Patent AU-2017204570-A2 (AU)
Title: Device and method for gas treatment using low-temperature plasma and catalyst medium
Inventor: IKEGAMI MAKOTO
IPC: B01J23/10
Filed: 2017-07-04
Abstract: DESCRIPTION DEVICE AND METHOD FOR GAS TREATMENT USING NON-THERMAL PLASMA AND CATALYST MEDIUM 5 [0001] This application is a divisional application of Australian application no. 2012311020 the disclosure of which is incorporated herein by reference. 0 Technical Field [0001a] The present invention relates to a device and a method for oxidation decomposition treatment of a hazardous gas using non-thermal plasma and a catalyst medium. Background Art [0002] In recent years, as a method and a device for decomposition of a hazardous gas, methods and devices using non-thermal plasma 0 have been proposed. Since the device using non-thermal plasma is simple and the non-thermal plasma is a chemical reaction in which an active species having a high reactivity can be used, the reaction instantaneously proceeds. For this reason, the non-thermal plasma is expected to effectively decompose a hazardous gas in a gas. 5 Further, the non-thermal plasma is easily combined with other 9246460_1 (GHMatters) P96427.AU.1 techniques. The non-thermal plasma is known to be applicable to various types of combined processes. However, when effective decomposition is not sufficient, a by-product is generated by the decomposition of a hazardous gas. For sufficiently effective 5 decomposition, the input of a large amount of energy is required. In this case, there are problems of generation of nitrogen oxides and a large amount of ozone from air. In order to make a practical application of a technique for removing a hazardous gas in air by the non-thermal plasma, it is an important object to suppress the 0 generation of nitrogen oxides and ozone and to improve the decomposition efficiency of the hazardous gas. [0003] As achievement of such an object, a method for decomposing an ethylene gas using plasma (Patent Literatures 1 and 2), a method 5 for providing a honeycomb-shaped catalyst between a discharge electrode and an earth electrode (ground electrode) (Patent Literature 3), and amethod for providing a manganese-based catalyst (Patent Literature 4) have been proposed. Further, a method of further remedying the generation of ozone and the generation of 0 by-products by decomposition of a hazardous gas in the conventional method of using non-themal plasma in combination with a known catalyst and a device for purifying the hazardous gas (Patent Literature 5) have been proposed. 5 Citation List 9246460_1 (GHMatters) P96427.AU.1 Patent Literature [0004] Patent Literature 1: Japanese Patent Application Laid-Open No. 2000-139198 5 Patent Literature 2: Japanese Patent Application Laid-Open No. 2003-158996 Patent Literature 3: Japanese Patent Application Laid-Open No. 2000-140562 Patent Literature 4: Japanese Patent Application Laid-Open 0 No. 2002-336343 Patent Literature 5: Japanese Patent Application Laid-Open No. 2005-230627 Technical Problem 5 [0005] The regeneration of an adsorbent in a short time is required for agas purificationmethodbasedon adsorption. Inaconventional method for regenerating an adsorbent, facilities for desorption by steam and desorption by heating are necessary. Therefore, the 0 facilities may be enlarged, and a drainage facility may be required according to a desorption method. In a method for providing pellets of a ferroelectric material between a discharge electrode and an earth electrode, a high voltage needs to be applied depending on the particle diameter of a dielectric material and filling amount 5 of the dielectric material. This results in problems of generation 9246460_1 (GHMatters) P96427.AU.1 of hazardous ozone andnitrogen oxides fromair. Further, inamethod for providing a honeycomb-shaped catalyst, the catalyst needs to surelycome into contactwithahazardous gas. Therefore, adistance between a discharge electrode and an earth electrode is elongated. 5 In addition, in order to stably generate plasma, a high voltage needs to be applied to produce a large amount of energy. As a result, there are problems of generation of nitrogen oxides and a large amount of ozone from air. In a method proposed by the present inventors, an adsorbent having a metallic catalytic function is 0 used. In this case, there is a problem in which the concentration of a hazardous gas to be treated is limited depending on the amount of the adsorbent having a metallic catalytic function. When a pellet-shaped or honeycomb-shaped catalyst is disposed, it is difficult that a purification device is flexibly designed in terms 5 of the structure. [0006] Embodiments of the present invention may alleviate some of the problems. Advantageously, an embodiment of the present invention provides a device and a method for oxidation