WO2009113463A1 - 複合構造物形成方法、調製粒子、および複合構造物形成システム - Google Patents
複合構造物形成方法、調製粒子、および複合構造物形成システム Download PDFInfo
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- WO2009113463A1 WO2009113463A1 PCT/JP2009/054344 JP2009054344W WO2009113463A1 WO 2009113463 A1 WO2009113463 A1 WO 2009113463A1 JP 2009054344 W JP2009054344 W JP 2009054344W WO 2009113463 A1 WO2009113463 A1 WO 2009113463A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/14—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas designed for spraying particulate materials
- B05B7/1404—Arrangements for supplying particulate material
- B05B7/144—Arrangements for supplying particulate material the means for supplying particulate material comprising moving mechanical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/12—Applying particulate materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/16—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by suspending the powder material in a gas, e.g. in fluidised beds or as a falling curtain
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
- B02C19/0012—Devices for disintegrating materials by collision of these materials against a breaking surface or breaking body and/or by friction between the material particles (also for grain)
- B02C19/0043—Devices for disintegrating materials by collision of these materials against a breaking surface or breaking body and/or by friction between the material particles (also for grain) the materials to be pulverised being projected against a breaking surface or breaking body by a pressurised fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
- B02C19/06—Jet mills
- B02C19/065—Jet mills of the opposed-jet type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
- B02C19/06—Jet mills
- B02C19/066—Jet mills of the jet-anvil type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/14—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas designed for spraying particulate materials
- B05B7/1404—Arrangements for supplying particulate material
- B05B7/144—Arrangements for supplying particulate material the means for supplying particulate material comprising moving mechanical means
- B05B7/1445—Arrangements for supplying particulate material the means for supplying particulate material comprising moving mechanical means involving vibrations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B19/00—Machines or methods for applying the material to surfaces to form a permanent layer thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B12/00—Arrangements for controlling delivery; Arrangements for controlling the spray area
- B05B12/08—Arrangements for controlling delivery; Arrangements for controlling the spray area responsive to condition of liquid or other fluent material to be discharged, of ambient medium or of target ; responsive to condition of spray devices or of supply means, e.g. pipes, pumps or their drive means
- B05B12/085—Arrangements for controlling delivery; Arrangements for controlling the spray area responsive to condition of liquid or other fluent material to be discharged, of ambient medium or of target ; responsive to condition of spray devices or of supply means, e.g. pipes, pumps or their drive means responsive to flow or pressure of liquid or other fluent material to be discharged
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/14—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas designed for spraying particulate materials
- B05B7/1404—Arrangements for supplying particulate material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- aspects of the present invention generally include formation of a composite structure by an aerosol deposition method in which an aerosol in which fine particles of a brittle material are dispersed in a gas is sprayed onto the base material to form a structure composed of the constituent material of the fine particles on the base material.
- the present invention relates to a method, prepared particles for use therein, and a composite structure forming system.
- Patent Document 1 Patent No. 3348154
- Patent Document 2 Japanese Patent Laid-Open No. 2006-200013
- Patent Document 3 Japanese Patent Laid-Open No. 2006-233334
- the brittle material fine particles are deformed or crushed and joined to form a film-like structure made of the fine particle constituent material directly on the substrate.
- a film-like structure can be formed at room temperature without requiring any heating means, and a film-like structure having mechanical strength equal to or higher than that of the fired body can be obtained. it can.
- the density, mechanical strength, electrical characteristics, and the like of the structure can be variously changed by controlling the conditions in which the fine particles collide, the shape and composition of the fine particles, and the like.
- Patent Document 1 Japanese Patent No. 3348154
- the particles stored in the storage mechanism are in a state as time passes. Changes may occur, leaving problems in the stable supply of aerosols.
- the following problems may occur. That is, when the brittle material fine particle powder originally contained in the accommodation mechanism is supplied from the accommodation mechanism due to the fact that the density is not controlled and the fluidity is not uniform, There is a possibility that the shape and density of the group of fine particles divided into shapes are not uniform. In some cases, there also occurs a problem that the brittle material fine particle powder is stacked in the accommodation mechanism. In such a case, it is difficult to generate an aerosol having a stable fine particle concentration from start to finish even if an aerosolization mechanism having a predetermined crushing capability is used.
- aspects of the present invention provide a composite structure forming method, prepared particles, and a composite structure forming system that can further stabilize the concentration of fine particles in an aerosol and can maintain a stable state for a long time. .
- an aerosol device in which a structure made of the constituent material of the brittle material fine particles is formed on the substrate by injecting an aerosol in which the fine particles of the brittle material are dispersed in a gas toward the substrate.
- a method for forming a composite structure by a position method wherein a plurality of prepared particles, which are aggregates of a plurality of particles including the brittle material fine particles, are accommodated in an accommodating mechanism, and the prepared particles are aerosolized from the accommodating mechanism.
- the composite structure of the structure and the base material is formed by pulverizing the supplied prepared particles in the aerosol generating mechanism to form an aerosol, and spraying the aerosol toward the base material.
- a composite structure forming method is provided.
- a structure made of the constituent material of the brittle material fine particles is sprayed on the substrate by injecting an aerosol in which the fine particles of the brittle material are dispersed in the gas toward the substrate.
- a prepared particle is provided.
- a composite structure of a structure made of a constituent material of the brittle material fine particles by causing an aerosol in which fine particles of the brittle material are dispersed in a gas to collide with the base material A composite structure forming system for use in an aerosol deposition method for forming a product, the storage mechanism for storing the prepared particles, a supply mechanism for supplying the prepared particles from the storage mechanism, and the supplied prepared particles
- a gas supply mechanism that introduces a gas toward the substrate, an aerosolization mechanism that crushes the prepared particles mixed with the gas to form an aerosol by applying an impact, and a discharge that injects the aerosol onto the substrate
- a composite structure forming system A composite structure forming system for use in an aerosol deposition method for forming a product, the storage mechanism for storing the prepared particles, a supply mechanism for supplying the prepared particles from the storage mechanism, and the supplied prepared particles
- a gas supply mechanism that introduces a gas toward the substrate, an aerosolization mechanism that crushes the prepared particles mixed with the gas to
- fine particles refers to particles formed by chemically bonding crystals of brittle materials.
- the fine particles used in the aerosol deposition method are, for example, Patent Document 1 (Japanese Patent No. 3348154).
- the average primary particle diameter is 0.1 ⁇ m or more and 5 ⁇ m or less as described in Japanese Patent Laid-Open (JP).
- JP Japanese Patent Laid-Open
- a method of calculating the equivalent circle diameter from a plurality (50 or more) of brittle material fine particle images by electron microscope observation can be employed.
- primary particle means the smallest unit (one particle) of fine particles.
- prepared particles refers to an aggregate obtained by solidifying a plurality of particles including brittle material fine particles having an average primary particle diameter of 0.1 ⁇ m or more and 5 ⁇ m or less. That is, the prepared particles are formed through a process of artificially hardening.
- the particles are in a state in which physical attraction (static electricity, van der Waals force, cross-linking attraction of water) is the main body of bonding, and at least one of the bonding strength and shape is intentionally It is controlled.
- physical attraction static electricity, van der Waals force, cross-linking attraction of water
- at least one of the bonding strength and shape is intentionally It is controlled.
- it is in a state where the shape is maintained with an attractive force that is broken when it is thrown into water and irradiated with ultrasonic waves, and at least one of the bonding strength and shape is intentionally controlled.
- the bond strength of the prepared particles can use the crush strength (compression fracture strength) as an index.
- the shape of the prepared particles can use the circularity as an index.
- it is desirable that the diameter of the prepared particles is intentionally controlled.
- the diameter of the prepared particles can be indicated by the average equivalent circle diameter.
- the particle size distribution of the prepared particles can use D10 or the particle size distribution deviation ratio as an index.
- the fine particles of the brittle material contained are not significantly solidified and bonded to each other by a chemical bond.
- the fine particles of brittle material are chemically bonded to each other, because the fine particles are affected by heat treatment, etc., causing fusion between the surfaces of the fine particles, causing neck formation, as if they were porous primary particles It points to what became. This can be identified by observation with an electron microscope. For example, if an aggregate of a plurality of fine particles is put into water or an alcohol solvent and dispersed into brittle material fine particles or does not easily disintegrate, chemical bonds exist. Can be judged.
- the diameter of the fine particles may be allowed for structure formation in the aerosol deposition method. Even if included, it is not a big problem. This state can also be known by observing fine particles of the brittle material that is well dispersed and fixed to the observation table by observation with an electron microscope.
- aggregated particles are aggregates of a plurality of fine particles, which are formed spontaneously, in which the fine particles are bonded to each other, and the bonding strength and shape are not controlled.
- crushing means that fine particles of brittle material by applying external forces such as impact, friction, vibration and charge to the prepared particles in which particles mainly composed of brittle materials are hardened by physical attraction. The act of the purpose of separating each. Note that it is not necessary to separate all the primary particles until the monodispersed state, and it is only necessary to ensure a separated state in which the structure is formed to such an extent that industrial use is possible by crushing, as will be described later.
- Whether the prepared particles are not crushed when supplied from the storage container is determined by measuring the stability of the supply amount of the prepared particles over time, comparing the shape of the prepared particles in the storage container and immediately before aerosolization, etc. Can do.
- the pulverization of the prepared particles in the aerosolization mechanism can be determined by observing the shape and state of the prepared particles immediately before the aerosolization and the prepared particles immediately after the aerosolization.
- the ratio of the number of prepared particles in a prepared particle weight before the crushing action to the number of prepared particles in the same weight after the crushing action is 1/5 or less, preferably 1/10 or less, More desirably, it can be said that it is crushed when it is 1/100 or less.
- aerosol refers to a solid-gas mixed phase body in which fine particles are dispersed in a gas such as helium, nitrogen, argon, oxygen, dry air, or a mixed gas containing these, and may include partially aggregated particles. However, it is substantially in a state where most of the fine particles are dispersed alone.
- the gas pressure and temperature of the aerosol are arbitrary, but the concentration of fine particles in the gas is 0.0003 mL / L at the time when the gas is injected from the discharge port when the gas pressure is converted to 1 atm and the temperature is converted to 20 degrees Celsius. It is preferable for the formation of the film-like structure to be in the range of ⁇ 10 mL / L.
- solid-gas mixed phase flow refers to a state in which prepared particles controlled to have a predetermined bond strength or shape are moving along a gas flow. In a solid-gas mixed phase flow, the prepared particles are present substantially alone in the gas flow. In addition, “solid phase” refers to a state in which prepared particles exist almost without being affected by a gas flow.
- stack refers to a state where the movement of particles is hindered or caused by the adhesion of particles or the aggregation of particles themselves in a container or a passage through which particles pass.
- a stack is likely to occur at a place where the cross-sectional shape of a passage through which particles pass is small, for example, at an outlet of a storage mechanism, an inlet of a supply mechanism, a supply path, etc., which will be described later.
- FIG. 1 is a schematic diagram for illustrating a basic configuration of a composite structure forming system according to a first embodiment of the present invention. That is, FIG. 1A is a block diagram for illustrating the basic configuration of a composite structure forming system (aerosol deposition apparatus). Moreover, FIG.1 (b) is the figure which represented typically the flow from the accommodation of preparation particle
- a composite structure forming system (aerosol deposition apparatus) 100 includes a storage mechanism 1, a quantitative supply mechanism 2, a gas supply mechanism 3, and an aerosolization mechanism. 4 and a discharge port 5.
- Quantitative supply mechanism 2 is installed after storage mechanism 1. Further, an aerosolization mechanism 4 is installed at the subsequent stage of the quantitative supply mechanism 2, and a discharge port 5 is installed at the subsequent stage of the aerosolization mechanism 4.
- the gas supply mechanism 3 is connected to the vicinity of the outlet of the fixed amount supply mechanism 2.
- the accommodation mechanism 1 accommodates preformed prepared particles 31. Then, the quantitative supply mechanism 2 supplies a predetermined amount of the prepared particles 31 stored in the storage mechanism 1 to the subsequent aerosolization mechanism 4 without impairing the shape and state of the prepared particles 31.
- the fixed amount supply mechanism 2 may be capable of stabilizing or changing the supply amount over time by feedback control as will be described later. Details of the prepared particles 31 will be described later.
- the prepared particles 31 supplied by the quantitative supply mechanism 2 form a solid-gas mixed phase flow 33 together with the gas G supplied by the gas supply mechanism 3, and are supplied to the aerosolization mechanism 4 through the supply path 16.
- the supplied prepared particles 31 are crushed in the aerosol generating mechanism 4, and the fine particles 30P are dispersed in the gas G, whereby an aerosol 32 is formed.
- the aerosol 32 is ejected from a discharge port 5 toward a base material (not shown), and a film-like structure (see FIG. 16) is formed on the base material.
