Method for manufacturing substrate with film and powder

Abstract

To provide a method for manufacturing a substrate with a film that can form a film containing a desired component readily and reliably.SOLUTION: A method for manufacturing a substrate with a film includes: a provision step of providing a substrate and powder that is a particulate aggregate; and a film formation step of spraying the powder onto the substrate and forming a film containing a component derived from powder on a surface of a substrate to obtain a substrate with a film. The powder has a bulk density of 0.3 g / cm3 or more. Particle size distribution of particulates of the powder has two or more maximum values.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a film-coated substrate and a powder. [Background technology]

[0002] Aerosol deposition is a known method for forming a film on the surface of a substrate. Patent Document 1 discloses a powder for improving the yield (adhesion rate) during film formation in aerosol deposition. This powder is produced through a process of preparing precursor particles by forming a rare earth ammonium fluoride double salt on the surface of rare earth oxide particles, and a process of heat-treating the precursor particles at a temperature of 350°C or higher and 700°C or lower. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2023-118797 Summary of the Invention [Problem to be solved by the invention]

[0004] However, to obtain the powder described in Patent Document 1, it takes 3 hours of mixing and aging, 16 hours of drying, and 3 hours of heat treatment. Therefore, the time, effort, and cost required for the entire film formation by the aerosol deposition method are enormous. [Means for solving the problem]

[0005] According to one aspect of the present invention, there is provided a method for producing a film-coated substrate. This production method includes a preparation step of preparing a substrate and a powder, which is an aggregate of particles, and a film-forming step of spraying the powder onto the substrate to form a film containing components derived from the powder on the surface of the substrate, thereby obtaining a film-coated substrate. The powder is 0.3 g / cm 3 The particle size distribution of the powder particles has two or more maximum values.

[0006] According to this embodiment, a film containing a desired component can be formed easily and reliably. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 2 is a schematic diagram showing the composition of a powder used to form a film on the surface of a substrate by spraying it onto the surface of the substrate. [Figure 2] FIG. 2 is a schematic diagram showing a cross section of a film-coated substrate formed by spraying powder onto the surface of a substrate. [Figure 3] FIG. 2 is an enlarged schematic view showing a cross section of a film-coated substrate. [Figure 4] FIG. 1 is a schematic view showing a manufacturing apparatus for a film-coated substrate. [Figure 5] FIG. 2 is a block diagram of a manufacturing apparatus for a film-coated substrate. [Figure 6] FIG. 10 is a diagram showing the measurement results of particle size distribution in Example 5. [Figure 7] FIG. 10 is a graph showing the measurement results of particle size distribution in Example 6. DETAILED DESCRIPTION OF THE INVENTION

[0008] [powder] First, powder P according to one embodiment will be described. This powder P is an aggregate of particles, and is used to form a film 3 on the face (surface) 21 of the substrate 2 by spraying it onto the surface of the substrate. Fig. 1 is a schematic diagram showing the structure of the powder used to form a film on the surface of the substrate by spraying it onto the surface of the substrate. Fig. 2 is a schematic diagram showing a cross section of a film-coated substrate formed by spraying powder onto the surface of the substrate.

[0009] The powder P contains two or more types of particles having different average particle sizes. In this embodiment, as shown in Fig. 1, a case will be described as an example in which the powder P contains small diameter particles 34 and large diameter particles 35 having an average particle size larger than that of the small diameter particles 34. The small diameter particles 34 and the large diameter particles 35 may exist as independent particles, or may exist as composite particles 33 containing one or more small diameter particles 34 and / or one or more large diameter particles 35, as shown by the dashed dotted line in Fig. 1.

[0010] The average particle diameters of the small-diameter particles 34 and the large-diameter particles 35 can be determined, for example, as follows. Based on an image of powder P obtained using a scanning electron microscope (SEM), the arithmetic mean of the equivalent-area circle diameters obtained in accordance with JIS Z8827-1:2018 (ISO 13322-1:2014) can be used as the average particle diameters of the small-diameter particles 34 and the large-diameter particles 35. That is, for example, from the small-diameter particles 34 and the large-diameter particles 35 in an image of powder P obtained using an SEM, 50 small-diameter particles 34 and 50 large-diameter particles 35 that are entirely contained in the image are selected, the equivalent-area circle diameter is obtained for each selected particle, and the arithmetic mean of the obtained equivalent-area circle diameters for the small-diameter particles 34 and the large-diameter particles 35 can be used as the average particle diameters of the small-diameter particles 34 and the large-diameter particles 35.

[0011] The powder P according to one embodiment is used in a film forming method such as an aerosol deposition method, an electrostatic fine particle coating method, or a cold spray method. In such a film formation method, a film is formed (deposited) by spraying a powder containing particles toward the surface of a substrate on which the film is to be formed. The particles in the powder sprayed toward the surface of the substrate collide with and deposit on the surface of the substrate, thereby forming a film on the surface. If the collision energy of the particles with the substrate is insufficient, the particles will not adhere to the surface and will not form a film. The higher the kinetic energy of the sprayed particles, the higher the collision energy.

[0012] The powder used in the above-described film-forming method is generally composed of particles having a particle size of 1 μm or less. However, the present inventors have found that when the powder is composed of particles having a particle size of 1 μm or less, even if the composition and average particle size of the particles in the powder are the same, there are cases where a film can be formed and cases where a film cannot be formed. Therefore, the inventors of the present invention have conducted extensive research and found that powders with high loose bulk density are more likely to form films, while powders with low loose bulk density are less likely to form films. The loose bulk density can be measured according to K 7365:1999 (ISO 60:1977) or a method conforming thereto. Specifically, powder is gently poured into a 100 mL container using a funnel without applying any external physical force (tapping, pushing, etc.), and the weight of the powder when it is leveled is divided by the volume (100 mL) to obtain the loose bulk density. In this specification, "bulk density" refers to the loose bulk density.

[0013] Generally, between small particles with an average particle size of approximately 500 nm or less, mutual attractive forces such as van der Waals forces and surface charges act, causing the particles to easily aggregate and form agglomerates. Therefore, powders composed of particles with such small particle sizes contain agglomerates. Here, the higher the degree of aggregation of particles in an agglomerate (hereinafter also referred to as the degree of aggregation), i.e., the more densely the particles in the agglomerate are aggregated, the smaller the volume of voids in the powder, and therefore the higher the bulk density of the powder. Furthermore, the lower the degree of aggregation, i.e., the looser the particles in the agglomerate are aggregated, the lower the bulk density of the powder tends to be.

[0014] The degree of aggregation is thought to correlate with the average pore size of the powder (aggregate). The smaller the average pore size, the smaller the gaps between particles in the aggregate, and therefore the higher the degree of aggregation. The larger the average pore size, the larger the gaps between particles in the aggregate, and therefore the lower the degree of aggregation. The average pore size is the 50% diameter in the volume cumulative pore size distribution of the aggregate, measured using a pore size distribution measuring device (e.g., a mercury porosimeter).

[0015] Therefore, it is considered that when the bulk density of the powder is large, the particles in the powder sprayed onto the substrate remain in an agglomerated state and collide with the substrate with high collision energy, making it easier to form a film.On the other hand, when the bulk density of the powder is small, the particles in the powder sprayed onto the substrate cannot maintain an agglomerated state and break up, colliding with the substrate with dispersed collision energy, making it difficult to form a film.

[0016] However, simply increasing the degree of aggregation of particles (aggregates) in order to maintain high collision energy of particles in powder poses a problem. First, the powders are composed of particles with a high degree of aggregation, i.e., a high bulk density, and the types of powders available commercially are limited. Therefore, the range of powder choices is narrow. In addition, to produce powders with a high bulk density, for example, it is necessary to aggregate the powder in a liquid phase over a long period of time, which requires a lot of time, effort, and cost to prepare the powder. Furthermore, film formation methods such as aerosol deposition are known to have low yields (adhesion rates) during film formation, which can lead to enormous time and costs required for the entire film formation process.

[0017] Second, it is generally known that agglomerates can cause a decrease in deposition rate and film quality in film formation methods such as aerosol deposition. Furthermore, it is known that agglomerates can be an obstacle when aerosolizing powder in aerosol deposition. Therefore, when particles with a high degree of agglomeration (aggregates) are used, problems such as a decrease in the quality of the formed film may occur.

