiment includes a pair of an anode 111 and a cathode 112 arranged at a predetermined interval, an ultrasonic vibrator 113 that applies ultrasonic waves to the anode 111, and a gap between the anode 111 and the cathode 112. And a power source 114 for energizing the current.
In the bubble generating device 110, at least a part of the anode 111 and the cathode 112 is used by being immersed in the liquid 120.

The anode 111 is provided on an insulating substrate 115 made of glass, ceramics, plastic, or the like. A nanostructure 116 is provided on the surface of the anode 111 opposite to the surface in contact with the insulating substrate 115.
As the anode 111, an electrode made of a metal such as aluminum, an aluminum alloy, platinum, or gold, or a carbon electrode is used.
As the nanostructure 116, the same nanostructure as that in the first embodiment described above is used.

The cathode 112 is provided on an insulating substrate 117 made of glass, ceramics, plastic, or the like.
As the cathode 112, the thing similar to the cathode 12 in the above-mentioned 1st embodiment is used.

The ultrasonic transducer 113 is provided on the upper end side of the anode 111 (the side opposite to the side immersed in the liquid 120) so as to be in contact with at least a part of the anode 111, the insulating base material 115, or the nanostructure 116. The ultrasonic wave is applied to the anode 111 directly or indirectly. Thereby, oxygen microbubbles (nanobubbles) 121 generated at the anode 111 can be taken out into the liquid 120.
As the ultrasonic transducer 113, the same transducer as the ultrasonic transducer 13 in the first embodiment described above is used.

Next, a bubble generation method using the bubble generation device 110 will be described with reference to FIG.
Here, the case where water is used as the liquid 120 is illustrated.
An anode 111 and a cathode 112 arranged at a predetermined interval are immersed in the liquid 120, and a direct current or a direct current is pulsed from the power source 114 between the anode 111 and the cathode 112. By doing so, the liquid 120 is electrolyzed.
At this time, at least a part of the anode 111 and the cathode 112 is immersed in the liquid 120.
Further, when a direct current is applied between the anode 111 and the cathode 112, ultrasonic waves are applied to the anode 111 and the nanostructure 116 provided on the insulating base 115 by the ultrasonic vibrator 113.

According to the bubble generator 110 of the present embodiment, oxygen microbubbles (nanobubbles) 121 having a diameter of 100 nm or less can be stably generated in the anode 111 by electrolysis of the liquid 120. The ultrasonic vibrator 113 can take out oxygen microbubbles (nanobubbles) 121 generated in the anode 111 into the liquid 120. Therefore, oxygen microbubbles (nanobubbles) 121 are stably dispersed, and the existing liquid 120 can be obtained.
On the other hand, although hydrogen bubbles 122 are generated at the cathode 112, the liquid 120 is vibrated by the ultrasonic waves applied to the anode 111 by the ultrasonic vibrator 113, so that the hydrogen bubbles 122 are discharged out of the liquid 120. .

(6) Sixth Embodiment FIG. 13 is a schematic perspective view showing a sixth embodiment of the bubble generating device.
The bubble generator 130 of this embodiment includes a cylindrical anode 131, a cathode 132 disposed in the center of the anode 131 in the anode 131, an ultrasonic vibrator 133 that applies ultrasonic waves to the cathode 132, an anode A power supply 134 for passing a current between 131 and the cathode 132 is schematically configured.
That is, in the bubble generator 130, the cylindrical anode 131 is provided so as to surround the cathode 132. And the cathode 132 arrange | positioned in the center and the anode 131 surrounding it are arrange | positioned at predetermined intervals.
In the bubble generator 130, the anode 131 and the cathode 132 are used by at least partly immersing them in the liquid 140.

 The anode 131 has a cylindrical shape in which the upper end 131a side is closed to form an upper surface (a surface opposite to the side immersed in the liquid 140) 131b, and the lower end 131c side is opened. . Therefore, when the lower end 131 c side of the anode 131 is immersed in the liquid 140, the liquid 140 enters the inside of the anode 131. As a result, the anode 131 and the cathode 132 disposed in the anode 131 are in contact with the liquid 140.

 The length and surface area of the cathode 132 with respect to the anode 131 are not particularly limited.

As the anode 131, the thing similar to the cathode 12 in the above-mentioned first embodiment is used.
As the cathode 132, the thing similar to the anode 11 in the above-mentioned 1st embodiment is used.