decomposition 0 treatment of a hazardous gas of a volatile organic compound (VOC) or the like at normal temperature. Summary of Invention[0007] A first aspect of the present invention is a gas treatment 5 device provided with: a flow channel through which an ethylene gas 9246460_1 (GHMatters) P96427.AU.1 to be treated flows; a plasma-generating unit including at least a first electrode, a second electrode, a dielectric material, which are arranged inside the flow channel, and a power-supply unit for supplying AC power 5 at an output frequency of 0.5 kHz or higher and 2.0 kHz or lower, wherein a voltage is applied between the first electrode and the second electrode by the power-supply unit to cause electrical discharging to occur, whereby plasma is generated; and a catalyst medium which is provided in a position where the 0 plasma generated by the plasma-generating unit inside the flow channel is present, is adapted for accelerating a reaction with the gas to be treated, has metallic catalytic particles present on an inorganic substance, and is Pt supported by A1 20 3 , wherein a discharge output of the electrical discharging is 3.0W 5 or lower. [0008] A second aspect of the present invention is the gas treatment device accordingtothe first aspect of thepresent invention, wherein the first electrode, the second electrode, the dielectric material, 0 and the catalyst medium are arranged in order in a flow direction of the gas to be treated, and are each permeable in the flow direction of the gas, and the catalyst medium is disposed in a space where the electrical discharging is caused to occur in the flow channel or on a downstream side of the space in the flow direction of the 5 gas. 9246460_1 (GHMatters) P96427.AU.1 [0009] A third aspect of the present invention is the gas treatment device accordingtothe first aspect of thepresent invention, wherein the first electrode, the second electrode, the dielectric material, 5 and the catalyst medium are arranged in order in a direction perpendicular to the flow direction of the gas. [0010] A fourth aspect of the present invention is the gas treatment device according to any one of the first to third aspects of the 0 present invention, wherein the catalyst medium is further provided with a substrate to which at least the metallic catalytic particles are fixed and which is made of an inorganic material. [0011] A fifth aspect of the present invention is the gas treatment 5 device according to any one of the first to third aspects of the present invention, wherein the catalyst medium is further provided with: inorganic particles to the surface of which the metallic catalytic particles are fixed; and 0 a substrate to which the inorganic particles are fixed and which is made of an inorganic material. [0012] A sixth aspect of the present invention is the gas treatment device according to any one of the first to third aspects of the 5 present invention, wherein the catalyst medium is filled with a 9246460_1 (GHMatters) P96427.AU.1 large number of inorganic particles supporting the metallic catalytic particles. [0013] A seventh aspect of the present invention is the gas treatment 5 device according to any one of the first to sixth aspects of the present invention, wherein the first electrode and the second electrode are each a comb-teeth-shaped electrode that is formed from a large number of electrodes extending in respective predetermined directions, and the gas to be treated flows through 0 a space formed by the comb-teeth-shaped electrodes, the dielectric material, and the catalyst medium. [0014] An eighth aspect of the present invention is the gas treatment device according to any one of the first to seventh aspects of the 5 presentinvention, whereintheplasmaisatleastonekindofdischarge plasma of silent discharge, creeping discharge, corona discharge, and pulse discharge. [0015] A ninth aspect of the present invention is the gas treatment 0 device according to any one of the first to eighth aspects of the present invention, wherein the metallic catalytic particles are made of at least one kind of Pt, Au, CeO 2 , PdO, MnO 2 , CuO, and Ag. [0016] A tenth aspect of the present invention is the gas treatment 5 device according to any one of the first to ninth aspects of the 9246460_1 (GHMatters) P96427.AU.1 present invention, whereinthepower-supplyunit supplies electrical power at an output frequency of 0.5 kHz or higher. [0017] An eleventh aspect of the present invention is a gas treatment 5 method including: generating plasma by discharging electricity at a discharge output of 3.0W of lower in a range where a catalyst medium for accelerating an oxidation decomposition reaction with a gas tobe treated is disposed, the electrical discharging occurring by supplying AC power at an output frequency of 0.5 kHz or higher 0 and 2.0 kHz or lower; and