[0018] Therefore, the inventors decided to increase the bulk density of the powder P as a whole by adding large diameter particles 35 to the small diameter particles 34. When such powder P is sprayed onto the surface 21 of the substrate 2, a film 3 as shown in FIG. 2 can be formed. As a result, even in cases where the small diameter particles 34 alone cannot form a film 3 due to the low degree of aggregation of the small diameter particles 34, that is, the low bulk density of the small diameter particles 34, by configuring the powder P as described above, the film 3 can be formed. This is thought to be because the large diameter particles 35, which have a large average particle size and large collision energy, can impart collision energy to the entire powder P including the small diameter particles 34. In other words, even if the degree of aggregation of the small diameter particles 34 is low, by adding the large diameter particles 35 and increasing the bulk density of the entire powder P, stable film formation can be achieved when the powder P is sprayed onto the substrate 2.

[0019] The bulk density of the powder P is preferably 0.3 g / cm 3 More preferably, it is about 0.4 g / cm 3 More preferably, it is about 0.5 g / cm 3 In this manner, by sufficiently increasing the bulk density of the powder P, the powder P can secure sufficient collision energy to form the film 3. The bulk density of the powder P is preferably 3 g / cm 3 More preferably, it is about 2 g / cm or less. 3 It is preferably about 1 g / cm or less. 3 or less. This gives the powder P appropriate fluidity, making it easy to spray the powder P onto the substrate 2. Furthermore, because the degree of aggregation of the small-diameter particles 34 in the powder P is not too high, the small-diameter particles 34 and the large-diameter particles 35 can be easily mixed with a low load when producing the powder P. This allows for a reduction in the energy consumption of the device used when mixing the small-diameter particles 34 and the large-diameter particles 35. That is, the bulk density of the powder P is preferably 0.3 g / cm 3 More than 3g / cm 3 More preferably, it is about 0.4 g / cm or less. 3 More than 2g / cm 3It is preferably about 0.5 g / cm or less. 3 More than 1g / cm 3 This embodiment allows for more reliable film formation on the substrate 2. Of course, the upper and lower limits of the bulk density of the powder P can be arbitrarily combined. For example, the bulk density of the powder is 0.5 g / cm 3 More than 3g / cm 3 It may be the following:

[0020] The mass and volume of the small-diameter particles 34 contained in the powder P are smaller than the mass and volume of the large-diameter particles 35. Specifically, the ratio of the total mass of the small-diameter particles 34 to the total mass of the powder P is preferably about 0.5 or less, more preferably about 0.4 or less, and even more preferably about 0.3 or less. In this case, the total mass of the large-diameter particles 35 is relatively large relative to the total mass of the powder P, making it easier to impart sufficient collision energy to the entire powder P including the small-diameter particles 34, thereby further improving the film formation rate. Furthermore, in a film formation method such as an aerosol deposition method with a low yield (adhesion rate), the amount of small-diameter particles 34 used, which increases production costs, can be reduced, and the production cost of the entire film-coated substrate 1 can be reduced. In this specification, the film formation rate means the ratio of the area on the surface 21 of the substrate 2 on which the film is actually formed to the area on which the film is to be formed.

[0021] The ratio of the total mass of the small-diameter particles 34 to the total mass of the powder P is preferably about 0.01 or more, more preferably about 0.03 or more, and even more preferably about 0.1 or more. In this case, a sufficient amount of the small-diameter particles 34 can be secured in the powder P, and the desired amount of the small-diameter particles 34 can be incorporated into the film 3. This makes it easy to form a dense and uniform film 3, thereby improving the mechanical strength of the entire film 3. Furthermore, because the entire film 3 can be easily manufactured uniformly in terms of components and structure, the chemical and physical properties of the film 3 can be easily predicted and controlled. That is, the ratio of the total mass of the small diameter particles 34 to the total mass of the powder P is preferably about 0.01 to 0.5, more preferably about 0.03 to 0.4, and even more preferably about 0.1 to 0.3.

[0022] The abundance ratio (weight ratio, volume ratio) of the small diameter particles 34 in the powder P may be determined, for example, by sieving the powder P and determining the weight after removing the large diameter particles 35. Alternatively, it may be calculated based on the proportion of the number of small diameter particles 34 in an image of the powder P acquired by a scanning electron microscope (SEM). The small diameter particles 34 and the large diameter particles 35 in the SEM image can be distinguished by their average particle diameters. Furthermore, when the aspect ratios of the small diameter particles 34 and the large diameter particles 35 are different, they may also be distinguished by the aspect ratios. Furthermore, depending on the properties of the small diameter particles 34 and the large diameter particles 35, the abundance ratio of the small diameter particles 34 can be obtained by a more accurate method described later.

[0023] The average particle size of the small-diameter particles 34 contained in the powder P is preferably about 10 nm or more and 700 nm or less, more preferably about 30 nm or more and 600 nm or less, and even more preferably about 40 nm or more and 550 nm or less. As a result, the average particle size of the small-diameter particles 34 is sufficiently small, so that the outermost surface 32 of the film 3 formed by spraying the powder P is unlikely to become significantly uneven. Therefore, objects passing near the outermost surface 32 are unlikely to interfere with the outermost surface 32, making it easy to prevent deterioration of the outermost surface 32. In addition, it is easy to form a dense and uniform film 3. Furthermore, since the average particle size of the small diameter particles 34 is sufficiently large, the small diameter particles 34 themselves have a certain degree of collision energy when the powder P is sprayed onto the surface 21 of the substrate 2. Therefore, the small diameter particles 34 easily adhere to the surface 21 of the substrate 2, which can improve the yield (adhesion rate) of film formation.

[0024] Because the small diameter particles 34 have a small average particle size of approximately 500 nm or less, they are likely to form aggregates 34a as shown by the dotted lines in Fig. 1, as described above. In other words, at least a portion of the small diameter particles 34 exist as aggregates 34a formed by aggregation of the small diameter particles 34. The average pore size of the aggregates 34a is preferably approximately 10 nm or more and 1000 nm or less, more preferably approximately 20 nm or more and 500 nm or less, and even more preferably approximately 50 nm or more and 300 nm or less. With this configuration, the average pore diameter of the aggregates 34a is not too small, so when preparing the powder P by mixing the small-diameter particles 34 and the large-diameter particles 35, it is easy to uniformly mix the two particles. As a result, when the powder P is sprayed onto the surface 21 of the substrate 2, the collision energy for forming the film 3 is less likely to be uneven, and the film 3 can be formed more reliably. It is also possible to form a homogeneous film 3. Furthermore, the manufacturing cost of the small-diameter particles 34 can be reduced, thereby reducing the manufacturing cost of the entire film-coated substrate 1. In addition, since the degree of aggregation of the aggregates 34a is somewhat high, the small-diameter particles 34 themselves as the aggregates 34a can be provided with a certain degree of collision energy, making it easy to improve the film formation rate.

[0025] Here, the bulk density of the small diameter particles 34 is preferably 0.02 g / cm 3 More than 1g / cm 3 More preferably, it is about 0.05 g / cm or less. 3 More than 0.8g / cm 3 or less, and more preferably 0.1 g / cm 3 More than 0.7g / cm 3 When the small diameter particles 34 have such a bulk density, it is easy to set the average pore size of the aggregates 34a as described above.

[0026] The ratio of the average diameter of the aggregates 34a to the average diameter of the small diameter particles 34 is preferably about 10 or more and 10,000 or less, more preferably about 50 or more and 5,000 or less, and even more preferably about 100 or more and 2,000 or less. As a result, the number of small-diameter particles 34 contained in the aggregates 34a is not too large, so when the powder P is prepared by mixing the small-diameter particles 34 and the large-diameter particles 35, the small-diameter particles 34 are easily dispersed throughout the powder P. This also reduces the manufacturing cost of the small-diameter particles 34, thereby reducing the manufacturing cost of the entire film-coated substrate 1. Furthermore, since the aggregates 34a contain a certain number of small-diameter particles 34, the mass of the aggregates 34a is high. Therefore, the small-diameter particles 34 themselves have a certain amount of collision energy, which makes it easy to improve the film formation rate. The average diameter of the aggregates 34 a can be determined in the same manner as the average diameters of the small diameter particles 34 and the large diameter particles 35 .

[0027] The average particle size of the large diameter particles 35 contained in the powder P is preferably about 500 nm or more and 50 μm or less, more preferably about 700 nm or more and 30 μm or less, and even more preferably about 900 nm or more and 10 μm or less. In this case, since the average particle size of the large diameter particles 35 is sufficiently large, sufficient collision energy can be imparted to the entire powder P including the small diameter particles 34, thereby improving the film formation rate. Furthermore, since the average particle size of the large diameter particles 35 is not too large, the collision energy imparted to the entire powder P including the small diameter particles 34 is appropriate, thereby preventing the large diameter particles 35 from damaging the film 3 being formed.