The ultrasonic transducer 133 is provided on the upper surface 131 b of the anode 131 so as to be in contact with at least a part of the cathode 132, and applies an ultrasonic wave directly to the cathode 132. Thereby, hydrogen micro bubbles (nano bubbles) 142 generated at the cathode 132 can be taken out into the liquid 140.
As the ultrasonic transducer 133, the same transducer as the ultrasonic transducer 13 in the first embodiment described above is used.

 Examples of the liquid 140 that is subjected to potential decomposition by the bubble generator 130 include the same liquids 20 as those in the first embodiment described above.

Next, a bubble generation method using the bubble generator 130 will be described with reference to FIG.
Here, the case where water is used as the liquid 140 is illustrated.
The anode 131 and the cathode 132 arranged at a predetermined interval are immersed in the liquid 140, and a direct current or a direct current is pulsed from the power source 134 between the anode 131 and the cathode 132. By doing so, the liquid 140 is electrolyzed.
At this time, at least a part of the anode 131 and the cathode 132 is immersed in the liquid 140.
Further, when a direct current is applied between the anode 131 and the cathode 132, an ultrasonic wave is applied to the cathode 132 by the ultrasonic vibrator 133.

According to the bubble generator 130 of the present embodiment, hydrogen microbubbles (nanobubbles) 142 having a diameter of 100 nm or less can be stably generated at the cathode 132 by electrolysis of the liquid 140. The ultrasonic vibrator 133 can take out hydrogen microbubbles (nanobubbles) 142 generated at the cathode 132 into the liquid 140. Therefore, hydrogen microbubbles (nanobubbles) 142 are stably dispersed, and the existing liquid 140 can be obtained.
On the other hand, oxygen bubbles 141 are generated in the anode 131, but the liquid bubbles 140 are vibrated by the ultrasonic waves applied to the anode 131 by the ultrasonic vibrator 133, so that the oxygen bubbles 141 are discharged out of the liquid 140. .

(7) Seventh Embodiment FIG. 14 is a schematic perspective view showing a seventh embodiment of the bubble generator.
The bubble generator 150 of this embodiment includes a pair of an anode 151 and a cathode 152 that are arranged at a predetermined interval, an ultrasonic vibrator 153 that applies ultrasonic waves to the cathode 152, and a space between the anode 151 and the cathode 152. And a power source 154 for energizing the current.
In the bubble generator 150, at least a part of the anode 151 and the cathode 152 is immersed in the liquid 160 and used.

The anode 151 is provided on an insulating substrate 155 made of glass, ceramics, plastic, or the like.
As the anode 151, the same one as in the fifth embodiment described above is used.

The cathode 152 is provided on an insulating substrate 156 made of glass, ceramics, plastic, or the like. A nanostructure 157 is provided on the surface of the cathode 152 opposite to the surface in contact with the insulating base 156.
As the nanostructure 157, the same nanostructure as that in the first embodiment described above is used.

The ultrasonic transducer 153 is provided on the upper end side of the cathode 152 (on the side opposite to the side immersed in the liquid 160) so as to be in contact with at least a part of the cathode 152, the insulating base material 156, or the nanostructure 157. The ultrasonic wave is applied to the cathode 152 directly or indirectly. Thereby, hydrogen microbubbles (nanobubbles) 162 generated at the cathode 152 can be taken out into the liquid 160.
As the ultrasonic transducer 153, the same transducer as the ultrasonic transducer 13 in the first embodiment described above is used.

Next, a bubble generation method using the bubble generation device 150 will be described with reference to FIG.
Here, the case where water is used as the liquid 160 is illustrated.
The anode 151 and the cathode 152 arranged at a predetermined interval are immersed in the liquid 160, and a direct current or a direct current is pulsed between the anode 151 and the cathode 152 from the power source 154. By doing so, the liquid 160 is electrolyzed.
At this time, at least a part of the anode 151 and the cathode 152 is immersed in the liquid 160.
Further, when a direct current is applied between the anode 151 and the cathode 152, ultrasonic waves are applied to the cathode 152 and the nanostructure 157 provided on the insulating base material 156 by the ultrasonic vibrator 153.

According to the bubble generator 150 of the present embodiment, hydrogen microbubbles (nanobubbles) 162 having a diameter of 100 nm or less can be stably generated at the cathode 152 by electrolysis of the liquid 160. The ultrasonic vibrator 153 can take out hydrogen microbubbles (nanobubbles) 162 generated at the cathode 152 into the liquid 160. Therefore, the hydrogen microbubbles (nanobubbles) 162 are stably dispersed, and the existing liquid 160 can be obtained.
On the other hand, oxygen bubbles 161 are generated in the anode 151, but the liquid 160 is vibrated by the ultrasonic wave applied to the anode 151 by the ultrasonic vibrator 153, so that the oxygen bubbles 161 are discharged out of the liquid 160. .