passing the gas to be treated in the plasma to cause oxidation decomposition, wherein the gas to be treated is an ethylene gas, and the catalyst medium is Pt supported by A1 20 3. [0018] 5 A twelfth aspect of the present invention is the gas treatment method according to the eleventh aspect of the present invention, wherein electrical power is supplied at an output frequency of 0.5 kHz or higher to cause electrical discharging to occur, whereby the plasma is generated. Advantageous Effects of Invention [0019] Inthegastreatmentdeviceinthepresent invention, acatalyst and plasma are used in combination. This allows a gas containing 5 a hazardous substance or the like to be converted into CO 2 by oxidation 9246460_1 (GHMatters) P96427.AU.1 decomposition at low temperature without leaving reaction intermediates such as CO and formaldehyde. Further, the plasma prevents the adsorption of impurities, reaction intermediates, and the like to the catalyst surface. Therefore, the degradation of 5 catalytic performance can be suppressed and a catalytic activity can be maintained for extended periods. In addition, a substrate for fixing a catalyst is made of an inorganic material. Thus, the substrate is resistant to plasma, and a catalyst medium can be used for extended periods. Accordingly, the present invention can 0 provide a gas treatment device capable of effectively oxidizing and decomposing a hazardous substance of a volatile organic compound (VOC) or the like that pollutes an environment and adversely affects the human body. 5 Brief Description of Drawings [0020] FIG. 1 is a schematic cross-sectional view of a gas treatment device according to an embodiment of the present invention. FIG. 2 is a schematicviewofacatalystmediumtowhich catalyst 0 fine particles are fixed, according to the embodiment of the present invention. FIG. 3 is a schematic view of a catalyst medium according to another embodiment of the present invention. FIG. 4 is a schematic view of a catalyst medium according to 5 another embodiment of the present invention. 9246460_1 (GHMatters) P96427.AU.1 FIG. 5 is a schematic view of a catalyst medium according to another embodiment of the present invention. FIG. 6 is a schematic view of a gas treatment device according to another embodiment of the present invention. 5 FIG. 7 is a schematic view of a gas treatment device according to another embodiment of the present invention. FIG. 8 is a schematic cross-sectional view of the gas treatment device according to the another embodiment of the present invention. FIG. 9 is a schematic cross-sectional view of a gas treatment 0 device according to another embodiment of the present invention. FIG. 10is a schematic view of a gas treatment device according to another embodiment of the present invention. FIG. 11 is a schematic view of a gas treatment device according to another embodiment of the present invention. 5 FIG. 12 is a schematic view of a gas treatment device according to another embodiment of the present invention. Description of Embodiments [0021] 0 Hereinafter, embodiments of the present invention will be described. [0022] (First Embodiment) FIG. 1 is a view schematically illustrating the cross section 5 of a gas treatment device 200 according to an embodiment of the 9246460_1 (GHMatters) P96427.AU.1 present invention. The gas treatment device 200 is disposed inside a flow channel supplied with a gas containing a gas to be treated. In FIG. 1, the gas treatment device 200 is a device in which a gas containing a gas to be treated that is supplied to the gas treatment 5 device 200 in an arrow A direction is converted into C02 by oxidation decomposition using plasma generated in the gas treatment device 200 and the function of a catalyst medium 100. [0023] The gas treatment device 200 is provided with an application 0 electrode 11, a ground electrode 12, a dielectric material 13, a catalyst medium 100, and a (high-voltage) power supply 14 as a power-supply unit. In the gas treatment device 200, the application electrode 11, the ground electrode 12, the dielectric material 13, and the power supply 14 constitute a member and a device 5 (plasma-generating unit) for generating plasma. When a voltage is applied by the power supply 14, a non-themal plasma reaction layer is formed by electrical discharging occurring between the application electrode 11 and the dielectric material 13 by the application electrode 11, the groundelectrode 12, andthe dielectric 0 material 13. In the gas treatment device 200, the application electrode 11, the catalyst medium 100, the ground electrode 12, and the dielectric material 13 are configured to be in close contact with one another. One of the application electrode 11 and the ground electrode 12 is a first electrode and the other is a second electrode. 