- the prepared particles 31 are supplied to the aerosolization mechanism 4, the supplied prepared particles 31 are crushed in the aerosolization mechanism 4, and the gas G supplied from the gas supply mechanism 3 to the aerosolization mechanism 4 Can be used to form the aerosol 32 in which the fine particles 30P are dispersed in the gas G (see FIG. 15).
- the prepared particles 31 can be accelerated not only to supply the prepared particles 31 but also toward the aerosolization mechanism 4. If the material is crushed by mechanical impact using the kinetic energy of the material, aerosolization will be performed smoothly.
- the gas supply mechanism 3 may be connected to the storage mechanism 1 or the quantitative supply mechanism 2 in order to reliably supply the prepared particles 31 to the aerosolization mechanism 4, and to adjust the fine particle concentration in the aerosol. It may be connected to the supply mechanism between the gasification mechanism 4 or the aerosolization mechanism 4 and the discharge port 5. In addition, the connection destination and connection combination of the gas supply mechanism 3 can be changed as appropriate.
- the fine particles used in the aerosol deposition method are mainly composed of a brittle material, and fine particles of the same material can be used alone or mixed with fine particles having different particle diameters.
- the fine particle material examples include brittle materials such as aluminum oxide, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, yttrium oxide, chromium oxide, hafnium oxide, beryllium oxide, magnesium oxide, silicon oxide, and calcium oxide.
- High toughness ceramics such as silicon, silicon, germanium, or semiconductor materials to which various doping materials such as phosphorus are added, compounds such as gallium arsenide, indium arsenide, cadmium sulfide, zinc sulfide, and metals mainly composed of these materials And a composite material with resin.
- the main component in forming the film-like structure is a brittle material.
- Examples of the gas G include inert gases such as air, hydrogen gas, nitrogen gas, oxygen gas, argon gas, and helium gas, organic gases such as methane gas, ethane gas, ethylene gas, and acetylene gas, and fluorine. Examples thereof include corrosive gases such as gases. Moreover, you may use these mixed gas as needed.
- the process of the aerosol deposition method is usually carried out at room temperature, and has one feature that a film-like structure can be formed at a temperature sufficiently lower than the melting point of the particulate material, that is, at a temperature of several hundred degrees Celsius or less.
- the crystalline particle size of the composite structure is smaller than that of the raw material fine particles.
- the crystal has substantially no crystal orientation.
- the grain boundary layer which consists of a glass layer does not exist substantially in the interface of brittle material crystals.
- an “anchor layer” that bites into the surface of the substrate is formed in the portion of the film-like structure. Since this anchor layer is formed, the membranous structure is firmly attached to the substrate with extremely high strength.
- the film-like structure formed by the aerosol deposition method is clearly different from the so-called “green compact” in which the fine particles are packed together by pressure and kept in physical form by adhesion, and has sufficient strength. is doing.
- the brittle material fine particles that have come to the surface are crushed and deformed on the substrate.
- the brittle material fine particles used as the raw material and the formed brittle material structure crystallites The size can be confirmed by measuring by an X-ray diffraction method or the like.
- the crystallite size of the film-like structure formed by the aerosol deposition method is smaller than the crystallite size of the raw material fine particles.
- the “displacement surface” and “fracture surface” formed by crushing and deformation of the fine particles are exposed to the atoms that were originally present inside the fine particles and bonded to other atoms. A “new face” is formed. Then, it is considered that this newly formed surface having a high surface energy and active is joined to the surface of the adjacent brittle material fine particles, the newly formed surface of the adjacent brittle material, or the surface of the base material to form a film-like structure.
- the mechanochemical acid-base dehydration reaction may occur due to local shear stress generated between the fine particles or between the fine particles and the structure when the fine particles collide. It is also possible to get up and join these together.
- the addition of continuous mechanical impact force from the outside causes these phenomena to occur continuously, and the joining progresses and densifies by repeated deformation, crushing, etc. of fine particles, and a film-like structure made of a brittle material Is considered to grow.
- the prepared particles 31 in the aerosolization mechanism 4 As a method for crushing the prepared particles 31 in the aerosolization mechanism 4, it is effective to use a mechanical impact force by causing the prepared particles 31 to collide with a wall, a protrusion, a rotating body, or the like.
- the prepared particles 31 are accelerated in the state of a solid-gas mixed phase flow 33 in which the gas G is mixed, the prepared particles 31 having a mass can easily collide with a wall or the like by inertial force.
- the crushing energy is determined by the mass and speed of the prepared particles 31, but in order to obtain the speed necessary for crushing, a pressure difference is required before and after the aerosolization mechanism 4 (inlet side and outlet side). It becomes.
- the type of gas for example, any one of air, nitrogen, oxygen, or a mixed gas containing the gas as a main component is used and converted to 1 atm.
- the minimum cross-sectional area of the supply passage gas supply amount 0.05 L / (min ⁇ mm 2) or more, 50.0 L / (min ⁇ mm 2) if the following volumetric flow, solid-gas multiphase flow.
- the concentration of fine particles in the sprayed aerosol is always stable. That is, in order to stabilize the quality and quality of the film, how to form an aerosol with a stable fine particle concentration is an important technical element of this method.
- Patent Document 1 Japanese Patent No. 3348154
- the state of the fine particles stored in the storage mechanism changes with the passage of time. Occurrence may be difficult.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2006-200013
- problems such as adhesion to the wall surface and stacking are likely to occur, and it may be difficult to generate aerosol with a stable fine particle concentration.
- Patent Document 3 Japanese Patent Laid-Open No. 2006-233334
- Japanese Patent Laid-Open No. 2006-233334 capable of forming an aerosol having the most stable fine particle concentration
- it is supplied from the storage mechanism or supplied to the aerosolization mechanism.
- the shape and density of the fine particles or the group of fine particles divided into a predetermined size and shape may become non-uniform, making it difficult to form an aerosol with an instantaneous but stable fine particle concentration.
- There is a fear For example, when supplied from the storage mechanism or in the process of supplying to the aerosolization mechanism, part of the population of fine particles is crushed and adheres to the wall surface, forming an instantaneous but stable aerosol with a fine particle concentration There is a risk that it will be difficult.
- the present inventor prepared in advance a prepared particle that is an aggregate of a plurality of particles including brittle material fine particles having an average primary particle size of 0.1 ⁇ m or more and 5 ⁇ m or less, and converted this into an aerosol from the storage mechanism. It was found that the supply could be made uniform and stable by supplying to the mechanism. Moreover, the knowledge that quantitative supply could be improved by intentionally controlling at least one of the bond strength and the shape of the prepared particles was also obtained.
- brittle material fine particles having a particle size of 0.1 ⁇ m or more and 5 ⁇ m or less are highly cohesive, and handling properties are very poor as they are. Also, agglomerated particles are often formed. Even if such brittle material particles are supplied by mechanical means, it is very difficult to ensure quantitativeness. Therefore, when forming an aerosol by the aerosol deposition method, there is a problem that it is difficult to ensure the uniformity and stability of the aerosol concentration over time.
- prepared particles that are aggregates of a plurality of particles including brittle material fine particles having an average primary particle size of 0.1 ⁇ m or more and 5 ⁇ m or less are prepared in advance, thereby supplying fine particles having strong viscosity and adhesion.
- Quantitative supply can be further enhanced by intentionally controlling at least one of the bond strength and shape of the prepared particles.
- the fine particle concentration does not fluctuate greatly even in the short term, and an aerosol with a fine particle concentration that is uniform over time and stable for a long time can be formed.
- the average crushing strength of the prepared particles 31 can be used as an index in order to improve the quantitative supply ability and the uniformity of the aerosol concentration. For example, if the average crushing strength is too low, since the prepared particles 31 are crushed and adhere to the wall surface when supplied from the storage mechanism 1 or in the process of supplying to the aerosolization mechanism 4, the quantitative supply property, aerosol concentration There is a risk that the uniformity of the film will deteriorate. In addition, if the average crushing strength is too high, the quantitative supply ability can be ensured, but since the crushing in the aerosolization mechanism 4 is hindered, the uniformity of the aerosol concentration may be lowered. Therefore, it is preferable that the average crushing strength of the prepared particles 31 is within a predetermined range.
- the prepared particles 31 have an average crushing strength necessary for preventing them from being substantially crushed when supplied from the storage mechanism 1.
- the prepared particles 31 are not substantially crushed while being supplied to the aerosolization mechanism 4 and have an average crushing strength necessary to be substantially crushed by the aerosolization mechanism 4. .
- the average crushing strength (average compressive fracture strength) is obtained by arbitrarily selecting a plurality (for example, 10 or more) of prepared particles 31 and measuring the crushing strength (compressive fracture strength) to calculate the average value. is there.
- crushing strength compression fracture strength
- average crushing strength average compression fracture strength
- formation of the composite structure First, measurement of crushing strength (compression breaking strength) will be described. Prepared particles containing brittle material fine particles having an average primary particle diameter of about 0.3 ⁇ m and an equivalent circle diameter in the range of 100 to 400 ⁇ m were prepared, and the crushing strength of these prepared particles was measured. The equivalent circle diameter will be described later.
- St 2.8P / ( ⁇ ⁇ d ⁇ d)
- St the crushing strength (Pa)
- P the test force (N) during crushing
- d the prepared particle diameter (mm).
- FIG. 2 is a graph for illustrating the measurement of the crushing strength.
- the horizontal axis represents displacement, and the vertical axis represents test force.
- the test force P at the time of crushing was a point where the change in the test force was almost constant and only the displacement increased.
- the prepared particle size d was measured using an optical instrument provided in the compression tester.
- the relationship between the average crush strength (average compressive fracture strength) and the formation of the composite structure will be described.
- Prepared particles having various crushing strengths having an equivalent circle diameter in the range of 100 to 400 ⁇ m were prepared, and a composite structure was formed by an aerosol deposition method using these prepared particles.
- a vibration-type supply apparatus as a quantitative supply mechanism, a system in which a solid-gas mixed phase flow collides with a ceramic plate as an aerosol generation mechanism, and nitrogen as a gas are used.
- the opening of the nozzle as the discharge port was 10 mm ⁇ 0.4 mm, and the gas flow rate of the aerosol ejected from the opening was 5 L / min.
- a SUS304 stainless steel plate was used as a base material for forming the composite structure.
- the stroke for reciprocating the substrate was 10 mm, and the time for forming the composite structure on the 10 mm ⁇ 10 mm surface (aerosol spraying time) was 10 minutes.
- FIG. 3 is a graph for illustrating the relationship between the average crushing strength and the formation of the composite structure.
- the horizontal axis represents the average crushing strength
- the vertical axis represents the film thickness of the film-like structure.
- the lower limit value of the average crushing strength is mainly determined from the viewpoint of quantitative supply. That is, if the average crushing strength is too low, the friction between the prepared particles and the contact stress between the prepared particles even under the condition of gently feeding operation when supplied from the storage mechanism or in the process of supplying to the aerosolization mechanism 4, The prepared particles may be crushed by various forces generated during the movement of the particles, such as friction with the wall surface, or some of the brittle material fine particles constituting the prepared particles may fall off the surface. . When brittle material fine particles generated by crushing or dropping off adhere to the wall surface, the movement of the prepared particles is hindered and the quantitative supply ability is impaired. Therefore, it is preferable that the average crushing strength is not less than a predetermined value.
- the present inventor uses the method of the fixed amount supply mechanism 2 (for example, a sieve shaking method, a supply method using a rotating disk, a supply method using ultrasonic vibration or electromagnetic vibration, a screw feeder, an electrostatic supply method, etc.)
- the average crushing strength is preferably 0.015 MPa or more from the viewpoint of quantitative supply. Therefore, the average crushing strength is preferably 0.46 MPa or less, and more preferably 0.34 MPa or less. The average crushing strength is preferably 0.015 MPa or more.
- the average equivalent circle diameter of the prepared particles 31 can be used as an index. For example, if the average equivalent circle diameter is too small, aggregation tends to occur, and there is a risk that the quantitative supply performance, the uniformity of the aerosol concentration, and the like may be impaired. Further, if the average equivalent circle diameter is too large, clogging in the supply path 16 or the like, or crushing failure in the aerosol generating mechanism 4 may occur. Therefore, it is preferable that the average equivalent circle diameter of the prepared particles 31 is within a predetermined range.
- the equivalent circle diameter refers to the diameter of an equivalent circle having the same area as that obtained by image analysis of the prepared particles 31.
- the equivalent circle diameter can be calculated by analyzing an optical micrograph of the prepared particles 31 using commercially available shape analysis software. As such a case, for example, analysis software (Win Roof manufactured by mitani corporation) incorporated in a polarizing optical microscope (LV-IMA manufactured by Nikon Corporation) can be exemplified.