(8) Eighth Embodiment FIG. 15 is a schematic perspective view showing an eighth embodiment of the bubble generator.
The bubble generator 170 of the present embodiment supplies a current between a pair of anode 171 and cathode 172 arranged at a predetermined interval, an agitator 180 for agitating the liquid 190, and the anode 171 and the cathode 172. And a power source 173.
In the bubble generator 170, at least a part of the anode 171 and the cathode 172 is immersed in the liquid 190 and used.

The anode 171 is provided on an insulating substrate 174 made of glass, ceramics, plastic, or the like. A nanostructure 175 is provided on the surface of the anode 171 opposite to the surface in contact with the insulating substrate 174.
As the anode 171, the same thing as the above-mentioned 5th embodiment is used.
As the nanostructure 175, the same nanostructure as that in the first embodiment described above is used.

The cathode 172 is provided on an insulating substrate 176 made of glass, ceramics, plastic, or the like.
As the cathode 172, the thing similar to the cathode 12 in the above-mentioned first embodiment is used.

The stirrer 180 is supported by the tip of the rotating shaft 181 and is generally configured by a stirring blade 182 that stirs the liquid 190 and a DC motor 183 that rotates the stirring blade 182 via the rotating shaft 181.
The stirring blade 182 is disposed between the anode 171 and the cathode 172, for example, and stirs the liquid 190 between the anode 171 and the cathode 172. Thus, oxygen microbubbles (nanobubbles) 191 generated at the anode 171 can be taken out into the liquid 190.

Next, a bubble generation method using the bubble generator 170 will be described with reference to FIG.
Here, the case where water is used as the liquid 190 is illustrated.
An anode 171 and a cathode 172 arranged at a predetermined interval are immersed in the liquid 190, and a direct current or a direct current is pulsed from the power source 173 between the anode 171 and the cathode 172. By doing so, the liquid 190 is electrolyzed.
At this time, at least a part of the anode 171 and the cathode 172 is immersed in the liquid 190.
Further, when a direct current is applied between the anode 171 and the cathode 172, the liquid 190 is stirred by the stirring device 180.

According to the bubble generator 170 of the present embodiment, oxygen microbubbles (nanobubbles) 191 having a diameter of 100 nm or less can be stably generated in the anode 171 by electrolysis of the liquid 190. Further, the oxygen microbubbles (nanobubbles) 191 generated at the anode 171 can be taken out into the liquid 190 by the stirring device 180. Accordingly, the microbubbles (nanobubbles) 191 of oxygen are stably dispersed, and the existing liquid 190 can be obtained.
On the other hand, hydrogen bubbles 192 are generated at the cathode 172. When the liquid 190 is stirred by the stirring device 180, the hydrogen bubbles 192 are discharged out of the liquid 190.

 The bubble generator 170 of this embodiment can also be applied to the case of generating hydrogen microbubbles (nanobubbles) as in the sixth and seventh embodiments described above.

(9) Ninth Embodiment FIG. 16 is a schematic perspective view showing a ninth embodiment of the bubble generator.
The bubble generating apparatus 200 of the present embodiment supplies a current between a pair of the anode 201 and the cathode 202 arranged at a predetermined interval, the stirring device 210 for stirring the liquid 220, and the anode 201 and the cathode 202. The power supply 203 is generally configured.
In the bubble generating apparatus 200, the anode 201 and the cathode 202 are used by at least partly immersing them in the liquid 220.

The anode 201 is provided on an insulating substrate 204 made of glass, ceramics, plastic, or the like. A nanostructure 205 is provided on the surface of the anode 201 opposite to the surface in contact with the insulating base material 204.
As the anode 201, the same one as in the fifth embodiment described above is used.
As the nanostructure 205, the same nanostructure as that in the first embodiment described above is used.

The cathode 202 is provided on an insulating substrate 206 made of glass, ceramics, plastic, or the like.
As the cathode 202, the thing similar to the cathode 12 in the above-mentioned first embodiment is used.

