JP7203295B1 - Discharge device manufacturing method and discharge device - Google Patents

Abstract

A step of injecting a solution (3) for forming a conductive film (4) into a dielectric tube (2) one end of which is sealed to form a conductive film (4) on the inner surface of the dielectric tube (2). to deposit a dense conductive film (4). Furthermore, a cylindrical power supply part (11) is inserted along the inner surface of the dielectric tube (2), and a conductive film (4) is formed between the power supply part (11) and the inner surface of the dielectric tube (2). The formation of the conductive film (4) and the connection of the power supply part (11) to the conductive film (4) are simultaneously performed, and the manufacturing process is low cost and high quality by a simple process.

Description

The present application relates to a method for manufacturing a discharge device and a discharge device.

There is a discharge device that generates ozone by discharge in a raw material gas containing oxygen. Some conventional discharge devices have a structure in which a dielectric tube is arranged inside a tubular ground electrode, and the outer surface of the dielectric tube faces the inner surface of the ground electrode with a gap therebetween. A conductive film for applying a high voltage is provided on the inner surface of the dielectric tube, and functions as a high voltage electrode for generating discharge. By supplying a raw material gas containing oxygen to the space and applying a high voltage between the electrodes, an electric discharge is generated in the space and an ozonized gas is generated by the electric discharge.

When manufacturing a discharge device as described above, a film forming process for forming a conductive film on the inner surface of the dielectric tube is required, and various methods have been disclosed. For example, in the method for manufacturing a discharge device disclosed in Patent Document 1, after an aluminum coating is formed on the inner surface of a dielectric tube by thermal spraying, a Ni—Cr coating is thermally sprayed on the aluminum coating to form a conductive film. A method of forming a film is shown. Further, in the method of manufacturing a discharge device disclosed in Patent Document 2, a method of forming a stainless steel film on the inner surface of a dielectric tube by a sputtering method or a vapor deposition method is disclosed.

JP-A-7-2501 (paragraph 0010, FIG. 1) JP 2007-169134 A (paragraph 0017, FIG. 1)

However, the film forming methods such as the thermal spraying method, the sputtering method, and the vapor deposition method described in Patent Documents 1 and 2 require complicated steps to form a conductive film, and the film forming apparatus itself is expensive. There was a problem. Furthermore, after the conductive film is formed on the inner surface of the dielectric tube, a separate step of joining the power supply section for connecting the high voltage electrode and the high voltage power source to the dielectric tube is required. There is a problem that peeling or poor electrical contact is a concern.

The present application discloses a technique for solving the above problems, and aims to obtain a low-cost, high-quality discharge device manufacturing method and a discharge device through simple steps.

A method for manufacturing a discharge device disclosed in the present application includes injecting a solution for forming a conductive film into the inside of a dielectric tube having one end sealed and having a cylindrical power supply portion inserted along the inner surface from the other end , forming the conductive film on the inner surface of the dielectric tube and between the feeding portion and the inner surface of the dielectric tube .

The discharge device disclosed in the present application includes a high-voltage electrode provided with the conductive film, a ground electrode facing the high-voltage electrode with a gap therebetween, and a high-voltage electrode between the high-voltage electrode and the ground electrode. and a power supply line connecting the high voltage power supply and the power supply part of the high voltage electrode.

According to the present application, it is possible to manufacture a low-cost, high-quality discharge device with a simple process, and to suppress the manufacturing cost of the device itself.

4 is a flow chart diagram for explaining steps of manufacturing a discharge device according to the method for manufacturing a discharge device according to Embodiment 1. FIG. FIG. 4 is a plan view showing a manufacturing process of the discharge device according to the discharge device manufacturing method according to the first embodiment; FIG. 4 is a perspective view showing a manufacturing process of a discharge device according to the method of manufacturing a discharge device according to Embodiment 1; FIG. 4 is a cross-sectional view showing a manufacturing process of the discharge device by the method of manufacturing the discharge device according to the first embodiment; FIG. 4 is a cross-sectional view showing a manufacturing process of the discharge device by the method of manufacturing the discharge device according to the first embodiment; 4 is a cross-sectional view showing the configuration of a high-voltage electrode formed by the method of manufacturing the discharge device according to Embodiment 1; FIG. FIG. 11 is a perspective view showing a power feeder used in the method for manufacturing a discharge device according to Embodiment 2; FIG. 11 is a cross-sectional view showing the configuration of a discharge device according to Embodiment 3;

Hereinafter, a method for manufacturing a discharge device and a discharge device according to embodiments for carrying out the present application will be described in detail with reference to the drawings. In each figure, the same reference numerals denote the same or corresponding parts.