- analysis software Win Roof manufactured by mitani corporation
- the average equivalent circle diameter is obtained by arbitrarily selecting a plurality of prepared particles, measuring the equivalent circle diameter, and calculating the average value. In the calculation, first, a substrate having a mirror surface such as a silicon wafer and having no scratches that cause noise is prepared as a base material on which the prepared particles are developed.
- the prepared fine particles to be measured are dispersed on the photograph determination screen. At this time, it is dispersed so that the area ratio in the photo determination screen is 40% or less.
- agglomerated grains and primary particles that do not have the characteristics as prepared particles, or a group of particles observed in a state where a plurality of primary particles are overlapped are excluded as much as possible.
- a dispersion state in which fine particles near the center particle diameter do not overlap each other is ensured.
- a data group measured with an average equivalent circle diameter of 5 ⁇ m or less that is determined to be insufficient as well as prepared particles is deleted. Further, in the photo determination image, the reliability of the value is ensured by deleting the data that is in contact with the boundary of the outer edge of the image, that is, the particles are not completely captured in the image.
- a histogram is obtained by equally dividing the minimum diameter and the maximum diameter by 10 to 20 data sections. Create In this case, in the case of having a peak at a value of 100 ⁇ m or more and another peak at 30 ⁇ m or less, even if this particle of 30 ⁇ m or less occupies about 80% in number frequency, it affects the supply amount standard deviation. Is known to give almost no. This is considered to be because relatively large preparation particles that occupy a large volume ratio dominate the quantitative supply. Such fine particles are considered to include fragments formed by partly dropping from the prepared particles and particles that were insufficiently formed.
- the average equivalent circle diameter is determined.
- the average equivalent circle diameter is calculated by excluding the particle group constituting the peak of fine particles. It is preferable to perform such careful selection of prepared particles, select 150 to 200 prepared particles to be counted, and obtain the average equivalent circle diameter from these values.
- photo determination for example, when using the above-described analysis software (Win Roof manufactured by mitani corporation), light is applied so that sufficient contrast between the substrate and the particles to be observed can be secured. Then, after obtaining sufficient contrast and focusing, the photograph is taken. The photographed photograph is converted into a monochrome image and binarized.
- the vicinity of the middle between the peak on the substrate side (generally white side) and the peak on the particle side (generally black side) of the monochrome image is selected as a threshold value. It is preferable to do. Even when such a threshold value is selected, a plurality of peaks may occur in the calculated value of the average equivalent circle diameter. Therefore, it becomes necessary to carry out the selection operation for counting the particle groups as described above.
- a vibration type supply device was used for the quantitative supply ability evaluation.
- the supply rate was 5 g / min
- the supply time was 30 minutes
- the weight of the prepared particles supplied from the vibration type supply device was measured using an electronic balance.
- the weighing resolution of the electronic balance is set to 0.01 g
- the supply amount over time is measured every 5 seconds
- the supply amount and the standard deviation of the supply amount are obtained using the supply amount data from 2 minutes to 30 minutes later. It was.
- the standard deviation of supply amount 0.01 is determined as a criterion for quality determination.
- FIG. 5 is a graph for illustrating the relationship between the average equivalent circle diameter and the supply amount standard deviation.
- the horizontal axis represents the average equivalent circle diameter
- the vertical axis represents the supply amount standard deviation.
- FIG. 5 shows that when the average equivalent circle diameter is 20 ⁇ m or more, the supply amount standard deviation is 0.01 or less, and the quantitative supply performance is good. On the other hand, when the average equivalent circle diameter is less than 20 ⁇ m, it can be seen that the supply amount becomes unstable with time and the quantitative supply ability is impaired.
- the upper limit value of the average equivalent circle diameter can be determined mainly from the viewpoints of clogging in the supply path 16 and the like and occurrence of crushing failure in the aerosolization mechanism 4. That is, when the average equivalent circle diameter is too large, clogging or the like occurs during supply from the storage mechanism or in the process of supply to the aerosolization mechanism 4 and the quantitative supply is impaired. Further, even in the crushing in the aerosolization mechanism 4, fragments that are not broken down to primary particles are generated. Such fragments do not contribute to the formation of the film-like structure, and as a result, the uniformity of the aerosol concentration is impaired.
- the average equivalent circle diameter is preferably 500 ⁇ m or less. Therefore, the average equivalent circle diameter is preferably 20 ⁇ m or more and 500 ⁇ m or less.
- the average circularity of the prepared particles 31 can be used as an index. For example, if the average circularity becomes too small, it becomes difficult to roll, and smooth supply becomes difficult. As a result, there is a risk that the quantitative supply ability, the uniformity of the aerosol concentration, and the like may be impaired. Therefore, it is preferable that the average circularity of the prepared particles 31 is equal to or greater than a predetermined value.
- circularity is a value calculated
- analysis software Win Roof manufactured by mitani corporation
- Circularity 4 ⁇ ⁇ (area of prepared particles in image) / (peripheral length of prepared particles in image) 2
- the circularity is 1 in the case of a perfect circle. That is, the maximum value of circularity is 1.
- the average circularity is obtained by arbitrarily selecting a plurality of prepared particles, measuring the circularity, and calculating the average value.
- aggregated particles and primary particles that do not have the characteristics as prepared particles, or a group of particles observed in a state where a plurality of primary particles are overlapped are excluded.
- a data group measured with an average equivalent circle diameter of 5 ⁇ m or less is deleted.
- the reliability of the value is ensured by deleting the data that is in contact with the boundary of the outer edge of the image, that is, the particles are not completely captured in the image.
- the number of prepared particles used for calculation is preferably 150 to 200. Further, when the particle size distribution has a large frequency of 30 ⁇ m or less, it is preferable to handle it in the same manner as in the case of calculating the average equivalent circle diameter. In addition, when using analysis software (Win Roof made by mitani corporation), data of average equivalent circle diameter and circularity can be collected simultaneously.
- a vibration type supply device was used for the quantitative supply ability evaluation.
- the supply rate was 5 g / min
- the supply time was 30 minutes
- the weight of the prepared particles supplied from the vibration type supply device was measured using an electronic balance.
- the weighing resolution of the electronic balance is set to 0.01 g
- the supply amount over time is measured every 5 seconds
- the supply amount and the standard deviation of the supply amount are obtained using the supply amount data from 2 minutes to 30 minutes later. It was.
- the standard deviation of supply amount 0.01 is determined as a criterion for quality determination.
- FIG. 6 is a graph for illustrating the relationship between the average circularity and the supply amount standard deviation.
- the horizontal axis represents the average circularity
- the vertical axis represents the supply amount standard deviation.
- FIG. 6 shows that when the average circularity is 0.79 or more, the supply amount standard deviation is 0.01 or less, and the quantitative supply performance is good. On the other hand, when the average circularity is less than 0.79, it can be seen that the supply amount becomes unstable over time, and the quantitative supply capability may be impaired.
- the upper limit value of the average circularity can be 1 (perfect circle). Therefore, the average circularity is preferably 0.79 or more.
- a plurality of prepared particles including brittle material fine particles having an average primary particle size of submicron are prepared, the circularity is measured, and the prepared particles for each circularity are measured by the following method.
- the quantitative supply of was evaluated.
- a vibration type supply device was used for evaluation of the quantitative supply ability.
- the supply speed is 0.5 g / min and 5 g / min
- the maximum supply time is 3 minutes
- the supply is made from the vibration type supply device every 0.1 second at 0.5 g / min and every second at 5 g / min.
- the flow rate obtained from the weight change of 0.1 seconds before and after the prepared particles was measured.
- the average value of the flow rate was calculated, and the standard deviation was obtained.
- FIG. 7 is a graph for illustrating the relationship between the average circularity and the supply amount standard deviation when the supply rate is 0.5 g / min.
- FIG. 8 is a graph for illustrating the relationship between the average circularity and the supply amount standard deviation when the supply rate is 5 g / min. 7 and 8, the horizontal axis represents the average circularity, and the vertical axis represents the supply amount standard deviation.
- the supply amount is stable when the average circularity is 0.65 or more.
- the average circularity is 0.59 or less, it can be seen that the supply amount becomes unstable with time and the quantitative supply ability is impaired. Even when the supply rate exceeded 5 g / min, the stability of the supply amount showed the same tendency.
- the D10 value of the prepared particles 31 can be used as an index. For example, if the D10 value becomes too small (if the particle size of the prepared particles is 10% from the smallest particle, the particle size becomes too small), adhesion or the like is likely to occur, so smooth supply is possible. It becomes difficult. As a result, there is a risk that the quantitative supply ability, the uniformity of the aerosol concentration, and the like may be impaired. Therefore, it is preferable that the D10 value of the prepared particles 31 is equal to or greater than a predetermined value.
- the D10 value refers to the particle size of a particle located 10% (10% from the bottom) from the smallest particle in the particle size distribution of the prepared particles.
- the D10 value is determined by the particle diameter of the particle closest to 10% from the smallest particle, by selecting a plurality of prepared particles arbitrarily, arranging the respective equivalent circle diameters in ascending order.
- the count of prepared particles used for the calculation is preferably 150 to 200.
- the primary particle diameter of the brittle material fine particles is 0.1 ⁇ m to 5 ⁇ m, and there are a plurality of aggregated particles, primary particles, or a plurality of primary particles that do not have the properties as prepared particles according to the primary particle diameter of the brittle material. Exclude groups of particles that are observed in a superimposed state.
- a data group measured with an average equivalent circle diameter of 5 ⁇ m or less is deleted. Further, in the photo determination image, the reliability of the value is ensured by deleting the data that is in contact with the boundary of the outer edge of the image, that is, the particles are not completely captured in the image.
- the particle size distribution has a high frequency of 30 ⁇ m or less, it is preferable to handle it in the same manner as the calculation of the average equivalent circle diameter described above.
- analysis software Win Roof made by mitani corporation
- data of average equivalent circle diameter and D10 value can be collected simultaneously.
- the D10 value can be calculated by analyzing an optical micrograph of the prepared particles 31 using commercially available shape analysis software.
- analysis software Win Roof manufactured by mitani corporation
- LV-IMA polarizing optical microscope
- prepared particles containing brittle material fine particles having an average primary particle size of about 0.3 ⁇ m and within the above-mentioned average crushing strength range are prepared, and these are prepared particles for each D10 value. Sorted. And the quantitative supply property of the preparation particle
- a vibration type supply device was used for the quantitative supply ability evaluation.
- the supply rate was 5 g / min
- the supply time was 30 minutes
- the weight of the prepared particles supplied from the vibration type supply device was measured using an electronic balance.
- the weighing resolution of the electronic balance is set to 0.01 g
- the supply amount over time is measured every 5 seconds
- the supply amount and the standard deviation of the supply amount are obtained using the supply amount data from 2 minutes to 30 minutes later. It was.
- the standard deviation of supply amount 0.01 is determined as a criterion for quality determination.
- FIG. 9 is a graph for illustrating the relationship between the D10 value and the supply amount standard deviation.
- the horizontal axis represents the D10 value
- the vertical axis represents the supply amount standard deviation.
- FIG. 9 shows that when the D10 value is 6.6 ⁇ m or more, the standard deviation of supply amount is 0.01 or less, and the quantitative supply performance is good. On the other hand, when the D10 value is less than 6.6 ⁇ m, it is understood that the supply amount becomes unstable with time and the quantitative supply ability is impaired.
- the upper limit value of the D10 value is not particularly limited, but is substantially equal to or less than the average equivalent circle diameter of the prepared particles, and is therefore 500 ⁇ m or less.
- the D10 value is preferably 6.6 ⁇ m or more.
- the particle size distribution deviation ratio of the prepared particles 31 can be used as an index. For example, if the particle size distribution deviation ratio becomes too large, that is, if the particle size distribution becomes too wide, smooth supply becomes difficult. As a result, there is a risk that the quantitative supply ability, the uniformity of the aerosol concentration, and the like may be impaired. Therefore, it is preferable that the particle size distribution deviation ratio of the prepared particles 31 is equal to or less than a predetermined value.
- the particle size distribution deviation ratio is a value calculated by (standard deviation ⁇ of equivalent circle diameter) / (average equivalent circle diameter).
- a plurality of prepared particles are arbitrarily selected, the equivalent circle diameter is measured, the average value of the equivalent circle diameter and the standard deviation ⁇ are obtained, and (standard deviation ⁇ of equivalent circle diameter) / (average circle) It can be obtained by calculating the equivalent diameter).
- the count of prepared particles used for the calculation is preferably 150 to 200.
- the value of the particle size distribution deviation ratio is in the range of 0 to 1, and the closer the value is to 0, the narrower the particle size distribution is, and it can be said that the prepared particles have a uniform particle size.
- the particle size distribution deviation ratio can be calculated by analyzing an optical micrograph of the prepared particles 31 using commercially available shape analysis software.
- analysis software Win Roof manufactured by mitani corporation
- LV-IMA polarizing optical microscope
- aggregated particles and primary particles that do not have the characteristics as prepared particles, or a group of particles observed in a state where a plurality of primary particles are overlapped are excluded.