[0028] The powder P, which is a mixture of small-diameter particles 34 and large-diameter particles 35 having the average particle diameters described above, preferably has a particle size distribution with two maximum values. In this specification, the term "particle size distribution" simply refers to the frequency distribution of particle sizes. Since the powder P may contain particles other than the small-diameter particles 34 and the large-diameter particles 35, the particle size distribution of the particles of the powder P preferably has two or more maximum values. In this way, the difference in average particle size between the small-diameter particles 34 and the large-diameter particles 35 is sufficiently large, and the small average particle size of the small-diameter particles 34 makes it possible to form a uniform, homogeneous, and dense film 3, while the large average particle size of the large-diameter particles 35 makes it easy to impart sufficient and appropriate collision energy to the entire powder P. In other words, the powder P preferably contains two or more types of particles that exhibit different particle size distributions. The maximum values ​​of these different particle size distributions correspond to two or more maximum values ​​of the powder P, respectively. Here, the particle size distribution may be based on either the number or volume, but in this specification, the volume-based particle size frequency distribution is used.

[0029] Furthermore, the powder P satisfies specific conditions. That is, when the cumulative 10% diameter D10 and the cumulative 90% diameter D90 are defined as the volume-based particle size distribution of all particles, including the small-diameter particles 34 and the large-diameter particles 35, the powder P has a D10 of approximately 0.05 μm to 1.0 μm and a D90 of approximately 0.8 μm to 5 μm. It is preferable that the D10 be approximately 0.1 μm to 0.8 μm and a D90 be approximately 1 μm to 4 μm. It is even more preferable that the D10 be approximately 0.2 μm to 0.7 μm and a D90 be approximately 1 μm to 3 μm. These values ​​are examples of particularly preferred ranges and can be combined with each other. For example, the D10 may be approximately 0.05 μm to 0.7 μm and a D90 be approximately 0.8 μm to 5 μm for all particles. By satisfying these conditions, the mixing balance between the small diameter particles 34 and the large diameter particles 35 and the relationship between the particle diameters of the small diameter particles 34 and the large diameter particles 35 can be appropriately set, thereby more reliably achieving the above-mentioned effects. That is, the particles constituting the powder P have a broad particle size distribution.

[0030] This particle size distribution can be measured, for example, by a particle size distribution analyzer using a laser diffraction / scattering method. Based on the obtained particle size distribution, the particle size at 10% cumulative from the smallest particle size can be calculated as D10, and the particle size at 90% cumulative from the smallest particle size as D90. Another method for measuring the particle size distribution may be to use, for example, a method in which an image of the powder P obtained using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) is read into image analysis software, and particles in the image are automatically or manually recognized to calculate the particle size distribution. In this case, 50 or more particles are used to calculate the particle size distribution. From the viewpoint of reproducibility, it is more preferable to measure the particle size distribution by a laser diffraction / scattering method.

[0031] The large diameter particles 35 contained in the powder P may differ from the small diameter particles 34 in at least one of chemical composition and crystal structure. That is, the powder contains two or more types of particles that differ from each other in at least one of chemical composition and crystal structure. With this configuration, the film 3 formed by spraying the powder P can be formed as a composite film having multiple functions.

[0032] As described above, by configuring the powder P to include the small diameter particles 34 and the large diameter particles 35, the powder P as a whole can have sufficient and appropriate collision energy. Therefore, even if any material is used as the constituent material of the small diameter particles 34 and the large diameter particles 35, the film 3 can be formed on the surface 21 of the substrate 2.

[0033] Furthermore, when the constituent materials of the small-diameter particles 34 and the large-diameter particles 35 are changed, conventionally, various conditions for spraying the powder had to be changed for each constituent material. However, by satisfying the above-mentioned conditions, the large-diameter particles 35 can impart sufficient collision energy to the entire powder P. Therefore, when spraying the powder P onto the substrate 2, the same conditions can be used for powder P of different constituent materials. Examples of such conditions include, in the aerosol deposition method, the pressure inside the chamber, the pressure inside the aerosol generator, the nozzle size, the type of carrier gas, the aerosol flow rate, the aerosol spray speed, and the distance between the nozzle and the substrate 2.

[0034] The small particles 34 and the large particles 35 can be made of a wide variety of materials, including, for example, ceramics, aluminosilicates (e.g., zeolites), resins, metals, metal-organic frameworks (MOFs), graphene, chitosan, etc. In particular, the powder P is preferably made of an oxide or nitride. By using these materials, it is easy to form a film 3 with high mechanical strength at low cost.

[0035] Ceramics include, for example, monooxides such as alumina (Al2O3), zirconia (ZrO2), titania (TiO2), and yttria (Y2O3), mullite (3Al2O3·2SiO2), and ferrite (M 2+ Oxides include double oxides such as O2·Fe2O3, barium titanate (BaTiO3), argon (Al2O3·ZrO2), and yttria-stabilized zirconia (Y2O3·ZrO2); nitrides such as aluminum nitride (AlN), titanium nitride (TiN), silicon nitride (Si3N3), boron nitride (BN), and gallium nitride (GaN); oxynitrides such as sialon (Si3N4·Al2O3); carbides such as silicon carbide (SiC), titanium carbide (TiC), and boron carbide (B4C); borides such as titanium boride (TiB2) and zirconium boride (ZrB6); and silicides such as barium silicide (BaSi2).

[0036] As the zeolite, for example, zeolites having a crystal structure such as LTA (A type), FAU (X type, Y type), BEA (beta type), MFI (ZSM-5 type), FER (ferrierite type), MOR (mordenite type), LTL (L type) can be used. Also, depending on the desired properties of the membrane 3, a zeolite having a maximum number of ring members of, for example, 6 to 30 can be selected.

[0037] The resin may be a thermosetting resin or a thermoplastic resin, and examples of the resin include polypropylene, polyethylene, polyurethane, polystyrene, polyamide, polyimide, and polytetrafluoroethylene.

[0038] In particular, it is preferable that the constituent material of at least one of the small diameter particles 34 and the large diameter particles 35 is zeolite, which can impart properties such as adsorption performance, molecular sieving action, ion exchange action, acidity, and catalytic action to the membrane 3. Of course, the constituent materials of the small diameter particles 34 and the large diameter particles 35 are not limited to the above-mentioned materials. The constituent materials of the small diameter particles 34 and the large diameter particles 35 may be different from each other, or at least one of the small diameter particles 34 and the large diameter particles 35 may be made of a plurality of constituent materials. The small diameter particles 34 and the large diameter particles 35 may have the same chemical composition and crystal structure. By configuring them in this way, a more uniform film 3 can be manufactured.

[0039] When the small particles 34 and the large particles 35 have different chemical compositions, the difference can be detected by, for example, elemental analysis using a scanning electron microscope (SEM)-energy dispersive X-ray spectroscopy (EDX). Furthermore, by superimposing an SEM image of the powder P with an image (element mapping image) in which colored areas are detected for one or more substances contained only in the small particles 34 or the large particles 35 in the powder P in the same field of view as the SEM image, the small particles 34 and the large particles 35 can be distinguished. Then, the abundance ratio (number ratio, volume ratio) of the small particles 34 and the large particles 35 can be obtained based on the colors of the detected areas in the superimposed image.

[0040] Furthermore, when the crystal structures of the small particles 34 and the large particles 35 are different, the difference can be detected by scanning electron microscope (SEM)-electron backscattered diffraction (EBSD) measurement. By superimposing an image (crystal structure (orientation) mapping image) on an SEM image of powder P, in which colored areas of the powder P in the same field of view as the SEM image show where the crystal structure of at least one of the small particles 34 and the large particles 35 is detected, the small particles 34 and the large particles 35 can be distinguished. Then, based on the color of the detected areas in the superimposed image, the abundance ratio (number ratio, volume ratio) of the small particles 34 and the large particles 35 can be obtained.

[0041] A method for obtaining the abundance ratio (volume ratio) of the small-diameter particles 34 and the large-diameter particles 35 in the powder P with greater accuracy is described below. When the small-diameter particles 34 and the large-diameter particles 35 have different crystal structures, their abundance ratio (volume ratio) can be measured with greater accuracy, for example, by combining a scanning electron microscope (SEM)-energy dispersive X-ray spectroscopy (EDX) method with X-ray diffraction (XRD) measurement. Phase identification of the XRD measurement results is performed based on elemental analysis of the powder P using the SEM-EDX method. By repeatedly performing this phase identification, more accurate crystal structure peaks can be obtained. Then, the crystal structure specific to the small-diameter particles 34 and the crystal structure specific to the large-diameter particles 35 are detected. For example, the abundance ratio (volume ratio) of the small-diameter particles 34 and the large-diameter particles 35 in the powder P can be obtained by calculating the areas of the crystal structure peaks corresponding to the small-diameter particles 34 and the large-diameter particles 35, respectively.