Embodiment 1.
FIG. 1 is a flow chart showing steps of manufacturing a discharge device according to a method for manufacturing a discharge device according to Embodiment 1 of the present application. 2 to 5 are diagrams for explaining each manufacturing process of FIG. FIG. 2 is a developed view of a power supply member used for forming a conductive film, and FIG. 3 is a perspective view of a processed power supply part. 4 and 5 are cross-sectional views of the dielectric tube into which the power supply portion is inserted, showing a state before forming a conductive film in the dielectric tube and a state in which a solution for forming the conductive film is injected, respectively. A method for manufacturing the discharge device according to Embodiment 1 of the present application will be described using these figures.

In the first manufacturing process, a power supply member made of a thin metal plate used for forming a conductive film is processed into a cylindrical shape for insertion into a dielectric tube whose one side is sealed (step S101 in FIG. 1). As shown in FIG. 2, the power supply member 1 is a metal plate having a thickness of about 0.1 mm, and is composed of a rectangular surface 1a having sides A and B and a rectangular surface 1b having sides C and D. It is

The direction parallel to side B is the X-axis direction, and the direction perpendicular to it is the Y-axis direction. The surface 1b is preferably located in the center of the side B, but does not necessarily have to be located in the center. Side A is preferably 20 mm or more, more preferably 20 to 40 mm. The side B is preferably 50 mm or more, more preferably 52.5 to 53 mm. By setting the length to 52.5 to 53 mm, when the surface 1a of the power supply member 1 is cylindrical and inserted into the dielectric tube, the power supply member 1 spreads inside the dielectric tube, and the adhesion can be further improved. Side C is preferably 5 mm or more. The side D is preferably 10 mm or more, and more preferably 10 to 20 mm from the viewpoint of the strength of the power supply member.

Further, although the side C is shorter than the side B in FIG. 2, it may have the same length as the side B. Examples of materials of the power supply member 1 include silver (Ag), copper (Cu), lithium (Li), nickel (Ni), manganese (Mn), zinc (Zn), and cobalt (Co). From the viewpoint of good electrical contact, Cu and Ag are preferable, and Cu is more preferable.

By processing the surface 1a of the power supply member 1 into a cylindrical shape by rounding the surface 1a of the power supply member 1 with the Y-axis direction as the rotation axis, the power supply part 11 having a cylindrical portion 11a as shown in FIG. 3 is formed. As a result, when inserting the power supply section into the dielectric tube, which is a step described later, the adhesion between the power supply section and the dielectric tube can be improved. It is desirable that the sides A of the cylindrical portion 11a are joined without gaps when being processed into a cylindrical shape, but they may be joined so as to overlap each other.

Subsequently, the cylindrical portion 11a of the feeding portion 11 processed into a cylindrical shape is inserted along the inner surface of the dielectric tube 2 (step S102 in FIG. 1). As shown in FIG. 4, the feeding section 11 has the cylindrical portion 11a completely inserted into the dielectric tube 2, but the lead wire 11b of the feeding section 11, which is the surface 1b, is part of the dielectric tube 2. As shown in FIG. It is installed inside the dielectric tube 2 at a position partly protruding outside the dielectric tube 2 . This makes it possible to easily connect the power supply line for connecting to the high-voltage power supply and the power supply unit. Although it is preferable that the cylindrical portion 11a is completely inserted inside the dielectric tube 2, a part of the cylindrical portion 11a may protrude outside the dielectric tube 2. FIG.

Next, a solution for forming a conductive film is injected into the dielectric tube 2 into which the power supply portion 11 is inserted (step S103 in FIG. 1). A solution 3 for forming the conductive film 4 on the dielectric tube 2 is injected up to the height of the side A of the power supply portion 11 . FIG. 5 shows the state after injecting the solution 3 for forming the conductive film 4 into the dielectric tube 2 . Solution 3 is a mixed solution containing a metal precursor liquid and an organic reducing agent. In solution 3, the contents of the metal precursor liquid and the organic reducing agent in the mixed solution obtained by mixing the metal precursor liquid and the organic reducing agent are not particularly limited.