- a data group measured with an average equivalent circle diameter of 5 ⁇ m or less is deleted.
- the reliability of the value is ensured by deleting the data that is in contact with the boundary of the outer edge of the image, that is, the particles are not completely captured in the image.
- the particle size distribution has a high frequency of 30 ⁇ m or less, it is preferable to handle it in the same manner as the calculation of the average equivalent circle diameter described above.
- a vibration type supply device was used for the quantitative supply ability evaluation.
- the supply rate was 5 g / min
- the supply time was 30 minutes
- the weight of the prepared particles supplied from the vibration type supply device was measured using an electronic balance.
- the weighing resolution of the electronic balance is set to 0.01 g
- the supply amount over time is measured every 5 seconds
- the supply amount and the standard deviation of the supply amount are obtained using the supply amount data from 2 minutes to 30 minutes later. It was.
- the standard deviation of supply amount 0.01 is determined as a criterion for quality determination.
- FIG. 10 is a graph for illustrating the relationship between the particle size distribution deviation ratio and the supply amount standard deviation.
- the horizontal axis represents the particle size distribution deviation ratio
- the vertical axis represents the supply amount standard deviation.
- FIG. 10 shows that when the particle size distribution deviation ratio is 0.59 or less, the supply amount standard deviation is 0.01 or less, and the quantitative supply performance is good. On the other hand, when the particle size distribution deviation ratio exceeds 0.59, it can be seen that the supply amount becomes unstable with time and the quantitative supply ability is impaired.
- the particle size distribution deviation ratio is preferably 0.59 or less.
- the angle of repose of the prepared particles 31 can be used as an index in order to improve the quantitative supply performance and the uniformity of the aerosol concentration. For example, if the angle of repose becomes too large, that is, if it becomes difficult for flow to occur, smooth supply becomes difficult. As a result, there is a risk that the quantitative supply ability, the uniformity of the aerosol concentration, and the like may be impaired. Therefore, it is preferable that the angle of repose of the prepared particles 31 is not more than a predetermined value.
- the angle of repose was obtained as follows. First, aiming at the center of a disk having a diameter of 30 mm, the prepared particles are dropped little by little at a speed of 5 g / min or less and deposited until the prepared particles start to leak from the disk. And, for example, take a picture from the side, measure the angle between the left and right slopes of the triangular pyramid where the prepared particles are deposited by image analysis, and calculate the average value to obtain the repose angle did.
- prepared particles containing brittle material fine particles having an average primary particle diameter of about 0.3 ⁇ m and within the above-mentioned average crushing strength range are prepared, and these are prepared as prepared particles for each angle of repose. Sorted. And the quantitative supply property of the prepared particle
- a vibration type supply device was used for the quantitative supply ability evaluation.
- the supply rate was 5 g / min
- the supply time was 30 minutes
- the weight of the prepared particles supplied from the vibration type supply device was measured using an electronic balance.
- the weighing resolution of the electronic balance is set to 0.01 g
- the supply amount over time is measured every 5 seconds
- the supply amount and the standard deviation of the supply amount are obtained using the supply amount data from 2 minutes to 30 minutes later. It was.
- the standard deviation of supply amount 0.01 is determined as a criterion for quality determination.
- FIG. 11 is a graph for illustrating the relationship between the angle of repose and the standard deviation of supply amount.
- the horizontal axis represents the angle of repose, and the vertical axis represents the supply amount standard deviation. From FIG. 11, it can be seen that when the angle of repose is 42.5 degrees or less, the standard deviation of supply amount is 0.01 or less and the quantitative supply performance is good. On the other hand, when the angle of repose exceeds 42.5 degrees, it can be seen that the supply amount becomes unstable over time, and the quantitative supply capability may be impaired.
- the upper limit of the angle of repose As can be seen from FIG. 11, even when the angle of repose is reduced, the quantitative supply performance is not impaired. Therefore, there is no particular limitation on the lower limit value of the angle of repose. That is, the angle of repose only needs to exceed 0 degree. Therefore, the angle of repose is preferably 42.5 degrees or less.
- the evaluation of the quantitative supply ability for a shorter time will be exemplified.
- quantitative supply in this case, first, a plurality of prepared particles including brittle material fine particles having an average primary particle size of submicron are prepared, the angle of repose is measured, and the prepared particles for each angle of repose are measured by the following method.
- the quantitative supply of was evaluated.
- a vibration type supply device was used for evaluation of the quantitative supply ability.
- the supply rate is 0.5 g / min and 5 g / min, the supply time is 3 minutes at maximum, 0.5 g / min every 0.1 second, and 5 g / min every second.
- the flow rate obtained from the weight change of 0.1 seconds before and after the supplied prepared particles was measured.
- the average value of the flow rate was calculated, and the standard deviation was obtained.
- FIG. 12 is a graph for illustrating the relationship between the angle of repose and the supply amount standard deviation when the supply rate is 0.5 g / min.
- FIG. 13 is a graph for illustrating the relationship between the angle of repose and the supply amount standard deviation when the supply rate is 5 g / min.
- the horizontal axis represents the angle of repose
- the vertical axis represents the supply amount standard deviation.
- the supply amount standard deviation is 0.192 or less in FIG. 12 and when the supply amount standard deviation is 1.018 or less in FIG.
- the supply amount standard deviation is 0.122 or less in FIG. 12 and when the supply amount standard deviation is 0.178 or less in FIG. 13 it was determined that the quantitative supply ability was remarkably excellent.
- the prepared particles having an angle of repose of 48 ° or less can be suitably used when forming a large-area film-like structure where the accuracy of the thickness of the structure to be formed is relatively unnecessary. Moreover, it can be used suitably also when forming a composite structure in which a polishing process is performed in a subsequent process. Moreover, it can be used suitably also when the thickness of the structure formed by reciprocating the relative movement between the nozzle and the substrate is increased and the thickness is averaged.
- the prepared particles having an angle of repose of 44 ° or less are very excellent in the stability of the injection amount of the brittle material fine particles from the nozzle. Therefore, a high production capability can be exhibited even when a structure requiring high thickness accuracy is formed or when a thin film-like structure having a thickness of several ⁇ m or less is formed. If prepared particles having an angle of repose of 44 ° or less are used for such applications, a more suitable structure can be formed.
- the composite structure can be formed satisfactorily when the water content of the prepared particles 31 is 0.45 wt% or less.
- the moisture content can be identified by measuring the weight loss when the prepared particles 31 are heated to about 300 ° C.
- the carbon content of the prepared particles 31 is preferably 1% by weight or less.
- a resin binder may be used.
- the resin binder When forming a composite structure using the aerosol deposition method in which film formation is performed at room temperature, if the resin binder is mixed in the prepared particles 31, it may be an obstacle to aerosolization or the resin may be contained in the composite structure. There is a risk of mixed problems. Therefore, it is necessary to subject the prepared particles containing the resin binder to a heat treatment of several hundred degrees to burn off the resin binder. In this case, if insufficient heat treatment is performed, carbon remains in the prepared particles, and impurities (carbon) may be mixed into the formed composite structure.
- the carbon content is 1% by weight or less, the composite structure can be formed satisfactorily and the influence is suppressed even when impurities are mixed in the composite structure. Can do.
- the prepared particles 31 as described above can be produced using, for example, a spray dryer method, a bread granulator, a pot granulator, or the like.
- a binder may be added in the production of the prepared particles 31, or water may be added.
- the spray dryer method the bread type granulator, the pot type granulator, etc., the description thereof is omitted.
- the shape, size, and hardness of the prepared particles are various control factors of these methods, for example, spraying amount and spraying state of spray dryer, temperature, etc., and usual factors such as the rotational speed and rotation time of the granulator, It can be changed by appropriately setting the structure and size of the granulator and the amount of water added to these.
- FIG. 14 is a schematic diagram for illustrating the basic configuration of the composite structure forming system according to the second embodiment of the present invention. That is, FIG. 14A is a block diagram for illustrating the basic configuration of a composite structure forming system (aerosol deposition apparatus). FIG. 14B is a diagram schematically showing the flow from storing the prepared particles to aerosolization. FIG. 14 (c) is a diagram showing a change in state during the period from storage of prepared particles to aerosolization. FIGS. 14B and 14C are drawn so as to correspond to the respective components shown in FIG.
- the composite structure forming system (aerosol deposition apparatus) 100a As shown in FIG. 14 (a), the composite structure forming system (aerosol deposition apparatus) 100a according to the present embodiment is housed in the same manner as the composite structure forming system 100 illustrated in FIG. 1 (a).
- a mechanism 1, a quantitative supply mechanism 2, a gas supply mechanism 3, an aerosolization mechanism 4, and a discharge port 5 are provided.
- a solid-gas mixed phase flow formation mechanism 6 is further provided between the quantitative supply mechanism 2 and the aerosolization mechanism 4.
- the solid-gas mixed phase flow formation mechanism 6 is for forming the solid-gas mixed phase flow 33 by the prepared particles 31 supplied by the quantitative supply mechanism 2 and the gas G supplied by the gas supply mechanism 3.
- the solid-gas mixed phase flow 33 formed by the solid-gas mixed phase flow forming mechanism 6 is supplied to the aerosol generating mechanism 4 through the supply path 16.
- the solid-gas mixed phase flow forming mechanism 6 If the solid-gas mixed phase flow forming mechanism 6 is provided, a homogeneous and stable solid-gas mixed phase flow 33 can be formed. If the solid-gas mixed phase flow 33 is formed, the prepared particles 31 can be accelerated toward the aerosol generating mechanism 4 as well as simply supplying the prepared particles 31. Therefore, since it can be crushed by the mechanical impact using the kinetic energy of the acceleration
- FIG. 15 is a schematic diagram for illustrating a basic configuration of a composite structure forming system according to the third embodiment of the present invention. That is, FIG. 15A is a block diagram for illustrating the basic configuration of a composite structure forming system (aerosol deposition apparatus). FIG. 15B is a diagram schematically showing the flow from the storage of the prepared particles to the aerosolization. FIG. 15 (c) is a diagram showing a state change from the storage of the prepared particles to the aerosolization. Note that FIG. 15B and FIG. 15C are drawn so as to correspond to the respective components shown in FIG.
- the composite structure forming system (aerosol deposition apparatus) 100b includes a storage mechanism 1, a quantitative supply mechanism 2, a gas supply mechanism 3, and an aerosolization mechanism. 4 and a discharge port 5.
- the prepared particles 31 are supplied from the quantitative supply mechanism 2 to the aerosolization mechanism 4 without forming the above-described solid-gas mixed phase flow 33. Further, the gas G is supplied from the gas supply mechanism 3 to the aerosol generating mechanism 4. The prepared particles 31 supplied in the aerosol generating mechanism 4 are crushed to form an aerosol 32 in which the fine particles 30P are dispersed in the gas G.
- the prepared particles 31 can be crushed by, for example, providing a “grinding mechanism” (not shown) in the aerosol-generating mechanism 4 so that the supplied prepared particles 31 are crushed. Further, the supplied prepared particles 31 can be accelerated by electrostatic attraction or gravity, and can be crushed by mechanical impact using the kinetic energy of the accelerated prepared particles 31.
- FIG. 16 is a schematic diagram for illustrating a first specific example of the composite structure forming system (aerosol deposition apparatus) according to the embodiment of the present invention.
- symbol is attached
- the structure forming chamber 8 is provided, and at least the tip portion of the discharge port 5 and the support scanning mechanism 10 that supports the substrate 7 are disposed in the structure forming chamber 8.
- the base material 7 carried into the structure forming chamber 8 is supported by, for example, an electrostatic chuck built in the support scanning mechanism 13.
- the internal space of the structure forming chamber 8 can be maintained in a reduced pressure state by the exhaust mechanism 9.
- the exhaust mechanism 9 for example, a rotary pump or the like can be used, and the inside of the structure forming chamber 8 can be maintained in a reduced pressure atmosphere lower than the atmospheric pressure.
- the aerosol generated in the aerosol generating mechanism 4 is jetted from the discharge port 5 toward the base material 7, and a film-like structure 26 made of raw material fine particles is formed on the base material 7.
- a film-like structure 26 made of raw material fine particles is formed on the base material 7.
- the “new surface” formed by the collision of the aerosol with the base material 7 can be maintained in an active state for a longer period of time. It becomes possible to increase the density and strength.
- the base material 7 is supported on the support scanning mechanism 10, and the film-like structure 26 can be formed while appropriately moving its position in at least one of the XYZ ⁇ directions. That is, by spraying the aerosol while appropriately scanning the substrate 7 by the support scanning mechanism 10, the film-like structure 26 is formed on the surface of the substrate 7 having a larger area than the beam size of the aerosol ejected from the discharge port 5. Can be made.