[0042] Even if the crystal structures of the small diameter particles 34 and the large diameter particles 35 are unknown, if they have different chemical compositions, the crystal structures of the small diameter particles 34 and the large diameter particles 35 can be determined by specifying elements and performing phase identification based on elemental analysis by SEM-EDX. Then, by calculating the areas of the peaks of the crystal structures corresponding to the small diameter particles 34 and the large diameter particles 35 based on the determination results, the abundance ratio (volume ratio) of the small diameter particles 34 to the large diameter particles 35 in the powder P can be obtained.

[0043] Furthermore, when the crystal structures of the small diameter particles 34 and the large diameter particles 35 are unknown and have the same chemical composition, it is advisable to determine whether the peak of the crystal structure comes from the small diameter particles 34 or the large diameter particles 35 using the following method. First, referring to an SEM image of the powder P, the small diameter particles 34 and the large diameter particles 35 are counted while distinguishing between the small diameter particles 34 and the large diameter particles 35 based on the difference in particle size or aspect ratio, and an approximate estimate of the abundance ratio (volume ratio) is obtained based on the number of small diameter particles 34 and the average particle size. Alternatively, the approximate estimate of the abundance ratio (volume ratio) may be obtained based on the area ratio occupied by the small diameter particles 34 and the large diameter particles 35 in the SEM image of the powder P. This approximate abundance ratio (volume ratio) correlates with the ratio of the peak areas of each crystal structure in the XRD measurement results obtained by phase identification based on elemental analysis using the SEM-EDX method. Therefore, by comparing the approximate abundance ratio (volume ratio) with the peak areas of each crystal structure, it is possible to determine whether each peak originates from small-diameter particles 34 or large-diameter particles 35.

[0044] [Substrate with film] Next, a film-coated substrate according to one embodiment will be described. As shown in FIG. 2, the film-coated substrate 1 includes a substrate 2 and a film 3 formed on a surface 21 of the substrate 2. The application of the film-coated substrate 1 is not particularly limited, and it can be used for various purposes, such as integrated circuits, displays, anti-reflection coated glass, and piezoelectric elements.

[0045] The substrate 2 supports the membrane 3. The shape and material of the substrate 2 are not particularly limited, and various embodiments can be adopted depending on the application of the membrane-coated substrate 1. The external shape of the substrate 2 may be, for example, a rectangular parallelepiped, a square pillar, a cylinder, a rectangular pillar, a flat plate, a circular tube, a square tube, a film, etc. The microstructure of the substrate 2 may be, for example, a shape without pores, or a shape with pores such as a porous shape, a honeycomb shape, a mesh shape, a sponge shape, or a monolith shape. The shape of the surface 21 of the substrate 2 on which the film 3 is formed may be, for example, spherical, curved, flat, or uneven, depending on the shape of the substrate 2.

[0046] Examples of materials for the substrate 2 include ceramic materials, metal materials, glass materials, carbon materials, and resin materials. Examples of ceramic materials include alumina, mullite, zirconia, titania, yttria, arugulus, yttria-stabilized zirconia, silicon nitride, gallium nitride, sialon, and silicon carbide. Examples of metal materials include aluminum or aluminum alloys, iron, stainless steel, titanium, and nickel. The resin material may be a thermosetting resin or a thermoplastic resin. Examples of resins include polypropylene, polyethylene, polyurethane, polystyrene, polyamide, polyimide, and polytetrafluoroethylene.

[0047] A film 3 is provided on a surface 21 of the substrate 2. Fig. 3 is a schematic diagram showing an enlarged cross section of the film-coated substrate. The film 3 contains at least a component 34' derived from small diameter particles. The component 34' derived from small diameter particles is a component derived from the small diameter particles 34 contained in the powder P. The component 34' derived from small diameter particles includes at least one of the small diameter particles 34 themselves, components formed by deformation of the small diameter particles 34, and small pieces detached from the small diameter particles 34. In other words, the film 3 is formed by at least a portion of one or more types of particles out of two or more types of particles being attached to the face (surface) 21 in a deformed state.

[0048] As shown in FIG. 3 , the component 34′ derived from small-diameter particles contained in the film 3 is greater than the component 35′ derived from large-diameter particles. Specifically, the proportion of the component 34′ derived from small-diameter particles in the film 3 is preferably about 50% by volume or more, more preferably about 75% by volume or more, and even more preferably about 90% by volume or more. In this way, the component 34′ derived from small-diameter particles is contained in a large amount, which makes the film 3 denser and improves the mechanical strength of the film 3. In addition, the unevenness of the outermost surface 32 of the film 3 is likely to be smaller, which reduces snagging, friction, and the like when an object passes near the outermost surface 32, making it easier to prevent damage to the film 3. The proportion of the components 34' derived from small-diameter particles among the components contained in the film 3 may be 100% by volume. In this case, the above-mentioned effects can be more significantly exhibited. In addition, the entire film 3 can be easily manufactured to be homogeneous in terms of components and structure, and the chemical and physical characteristics of the film 3 can be easily predicted and controlled.

[0049] 3, the film 3 contains both a component 34' derived from small-diameter particles and a component 35' derived from large-diameter particles. That is, the large-diameter particles 35 act to impart collision energy to the entire powder P (small-diameter particles 34), and may also function as a constituent component of the film 3. In other words, one or more types of particles among the two or more types of particles may act to impart collision energy to the powder P, and the film 3 may contain components derived from both of the two or more types of particles. The component 35' derived from large diameter particles is a component derived from the large diameter particles 35 contained in the powder P. The component 35' derived from large diameter particles includes at least one of the large diameter particles 35 themselves, components formed by deformation (change in shape) of the large diameter particles 35, and small pieces detached from the large diameter particles 35. Of these, the component 35' derived from large diameter particles preferably includes those formed by small pieces detached from the large diameter particles 35 being incorporated into the film 3. As a result, since the small pieces are incorporated into the film 3 rather than the large diameter particles 35 themselves, the difference in average particle size between the components contained in the film 3 (component 34' derived from small diameter particles and the small pieces) becomes smaller. This makes the film 3 more homogeneous overall.

[0050] In one embodiment, the membrane 3 can be manufactured to intentionally contain a component 35' derived from large-diameter particles. For example, the membrane 3 may be configured so that the proportion of the component 35' derived from large-diameter particles is approximately 10% by volume or more, approximately 30% by volume or more, or approximately 50% by volume or more. In this case, the unevenness of the outermost surface 32 of the membrane 3 can be easily increased, thereby ensuring an appropriately large contact area between the outermost surface 32 and an object (particularly, a liquid or gas) passing near the outermost surface 32. This is advantageous, for example, when the membrane 3 functions as a separation membrane. Furthermore, as will be described later, since small-diameter particles and large-diameter particles differ in at least one of chemical composition and crystalline structure, the membrane 3 can be configured as a composite membrane having a plurality of different functions.

[0051] The proportion of components 34' derived from small diameter particles in film 3 is greater than the proportion of small diameter particles 34 in powder P. This is thought to be because the collision energy of large diameter particles 35 in powder P is too great, causing the large diameter particles 35 to be repelled in the process of colliding with substrate 2. For this reason, it is expected that most of the large diameter particles 35 will not be able to adhere to substrate 2 and will not be able to form film 3. In this way, small-diameter particle-derived components 34' derived from small-diameter particles 34 are preferentially incorporated into film 3. In other words, the amount of small-diameter particles 34 that is incorporated into film 3 can be increased while saving effort, time, and cost in preparing small-diameter particles 34 during the preparation process of powder P. This makes it possible to easily manufacture a dense film 3 with minimal irregularities.

[0052] Specifically, the proportion (%) of the component 34' derived from small diameter particles in the film 3 is preferably about 2 to 20 times, more preferably about 3 to 15 times, and even more preferably about 5 to 10 times, the proportion (%) of the small diameter particles 34 in the powder P. By adjusting the ratio of the small diameter particles 34 to the large diameter particles 35 contained in the powder P, the ratio of the component 34' derived from small diameter particles to the component 35' derived from large diameter particles contained in the film 3 can be changed (controlled). Specifically, the proportion of the component 34' derived from small diameter particles in the powder P increases as the proportion of the small diameter particles 34 contained in the powder P increases. Therefore, a film 3 containing the component 34' derived from small diameter particles and the component 35' derived from large diameter particles in a desired ratio can be produced.