The metal precursor liquid is a mixed solution containing at least one selected from the group consisting of metal complexes and metal salts (hereinafter collectively referred to as specific metal compounds), at least one selected from ammonia and amines, and a solvent. . Examples of metals contained in the metal precursor liquid include Ag, Cu, Li, Ni, Mn, Zn, and Co.

Metal complexes can be formed from _NH3 ligands, _RNH2 ligands (R represents an alkylene group), OH2 ligands, and diamine _- derived ligands such as ethylenediamine and hexamethylenediamine, which can form metal complexes. It is preferably a reaction product of one or more metal complex-forming compounds selected from compounds having a partial structure and a metal ion. The metal in the metal complex is preferably of the same type as that of the power supply member 1 of the power supply section 11 . As the metal complex, for example, copper ethylenediaminetetraacetate, copper tetraammine, etc., which contain Cu as a metal, are preferably exemplified. From the viewpoint of good electrical contact, Cu, Ag, etc. are preferable, and Cu is more preferable.

A metal salt is a metal compound that dissociates into a metal ion in a solvent containing water and has the ability to form a metal complex. A metal salt in the present disclosure refers to a metal salt that is soluble in water at 25°C. Soluble in water at 25°C means that the solubility in water at 25°C is 0.1% by mass or more, and the solubility is preferably 1% by mass or more. Since the metal salt is soluble in water, the metal salt is dissociated in a solvent containing water to form metal ions, and the metal ions react with amines contained in the solvent to obtain a metal complex. Furthermore, when the solvent optionally contains a complex-forming compound, the metal ion may react with the complex-forming compound to form a metal complex.

More specifically, the compound for forming a metal complex includes at least one selected from ammonia, ammonium formate, and ethylenediaminetetraacetic acid (hereinafter referred to as H ₄ EDTA). It is preferably contained in the mixed liquid. Above all, it is more preferable that the mixed solution contains an H ₄ EDTA aqueous solution as the metal complex-forming compound.

In addition, the metal precursor liquid may contain both the metal complex and the metal salt. When the mixture contains two or more specific metal compounds, for example, it may be a combination of metal complexes containing the same metal and having different ligands, or a combination of metal complexes containing different metals. From the point of view of synthesis aptitude, it is preferable to combine metal complexes containing the same kind of metal.

Since ammonia has basicity similar to that of amines, at least one selected from ammonia and amines may be collectively referred to as "amines" hereinafter. Amines may be contained as a salt compound in the mixed solution. The mixed solution may contain only one type of amines, or may contain two or more types.

As the solvent, an aqueous solvent such as water or a mixture of water and alcohol can be used. The water preferably has a low content of impurities, particularly ions other than metal ions, and from such a point of view, it is preferable to use purified water, ion-exchanged water, pure water, or the like. Examples of alcohols include monohydric alcohols having 1 to 10 carbon atoms such as methanol, ethanol, isopropanol, n-propanol, isobutanol and n-butanol, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin. A polyhydric alcohol is mentioned. From the viewpoint of the solubility and handling properties of the specific metal compound, the aqueous solvent is preferably water or a mixture of water and a monohydric alcohol having 1 to 5 carbon atoms, such as water or water and methanol or ethanol. , and an alcohol selected from propanol, more preferably water.

The metal precursor liquid can be prepared by containing a specific metal compound and amines in a solvent and sufficiently stirring and mixing them. Mixing may be performed at normal temperature, or may be performed by heating the solvent to 40° C. to 60° C. for the purpose of promoting dissolution.

The organic reducing agent preferably contains at least one selected from compounds having a carboxy group. As the organic reducing agent, it is preferable to appropriately select and use an organic carboxylic acid compound having a carboxy group in the molecule and functioning as a reducing agent.

Examples of the organic reducing agent include at least one selected from ascorbic acid, citric acid, oxalic acid, formic acid, 3,4,5-trihydroxybenzoic acid and the like. From the viewpoint that there is a is more preferred.

Including ascorbic acid as an organic reducing agent is one of the preferred embodiments of the present disclosure. The organic reducing agent is preferably used as an aqueous solution. The water used for preparing the aqueous solution preferably does not contain metal ions or has a metal ion concentration as low as possible from the viewpoint of the uniformity of the resulting metal film. It is preferable to use purified water, ion-exchanged water, pure water, or the like. When dissolving the specific reducing agent in water, the solvent water may be heated to 30° C. to 60° C., preferably 35° C. to 45° C., for the purpose of improving solubility. . Further, dissolution may be performed while stirring.