5 In other embodiments, a plurality of application electrodes 11 and 9246460_1 (GHMatters) P96427.AU.1 a plurality of ground electrodes 12 are combined. Even in these cases, one kind of electrodes are each a first electrode and the other kind of electrodes are each a second electrode. [0024] 5 The application electrode 11 is an electrode to whichavoltage isappliedbythepowersupply14. The groundelectrode 12 is grounded by a ground wire 12a. The application electrode 11, the ground electrode 12, and the dielectric material 13 have a permeable structure in which a gas can pass through the electrodes. Specific 0 examples of the structures of the application electrode 11, the ground electrode 12, and the dielectric material 13 may include a lattice structure, a reed screen structure, a porous structure processed by punching, and an expanded mesh structure. As the structures, a combination of two or more of these structures may 5 be used. The application electrode 11 and the ground electrode 12 may have an acicular structure. The application electrode 11, the ground electrode 12, and the dielectric material 13 may have the same shape and structure among the above-described shapes and structures. In FIG. 1, the application electrode 11 has many small 0 apertures like a mesh, and the ground electrode 12 and the dielectric material 13 have a small number of large apertures like a porous structure processed by punching. [0025] As the application electrode 11 and the ground electrode 12, 5 a material functioning as an electrode can be used. As materials 9246460_1 (GHMatters) P96427.AU.1 for the application electrode 11 and the ground electrode 12, for example, a metal such as Cu, Ag, Au, Ni, Cr, Fe, Al, Ti, W, Ta, Mo, and Co and an alloy thereof can be used. [0026] 5 Thedielectricmaterial13mayhaveapropertytobeaninsulator. Examples of the material for the dielectric material 13 may include an inorganic material such as ZrO2 , y-A1 20 3 , u-A12 0 3 , O-A1 20 3 , T1-A1203, amorphous A1 2 0 3 , alumina nitride, mullite, steatite, forsterite, cordierite, magnesium titanate, barium titanate, SiC, Si 3 N4 , Si-SiC, 0 mica, and glass, and a polymeric material such as polyimide, liquid crystal polymer, poly tetra fluoro ethylene (PTFE), ethylene tetra fluoro ethylene (ETFE), poly vinyl fluoride (PVF), poly vinylidene difluoride (PVDF), polyetherimide, and polyamide imide. In terms of plasma resistance and heat resistance, an inorganic material 5 is more preferable. [0027] When the catalyst medium 100 described below has a function as a dielectric material (for example, when a portion of the catalyst medium is an insulator), the catalyst medium 100 can be used as 0 a dielectric material. In this case, the dielectric material 13 may not be provided. [0028] Next, the catalyst medium 100 will be described. FIG. 2 is a view schematically illustrating a portion of the cross section 5 ofthe catalystmedium100 accordingtothe embodiment. The catalyst 9246460_1 (GHMatters) P96427.AU.1 medium 100 is a catalyst for accelerating a reaction in which a gas to be treated is converted into carbon dioxide (CO2) by oxidation decomposition. In the embodiment, since the catalyst medium 100 is subjected to plasma, an oxidation decomposition reaction 5 accelerated by the catalyst medium 100 is further accelerated. [0029] The catalyst medium 100 of the present embodiment is apermeable plate-shaped or sheet-shaped member through which gas can pass. The catalyst medium 100 is configured to include a substrate 10, 0 a catalyst 1 fixed to the substrate 10, and the like. The catalyst medium 100 is disposed in a position (region) where plasma generated bytheplasma-generatingunitispresent. Inthepresentembodiment, the catalyst medium 100 is specifically disposed between the application electrode 11 and the dielectric material 13 (in a 5 discharge space) . A gas can pass through the catalyst medium 100 in directions of a double-headed dashed-line arrow B in FIG. 2. For this reason, the catalyst medium 100 of the present embodiment has a structure in which the catalyst 1 is fixed to the substrate 10 so as to maintain permeability. The substrate 10 has permeable 0 structure such as a filter structure, a mesh structure, or a structure in which a plurality of holes are formed on a plate shaped member by perforation such as punching. It is preferable that the catalyst medium 100 be disposed so that a face fixing the catalyst 1 is oriented toward a side of the application electrode 11 (an upstream side 5 of gas flowdirection) in the gas treatment device 200. Forexample, 9246460_1 (GHMatters) P96427.AU.1 when the substrate 10 has a filter-shaped or mesh-shaped structure, a space can be formed inside the substrate 10. In this case, the catalyst 1 can be fixed to the inside of the substrate 10 according to a method for producing the catalyst medium 100. Alternatively, 5 the catalyst 1 may be fixed to both faces of the substrate 10. When the catalyst 1 is fixed to the inside of the substrate 10 or to the both faces of the substrate 10, the catalyst medium 100 may be disposed toward either direction. [0030] 0 In the catalyst 1, catalyst fine particles 1-a are supported by carrier fine particles 1-b. The catalyst 1 is fixed to the substrate 10 by binding silane monomers 2 bound to each of the carrier fine particles 1-b to the substrate 10 through chemical bonds 3. The fixation using the silane monomers 2 will be described below. 