[0053] The proportion of the component 34' derived from small diameter particles (or the component 35' derived from large diameter particles) in the film 3 can be measured, for example, by SEM-EDX when the chemical compositions of the small diameter particles 34 and the large diameter particles 35 are different, or by SEM-EBSD when the crystal structures are different. When measuring by these methods, the abundance ratio (volume ratio) of each component in the film 3 can be calculated by calculating the abundance ratio (area ratio) of the component 34' derived from small diameter particles or the component 35' derived from large diameter particles contained in the field of view of an arbitrary cross section of the film 3.

[0054] Furthermore, to obtain the abundance ratio (volume ratio) of the component 34' derived from small diameter particles and the component 35' derived from large diameter particles in the film 3 with even greater precision, it is advisable to combine the SEM-EDX method with XRD measurement, as in obtaining the abundance ratio (volume ratio) of the small diameter particles 34 and the large diameter particles 35 in the powder P. For elemental analysis using the SEM-EDX method, it is sufficient to observe any cross section of the film 3, and for XRD measurement, it is sufficient to scrape off any location of the film 3 to prepare a measurement sample.

[0055] In one embodiment, the film 3 is formed by attaching the small diameter particles 34 and the large diameter particles 35 in a state where at least some of the particles have changed shape to the surface 21 (surface) of the substrate 2. For example, as shown in FIG. 3 , the components 34′ derived from the small diameter particles and the components 35′ derived from the large diameter particles are attached to the surface 21 of the substrate 2 in a state where the small diameter particles 34 and the large diameter particles 35 are crushed in the thickness direction of the film 3. This is thought to be because the powder P collides with the surface 21 of the substrate 2 with a collision energy high enough to deform (change the shape of) at least some of the small diameter particles 34 and large diameter particles 35, and moderate enough to allow the particles to adhere to the surface 21 of the substrate 2 and form the film 3. In this case, the film 3 can be firmly adhered to the surface 21 of the substrate 2, and therefore the peel strength of the film 3 to the surface 21 can be improved.

[0056] The porosity of the membrane 3 is preferably about 30% or less, more preferably about 20% or less, and even more preferably about 10% or less. By configuring the porosity of the membrane 3 to be low in this way, the mechanical strength of the membrane 3 can be improved. Note that the porosity of the membrane 3 may be intentionally increased in order to impart permeability to the membrane 3. In this case, the porosity should be set in accordance with the size of the substance to be permeated. Furthermore, the film 3 may be provided on at least one surface 21 of the substrate 2, but may also be provided on two or more surfaces or all surfaces of the substrate 2 depending on the application of the film-coated substrate 1. The porosity of the membrane 3 can be calculated based on the measurement results of the average pore size (e.g., volume cumulative pore size distribution) measured by a pore size distribution measurement device (e.g., a mercury porosimeter) and the results of the cell volume used in the measurement.

[0057] [Manufacturing equipment] Next, a description will be given of a manufacturing apparatus for a film-coated substrate for manufacturing the film-coated substrate 1. In this specification, a case where the film 3 is formed on the entire surface 21 of the flat plate-shaped substrate 2 will be described as an example.

[0058] Incidentally, the program for realizing the software appearing in one embodiment may be provided as a non-transitory computer-readable medium, or may be provided so that it can be downloaded from an external server, or may be provided so that the program is started on an external computer and its functions are realized on a client terminal (so-called cloud computing).

[0059] Furthermore, various information processing according to an embodiment may realize input and output corresponding to the input. Here, the form of information referenced in such information processing (hereinafter referred to as reference information) is not limited as long as an output is obtained as a result of the input. The reference information may be, for example, rule-based information such as a database, a lookup table, or a predetermined function (including a decision formula such as a regression formula constructed using a statistical method), a trained model that has previously trained the correlation between input and output, or a large-scale language model that can output a desired result by inputting a prompt.

[0060] In one embodiment, a "unit" may include, for example, a combination of hardware resources implemented by a circuit in the broad sense and software information processing that can be specifically realized by these hardware resources. In one embodiment, various information is handled, and this information is represented, for example, by physical values ​​of signal values ​​representing voltage and current, high and low signal values ​​as a binary bit set consisting of 0 or 1, or quantum superposition (so-called quantum bits), and communication and calculations can be performed on a circuit in the broad sense.

[0061] Furthermore, a circuit in the broad sense is a circuit realized by at least an appropriate combination of a circuit, circuitry, processor, memory, etc. The processor may be a general-purpose processor or a dedicated circuit. That is, it includes an application specific integrated circuit (ASIC), a programmable logic device (e.g., a simple programmable logic device (SPLD), a complex programmable logic device (CPLD), and a field programmable gate array (FPGA)), etc.

[0062] Fig. 4 is a schematic diagram showing an apparatus for producing a film-coated substrate, and Fig. 5 is a block diagram of the apparatus for producing a film-coated substrate. The film-coated substrate manufacturing apparatus 4 shown in FIG. 4 is an apparatus used to manufacture the film-coated substrate 1. The film-coated substrate manufacturing apparatus 4 includes a chamber 5, a support mechanism 6 that supports a flat substrate 2 within the chamber 5, and a spray mechanism 7 that sprays powder P containing small-diameter particles 34 and large-diameter particles 35 toward the substrate 2.

[0063] The support mechanism 6 has a stage (XY stage) 61 that supports the flat substrate 2 from above, a movement mechanism 63 that moves the stage 61 in the horizontal direction and the depth direction of the paper, and an arm 62 that connects the movement mechanism 63 to the stage 61. The substrate 2 is fixed to a support surface 611 of the stage 61 by, for example, adhesive tape.

[0064] The movement mechanism 63 is a mechanism for generating a linear motion in the support mechanism 6. The movement mechanism 63 has, for example, a motor and a cam mechanism that converts rotation from the motor into linear motion. The moving mechanism 63 transmits linear kinetic energy to the arm 62 and the stage 61. As a result, the flat substrate 2 is moved in its horizontal and depth directions, i.e., in directions parallel to the surface 21 (in-plane directions), while the substrate is supported on the stage 61. With this configuration, it is easy to form the film 3 uniformly and homogeneously over the entire surface 21 of the substrate 2.

[0065] The moving speed of the substrate 2 is preferably about 0.1 cm / sec to 30 cm / sec, more preferably about 0.5 cm / sec to 20 cm / sec, and even more preferably about 1 cm / sec to 15 cm / sec. By moving the substrate 2 at such a moving speed, it is easier to improve the uniformity and homogeneity of the film 3 along the longitudinal direction of the substrate 2.

[0066] The ejection mechanism 7 has a nozzle 71 that ejects the powder P. The nozzle 71 faces the support surface 611 of the stage 61. In the ejection mechanism 7, a nozzle 71 is connected to a gas cylinder 72 via a transfer pipe 73. A mass flow controller 74, an aerosol generator 75, a disintegrator 76, and a classifier 77 are provided in this order from the gas cylinder 72 side along the transfer pipe 73.

[0067] In the film-coated substrate manufacturing apparatus 4, a carrier gas is supplied from a gas cylinder 72 to a carrier pipe 73, and the flow rate of the carrier gas is adjusted by a mass flow controller 74. The aerosol generator 75 sprays powder P to be sprayed onto the surface 21 of the substrate 2 at a spray speed of at least subsonic but not exceeding supersonic speed. Furthermore, a pump 81 is connected to the chamber 5 as a pressure reducing mechanism 8, and the pressure inside the chamber 5 can be adjusted.

[0068] The film-coated substrate manufacturing apparatus 4 further includes a control means 9. The control means 9 is configured to control the operation of the apparatus 4 for producing a film-coated substrate. 4, the control means 9 is electrically connected to the movement mechanism 63 and the pump 81. Although not shown, the control means 9 is also electrically connected to an operation unit, a display unit, a power supply unit, and the like. The control means 9 includes a calculation unit 91 and a storage unit 92 built therein.

[0069] The calculation unit 91 is configured with, for example, a CPU (Central Processing Unit), an MPU (Micro Processing Unit), etc. The calculation unit 91 realizes various functions related to the film-coated substrate manufacturing apparatus 4 by reading out predetermined programs stored in the storage unit 92. That is, information processing by the software stored in the storage unit 92 is specifically realized by the calculation unit 91. The calculation unit 91 is not limited to being a single unit, and multiple calculation units 91 may be provided for each function. A combination of these may also be used. In particular, a calculation unit 91 for controlling the movement of the stage 61 by the movement mechanism 63 in the horizontal direction of the page in FIG. 4 may be provided, separate from the calculation unit 91 related to the movement of the stage 61 by the movement mechanism 63 in the depth direction of the page in FIG. 4.