Subsequently, the solution for forming the conductive film is allowed to stand on the dielectric tube 2 for a predetermined time to form the conductive film 4 on the dielectric tube 2 (step S104 in FIG. 1). By leaving the dielectric tube 2 in which the solution 3 for forming the conductive film 4 shown in FIG. The conductive film 4 is also formed between the power supply portion 11 and the inner surface of the dielectric tube 2 . Corrosion resistance can be improved by forming a dense film.

Since the solution 3 permeates between the power feeding portion 11 and the dielectric tube 2, the power feeding portion 11 and the conductive film 4 are made of the same kind of metal, and the power feeding portion 11 and the conductive film 4 have excellent adhesion. For example, when Cu is used as the metal, Cu nanoparticles derived from the Cu complex adhere to the substrate to form a Cu film, resulting in good electrical contact. From the viewpoint of conductivity, the particle size of the metal particles formed as a film is preferably 0.1 to 10 μm, more preferably 1 μm. Moreover, the film thickness of the conductive film 4 formed on the inner surface of the dielectric tube 2 is preferably 0.1 to 10 μm from the viewpoint of corrosion resistance, electrical conductivity, and productivity.

Moreover, when the metal complex contained in the solution 3 has an ammonium group, a ligand derived from ethylenediamine, or the like, the metal complex has good adhesion to the dielectric tube. Therefore, it can be expected that the conductive film formed using the metal complex has excellent adhesion to the dielectric tube.

The standing time is preferably 6 hours or longer, more preferably 12 hours or longer, at room temperature (25° C.), for example. By leaving the composition layer for forming the conductive film 4 which is a metal film formed inside the dielectric tube 2 as a base material, the metal contained in the solution 3 is adsorbed to the base material and the conductive film 4 is formed. is formed. The upper limit of the standing time is not particularly limited, but considering productivity and the like, it can be set to 120 hours or less, preferably 90 hours or less. When the dielectric tube 2 is left standing, there is no particular limitation on the installation method of the dielectric tube 2. For example, while the dielectric tube 2 is standing still in order to form the conductive film, You may rotate by angles, such as 90 degrees and 180 degrees, in the circumferential direction.

Finally, the solution used to form the conductive film 4 is discharged from the dielectric tube 2 (step S105 in FIG. 1), and the inside of the dielectric tube 2 is dried to complete the formation of the conductive film 4. FIG. FIG. 6 shows a high-voltage electrode using a dielectric tube 2 on which a conductive film 4 is formed by the method for manufacturing a discharge device according to the first embodiment.

As described above, according to the method of manufacturing a discharge device according to the first embodiment, the solution 3 for forming the conductive film 4 is injected into the dielectric tube 2 whose one end is sealed, and the dielectric tube 2 is Since the step of forming the conductive film 4 on the inner surface of the substrate is included, a dense conductive film can be formed at a lower cost than the thermal spraying method and the sputtering method. Furthermore, since it includes the step of inserting the cylindrical power supply portion 11 along the inner surface of the dielectric tube 2 and forming the conductive film 4 between the power supply portion 11 and the inner surface of the dielectric tube 2, The formation of the conductive film and the connection of the power supply portion to the conductive film can be performed at the same time, and a low-cost, high-quality discharge device can be manufactured by a simple process.

Embodiment 2.
In the first embodiment, the case of using a normal metal thin plate for forming the power supply portion 11 is described, but in the second embodiment, the case of using a metal thin plate provided with a through hole will be described.

FIG. 7 is a perspective view showing a power feeder used in the method for manufacturing a discharge device according to Embodiment 2 of the present application. As shown in FIG. 7, the feeding portion 21 used in the second embodiment has a plurality of through holes 21h provided in a tubular portion 21a which is a joint surface of the feeding portion 21 connected to the inner surface of the dielectric tube 2. there is The outer diameter of the through hole 21h is preferably 2-5 mm. Although it is preferable that there are a plurality of through-holes 5, there may be only one. Other configurations of the high-voltage electrode formed by the method for manufacturing the discharge device according to the second embodiment and the method for manufacturing the same are the same as those of the high-voltage electrode formed by the method for manufacturing the discharge device according to the first embodiment. The explanation is omitted.

By providing the through hole 21 h in the power supply portion 21 in this manner, the adhesion between the power supply portion 21 and the conductive film 4 can be further improved.