5 [0031] The catalyst fine particles 1-a of the catalyst 1 are not limited as long as they have a catalytic function for accelerating a reaction in which a gas to be treated is converted into C02 by oxidation decomposition. It is preferable that the catalyst fine particles 0 be made of Au, Pt, CeO 2 , PdO, MnO 2 , or CuO, that has a high oxidation catalytic function. [0032] The catalyst fine particles 1-a may have a particle diameter of about 0.5 nm or larger and about 200 nm or smaller. The amount 5 of the catalyst fine particles 1-a to be fixed to the carrier fine 9246460_1 (GHMatters) P96427.AU.1 particles 1-b is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass. When 20% by mass or more of the catalyst fine particles are supported, catalyst fine particles that are the catalyst fine particles 1-a are aggregated. This is because the 5 catalytic activity is low. When the amount is 0.1% by mass or less, the catalytic activity is not sufficiently obtained. Therefore, this range is not preferable. [0033] The catalyst fine particles 1-a need to include a fine particle 0 having a catalytic function for accelerating a reaction in which at least a gas to be treated is converted into carbon dioxide by oxidation decomposition as described above, but the catalyst fine particles 1-amaybe combinedwith another substance. Specifically, the catalyst fine particles 1-a may be a mixture of catalyst fine 5 particles and promoter fine particles, or a composite catalyst including composite fine particles obtained by combining various metal elements with catalyst fine particles. When the catalyst fine particles are singly used or when a promoter is mixed in the catalyst fine particles, the catalyst fine particles may have a polyhedral 0 shape and the sizes thereof may fall within the above-described range. When composite fine particles combined with another metal element are used, the size of the catalyst fine particles may fall within the above-described range. Examples of metal fine particles (nanoparticles) other than the catalyst fine particle used for the 5 promoter or the composite catalyst may include noble metal such 9246460_1 (GHMatters) P96427.AU.1 as Pt, Pd, and Ir and an oxide thereof, and base metal and an oxide thereof. Two or more kinds of fine particles of noble metal and an oxide thereof and base metal and an oxide thereof may be mixed and supported by the surface of the carrier fine particles 1-b. 5 [0034] The carrier fine particles 1-b are particle which support the catalyst fine particles 1-a and through which the catalyst fine particles 1-a are fixed to the substrate 10. The carrier fine particles 1-b are not limited to particular ones as long as the 0 particles can support the catalyst fine particles 1-a. It is preferable that as the carrier fine particles 1-b, a metal oxide or an inorganic compound mainly having a physical absorptive property be used. [0035] 5 Examples of the metal oxide may include a single inorganic oxide such as y-A1 2 0 3 , uo-A1 2 0 3 , O-A1 2 0 3 , Tl-A1203, amorphous A1 2 0 3 , TiO2 , ZrO2 , SnO2 , SiO2 , MgO, ZnO2 , Bi20 3 , In 2 0 3 , MnO 2 , Mn 2O 3 , Nb 2 0 5 , FeO, Fe 2O 3 , Fe 30 4 , Sb 2 0 3 , CuO, Cu 2 0, NiO, Ni 30 4 , Ni 20 3 , CoO, C0304, C0203, W0 3 , CeO 2 , PrO 1 1 , Y2 0 3 , In 2 0 3 , PbO, and ThO2 . For example, the metal oxide may 0 be a composite oxide such as SiO2 -A1 2 0 3 , SiO2 -B 2 0 3 , SiO2 -P 2 0 5 , SiO2 -TiO 2 , SiO2 -ZrO 2 , A1 2 0 3 -TiO 2 , A1 20 3-ZrO 2 , A1 20 3 -CaO, A1 2 0 3 -B 2 0 3 , A1 20 3 -P 2 0 5 , A1 20 3 -CeO 2 , A1 2 0 3 -Fe 2O 3 , TiO2 -CeO 2 , TiO2 -ZrO 2 , TiO2 -WO 3 , ZrO2 -WO 3 , SnO2 -WO 3 , CeO 2 -ZrO 2 , SiO2-TiO 2 -ZrO 2 , A1 20 3 -TiO2 -ZrO 2 , SiO2 -A1 20 3-TiO 2 , or SiO2-TiO 2 -CeO 2 , or a cerium-zirconium-bismuth composite oxide. 5 A cerium-zirconium-bismuth composite oxide is a solid solution 9246460_1 (GHMatters) P96427.AU.1 represented by a general formula: Celx-yZrxBiYO 2-6, wherein X, Y, and 6 fall within a range of 0.1 X 0.3, 0.1 Y 0.3, and 0.05 : 0.15, respectively. [0036] 5 Examplesoftheinorganiccompoundhavingaphysicalabsorptive property may include a silicate including synthesis zeolite such as zeolite A, zeolite P, zeolite X, and zeolite Y, natural zeolite such as clinoptilolite, cepiolite, andmordenite, a layered silicate compound such as kaolinite, montmorillonite, acid clay, and 0 kieselguhr, and a cyclic silicate compound such as wollastonite and neptunite. Examples thereof may further include a phosphate compound including tricalciumphosphate, calcium hydrogen phosphate, calcium pyrophosphate, calcium metaphosphate, and hydroxyapatite, activated carbon, and porous glass. 