[0070] The memory unit 92 stores various pieces of information controlled as described above. This can be implemented, for example, as a storage device such as a solid state drive (SSD) that stores various programs related to the film-coated substrate manufacturing apparatus 4 executed by the calculation unit 91, or as a memory such as a random access memory (RAM) that stores temporarily required information (arguments, arrays, etc.) related to the program calculations. Alternatively, it may be a combination of these. The storage unit 92 also stores various programs, variables, and the like related to the apparatus 4 for manufacturing a film-coated substrate, which are executed by the calculation unit 91.

[0071] The apparatus 4 for manufacturing a film-coated substrate is not limited to the configuration described above, and various omissions, substitutions, and modifications can be made. For example, the stage 61 may be further configured to move in one or more directions. Examples of the one or more directions include rotation or tilt about the direction perpendicular to the plane of the page (Z-axis). The base material 2 may be tubular. In this case, a support rod extending horizontally to the plane of the page in FIG. 4 may be inserted into the inner surface of the base material 2, and the support mechanism 6 may include a motor for rotating the support rod. Furthermore, although the case where the film-coated substrate 1 is manufactured by fixing the nozzle 71 of the film-coated substrate manufacturing apparatus 4 and moving the substrate 2 has been described, the film-coated substrate 1 may also be manufactured by fixing the substrate 2 and moving the nozzle 71 of the film-coated substrate manufacturing apparatus 4.

[0072] [Method of manufacturing film-coated substrate] Next, a method for producing the film-coated substrate 1 will be described. The method for producing the film-coated substrate 1 can suitably use a film-coated substrate production apparatus 4. In the following, the explanation will be given assuming that the film-coated substrate 1 is produced using the film-coated substrate production apparatus 4. This method for manufacturing a film-coated substrate 1 includes a preparation step and a film-forming step. In the preparation step, a substrate 2 and powder P are prepared, and in the film-forming step, the powder P is sprayed onto the substrate 2 to form a film 3 containing components derived from the powder (components 34' derived from small-diameter particles and / or components 35' derived from large-diameter particles) on the surface of the substrate 2, thereby obtaining a film-coated substrate 1. Of these steps, the film-forming step is performed by spraying the powder P from a spraying mechanism 7 toward the substrate 2 in a state in which the substrate 2 is supported by a support mechanism 6 within a chamber 5.

[0073] (preparation process) First, a powder P, which is an aggregate of particles including small diameter particles 34 and large diameter particles having an average particle size larger than that of the small diameter particles 34, and a substrate 2 are prepared. The small diameter particles 34 and the large diameter particles 35 may differ in at least one of the chemical composition and the crystalline structure, or may have the same chemical composition and the crystalline structure. The small particles 34 and the large particles 35 can be produced by various methods depending on the desired properties of the film 3. For example, the small particles 34 and the large particles 35 may be produced by processing raw materials into small particles using physical methods such as milling, gas condensation, electrospraying, and atomization, or by growing raw materials at the molecular level using chemical methods such as microemulsion, hydrothermal synthesis, and thermal decomposition. For example, if the microstructure of the small diameter particles 34 and the large diameter particles 35 is an issue, it is preferable to produce each particle by a method that can control the microstructure, such as hydrothermal synthesis. Alternatively, if the microstructure of each particle is not an issue, it is preferable to produce each particle by a method that can produce a large amount of particles in a short time, such as milling. Of course, the small diameter particles 34 and the large diameter particles 35 may be produced by different methods, or at least one of them may be a commercially available product.

[0074] The average particle size of the small diameter particles 34 is preferably about 10 nm to 500 nm, more preferably about 30 nm to 450 nm, and even more preferably about 40 nm to 300 nm. The average particle size of the large diameter particles 35 is preferably about 500 nm to 50 μm, more preferably about 700 nm to 30 μm, and even more preferably about 900 nm to 10 μm. By satisfying these conditions, it is easy to uniformly mix the particles contained in the powder P. In addition, the powder P can be ejected from the ejection port 711 of the nozzle 71 at a higher speed.

[0075] Furthermore, within the above-mentioned range, the larger the average particle size of the small-diameter particles 34, the thicker the film 3 formed per film formation (per scan). One scan refers to the tip (spout 711) of the nozzle 71 passing once over a position facing the same location on the surface 21 of the substrate 2. In other words, the film formation rate improves. Therefore, when a thick film 3 is to be produced, the average particle size of the small-diameter particles 34 is preferably, for example, about 50 nm to 500 nm, and more preferably about 100 nm to 450 nm. Conversely, when it is desired to precisely control the thickness of the film 3, a smaller average particle size of the small-diameter particles 34 is preferable. In this case, for example, the average particle size of the small-diameter particles 34 is preferably, for example, about 1 nm to 300 nm, and more preferably about 10 nm to 300 nm. The thickness of the film 3 can be measured using a film thickness meter.

[0076] The obtained small diameter particles 34 and large diameter particles 35 are then wet or dry mixed to obtain powder P. As described above, the particles contained in powder P are easily mixed uniformly, so dry mixing, which is a simpler mixing method, can be used. The powder P thus obtained has a density of 0.3 g / cm 3 The bulk density of the powder P is, for example, 0.3 g / cm or more. 3 More than 3g / cm 3 Less than or equal to 0.4g / cm 3 More than 2g / cm 3 Less than or equal to 0.5g / cm 3 More than 1g / cm 3 , or the bulk density of the powder is 0.5 g / cm 3 More than 3g / cm 3 Furthermore, since the powder P contains small diameter particles 34 and large diameter particles 35, the particle size distribution of the particles in the powder P has two or more maximum values.

[0077] On the other hand, the substrate 2 can be prepared by producing it in various ways or by purchasing it according to the application, properties, etc. of the film-coated substrate 1 .

[0078] (film formation process) Next, the substrate 2 is mounted on the stage 61 of the support mechanism 6 . Thereafter, the pressure inside the chamber 5 is reduced. The pressure inside the chamber 5 (reduced pressure) is not particularly limited, but is preferably about 5 Pa or more and 1000 Pa or less. By reducing the pressure to this level, convection inside the chamber 5 is suppressed, making it easier to spray the powder onto the surface 21 of the substrate 2. In this state, the movement mechanism 63 is operated to start movement of the base material 2 in the horizontal direction and the depth direction of the paper surface of FIG.

[0079] Next, a carrier gas is supplied from a gas cylinder 72 to a carrier pipe 73, and while the flow rate of the carrier gas is adjusted by a mass flow controller 74, it is supplied to an aerosol generator 75 filled with powder P. This causes the powder P to be dispersed and accelerated in the carrier gas, generating an aerosol. Thereafter, the aerosol (powder P) passes through a disintegrator 76 and a classifier 77, and is then sprayed from the nozzle 71 toward the surface 21 of the substrate 2. At this time, an inert gas may be supplied to the aerosol, and the aerosol may be further accelerated by the supply pressure of at least one of the carrier gas and the inert gas.

[0080] The carrier gas may be, for example, O2, N2, Ar, He, or air. The flow rate and the flow rate of the carrier gas may be appropriately set depending on the supply amount, flow rate and the flow rate of the aerosol, the desired film quality, etc. The flow rate and the flow rate of the carrier gas may be set in conjunction with the flow rate and the flow rate of the inert gas. The aerosol is sprayed from the nozzle 711 of the nozzle 71 at a speed equal to or greater than subsonic speed and equal to or less than supersonic speed, depositing powder on the surface 21 of the substrate 2. At this time, the spraying speed of the aerosol (powder P) onto the surface 21 of the substrate 2 is preferably set to about 10 m / sec or more and 1000 m / sec or less, and more preferably set to about 10 m / sec or more and 250 m / sec or less.

[0081] As described above, since the large diameter particles 35 can impart sufficient collision energy to the entire powder P, even if the constituent material of the small diameter particles 34 or the large diameter particles 35 is changed, it is possible to omit operations for changing various spraying conditions such as the pressure inside the chamber 5 during spraying, the pressure inside the aerosol generator 75, the size of the nozzle 71, the aerosol ejection speed, the aerosol ejection amount, the moving speed of the substrate 2, and the distance between the nozzle 71 and the substrate 2.

[0082] The small diameter particles 34 and large diameter particles 35 contained in the powder P collide with the substrate 2, and are crushed (pulverized) and / or deformed (changed in shape), and are deposited on the surface 21 of the substrate 2 as components 34' derived from the small diameter particles or components 35' derived from the large diameter particles. The method described above is a method called an aerosol deposition method, which is a type of vacuum dry process.

[0083] In addition to the nozzle 71 that sprays the powder P, a nozzle that sprays gas may be provided near the position on the surface 21 of the base material 2 where the powder P has been sprayed. This makes it possible to remove excess powder P on the surface 21 of the base material 2 (powder P that could not be bonded to the surface 21). The removed powder P may be collected and reused as material for the powder P.