- the supply amount can be easily quantified by storing the prepared particles 31 in the storage mechanism 1 and supplying the prepared particles 31 by the quantitative supply mechanism 2 with certainty.
- the pulverization in the supply process to the aerosol generating mechanism 4 and the accompanying adhesion and stacking can be suppressed, so that the quantitative supply ability can be remarkably improved. Therefore, the fine particle concentration in the aerosol can be made constant.
- the concentration of fine particles in the aerosol is kept constant. Therefore, the film thickness and film quality can be made uniform over a large area.
- FIG. 17 is a schematic view for illustrating a second specific example of the composite structure forming system (aerosol deposition apparatus) according to the embodiment of the invention.
- the same parts as those described in FIGS. 14 and 16 are denoted by the same reference numerals, and the description thereof is omitted.
- the prepared particles 31 housed in the housing mechanism 1 are supplied to the solid-gas mixed phase flow forming mechanism 6 by the quantitative supply mechanism 2. Then, in the solid-gas mixed phase flow formation mechanism 6, a solid-gas mixed phase flow is formed by the prepared particles 31 supplied by the quantitative supply mechanism 2 and the gas supplied by the gas supply mechanism 3. Is supplied to the aerosol generating mechanism 4 through the supply path 16.
- a discharge port 11 having acceleration means and rectification means is provided, and a support scanning mechanism 12 is connected to the discharge port 11.
- the aerosol generated in the aerosol generating mechanism 4 is jetted from the discharge port 11 toward the base material 7a through the pipe 13.
- the aerosol can be accelerated by utilizing the jet air flow, compression effect, and the like obtained by providing a difference in the acceleration means of the discharge port 11 and the flow path diameter.
- the discharge port 11 is supported by the support scanning mechanism 12 and is movable in at least one of XYZ ⁇ directions.
- the aerosol can be sprayed while moving the discharge port 11 to form a uniform film-like structure 26a over a large area on the substrate 7a.
- the flexible pipe 13 include a pipe made of an elastic material such as rubber and a pipe such as a bellows.
- the discharge port 11 and the base material 7a may be moved relatively, and the support scanning mechanism 10 may be movable in at least one direction of XYZ ⁇ .
- the supply amount can be easily quantified by storing the prepared particles 31 in the storage mechanism 1 and reliably supplying the prepared particles 31 by the quantitative supply mechanism 2.
- the pulverization in the supply process to the aerosol generating mechanism 4 and the accompanying adhesion and stacking can be suppressed, so that the quantitative supply ability can be remarkably improved. Therefore, the fine particle concentration in the aerosol can be made constant.
- the discharge port 11 and the base material 7a are relatively scanned to form the film-like structure 26a on the surface of the base material 7a where the three-dimensional or film-like structure 26a is scattered. Even in this case, since the concentration of fine particles in the aerosol can be maintained constant, the film thickness and film quality can be made uniform over a large area.
- FIG. 18 is a schematic view for illustrating a third specific example of the composite structure forming system (aerosol deposition apparatus) according to the embodiment of the invention.
- the same parts as those described in FIGS. 1 and 16 are denoted by the same reference numerals, and the description thereof is omitted.
- a measuring mechanism 14 for measuring the concentration of fine particles in the aerosol is provided between the discharge port 5 and the substrate 7.
- the weighing mechanism 14 is electrically connected to the control mechanism 15.
- the control mechanism 15 is also electrically connected to the quantitative supply mechanism 2, the gas supply mechanism 3, and the exhaust mechanism 9 for feedback control described later.
- the measuring mechanism 14 can be provided at a place where the concentration of fine particles contained in the aerosol can be measured.
- the measuring mechanism 14 may be provided outside or inside the structure forming chamber 8, or may be provided inside or outside the structure forming chamber 8. Further, the number to be provided can be changed as appropriate.
- the concentration of fine particles contained in the aerosol ejected from the discharge port 5 is measured by the measuring mechanism 14, and the measured information is transmitted from the measuring mechanism 14 to the control mechanism 15.
- the control mechanism 15 performs feedback control to the quantitative supply mechanism 2, the gas supply mechanism 3, and the exhaust mechanism 9 based on the transmitted information.
- the feedback control may be performed at least for the quantitative supply mechanism 2.
- the measuring mechanism 14 may include, for example, a light projecting unit 1402 such as a laser and a light receiving unit 1404 that monitors the light.
- a light projecting unit 1402 such as a laser
- a light receiving unit 1404 that monitors the light.
- the aerosol may be irradiated from the light projecting unit 1402 such as a laser, and the reflected light may be monitored by the light receiving unit 1404a such as a CCD (Charge Coupled Device) sensor.
- the light projecting unit 1402 such as a laser
- the reflected light may be monitored by the light receiving unit 1404a such as a CCD (Charge Coupled Device) sensor.
- CCD Charge Coupled Device
- the supply amount can also be measured by providing a load cell in the quantitative supply mechanism 2 and measuring the weight change of the quantitative supply mechanism 2. If the amplitude of the vibrator is changed by changing the weight, the prepared particles 31 having a constant weight can be always supplied. In this case, if a multistage quantitative supply mechanism is provided to make it easy to read the change in weight, it is possible to measure and control the supply amount with higher accuracy.
- the supply amount can be easily quantified by storing the prepared particles 31 in the storage mechanism 1 and reliably supplying the prepared particles 31 by the quantitative supply mechanism 2.
- the pulverization in the supply process to the aerosol generating mechanism 4 and the accompanying adhesion and stacking can be suppressed, so that the quantitative supply ability can be remarkably improved. Therefore, the fine particle concentration in the aerosol can be made constant.
- the concentration of fine particles contained in the aerosol after ejection fluctuates or changes over time
- the concentration of the contained fine particles can be precisely controlled.
- the concentration of fine particles in the aerosol can be maintained constant, the film thickness and film quality can be made uniform over a large area.
- the accuracy of the feedback control described above is high and suitable.
- FIG. 22 is a schematic diagram for illustrating a first specific example of the quantitative supply mechanism 2. That is, FIG. 22 is a schematic perspective view of the main part of the quantitative supply mechanism 2.
- an opening is provided vertically below the storage mechanism 1 in which the prepared particles 31 are stored, and a roller 210 is provided so as to close the opening.
- the roller 210 is provided with a plurality of recesses 212 on its surface and rotates in the direction of arrow A or in the opposite direction.
- the recess 212 has a sufficiently larger volume than the prepared particles 31.
- the gap between the inner side wall of the storage mechanism 1 and the surface of the roller 210 is sufficiently narrow as long as the rotation of the roller 210 is not hindered, and the prepared particles 31 are prevented from spilling from the gap.
- an elastic seal such as rubber may be provided on the inner side wall or the opening end of the accommodation mechanism 1 so as to contact the surface of the roller 210.
- the prepared particles 31 are filled in the concave portion 212 of the roller 210 by its own weight, and are supplied to the outside (lower side) of the accommodation mechanism 1 by the rotation of the roller 210.
- the prepared particles 31 fall due to their own weight.
- a predetermined amount of the prepared particles 31 filled in the recess 212 is supplied from the storage mechanism 1 as the roller 210 rotates, and drops toward the solid-gas mixed phase flow formation mechanism 6 or the aerosolization mechanism 4. To do. That is, a predetermined amount of the prepared particles 31 can be supplied one after another.
- grains 31 are filled into the recessed part 212 of the roller 210 with the dead weight in the accommodation mechanism 1, they are not compressed too much. That is, since the prepared particles 31 are supplied without being crushed, it is possible to suppress the supply of the prepared particles 31 whose properties have changed from the quantitative supply mechanism 2. Furthermore, since the prepared particles 31 are not excessively pressed into the recesses 212, when the recesses 212 are directed vertically downward by the rotation of the roller 210, the prepared particles 31 therein can be smoothly dropped by their own weight. That is, the problem that the prepared particles 31 are less likely to fall out of the recesses 212 can be suppressed, and the prepared particles 31 can be stably supplied. Therefore, since the prepared particles 31 whose properties such as the average crushing strength, the circularity, and the angle of repose described above are prepared can be supplied as they are, the supply is stable and the stable supply as the target is achieved without a stack. can do.
- FIG. 23 is a schematic diagram for illustrating a second specific example of the quantitative supply mechanism 2. Also in this specific example, an opening is provided vertically below the storage mechanism 1 in which the prepared particles 31 are stored. A roller 222 is provided so as to close the opening. A plurality of convex portions 224 are provided on the surface of the roller 222 and rotate in the direction of arrow A or in the opposite direction.
- the convex part 224 since the convex part 224 is provided on the surface of the roller 222, the height of the convex part 224 corresponds to the surface of the roller 222 and the inner side wall of the housing mechanism 1. A gap is created. However, the prepared particles are formed from the gap between the opening at the lower end of the housing mechanism 1 and the surface of the roller 222 by providing the convex portions 224 densely to some extent on the surface of the roller 222 or by appropriately adjusting the shape and arrangement of the convex portions 224 It is possible to prevent 31 from spilling continuously.
- the prepared particles 31 housed in the housing mechanism 1 are pushed out by the convex portion 224, fall down by their own weight, and supplied to the solid-gas mixed phase flow forming mechanism 6 or the aerosol generating mechanism 4.
- the prepared particles 31 are brought into contact with the surface of the roller 222 due to their own weight in the containing mechanism 1 and are pushed out by the convex portion 224, so that they are not excessively compressed. That is, since the prepared particles 31 are supplied without being crushed, it is possible to suppress the supply of the prepared particles 31 whose properties have changed from the quantitative supply mechanism 2. Therefore, since the prepared particles 31 having the properties such as the average crushing strength, the circular diameter, and the angle of repose described above can be supplied as they are, the supply is stable, and the stable supply as the target without a stack is achieved. can do.
- FIG. 24 is a schematic diagram for illustrating a third specific example of the quantitative supply mechanism 2.
- a substantially circular opening is provided vertically below the storage mechanism 1 in which the prepared particles 31 are stored.
- a mesh 230 is provided in the opening. The mesh 230 rotates in the direction of arrow A or the opposite direction while contacting the bottom surface of the storage mechanism 1.
- the prepared particles 31 fall through the opening of the mesh 230.
- the amount of the prepared particles 31 dropped varies depending on the opening size of the mesh 230, the rotation speed, and the like.
- the opening size of the mesh is in a range of 2 to 7 times the average particle diameter of the prepared particles 31, the prepared particles 31 can be bridged when the mesh 230 is stationary, which is unnecessary. Can be prevented from falling.
- the supply amount of the prepared particles 31 by the rotation of the mesh 230 can be easily controlled.
- the prepared particles 31 are brought into contact with the surface of the mesh 230 due to their own weight in the containing mechanism 1 and fall to the outside through the opening, so that they are not excessively compressed. That is, since the prepared particles 31 are supplied without being crushed, it is possible to suppress the supply of the prepared particles 31 whose properties have changed from the quantitative supply mechanism 2. Therefore, since the prepared particles 31 having the properties such as the average crushing strength, the circular diameter, and the angle of repose described above can be supplied as they are, the supply is stable, and the stable supply as the target without a stack is achieved. can do.
- the plurality of prepared particles 31 are supplied almost simultaneously and continuously through the plurality of openings of the mesh 230. That is, a large number of prepared particles 31 are always continuously supplied to the solid-gas mixed phase flow forming mechanism 6 or the aerosol generating mechanism 4, and the supply amount of the prepared particles 31 is averaged over time. Accordingly, since a constant amount of the prepared particles 31 is always supplied stably, an aerosol having a constant fine particle concentration can be generated stably.
- FIG. 25 is a schematic diagram for illustrating a fourth specific example of the quantitative supply mechanism 2.
- a circular opening is provided vertically below the storage mechanism 1 in which the prepared particles 31 are stored in the same manner as described above with respect to the third specific example.
- a mesh 230 is provided in the opening.
- a brush 232 is installed on the mesh 230 and rotates in the direction of arrow A or the opposite direction while contacting the mesh 230.
- the accommodation mechanism 1 is provided with a vibrator 234.
- the vibrator 234 functions to vibrate the wall surface of the storage mechanism 1 and the like so that the prepared particles 31 stored in the storage mechanism 1 are smoothly dropped and supplied toward the brush 232 and the mesh 230.
- liquidity is also acquired by giving the vibration to the preparation particle
- the vibrator 234 can be similarly provided for each of the first to third specific examples to obtain the same function and effect.
- the prepared particles 31 pass through the opening of the mesh 230 and fall.
- the amount of the prepared particles 31 dropped depends on the opening size of the mesh 230 and the brush density and rotation speed of the brush 232.
- the opening size of the mesh is in a range of 2 to 7 times the average particle diameter of the prepared particles 31, the prepared particles 31 can be bridged when the mesh 230 is stationary, which is unnecessary. Can be prevented from falling.
- the supply amount of the prepared particles 31 by the rotation of the mesh 230 can be easily controlled.