As described above, according to the method of manufacturing the discharge device according to the second embodiment, since the through hole 21h is provided in the joint surface with the dielectric tube 2 in the power feeding portion 21, In addition to the effect of (1), the adhesion between the power supply portion and the conductive film can be further improved, and a higher quality discharge device can be manufactured.

Embodiment 3.
FIG. 8 is a cross-sectional view showing the configuration of a discharge device according to Embodiment 3 of the present application. As shown in FIG. 8, the discharge device 100 of the third embodiment includes a high-voltage electrode 6 provided with a conductive film 4 formed by the discharge device manufacturing method described in the first and second embodiments. , a ground electrode 8 facing the high voltage electrode 6 with a gap therebetween, a high voltage power source 9 for applying a high voltage between the high voltage electrode 6 and the ground electrode 8, and a power supply unit 11 connected to the high voltage power source 9. and a power supply line 10 for supplying raw material gas to the gap and applying a high voltage between the high-voltage electrode 6 and the ground electrode 8 to generate active species in the gap.

The raw material gas contains, for example, oxygen, and at this time, oxygen atoms, ozone, and the like are generated as active species.

As described above, the discharge device 100 is provided with the high-voltage electrode 6 provided with the conductive film 4 formed by the discharge device manufacturing method described in the first and second embodiments. Manufacturing costs can be suppressed.

As described above, according to the discharge device 100 according to the third embodiment, the high voltage discharge device provided with the conductive film 4 formed by the discharge device manufacturing method described in the first and second embodiments is provided. an electrode 6, a ground electrode 8 facing the high voltage electrode 6 with a gap therebetween, a high voltage power supply 9 applying a high voltage between the high voltage electrode 6 and the ground electrode 8, and a high voltage power supply 9 and the high voltage. Since the power supply line 10 that connects the power supply part 11 of the electrode 6 is provided, the manufacturing cost of the device itself can be suppressed.

While this application describes various exemplary embodiments and examples, various features, aspects, and functions described in one or more embodiments may not apply to particular embodiments. can be applied to the embodiments singly or in various combinations. Accordingly, numerous variations not illustrated are envisioned within the scope of the technology disclosed herein. For example, modification, addition or omission of at least one component, extraction of at least one component, and combination with components of other embodiments shall be included.

2 dielectric tube, 3 solution, 4 conductive film, 11 feeding part, 11a tubular part, 100 discharge device.

Claims (10)

A solution for forming a conductive film is injected into a dielectric tube having one end sealed and a tubular feeder inserted along the inner surface from the other end, so that the inner surface of the dielectric tube, the feeder and the feeder are injected. forming the conductive film between the inner surface of the dielectric tube ;
A method of manufacturing a discharge device, comprising: 2. The method of manufacturing a discharge device according to claim 1 , wherein the power supply portion is made of the same kind of metal as the conductive film. 3. The method of manufacturing a discharge device according to claim 2 , wherein the power supply portion is formed by processing a thin metal plate into a cylindrical shape. 4. The method of manufacturing a discharge device according to claim 3 , wherein the power supply portion has a through hole formed in a joint surface with the dielectric tube. 5. The method of manufacturing a discharge device according to claim 4 , wherein the solution for forming the conductive film contains a metal precursor liquid and an organic reducing agent. 6. The method of manufacturing a discharge device according to claim 5 , wherein the metal precursor liquid contains at least one selected from the group consisting of Ag, Cu, Li, Ni, Mn, Zn and Co. 7. The organic reducing agent according to claim 6 , comprising at least one selected from the group consisting of ascorbic acid, citric acid, oxalic acid, formic acid, and 3,4,5-trihydroxybenzoic acid. manufacturing method of the discharge device. 8. The method of manufacturing a discharge device according to claim 7 , wherein the formed conductive film has metal particles with a particle size of 0.1 to 10 μm. 9. The method of manufacturing a discharge device according to claim 8 , wherein the formed conductive film has a film thickness of 0.1 to 10 μm. a high-voltage electrode provided with the conductive film formed by the method for manufacturing a discharge device according to any one of claims 1 to 9 ;
a ground electrode facing the high voltage electrode with a gap therebetween;
a high voltage power supply that applies a high voltage between the high voltage electrode and the ground electrode;
a power supply line connecting the high voltage power supply and the power supply part of the high voltage electrode;
A discharge device comprising:

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