[0084] Furthermore, regardless of whether or not a nozzle for spraying gas is used, the powder P that has fallen, adhered, or floated in the chamber 5 without being able to form the film 3 may be collected and reused as material for the powder P. That is, the method for manufacturing the film-coated substrate 1 may further include a recycling step in which, after the film formation step, at least a portion of the powder P that was not used to form the film 3 is reused. In this case, it is possible to reduce the amount of small-diameter particles 34 and large-diameter particles 35 produced when manufacturing the film 3, and the amount of powder P that was not used to form the film 3, which is discarded. Therefore, it is possible to reduce the environmental impact and manufacturing costs incurred when manufacturing the film-coated substrate 1.

[0085] As described above, the mass and volume of the small diameter particles 34 contained in the powder P are smaller than the mass and volume of the large diameter particles 35, and the components 34' derived from the small diameter particles contained in the film 3 are greater than the components 35' derived from the large diameter particles. In other words, it is expected that the majority of the powder P not used to form the film 3 is the large diameter particles 35. Here, it is considered that the powder P that was not used to form the film 3 may have undergone deformation (change in shape), deterioration, etc. However, since most of the powder P is large-diameter particles 35, it is difficult for the powder P to be ultimately incorporated into the film 3. Therefore, even if the powder P that was not used to form the film 3 is reused, it is possible to prevent deterioration in the quality of the film 3.

[0086] According to the method for producing the film-coated substrate 1 as described above, the film-coated substrate 1 can be produced easily and reliably using desired materials. In each of the above-described aspects of the present invention, it is possible to provide a method for manufacturing a film-coated substrate 1 that can easily and reliably manufacture a film-coated substrate 1 using a desired material, and a powder P for manufacturing the film-coated substrate 1. Furthermore, it may be provided in the following aspects.

[0087] (1) A method for producing a film-coated substrate, comprising: a preparation step of preparing a substrate and a powder that is an aggregate of particles; and a film-forming step of spraying the powder onto the substrate to form a film containing components derived from the powder on the surface of the substrate, thereby obtaining the film-coated substrate, wherein the powder has a density of 0.3 g / cm 3 and the particle size distribution of the particles of the powder has two or more maximum values.

[0088] (2) In the method for producing a film-coated substrate described in (1) above, when the cumulative 10% diameter in the volume-based particle size distribution of the particles is defined as D10 and the cumulative 90% diameter is defined as D90, D10 is 0.05 μm or more and 0.7 μm or less, and D90 is 0.8 μm or more and 5 μm or less.

[0089] (3) In the method for producing a film-coated substrate according to (1) or (2), the bulk density of the powder is 0.5 g / cm 3 More than 3g / cm 3 The following is a method for producing a film-coated substrate.

[0090] (4) The method for producing a film-coated substrate according to any one of (1) to (3) above, wherein the powder contains two or more types of particles having different chemical compositions.

[0091] (5) The method for producing a film-coated substrate according to any one of (1) to (4) above, wherein the powder contains two or more types of particles having different crystal structures.

[0092] (6) The method for producing a film-coated substrate according to any one of (1) to (5) above, wherein the powder contains two or more types of particles that exhibit different particle size distributions.

[0093] (7) The method for producing a film-coated substrate according to (6) above, wherein the two or more types of particles differ from each other in at least one of chemical composition and crystal structure.

[0094] (8) The method for producing a film-coated substrate according to any one of (4) to (7) above, wherein the film is formed by adhering at least a portion of one or more types of particles out of the two or more types of particles to the surface in a state where the shape of the particles has been changed.

[0095] (9) A method for producing a film-coated substrate according to any one of (4) to (8) above, wherein one or more types of particles among the two or more types of particles act to impart collision energy to the powder, and the film contains components derived from both of the two or more types of particles.

[0096] (10) The method for producing a film-coated substrate according to any one of (1) to (9) above, further comprising a recycling step of reusing at least a portion of the powder that was not used in forming the film after the film formation step.

[0097] (11) The method for producing a film-coated substrate according to any one of (1) to (10) above, wherein in the film-forming step, the powder is sprayed onto the substrate under a vacuum process.

[0098] (12) The method for producing a film-coated substrate according to any one of (1) to (11) above, wherein in the film forming step, the powder is sprayed onto the substrate by an aerosol deposition method.

[0099] (13) The method for producing a film-coated substrate according to any one of (1) to (12) above, wherein the powder is made of an oxide or nitride.

[0100] (14) A powder which is an aggregate of particles and is used to form a film on the surface of a substrate by spraying the powder on the surface of the substrate, and the powder has a density of 0.3 g / cm 3 and the particle size distribution of the particles of the powder has two or more maxima. Of course, this is not the case.

[0101] As described above, various embodiments of the present invention have been described, but these are presented as examples and do not limit the scope of the invention in any way. The novel embodiments can be embodied in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. Such embodiments and their modifications are included within the scope and spirit of the invention, and are also included in the inventions and their equivalents as set forth in the claims.

[0102] For example, the powder P may further include one or more types of medium-sized particles in addition to the small-sized particles 34 and the large-sized particles 35. The medium-sized particles have an average particle size between the small-sized particles 34 and the large-sized particles 35. When the powder P contains such medium-sized particles, it is easier to further improve the homogeneity and uniformity of the film 3. Furthermore, by selecting the small-sized particles 34, the medium-sized particles, and the large-sized particles 35, it is possible to impart three or more functions to the film 3.

[0103] Furthermore, for example, one or more layers having any desired function may be provided between the substrate 2 and the membrane 3. Such a function is preferably, for example, a function to increase the adhesion between the substrate 2 and the membrane 3, a function to prevent a sudden change in the average pore size at the boundary between the substrate 2 and the membrane 3, or a function to relieve stress between the substrate 2 and the membrane 3. [Example]

[0104] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0105] 1. Manufacturing of film-coated substrate Example 1 Substrate preparation As the substrate 2, a glass substrate having a thickness of 1 mm was cut into a substantially rectangular shape of 10 mm×20 mm and used. Preparation of powder P 2 g of zeolite (LTA type) having an average particle size of 50 nm as small diameter particles 34, 98 g of titania having an average particle size of 1 μm as large diameter particles 35, and 60 g of ethanol (99.5 mass%) were placed in a container and kneaded using a planetary centrifugal mixer. The kneading was carried out for 2 minutes at a revolution speed of 2000 rpm and a rotation speed of 800 rpm. The slurry obtained after kneading was left at 70°C for 3 hours, and then left at 100°C for 1 hour to dry. The dried product obtained by drying was pulverized at 20,000 rpm for 1 minute using a blade mill. This resulted in powder P. That is, the mixing ratio of small diameter particles 34 in powder P was 2%.

[0106] - Formation of a film on the surface of a substrate The film 3 was formed using a film-coated substrate manufacturing apparatus 4 shown in FIGS. First, the four ends (four sides) of the substrate 2 were fixed to the ends of the support surface 611 of the stage (XY stage) 61 with Kapton tape. Next, the powder P was sprayed onto the surface 21 of the substrate 2 at about 20°C. Specifically, the powder P to be sprayed was loaded into the aerosol generator 75, and the pressure inside the chamber 5 containing the substrate 2 was reduced to 5 Pa by the pump 81. In this state, powder P was sprayed onto the substrate 2 from a nozzle 71 having a rectangular nozzle 711 measuring 10 mm×0.5 mm in plan view while the substrate 2 was moved along the in-plane directions of the surface 21 (X direction and Y direction).

[0107] At this time, nitrogen gas (N2) was used for transport adjustment, and this nitrogen gas was supplied from a gas cylinder 72 to an aerosol generator 75 filled with powder P, thereby dispersing the powder P in the nitrogen gas to generate an aerosol. The flow rate of the nitrogen gas was adjusted by a mass flow controller 74 provided upstream of the aerosol generator 75. Thereafter, the aerosol was passed through a disintegrator 76 and a classifier 77 and then ejected from a nozzle 71 toward the substrate 2 to form a film 3. The ejection speed of the aerosol from the nozzle 71 was 250 mm / sec, and the distance from the nozzle 71 to the surface 21 of the substrate 2 was 10 mm. The number of scans was adjusted to 12.

[0108] (Examples 2 to 13, Comparative Examples 1 to 3) A film-coated substrate was produced in the same manner as in Example 1, except that the constituent materials, masses, and particle sizes of the small diameter particles 34 and the large diameter particles 35 were changed as shown in Table 1.

[0109] 2. Measurement and testing (Measurement of average particle size) The average particle sizes of the small diameter particles 34 and the large diameter particles 35 were obtained in accordance with JIS Z 8827-1: 2018 (ISO 13322-1: 2014) by the following procedure. The average particle size of the small diameter particles 34 will be described below as an example, but the average particle size of the large diameter particles 35 was also measured by the same procedure.