The agitator 210 has a liquid circulation pump 211, one end immersed in the liquid 220, the other end connected to the liquid circulation pump 211, and an introduction pipe 212 for introducing the liquid 220 into the liquid circulation pump 211, and one end liquid circulation. A discharge pipe 213 is connected to the pump 211 and the other end is immersed in the liquid 220 and the liquid 220 sucked by the liquid circulation pump 211 is discharged (returned) into a container (not shown) in which the liquid 220 is stored. It is roughly structured.
In the stirring device 210, at least the discharge pipe 213 is disposed between the anode 201 and the cathode 202. Then, by repeating the circulation of the liquid 220, the liquid 220 sucked through the introduction pipe 212 by the liquid circulation pump 211 is returned to the container in which the liquid 220 is accommodated through the discharge pipe 213. As a result, the liquid 220 220 is agitated. Thus, oxygen microbubbles (nanobubbles) 221 generated at the anode 201 can be taken out into the liquid 220.

Next, a bubble generation method using the bubble generation device 200 will be described with reference to FIG.
Here, the case where water is used as the liquid 220 is illustrated.
The anode 201 and the cathode 202 arranged at a predetermined interval are immersed in the liquid 220, and a direct current or a direct current is pulsed between the anode 201 and the cathode 202 from the power source 203. By doing so, the liquid 220 is electrolyzed.
At this time, at least a part of the anode 201 and the cathode 202 is immersed in the liquid 220.
Further, when a direct current is applied between the anode 201 and the cathode 202, the liquid 220 is stirred by the stirring device 210.

According to the bubble generator 200 of the present embodiment, oxygen microbubbles (nanobubbles) 221 having a diameter of 100 nm or less can be stably generated in the anode 201 by electrolysis of the liquid 220. The stirring device 210 can take out oxygen microbubbles (nanobubbles) 221 generated in the anode 201 into the liquid 220. Therefore, oxygen microbubbles (nanobubbles) 221 are stably dispersed, and the existing liquid 220 can be obtained.
On the other hand, hydrogen bubbles 222 are generated at the cathode 202, and the hydrogen bubbles 222 are discharged out of the liquid 220 when the liquid 220 is stirred by the stirring device 210.

 The bubble generator 200 of this embodiment can also be applied to the case where hydrogen microbubbles (nanobubbles) are generated as in the sixth and seventh embodiments described above.

 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.

"Example 1"
Water electrolysis was performed using the bubble generator shown in FIG.
As the anode, an anode having a nanostructure made of a porous film formed by anodizing an aluminum substrate in an oxalic acid aqueous solution was used.
The distance between the anode and the cathode was 5 mm.
Next, the anode and the cathode were immersed in water contained in the container at 20 ° C.
In this state, a DC voltage (peak value) of ± 30 V was applied between the anode and the cathode for 1 minute. At this time, the interval between the anode and the cathode was adjusted so that the current density of the applied electric field was 1.0 mA / cm ² .
Further, while applying a DC voltage between the anode and the cathode, ultrasonic waves having a frequency of 20 kHz were applied to the anode by an ultrasonic vibrator.
Then, oxygen bubbles were generated from the anode while a DC voltage was applied between the anode and the cathode.
Using a fiber optic dynamic light scattering photometer (trade name: FDLS-3000, manufactured by Otsuka Electronics Co., Ltd.), the particle size of oxygen bubbles generated from the anode was measured. The results are shown in FIG. In FIG. 17, the vertical axis represents the existence frequency (scattering intensity distribution) of the particle size, and the horizontal axis represents the bubble particle size.
From the results of FIG. 17, it was found that according to the bubble generator of Example 1, oxygen nanobubbles having an average particle size of 30 nm can be generated.

"Comparative Example 1"
Water was electrolyzed using a bubble generator in the same manner as in Example 1 except that an aluminum substrate was used as the anode.
Further, in the same manner as in Example 1, the particle size of oxygen bubbles generated from the anode was measured. The results are shown in FIG. In FIG. 18, the vertical axis represents the existence frequency (scattering intensity distribution) of the particle size, and the horizontal axis represents the bubble particle size.
From the results of FIG. 18, it was found that the bubble generator of Comparative Example 1 can generate only oxygen bubbles having an average particle diameter of several μm.