- the prepared particles 31 are pushed out from the opening in accordance with the operation in which each brush tip of the brush 232 passes through the opening of the mesh 230. That is, when viewed microscopically, the prepared particles 31 are lightly pushed out of the mesh, dropped and supplied to the solid-gas mixed phase flow forming mechanism 6 or the aerosol mechanism 4. That is, since the prepared particles 31 are supplied without being crushed, it is possible to suppress the supply of the prepared particles 31 whose properties have changed from the quantitative supply mechanism 2. Therefore, since the prepared particles 31 having the properties such as the average crushing strength, the circular diameter, and the angle of repose described above can be supplied as they are, the supply is stable, and the stable supply as the target without a stack is achieved. can do.
- the plurality of prepared particles 31 are supplied almost simultaneously and continuously through the plurality of openings of the mesh 230. That is, in the aerosol generating mechanism 4, a large number of prepared particles 31 are always supplied continuously, and the supply amount of the prepared particles 31 is averaged over time. Therefore, a constant amount of the prepared particles 31 is always supplied stably, and an aerosol having a constant fine particle concentration can be generated stably.
- FIG. 26 is a schematic diagram for illustrating a fifth specific example of the quantitative supply mechanism 2.
- a supply path 235 is provided below the storage mechanism 1 in which the prepared particles 31 are stored, and a vibrator 234 is installed in the supply path 235.
- the prepared particles 31 accommodated in the accommodation mechanism 1 pass through an orifice (not shown), and a predetermined amount is supplied to the supply path 235.
- the prepared particles 31 supplied to the supply path 235 are supplied from the supply path 235 by the vibration of the vibrator 234.
- the prepared particles 31 pass through an orifice (not shown) due to their own weight and fall to the outside (supply path 235) in the accommodation mechanism 1, and thus are not excessively compressed.
- the prepared particles 31 supplied to the supply path 235 also fall to the outside due to the vibration of the vibrator 234, the properties of the prepared particles 31 do not change. That is, the prepared particles 31 are supplied to the outside from the quantitative supply mechanism 2 without changing their properties. Therefore, since the prepared particles 31 having the properties such as the average crushing strength, the circular diameter, and the angle of repose described above can be supplied as they are, the supply is stable, and the stable supply as the target without a stack is achieved. can do.
- the plurality of prepared particles 31 are supplied almost simultaneously and continuously. That is, in the aerosol generating mechanism 4, a large number of prepared particles 31 are always supplied continuously, and the supply amount of the prepared particles 31 is averaged over time. Therefore, a constant amount of the prepared particles 31 is always supplied stably, and an aerosol having a constant fine particle concentration can be generated stably.
- FIG. 27 is a schematic diagram for illustrating a sixth specific example of the quantitative supply mechanism 2.
- a rotating disk with a groove formed in the lower part of the storage mechanism 1 in which the prepared particles 31 are stored is disposed, and a scraper is disposed at the tip of the rotating disk in the rotational direction.
- the prepared particles 31 introduced into the groove of the turntable are supplied from the storage mechanism 1 as the turntable rotates. Then, the prepared particles 31 introduced into the groove are scraped out by a scraper.
- the prepared particles 31 are brought into contact with the surface of the rotating disk by their own weight in the accommodation mechanism 1 and are scraped out by the scraper after being introduced into the groove, so that the prepared particles 31 are not excessively compressed. . That is, since the prepared particles 31 are supplied without being crushed, it is possible to suppress the supply of the prepared particles 31 whose properties have changed from the quantitative supply mechanism 2. Therefore, the prepared particles 31 having the properties such as the average crushing strength, the circularity, and the angle of repose described above can be supplied as they are, so that the supply is stable and the stable supply as the target is achieved without any stack. can do.
- the plurality of prepared particles 31 are supplied almost simultaneously and continuously through the plurality of grooves of the rotating disk. That is, in the aerosol generating mechanism 4, a large number of prepared particles 31 are always supplied continuously, and the supply amount of the prepared particles 31 is averaged over time. Therefore, in the aerosol generating mechanism 4, a constant amount of the prepared particles 31 is always supplied stably, and an aerosol having a constant fine particle concentration can be generated stably.
- FIG. 28 is a schematic diagram for illustrating a seventh specific example of the quantitative supply mechanism 2.
- a screw is provided in the lower part of the storage mechanism 1 in which the prepared particles 31 are stored, and a motor (not shown) for rotating the screw is provided at the end of the screw.
- the outer wall of a fixed length is provided in the screw, and the both ends of the outer wall are open
- the prepared particles 31 introduced into the groove of the screw are supplied from the storage mechanism 1 as the screw rotates. At this time, the prepared particles 31 are moved to a constant amount by clearance with the outer wall, and fall at a constant speed from the end of the outer wall.
- the prepared particles 31 in the accommodation mechanism 1 are brought into contact with the surface of the screw by their own weight, and thus are not excessively compressed. That is, since the prepared particles 31 are supplied without being crushed, it is possible to suppress the supply of the prepared particles 31 whose properties have changed from the quantitative supply mechanism 2. Therefore, since the prepared particles 31 having the properties such as the average crushing strength, the circular diameter, and the angle of repose described above can be supplied as they are, the supply is stable, and the stable supply as the target without a stack is achieved. can do.
- a plurality of prepared particles 31 are supplied almost simultaneously and continuously by a screw. That is, in the aerosol generating mechanism 4, a large number of prepared particles 31 are always supplied continuously, and the supply amount of the prepared particles 31 is averaged over time. Therefore, in the aerosol generating mechanism 4, a constant amount of the prepared particles 31 is always supplied stably, and an aerosol having a constant fine particle concentration can be generated stably.
- FIG. 29 is a schematic diagram for illustrating an eighth specific example of the quantitative supply mechanism 2.
- an orifice 237 is provided in the lower part of the storage mechanism 1 in which the prepared particles 31 are stored, and a belt conveyor 236 is disposed substantially horizontally with respect to the ground axis below the orifice 237.
- the prepared particles 31 scraped by the orifice 237 are supplied on the upper part of the belt conveyor 236. Since the belt conveyor 236 is operated at a constant speed, the prepared particles 31 fall at a constant speed from the end of the belt conveyor 236 after moving a predetermined length.
- the prepared particles 31 pass through the orifice 237 and fall onto the belt conveyor 236 by its own weight in the accommodation mechanism 1, they are not excessively compressed. That is, since the prepared particles 31 are supplied without being crushed, it is possible to suppress the supply of the prepared particles 31 whose properties have changed from the quantitative supply mechanism 2. Therefore, since the prepared particles 31 having the properties such as the average crushing strength, the circular diameter, and the angle of repose described above can be supplied as they are, the supply is stable, and the stable supply as the target without a stack is achieved. can do.
- the plurality of prepared particles 31 are supplied almost simultaneously and continuously via the belt conveyor 236. That is, in the aerosol generating mechanism 4, a large number of prepared particles 31 are always supplied continuously, and the supply amount of the prepared particles 31 is averaged over time. Therefore, in the aerosol generating mechanism 4, a constant amount of the prepared particles 31 is always supplied stably, and an aerosol having a constant fine particle concentration can be generated stably.
- FIG. 30 is a schematic diagram for illustrating a ninth specific example of the quantitative supply mechanism 2.
- an orifice 238 is provided in the lower part of the storage mechanism 1 in which the prepared particles 31 are stored, and a shutter 239 for opening and closing the orifice 238 is further provided.
- the opening shape of the orifice 238 is appropriately determined according to the size of the prepared particle 31, and the supply and stop of the prepared particle 31 can be stopped by opening and closing the shutter 239.
- the prepared particles 31 pass through the orifice 238 and fall to the outside due to their own weight in the accommodation mechanism 1, they are not excessively compressed. That is, since the prepared particles 31 are supplied without being crushed, it is possible to suppress the supply of the prepared particles 31 whose properties have changed from the quantitative supply mechanism 2. Therefore, since the prepared particles 31 having the properties such as the average crushing strength, the circular diameter, and the angle of repose described above can be supplied as they are, the supply is stable, and the stable supply as the target without a stack is achieved. can do.
- the plurality of prepared particles 31 are supplied almost simultaneously and continuously via the orifice 238. That is, in the aerosol generating mechanism 4, a large number of prepared particles 31 are always supplied continuously, and the supply amount of the prepared particles 31 is averaged over time. Therefore, in the aerosol generating mechanism 4, a constant amount of the prepared particles 31 is always supplied stably, and an aerosol having a constant fine particle concentration can be generated stably.
- FIG. 31 is a schematic diagram for illustrating a first specific example of the aerosolization mechanism.
- the aerosolization mechanism 4a is provided with a supply port 1502 for ejecting the prepared particles 31 together with a gas, an impact plate 1504 as a mechanical barrier provided in front of the supply port 1502, and a discharge port 1505.
- the prepared particles 31 ejected from the supply port 1502 receive an impact force when they collide with the impact plate 1504. Due to this impact force, the prepared particles 31 are crushed, and the primary particles 30P or the particles containing the aggregated particles 30Q in the degree of aggregation of several primary particles 30P are dispersed in the gas to become the aerosol 32.
- the aerosol 32 is discharged from the discharge port 1505 along the gas flow.
- the motion vector at the collision point of the prepared particles 31 becomes substantially opposite to the motion vector of the injection of the aerosol 32, so that the impact force on the prepared particles 31 is increased. Can do. As a result, the concentration of fine particles in the aerosol 32 can be further homogenized.
- the material of the impact plate 1504 is preferably a hard material, and for example, ceramics such as alumina, silicon carbide, silicon nitride, and aluminum nitride can be used.
- the speed at which the impact particle 1504 collides with the impact plate 1504 may be such that the prepared particles 31 are sufficiently crushed, and is preferably slower than the extent that a structure is formed on the surface of the impact plate 1504 by the impact of the impact.
- the prepared particles 31 are completely crushed up to the primary particles 30P that contribute to the structure formation in the aerosol deposition method by this mechanical impact, and at this time, the structure formation efficiency is most improved.
- FIG. 32 is a schematic diagram for illustrating a second specific example of the aerosolization mechanism.
- the aerosol generating mechanism 4b is provided with a supply port 1502 for supplying the prepared particles 31, a collision plate 1504a as a mechanical barrier provided in front of the supply port 1502, and a discharge port 1505.
- the gas supply port 1507 is provided so as to be substantially parallel to the collision plate 1504a, and a discharge port 1505 is provided in front of the gas supply port 1507.
- the prepared particles 31 are supplied in a gas flow, and collide with the collision plate 1504a, whereby the primary particles 30P or the aggregated particles 30Q to the extent that several primary particles 30P are aggregated are crushed.
- the gas supply port 1507 By injecting gas from the gas supply port 1507 to the point of collision, the green compact adhering to the collision plate 1505a can be blown off, and uniform aerosol can be generated.
- FIG. 33 is a schematic diagram for illustrating a third specific example of the aerosolization mechanism.
- the aerosolization mechanism 4c is provided with a supply port 1502 for supplying the prepared particles 31, a gas supply port 1507a for forming a pressure barrier in front of the supply port 1502, and a discharge port 1505. Further, the gas supply port 1507a is provided substantially coaxially with the pipe line provided with the discharge port 1505.
- the prepared particles 31 are supplied in a gas flow and collide with a pressure barrier formed by the gas supply port 1507a. At this time, since a shearing force acts on the prepared particles 31, the prepared particles 31 are crushed into primary particles 30 ⁇ / b> P or agglomerated particles 30 ⁇ / b> Q having a degree of aggregation of several primary particles 30 ⁇ / b> P. A uniform aerosol is formed by the gas injected from the gas supply port 1507.
- FIG. 34 is a schematic diagram for illustrating a fourth specific example of the aerosolization mechanism.
- the aerosol generating mechanism 4d is provided with locations 1506 having a large channel diameter and locations 1508 having a small channel diameter alternately along the channel through which the aerosol flows. If it does in this way, gas will be compressed in the location 1508 with a small flow path diameter, and gas will expand in the location 1506 with a large flow path diameter.
- a shearing force acts on the prepared particles 31 contained in the aerosol. Due to this shearing force, the prepared particles 31 are crushed into primary particles 30P or agglomerated particles 30Q to the extent that several primary particles 30P are aggregated.
- the number of locations 1506 having a large flow path diameter and locations 1508 having a small flow path are not limited to those illustrated, and can be appropriately changed according to the size and strength of the prepared particles 31 to be supplied.
- FIG. 35 is a schematic diagram for illustrating a fifth specific example of the aerosolization mechanism.
- the aerosol generating mechanism 4e is provided with a first gas supply port 1507b and a second gas supply port 1507c.
- the first gas supply port 1507b and the second gas supply port 1507c are provided so that their axes intersect each other.
- the prepared particles 31 supplied from the first gas supply port 1507b and the second gas supply port 1507c can collide with each other.