[0110] A scanning electron microscope (SEM) was used to observe the small diameter particles 34. The magnification was adjusted to a value that allowed observation of at least 20 small diameter particles 34, and images were acquired. The accelerating voltage was set to a range of 1.0 kV to 15 kV. One image was taken from any field of view, and 50 small particles 34 that were entirely included in the image were randomly selected from the small particles 34. Using image analysis software ("Mac-View" manufactured by Mountec Co., Ltd.), the equivalent circle diameter was measured for each selected small diameter particle 34. The arithmetic mean of the 50 measured equivalent circle diameters was calculated to obtain the average particle size of the small diameter particles 34.

[0111] (Bulk density measurement) The bulk density of powder P was obtained according to K 7365:1999 (ISO 60:1977) by the following procedure.

[0112] First, a stainless steel funnel with an upper inner diameter of 115 mm, an upper outer diameter of the leg of 30 mm, a lower outer diameter of 15 mm, a leg length of 45 mm, a height of 100 mm, and a plate thickness of 1.0 mm was prepared, along with a stainless steel cylinder with a volume of 100 mL and an inner diameter of 35 mm. The funnel was held vertically so that the lower opening of the funnel was located 20 to 30 mm above the cylinder and the axes of the funnel and cylinder were aligned. The damper at the lower opening of the funnel was closed, and 100 mL of powder P was poured into the funnel. The damper was quickly removed, allowing the powder P to flow down into the cylinder. When the cylinder was filled with powder P up to the top opening, the funnel was moved from above the cylinder. The powder P that had risen from the cylinder was scraped off with the handle of a medicine spoon, and the mass of the powder P in the cylinder was measured.

[0113] In each of the Examples and Comparative Examples, the mass of the powder P was measured twice, and the arithmetic mean value of the two mass measurement results was calculated. The arithmetically averaged mass was divided by the volume of the cylinder (100 mL) to obtain the bulk density of the powder P.

[0114] (Particle size distribution measurement) The particle size distribution of the powder P was measured by the following procedure. 10 mg of powder P of Examples 1 to 11 and Comparative Examples 1 to 3 was added to 10 ml of water, and it was confirmed that the powder sank in water. That is, it was confirmed that powder P had dispersibility in water. Then, ultrasonic vibrations were applied to the water containing powder P using an ultrasonic homogenizer for 5 minutes to obtain a measurement sample. When 10 mg of powder P of Examples 12 and 13 was added to 10 ml of water, the powder P did not sink in the water. Therefore, for Examples 12 and 13, 0.2 wt% of sodium hexametaphosphate was added as a dispersant to the water containing the powder P, and then ultrasonic vibrations were applied for 5 minutes using an ultrasonic homogenizer to obtain a measurement sample.

[0115] The particle size distribution of the measurement sample was measured on a volume basis using a particle size distribution measuring device (laser diffraction / scattering method). The measurement was performed for 120 seconds with an upper measurement limit of 6540 nm, a lower measurement limit of 0.800 nm, and a solvent refractive index of 1.33 (the refractive index of water). When measuring powder P (Examples 1 to 13, Comparative Example 2) in which particles with different chemical compositions or crystal structures were mixed, the particle refractive index was set to match that of the particles with the larger refractive index, and the particle size distribution was measured. Next, based on the measured particle size distribution, the particle size D10 corresponding to the 10% cumulative particle size from the smallest particle size and the particle size D90 corresponding to the 90% cumulative particle size were obtained.

[0116] (Measurement of film formation rate) For the film-coated substrate 1, the area on the surface 21 of the substrate 2 where the film 3 was formed was measured. The measured area was taken as the film-formed area, and the area of ​​the surface 21 of the substrate 2 that was not covered with Kapton tape was 64 mm 2The film formation rate was calculated by dividing the film formation area by the film formation area and multiplying the result by 100.

[0117] (film formation rate measurement) The film thickness was measured with a stylus film thickness meter at three arbitrarily selected points on the surface 21 of each film-coated substrate 1. The arithmetic average of the film thicknesses at the three points was divided by the number of scans (12 times) to calculate the film formation rate.

[0118] 3.Results The measurement results of Examples 1 to 13 and Comparative Examples 1 to 3 are summarized in Tables 1 and 2 below. The measurement results of particle size distribution in Examples 5 and 6 are shown in Figures 6 and 7. Figure 6 is a diagram showing the measurement results of particle size distribution in Example 5. Figure 7 is a diagram showing the measurement results of particle size distribution in Example 6. As shown in Figures 6 and 7, the particle size distribution of powder P in Examples 5 and 6 showed two maximal values. Although not shown in the figures, the particle size frequency distribution of powder P also showed two maximal values ​​in Examples 1 to 4, 7 to 13 and Comparative Example 2.

[0119] [Table 1] [Table 2]

[0120] As shown in Tables 1 and 2, according to the present invention, films can be easily and reliably formed even when different materials are used. [Explanation of symbols]

[0121] 1: Film-coated substrate 2: Base material 21: Face 3: Membrane 32: Top surface 33: Composite particles 34: Small particles 34': Ingredients 34a: aggregate 35: Large particles 35': Ingredients 4: Manufacturing equipment 5: Chamber 6: Support mechanism 61: Stage 611: Support surface 62: Arm 63: Movement mechanism 7:Ejection mechanism 71: Nozzle 711: Spout 72: Gas Cylinder 73: Conveyor pipe 74: Mass flow controller 75: Aerosol generator 76:Crusher 77: Classifier 8: Pressure reduction mechanism 81: Pump 9: Control means 91: Arithmetic section 92: Storage section P: Powder

Claims

1. A method for producing a film-coated substrate, a preparation step of preparing a base material and a powder which is an aggregate of particles; a film-forming step of spraying the powder onto the substrate to form a film containing a component derived from the powder on the surface of the substrate, thereby obtaining the film-coated substrate; The powder has a density of 0.3 g / cm ３ and having a bulk density of at least The particle size distribution of the particles of the powder has two or more maxima. Method for manufacturing a film-coated substrate.

2. The method for producing a film-coated substrate according to claim 1, When the cumulative 10% diameter in the volume-based particle size distribution of the particles is defined as D10 and the cumulative 90% diameter is defined as D90, D10 is 0.05 μm or more and 0.7 μm or less, and D90 is 0.8 μm or more and 5 μm or less. Method for manufacturing a film-coated substrate.

3. The method for producing a film-coated substrate according to claim 1, The bulk density of the powder is 0.5 g / cm ３ 3g / cm or more ３ Below is the Method for manufacturing a film-coated substrate.

4. The method for producing a film-coated substrate according to claim 1, The powder contains two or more types of particles having different chemical compositions. Method for manufacturing a film-coated substrate.

5. The method for producing a film-coated substrate according to claim 1, The powder contains two or more types of particles having different crystal structures. Method for manufacturing a film-coated substrate.

6. The method for producing a film-coated substrate according to claim 1, The powder contains two or more types of particles that exhibit different particle size distributions. Method for manufacturing a film-coated substrate.

7. The method for producing a film-coated substrate according to claim 6, The two or more types of particles differ from each other in at least one of chemical composition and crystal structure. Method for manufacturing a film-coated substrate.

8. The method for producing a film-coated substrate according to claim 4, the film is formed by at least one type of particle among the two or more types of particles being attached to the surface in a state in which at least a part of the particle's shape has changed. Method for manufacturing a film-coated substrate.

9. The method for producing a film-coated substrate according to claim 4, one or more types of particles among the two or more types of particles act to impart collision energy to the powder, The film contains components derived from both of the two or more types of particles. Method for manufacturing a film-coated substrate.

10. The method for producing a film-coated substrate according to claim 1, The method further includes a recycling step of reusing at least a portion of the powder that was not used in forming the film after the film forming step. Method for manufacturing a film-coated substrate.

11. The method for producing a film-coated substrate according to claim 1, In the film forming step, the powder is sprayed onto the substrate under a vacuum process. Method for manufacturing a film-coated substrate.

12. The method for producing a film-coated substrate according to claim 1, In the film forming step, the powder is sprayed onto the substrate by an aerosol deposition method. Method for manufacturing a film-coated substrate.

13. The method for producing a film-coated substrate according to claim 1, The constituent material of the powder is an oxide or a nitride. Method for manufacturing a film-coated substrate.

14. A powder that is an aggregate of particles and is used to form a film on the surface of a substrate by spraying it onto the surface of the substrate, The powder has a density of 0.3 g / cm ３ and having a bulk density of at least The particle size distribution of the particles of the powder has two or more maxima. powder.

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