5 [0037] The carrier fine particles 1-b to be used are selected depending on the kind of gas to be treated. The average particle diameter of the carrier fine particles 1-b may be 0.1 pim or larger and 500 pm or smaller. The carrier fine particles 1-b may be used singly 0 or two or more kinds thereof may be used in a mixture. The average particle diameter used herein refers to a volume average particle diameter. Unless otherwise noted, the average particle diameter herein represents a volume average particle diameter. [0038] 5 Amethod for producing the catalyst 1 will be described. This 9246460_1 (GHMatters) P96427.AU.1 method for producing the catalyst 1 may be a method in which the catalyst fine particles 1-a have a polyhedral structure and the catalyst fine particles 1-a can be fixed to the carrier fine particles 1-b. Examples of the method may include a coprecipitation method, 5 a deposition-precipitation method, a sol-gel method, a neutralization-precipitation method using dropping, a reductant addition method, a neutralization-precipitation method using pH-control, and a carboxylic acid metal salt addition method. The methods can be appropriately used depending on the kind of carrier. 0 [0039] The substrate 10 is a substrate constituting the catalyst medium 100 as a plate-shaped member to which the catalyst 1 is fixed. The substrate 10 has a permeable structure as described above. For example, a sheet-shaped substrate having many through pores formed 5 by punching, or a fibrous, cloth-shaped, or mesh-shaped substrate having a fibrous structure (filter-shaped) that is made of woven fabric, knitting, or nonwoven fabric can be used. In addition, substrates having various shapes and sizes can be appropriately used depending on intended use. 0 [0040] It is preferable that the substrate 10 be made from an inorganic material having excellent plasma resistance and heat resistance. The plasma resistance is required since the substrate 10 is disposed in a region where plasma is present. When the substrate 10 has plasma 5 resistance, the catalytic function of the catalyst medium 100 can 9246460_1 (GHMatters) P96427.AU.1 be maintained for extended periods. The heat resistance is required since the gas to be treated in the gas treatment device 200 may be an exhaust gas that is discharged during burning a fuel and has a comparatively high temperature. When the exhaust gas is treated, 5 the substrate needs to have heat resistance. The plasma resistance is a durability in an atmosphere of plasma, and shows difficulty of occurrence of erosion by plasma. [0041] It is preferable that the inorganic material used for the 0 substrate 10 be specifically a metal material, ceramics, or glass, and more preferably metal, a metal oxide, or glass. In the present embodiment, the carrier fine particles 1-b supporting the catalyst fine particles 1-a are fixed to the substrate 10 through the silane monomers 2. When the silane monomers 2 are fixed to the substrate 5 10 by a dehydration-condensation reaction through a covalent bond, it is preferable that a thin film of an oxide be formed on the surface of the substrate 10. [0042] As the metal material used for the substrate 10 of the present 0 invention, metal having a high melting point such as tungsten, molybdenum, tantalum, niobium, titanium zirconiummolybdenum (TZM), andtungsten-rhenium (W-Re), noble metal such as silver and ruthenium and an alloy or an oxide thereof, special metal such as titanium, nickel, zirconium, chromium, inconel, and hastelloy, 5 general-purpose metal such as aluminum, copper, stainless steel, 9246460_1 (GHMatters) P96427.AU.1 zinc, magnesium, and iron, an alloy including the general-purpose metal, oranoxideofthegeneral-purposemetalmaybeused. Further, a member having a film of the metal, the alloy, or the oxide formed by various plating, vacuum evaporation, a CVD method, or a sputtering 5 method may be used as the metal material. [0043] A naturally oxidized thin film is generally formed on the surface of the metal and the surface of the alloy. In order to bind the silane monomers 2 thereto, the naturally oxidized thin film 0 canbeused. Inthis case, it ispreferablethat oils anddirt adhering to the surface of the oxidized thin film be removed by an ordinary method in advance. This is because the carrier fine particles 1-b can be fixed stably and uniformly. Instead of use of the naturally oxidized film for binding of the silane monomers 2, an oxidized 5 thin film may