- the prepared particles 31 are crushed into primary particles 30P or agglomerated particles 30Q to the extent that several primary particles 30P are aggregated.
- the collision to the wall surface of the preparation particle 31 is avoided and there exists an advantage that an impurity cannot enter easily.
- the prepared particles By using prepared particles having a bond strength of a certain value or less and a controlled shape in the above-described aerosolization mechanism, the prepared particles are easily crushed and easily become a primary particle-rich aerosol. Therefore, it is suitable for forming a composite structure.
- a composite structure forming method, prepared particles, and a composite structure forming system capable of further stabilizing the concentration of fine particles in an aerosol and maintaining a stable state for a long time.
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Abstract
Description
2 定量供給機構
3 ガス供給機構
4 エアロゾル化機構
5 吐出口
6 固気混相流形成機構
30P 微粒子
31 調製粒子
32 エアロゾル
33 固気混相流
100 複合構造物形成システム(エアロゾルデポジション装置)
本明細書において「微粒子」とは、脆性材料の結晶が化学的に結合して形成された粒子を指し、エアロゾルデポジション法で使用されるこの微粒子は、例えば、特許文献1(特許第3348154号公報)に記載されているように平均一次粒子径が0.1μm以上5μm以下のものをいう。尚、平均一次粒子径の同定には、電子顕微鏡観察による複数(50個以上を目処とする)の脆性材料微粒子の画像から円相当径として算出する方法を採用することができる。
また、調製粒子においては、その径が意図的に制御されていることが望ましい。調製粒子の径は、その平均円相当径を指標とすることができる。
また、「固相」とは、調製粒子がほぼガス流の影響を受けずに存在している状態をいう。
図1は、本発明の第1の実施の形態にかかる複合構造物形成システムの基本構成を例示するための模式図である。すなわち、図1(a)は複合構造物形成システム(エアロゾルデポジション装置)の基本構成を例示するためのブロック図である。また、図1(b)は調製粒子の収容からエアロゾル化されるまでの流れを模式的に表した図である。また、図1(c)は調製粒子の収容からエアロゾル化されるまでの間の状態変化を表した図である。尚、図1(a)に示した各構成要素に対応するようにして、図1(b)、図1(c)を描いている。
エアロゾルデポジション法において利用される微粒子は、脆性材料を主体とし、同一材質の微粒子を単独であるいは粒径の異なる微粒子を混合させて用いることができる。
定量供給性、エアロゾル濃度の均一性などを向上させるためには調製粒子31の平均圧壊強度を指標とすることができる。
例えば、平均圧壊強度が低すぎると、収容機構1から供給される際、あるいはエアロゾル化機構4への供給の過程において、調製粒子31が解砕されて壁面に付着するため定量供給性、エアロゾル濃度の均一性などが低下するおそれがある。また、平均圧壊強度が高すぎると、定量供給性は確保することができるが、エアロゾル化機構4における解砕が阻害されるのでエアロゾル濃度の均一性などが低下するおそれがある。そのため、調製粒子31の平均圧壊強度が所定の範囲内になるようにすることが好ましい。
まず、圧壊強度(圧縮破壊強度)の測定について説明をする。
平均一次粒子径が0.3μm程度の脆性材料微粒子を含み、円相当径が100~400μmの範囲内にある調製粒子を準備し、これらの調製粒子の圧壊強度を測定した。尚、円相当径については後述する。
St=2.8P/(π×d×d)
ここで、Stは圧壊強度(Pa)、Pは圧壊時の試験力(N)、dは調製粒子径(mm)である。
この圧壊強度の測定においては、図2に示すように試験力の変化がほぼ一定となり変位のみが増加する点を圧壊時の試験力Pとした。尚、調製粒子径dは、圧縮試験機に備えられている光学機器を用いて測定した。
円相当径が100~400μmの範囲内にある様々な圧壊強度を持つ調製粒子を準備し、これらの調製粒子を用いてエアロゾルデポジション法により複合構造物の形成を行った。エアロゾルデポジション法に用いる装置としては、定量供給機構として振動型供給装置、エアロゾル化機構としてセラミックスの板へ固気混相流を衝突させる方式のものを備え、ガスとして窒素を用いるものとした。
図3から分かるように、平均圧壊強度を0.47MPaを超えるものとすれば、薄い膜しか形成することができず生産性に問題が生じる。これは、調製粒子の圧壊強度が高すぎるためエアロゾル化機構における調製粒子の解砕が阻害されたためであると考えられる。本発明者の得た知見によれば、平均圧壊強度を0.47MPa以下とすれば、生産性の観点から好ましい複合構造物の形成を行うことができる。また、平均圧壊強度を0.34MPa以下とすれば生産性の観点からより好ましい複合構造物の形成を行うことができる。
前述したように平均圧壊強度の下限値は主に定量供給性の観点から決定される。すなわち、平均圧壊強度が低すぎると、収容機構から供給される際、あるいはエアロゾル化機構4への供給の過程において、緩やかに送る操作の条件下においても調製粒子同士の摩擦やお互いの接触応力、壁面との摩擦などの、粒子の移動の際に発生する様々な力を受けて調製粒子が解砕されたり、調製粒子を構成する脆性材料微粒子の一部が表面から脱落してしまうおそれがある。そして、解砕や脱落により生じた脆性材料微粒子が壁面へ付着すると調製粒子の移動が阻害され定量供給性が損なわれる。そのため、平均圧壊強度は所定の値以上であることが好ましい。
例えば、平均円相当径が小さくなりすぎると凝集が起こりやすくなるので定量供給性、エアロゾル濃度の均一性などが損なわれるおそれがある。また、平均円相当径が大きくなりすぎると供給路16などにおける詰まりやエアロゾル化機構4における解砕不良が発生するおそれがある。そのため、調製粒子31の平均円相当径が所定の範囲内になるようにすることが好ましい。
また、平均円相当径は、複数の調製粒子を任意に選び、これらの円相当径を測ってその平均値を算出したものである。算出に際しては、まず、シリコンウェーハなどのように鏡面を持ち、ノイズとなるような傷を持たないものを調製粒子を展開する基材として準備する。次に、この上に写真判定画面上で測定の対象となる調製微粒子を分散させる。この際、写真判定画面に占める面積割合が40%以下となるように分散させる。その上で調製粒子としての性格を有していない凝集粒や一次粒子、あるいは一次粒子が複数個重なった状態で観察されるような粒子の群は極力除外する。特に中心粒径付近の微粒子はお互いに重なりあわないような分散状態を確保するようにする。また、写真判定に際して、定量供給性が優れず、調製粒子としてはもとより不十分と判断される平均円相当径が5μm以下で計測されたデータ群は削除する。また写真判定画像において、画像の外縁部境界に接する、すなわち粒子が完全に画像内に捉えられていないデータについても削除することで、値の信頼性を確保させる。
このような微小な粒子には、調製粒子から一部脱落して形成された断片や調製粒子形成が不十分であったものが含まれると考えられる。このように、算出目的となる大粒径の調製粒子のピークと、算出目的外の微小な粒子のピークとを併せてもつ分布であると明快に判断できる場合には、平均円相当径の判定において微小な粒子のピークを構成する粒子群を除いて平均円相当径を算出するようにする。
このような慎重な調製粒子の選択操作を行い、カウントする調製粒子数を150~200個選び、これらの数値から平均円相当径を求めるようにすることが好ましい。
このような閾値の選択を行ってもなお往々にして、前述した平均円相当径の算出値に複数のピークが生じ得る。そのため、前述したような粒子群のカウントに対する選択操作を実施する必要性が生ずることになる。
図5からは、平均円相当径が20μm以上の場合には、供給量標準偏差が0.01以下となり定量供給性が良好となることが分かる。一方、平均円相当径が20μm未満となる場合には、供給量が経時的に不安定となり、定量供給性が損なわれることが分かる。
そのため、平均円相当径は、20μm以上、500μm以下とすることが好ましい。
例えば、平均の円形度が小さくなりすぎると転がりにくくなるので円滑な供給が困難となる。その結果、定量供給性、エアロゾル濃度の均一性などが損なわれるおそれがある。そのため、調製粒子31の平均の円形度が所定の値以上になるようにすることが好ましい。
円形度=4π×(画像における調製粒子の面積)/(画像における調製粒子の周囲長)2
ここで、円形度は真円の場合1となる。すなわち、円形度の最大値は1となる。
図6からは、平均の円形度が0.79以上の場合には、供給量標準偏差が0.01以下となり定量供給性が良好となることが分かる。一方、平均の円形度が0.79未満となる場合には、供給量が経時的に不安定となり、定量供給性が損なわれるおそれがあることが分かる。
そのため、平均の円形度は、0.79以上とすることが好ましい。
この場合の定量供給性の評価においては、まず、平均一次粒子径がサブミクロンの脆性材料微粒子を含む複数の調製粒子を準備し、円形度を測定し、以下の方法により円形度毎の調製粒子の定量供給性を評価した。
定量供給性の評価には、振動型供給装置を用いた。そして、供給速度を0.5g/minおよび5g/min、供給時間を最大3分とし、0.5g/minでは0.1秒毎に、5g/minでは1秒毎に振動型供給装置から供給される調製粒子の前後0.1秒間の重量変化から求まる流量を測定した。この流量の平均値を算出し、その標準偏差を求めた。
なお、図7、図8における横軸は平均の円形度を表し、縦軸は供給量標準偏差を表している。
例えば、D10値が小さくなりすぎると(調製粒子の粒度分布において、一番小さい粒子から10%のところに位置するものの粒径が小さくなりすぎると)、付着などが生じやすくなるので円滑な供給が困難となる。その結果、定量供給性、エアロゾル濃度の均一性などが損なわれるおそれがある。そのため、調製粒子31のD10値が所定の値以上になるようにすることが好ましい。
図9からは、D10値が6.6μm以上の場合には、供給量標準偏差が0.01以下となり定量供給性が良好となることが分かる。一方、D10値が6.6μm未満となる場合には、供給量が経時的に不安定となり、定量供給性が損なわれることが分かる。
そのため、D10値は6.6μm以上とすることが好ましい。
例えば、粒度分布偏差割合が大きくなりすぎる、すなわち、粒度分布が広くなりすぎると円滑な供給が困難となる。その結果、定量供給性、エアロゾル濃度の均一性などが損なわれるおそれがある。そのため、調製粒子31の粒度分布偏差割合が所定の値以下になるようにすることが好ましい。
図10からは、粒度分布偏差割合が0.59以下の場合には、供給量標準偏差が0.01以下となり定量供給性が良好となることが分かる。一方、粒度分布偏差割合が0.59を超える場合には、供給量が経時的に不安定となり、定量供給性が損なわれることが分かる。
そのため、粒度分布偏差割合は、0.59以下とすることが好ましい。
例えば、安息角が大きくなりすぎる、すなわち、流動が起こりにくくなると円滑な供給が困難となる。その結果、定量供給性、エアロゾル濃度の均一性などが損なわれるおそれがある。そのため、調製粒子31の安息角が所定の値以下になるようにすることが好ましい。
図11からは、安息角が42.5度以下の場合には、供給量標準偏差が0.01以下となり定量供給性が良好となることが分かる。一方、安息角が42.5度を超える場合には、供給量が経時的に不安定となり、定量供給性が損なわれるおそれがあることが分かる。
そのため、安息角は42.5度以下とすることが好ましい。
この場合の定量供給性の評価においては、まず、平均一次粒子径がサブミクロンの脆性材料微粒子を含む複数の調製粒子を準備し、安息角を測定し、以下の方法により安息角毎の調製粒子の定量供給性を評価した。
定量供給性の評価には、振動型供給装置を用いた。そして、供給速度を0.5g/minおよび5g/min、供給時間を最大3分とし、0.5g/minでは0.1秒毎に、5g/minでは1秒毎に、振動型供給装置から供給される調製粒子の前後0.1秒間の重量変化から求まる流量を測定した。この流量の平均値を算出し、標準偏差を求めた。
この場合、図12においては供給量標準偏差が0.192以下のときに、また図13においては供給量標準偏差が1.018以下のときに、定量供給性に優れていると判断された。さらには図12において供給量標準偏差が0.122以下のとき、また図13において供給量標準偏差が0.178以下のときに、定量供給性が格段に優れていると判断された。
そのため、高い厚みの精度が要求される構造物を形成する場合や、構造物の厚みが数μm以下の薄い膜状構造物を形成する場合などにおいても高い製造能力を発揮することができる。そして、安息角が44°以下の調製粒子をこの様な用途に用いれば、より好適な構造物を形成することができる。
固気混相流形成機構6は、定量供給機構2により供給された調製粒子31と、ガス供給機構3により供給されたガスGとにより固気混相流33を形成させるためのものである。そして、固気混相流形成機構6により形成された固気混相流33は供給路16を通じてエアロゾル化機構4へと供給される。