"Example 2"
Water was electrolyzed using the bubble generator shown in FIG.
As an anode, an indium tin oxide (ITO) film having a film thickness of 1.0 μm is formed on a glass substrate by sputtering, and copper particles having an average particle diameter of 200 μm are further electrodeposited thereon. Was used.
The distance between the anode and the cathode was 5 mm.
Next, the anode and the cathode were immersed in water contained in the container at 20 ° C.
In this state, a DC voltage (peak value) of ± 50 V was applied between the anode and the cathode for 1 minute. At this time, the interval between the anode and the cathode was adjusted so that the current density of the applied electric field was 5.0 mA / cm ² .
Further, while applying a DC voltage between the anode and the cathode, ultrasonic waves having a frequency of 20 kHz were applied to the anode by an ultrasonic vibrator.
Then, oxygen bubbles were generated from the anode while a DC voltage was applied between the anode and the cathode.
Using a fiber optic dynamic light scattering photometer (trade name: FDLS-3000, manufactured by Otsuka Electronics Co., Ltd.), the particle size of oxygen bubbles generated from the anode was measured. The results are shown in FIG. In FIG. 19, the vertical axis represents the existence frequency (scattering intensity distribution) of the particle diameter, and the horizontal axis represents the bubble particle diameter.
From the results of FIG. 19, it was found that according to the bubble generator of Example 2, oxygen nanobubbles having an average particle size of 300 nm can be generated.

 The bubble generating device of the present invention includes a washing machine (such as washing soil removal and drum mold suppression), a refrigerator (such as purification of health water and tank mold suppression), a steam oven (such as mold suppression in the oven), It can be used for irons (mold suppression by steam, etc.), rice cookers, water purifiers, air conditioners, humidifiers, etc.

10, 50, 70, 90, 110, 130, 150, 170, 200 Bubble generator 11, 52, 71, 91, 111, 131, 151, 171, 201 Anode 12, 51, 72, 92, 112, 132, 152, 172, 202 Cathodes 13, 53, 73, 93, 113, 133, 153 Ultrasonic vibrators 14, 54, 74, 94, 114, 134, 154, 173, 203 Power supplies 20, 60, 80, 100, 120 , 140, 160, 190, 220 Liquid 55, 75, exhaust ports 95, 96, 115, 117, 155, 156, 174, 176, 204, 206 Insulating substrate 116, 157, 175, 205 Nanostructure 180, 210 Stirring device 181 Rotating shaft 182 Stirring blade 183 DC motor 211 Liquid circulation pump 212 Inlet pipe 213 Discharge pipe

Claims (12)

A plurality of electrodes of different polarities at least partially immersed in the liquid; and means for electrolyzing and gasifying the liquid; and means for applying vibration to at least one of the electrodes A bubble generator,
Nanostructures are provided on at least one surface of the plurality of electrodes, and microbubbles generated in the plurality of electrodes are caused by vibration applied to at least one of the plurality of electrodes by the means for applying vibration. A bubble generating device that is taken out of the liquid or out of the liquid.  The bubble generating apparatus according to claim 1, wherein the means for applying the vibration is a means for applying an ultrasonic wave. A bubble generator comprising a plurality of electrodes of different polarities at least partially immersed in a liquid, and means for electrolyzing and gasifying the liquid, and means for stirring the liquid ,
A nanostructure is provided on at least one surface of the plurality of electrodes, and microbubbles generated at the plurality of electrodes are taken out into or out of the liquid by means of stirring the liquid. Bubble generator.  The electrode of the plurality of electrodes that is not provided with the nanostructure is disposed so as to surround the electrode of the plurality of electrodes that is provided with the nanostructure. The bubble generator of any one of Claims.  The electrode of the plurality of electrodes provided with the nanostructure is disposed so as to surround the electrode of the plurality of electrodes not provided with the nanostructure. The bubble generator of any one of Claims.  The bubble generating device according to claim 1, wherein at least one of the plurality of electrodes is provided on an insulating base material.  The bubble generating apparatus according to claim 6, wherein the nanostructure is provided on a surface of the conductive film.  The bubble generation device according to claim 1, wherein an electrode provided with a nanostructure among the plurality of electrodes has a positive potential.  The bubble generating apparatus according to any one of claims 1 to 8, wherein the nanostructure includes a porous film formed by anodizing aluminum or an aluminum alloy.  The bubble generating apparatus according to claim 1, wherein the nanostructure includes at least one selected from the group consisting of nanotubes and nanoparticles.  The electrode provided with the nanostructure among the plurality of electrodes is made of an indium tin oxide film (ITO) or an indium zinc oxide film (IZO). The bubble generator described in 1.  The bubble generator according to any one of claims 1 to 11, further comprising means for exhausting at least one of gases generated by electrolysis of the liquid.