尚、その他の構成やその作用については、図1において説明をしたものと同様のためその説明は省略する。
また、供給された調製粒子31を静電引力や重力で加速し、加速された調製粒子31の運動エネルギーを利用した機械的衝撃により解砕するようにすることもできる。
尚、図1で説明をしたものと同様の部分には同じ符号を付しその説明は省略する。
尚、図14、図16で説明をしたものと同様の部分には同じ符号を付しその説明は省略する。
本具体例においては、吐出口11が支持走査機構12により支持され、XYZθの少なくともいずれかの方向に移動可能とされている。基材7aが立体形状を有している、あるいは膜状構造物26aを形成させる場所が点在するなどの場合に応じて、吐出口11と基材7a表面との直線距離を保った状態で、吐出口11を移動させつつエアロゾルを噴射させ、基材7a上に大面積に亘り均一な膜状構造物26aを形成させることができる。尚、この場合、可撓性を有する配管13を設けるものとすれば、吐出口11の移動による変位を吸収させることができる。可撓性を有する配管13としては、例えば、ゴムなどの弾性材料からなる配管や、ベローズ(じゃばら)などの配管を例示することができる。尚、吐出口11と基材7aは相対的に移動すればよく、支持走査機構10をXYZθの少なくともいずれかの方向に移動可能としてもよい。
尚、図1、図16などにおいて説明をしたものと同様の部分には同じ符号を付しその説明は省略する。
図19に示すように、計量機構14は、例えば、レーザなどの投光手段1402と、その光をモニタする受光手段1404などを備えたものとすることができる。この場合、エアロゾルに投光手段1402からのレーザを照射し、その透過量をモニタすることにより、エアロゾルに含まれる微粒子の濃度を計量することができる。
図22は、定量供給機構2の第1の具体例を例示するための模式図である。
すなわち、図22は、定量供給機構2の要部の模式斜視図である。
本具体例においては、調製粒子31が収容された収容機構1の鉛直下方に開口が設けられ、この開口を塞ぐようにローラ210が設けられている。ローラ210は、その表面に複数の凹部212が設けられ、矢印Aの方向あるいはその反対の方向に回転する。凹部212は調製粒子31よりも十分に大きな容積を有している。収容機構1の内部側壁と、ローラ210の表面と、の間の隙間はローラ210の回転を妨げない範囲で十分に狭くされ、この隙間から調製粒子31がこぼれ落ちないようにされている。尚、収容機構1の内部側壁あるいは開口端に、ゴムなどの弾力性を有するシールを設けてローラ210の表面に接触させるようにしてもよい。
またさらに、調製粒子31が凹部212の中に過度に押し固められないので、ローラ210の回転により凹部212が鉛直下方を向いた時に、その中の調製粒子31は、自重により円滑に落下できる。つまり、調製粒子31が凹部212の中から落ちにくくなるという問題も抑制することができ、調製粒子31を安定的に供給することができる。そのため、前述した平均圧壊強度、円径度、安息角などの性状が調製がされた調製粒子31をそのまま供給することができるので、供給が安定し、スタックも無く目標どおりの安定した供給を達成することができる。
本具体例においても、調製粒子31が収容された収容機構1の鉛直下方に開口が設けられている。そして、この開口を塞ぐようにローラ222が設けられている。ローラ222の表面には複数の凸部224が設けられ、矢印Aの方向あるいはその反対の方向に回転する。
本具体例においては、調製粒子31が収容された収容機構1の鉛直下方に略円形の開口が設けられている。そして、この開口にはメッシュ230が設けられている。メッシュ230は収容機構1の底面に接触しながら、矢印Aの方向あるいはその反対の方向に回転する。
本具体例においても、第3の具体例に関して前述したものと同様に、調製粒子31が収容された収容機構1の鉛直下方に円形の開口が設けられている。そして、この開口にはメッシュ230が設けられている。メッシュ230の上にはブラシ232が設置され、メッシュ230に接触しながら、矢印Aの方向あるいはその反対の方向に回転する。そしてさらに、収容機構1には振動子234が付設されている。振動子234は、収容機構1の壁面などを振動させ、収容機構1に収容されている調製粒子31を円滑にブラシ232及びメッシュ230に向けて落下供給させる作用を奏する。また、収容機構1の中の調製粒子31に振動を与えることにより、流動性を向上させる効果も得られる。
尚、振動子234は、第1~第3の各具体例についても同様に設けて同様の作用効果を得ることができる。
本具体例においては、調製粒子31が収容された収容機構1の下部には供給路235が設けられ、その供給路235には振動子234が設置されている。収容機構1に収容された調製粒子31は、図示しないオリフィスを通過して所定の量が供給路235に供給される。供給路235に供給された調製粒子31は、振動子234の振動により供給路235から供給される。
本具体例においては、調製粒子31が収容された収容機構1の下部に溝が形成された回転盤が配置され、回転盤の回転方向の先にはスクレーパが配置されている。
本具体例においては、調製粒子31が収容された収容機構1の下部に、スクリューが設けられ、スクリューの端部にはスクリューを回転させるための図示しないモータが備えられている。また、スクリューをスムーズに回転させるために、スクリューには一定の長さの外壁が設けられており、外壁の両端部は開放されている。スクリューの溝に導入された調製粒子31は、スクリューが回転することで収容機構1より供給される。このとき、調製粒子31は外壁とのクリアランスで一定量にすりきられて移動し、外壁の端部より一定速度で落下する。
本具体例においては、調製粒子31が収容された収容機構1の下部には、オリフィス237が設けられ、その下方にはベルトコンベア236が地軸に対してほぼ水平に配置されている。
本具体例においては、調製粒子31が収容された収容機構1の下部にオリフィス238が設けられ、更にそのオリフィス238を開閉するためのシャッター239が設けられている。オリフィス238の開口形状は調製粒子31の大きさに応じて適宜決定されており、シャッター239を開閉することで、調製粒子31の供給と停止をさせることができる。
図31は、エアロゾル化機構の第1の具体例を例示するための模式図である。
エアロゾル化機構4aには、調製粒子31をガスと共に噴出する供給口1502と、その前方に設けられた機械的障壁としての衝撃板1504と、排出口1505とが設けられている。
エアロゾル化機構4bには、調製粒子31を供給する供給口1502と、その前方に設けられた機械的障壁としての衝突板1504aと、排出口1505とが設けられている。ガス供給口1507は、衝突板1504aに対して略平行となるように設けられ、ガス供給口1507の前方には排出口1505が設けられている。
エアロゾル化機構4cには、調製粒子31を供給する供給口1502と、その前方に圧力障壁を形成させるためのガス供給口1507aと、排出口1505とが設けられている。また、ガス供給口1507aは、排出口1505が設けられた管路と略同軸に設けられている。
エアロゾル化機構4dには、エアロゾルが流れる流路に沿って、流路径の大きい箇所1506と小さい箇所1508とが交互に設けられている。このようにすると、流路径の小さい箇所1508においてはガスが圧縮され、流路径の大きい箇所1506においてはガスが膨張する。このような圧縮と膨張とを繰り返すと、エアロゾルに含まれる調製粒子31に剪断力が作用する。この剪断力により、調製粒子31は一次粒子30P、または数個の一次粒子30Pが凝集した程度の凝集粒30Qに解砕される。
エアロゾル化機構4eには、第1のガス供給口1507bと、第2のガス供給口1507cとが設けられている。そして、第1のガス供給口1507bと、第2のガス供給口1507cとは、その軸線が互いに交差するようにして設けられている。
Claims (28)
- 脆性材料微粒子をガス中に分散させたエアロゾルを基材に向けて噴射することにより前記脆性材料微粒子の構成材料からなる構造物を基材上に形成させるエアロゾルデポジション法による複合構造物形成方法であって、前記脆性材料微粒子を含む複数の粒子を固めた集合体である調製粒子を複数、収容機構に収容し、
前記収容機構から前記調製粒子をエアロゾル化機構に供給し、
前記エアロゾル化機構において前記供給された前記調製粒子を解砕してエアロゾルを形成し、
前記エアロゾルを基材に向けて噴射することにより前記構造物と前記基材との複合構造物を形成すること、を特徴とする複合構造物形成方法。 - 前記調製粒子と、ガス供給機構から導入されたガスと、を混合して固気混相流とし、
前記固気混相流を前記エアロゾル化機構に供給すること、を特徴とする請求項1に記載の複合構造物形成方法。 - 前記調製粒子は、前記収容機構から供給される際に実質的に解砕されないようにするために必要な平均圧壊強度を有すること、を特徴とする請求項1または2に記載の複合構造物形成方法。
- 前記調製粒子は、前記エアロゾル化機構へ供給される途中では実質的に解砕されず、エアロゾル化機構において実質的に解砕されるのに必要な平均圧壊強度を有すること、を特徴とする請求項1~3のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子は、前記エアロゾル化機構において機械的衝撃を加えられることで解砕されること、を特徴とする請求項1~4のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子の平均圧壊強度は、0.47MPa以下であること、を特徴とする請求項1~5のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子の平均圧壊強度は、0.34MPa以下であること、を特徴とする請求項1~5のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子の平均圧壊強度は、0.015MPa以上であること、を特徴とする請求項1~7のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子の平均の円形度は、0.65以上であること、を特徴とする請求項1~8のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子に含まれる前記脆性材料微粒子同士が化学的結合をしていないこと、を特徴とする請求項1~9のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子の平均円相当径は、20μm以上、500μm以下であること、を特徴とする請求項1~10のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子のD10は、6.6μm以上であること、を特徴とする請求項1~11のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子の粒度分布偏差割合は、0.59以下であること、を特徴とする請求項1~12のいずれか1つに記載の複合構造物形成方法。
- 前記調製粒子の安息角は、48度以下であること、を特徴とする請求項1~13のいずれか1つに記載の複合構造物形成方法。
- 脆性材料微粒子をガス中に分散させたエアロゾルを基材に向けて噴射することにより前記脆性材料微粒子の構成材料からなる構造物を基材上に形成させるエアロゾルデポジション法に用いられる調製粒子であって、
前記調製粒子は、平均一次粒子径が0.1μm以上、5μm以下の前記脆性材料微粒子を含む複数の粒子を固めた集合体であること、を特徴とする調製粒子。 - 前記調製粒子は、収容機構から供給される際に実質的に解砕されないようにするために必要な平均圧壊強度を有すること、を特徴とする請求項15記載の調製粒子。
- 前記調製粒子は、エアロゾル化機構へ供給される途中では実質的に解砕されず、エアロゾル化機構において実質的に解砕されるのに必要な平均圧壊強度を有すること、を特徴とする請求項15または16に記載の調製粒子。
- 前記調製粒子の平均圧壊強度は、0.47MPa以下であること、を特徴とする請求項15~17のいずれか1つに記載の調製粒子。
- 前記調製粒子の平均圧壊強度は、0.34MPa以下であること、を特徴とする請求項15~18のいずれか1つに記載の調製粒子。
- 前記調製粒子の平均圧壊強度は、0.015MPa以上であること、を特徴とする請求項15~19のいずれか1つに記載の調製粒子。
- 前記調製粒子の平均の円形度が0.65以上であること、を特徴とする請求項15~20のいずれか1つに記載の調製粒子。
- 前記調製粒子に含まれる前記脆性材料微粒子同士が化学的結合をしていないこと、を特徴とする請求項15~21のいずれか1つに記載の調製粒子。
- 前記調製粒子の平均円相当径が20μm以上、500μm以下であること、を特徴とする請求項15~22のいずれか1つに記載の調製粒子。
- 前記調製粒子のD10が6.6μm以上であること、を特徴とする請求項15~23のいずれか1つに記載の調製粒子。
- 前記調製粒子の粒度分布偏差割合が0.59以下であること、を特徴とする請求項15~24のいずれか1つに記載の調製粒子。
- 前記調製粒子の安息角が48度以下であること、を特徴とする請求項15~25のいずれか1つに記載の調製粒子。
- 脆性材料微粒子をガス中に分散させたエアロゾルを基材に衝突させて前記脆性材料微粒子の構成材料からなる構造物と前記基材との複合構造物を形成するエアロゾルデポジション法に用いる複合構造物形成システムであって、
請求項15~26のいずれか1つに記載の調製粒子を収容する収容機構と、
前記収容機構から前記調製粒子を供給する供給機構と、
前記供給された調製粒子に向けてガスを導入するガス供給機構と、
前記ガスを混流した前記調製粒子に対して衝撃を加えることで解砕してエアロゾルを形成させるエアロゾル化機構と、
前記エアロゾルを基板上に噴射する吐出口と、を備えることを特徴とする複合構造物形成システム。 - 前記供給した前記調製粒子と、前記ガス供給機構から導入されたガスと、を混合して固気混相流を形成する固気混相流形成機構と、を備えることを特徴とする請求項27記載の複合構造物形成システム。
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