KR102232833B1 - Fluidized atomic layer deposition for functional coating of low density glass bubble microparticles and coating method using thereof - Google Patents

Abstract

The present invention relates to an atomic layer evaporator for functional coating of low-density glass bubble fine particles and a coating method using the same, and more specifically, to form a coating thin film of uniform number or tens of nanometers on light and low-density glass bubble fine particles By injecting reactive gas from bottom to top to make the glass bubble microparticles fluidized, the reaction probability of the reaction gas and the glass bubble microparticles is made equal, and by minimizing the loss of the glass bubble microparticles having a low density, uniform functionality The present invention relates to an atomic layer evaporator for functional coating of low-density glass bubble fine particles capable of mass-producing fine particles of a core-shell structure capable of representing, and a coating method using the same.

Description

{Fluidized atomic layer deposition for functional coating of low density glass bubble microparticles and coating method using thereof}

The present invention relates to an atomic layer evaporator for functional coating of low-density glass bubble fine particles and a coating method using the same, and more specifically, to a uniform number or tens of nanometers (nm) thick on light and low-density glass bubble fine particles. By injecting a reactive gas from the bottom up to form a coating thin film to fluidize the glass bubble fine particles, making the reaction probability of the reactive gas and the glass bubble fine particles equal, and minimizing the loss of the glass bubble fine particles having a low density. , Functionality of low-density glass bubble microparticles capable of mass-producing microparticles of double shell structure, characterized in that a coating layer capable of showing uniform functionality is formed on the surface of glass bubble microparticles of a shell structure. It relates to an atomic layer evaporator for coating and a coating method using the same.

Glass bubble fine particles are generally composed of a material such as Soda Lime Borosilicate Glass or silica (SiO ₂ ), and have a size of several tens of nanometers (nm) or tens of micrometers (um). It is a spherical fine particle having a, characterized in that it has a shell structure in which only the shell portion is left because the inside of the fine particle (core) is empty. Compared to the density of the spherical SiO ₂ fine particles filled inside (~ 2.65 g/cm ³ ), since the inside is empty and has a very low density (< 0.2 g/cm ³ ), it is a single or polymer, metal, ceramic material It is used together with, and is used as a basic material for manufacturing various materials and parts, such as fields requiring weight reduction, insulation properties using an internal air layer, low dielectric constant, or high surface area.

It can be used to make electric vehicle shielding materials and products by utilizing glass bubble fine particles. Recently, according to the rapid development of electronic devices, there are significant benefits in terms of convenience in real life, but harmfulness to the human body due to electromagnetic waves, performance degradation, and malfunction of devices have also increased significantly. In other words, research is being conducted to block electromagnetic waves along with international regulation of electromagnetic waves, and it is advantageous to have good conductivity and high surface area as an electromagnetic wave shielding material. Therefore, a method of coating and utilizing a material such as silver (Ag) having the highest electrical conductivity on the surface of low-density glass bubble microparticles having a size of several tens of nanometers (nm) or tens of micrometers (um) that is light and capable of various applications is devised. It is being utilized.

In general, a wet method has been used in the past to coat a conductive material on the surface of the low-density glass bubble fine particles having a shell structure and empty inside. Since many studies on the wet method are in progress, coating of various types and materials is possible, but due to the nature of the wet method, a rather complicated process such as pre-treatment, post-treatment, filtration and drying processes is required. Therefore, it takes a lot of time in the manufacturing process and is directly connected to economic problems. In addition, in the case of wet coating, the formed coating layer is not uniform, and coagulation of the coating layer may occur, thereby deteriorating the performance of the coated fine particles. In order to improve the uniformity problem, since a thicker silver is coated by a wet method, there is a problem in that the manufacturing price increases.

In recent years, with the development of highly direct devices, the dry coating film deposition process of atomic layer deposition (ALD) is widely used in the semiconductor and display fields to form a functional coating layer at the level of several or tens of nanometers (nm). . The atomic layer deposition method is a kind of dry coating film deposition method and does not require a more complicated process than the wet method, so it can contribute to economic savings due to mass production. In addition, the atomic layer deposition method generates a magnetic saturation surface reaction through a chemical adsorption reaction between the surface of the object on which the coating film is formed and the reactant by periodically supplying and discharging the reactant, and forming the coating layer in atomic layer units provides excellent uniformity. Can be formed.

Conventionally, various types of atomic layer deposition methods have been devised in order to introduce a coating film on the surface of fine particles having various sizes and shapes by the atomic layer deposition method. First, research on the atomic layer deposition method preceded by a method of depositing in a static state by injecting fine particles into a grooved space like a method of depositing on a general flat plate. In this method, since the fine particles are placed in a static state, in order to deposit evenly from the fine particles on the surface of the substrate to the fine particles at the bottom, it is necessary to inject for a long time so that the reactants can sufficiently diffuse to the fine particles below the substrate. Due to the problem, it is difficult to obtain a uniform coating layer, so the process time is lengthened, and it is difficult to utilize in mass production due to waste and non-uniformity of properties of reactants that cannot react.

Therefore, research is being conducted to reduce the process time and obtain a uniform coating layer by fluidizing fine particles in a vacuum chamber. For example, as in Korean Patent Laid-Open Publication No. 10-2014-0006420, 10-2014-0128645, or Korean Utility Model Publication No. 20-2016-0004136, the inside of the chamber is made into a tubular shape, and fine particles inside the chamber are rotated through rotation. A rotary flow method was devised in which the reactant gas was injected through a metal sintering filter while stirring and discharged through a plurality of holes formed in the body. However, in this method, since the rotating tubular chamber and the part providing the reactant are connected, it is difficult to separate the chamber and recover the coated fine particles, so there is a problem with respect to the overall yield, and the device becomes complicated. Exists. In addition, even if a uniform coating is induced by a rotating fluidized bed, there is a high probability of a chemical reaction between the reactant and the powder at a position close to the cylinder surface to the reactant gas injection port injected horizontally, but the probability of reacting to the powder farthest from the reactant gas injection port. Will fall. One of the biggest problems is that gas is discharged through a number of holes opposite the injection port on the cylindrical surface, and the powder accumulates at the discharge port and becomes clogged. The probability of chemical reaction to the particles decreases.

In addition to such a rotary fluidized bed method, there is a stirring flow method in which fine particles are flowed by inserting a stirring device into the reactor, as in Korean Laid-Open Patent Publication No. 10-2015-0008667. However, there is a problem in that the powder particles are not sufficiently suspended despite the stirring device, and the powder present at the angled corners in the reactor also has a low reaction probability, so that it is difficult to add more reactants and form a uniform coating layer.

In particular, in the case of the above-mentioned atomic layer evaporator of the rotary flow method and the agitated flow method, when light and low-density particles such as the glass bubble fine particles of the present invention are applied, the loss of fine particles has a very high problem. .

Accordingly, in order to compensate for the above-described problems, the present inventors recognized that it is urgent to develop an atomic layer evaporator for functional coating of low-density glass bubble fine particles and a coating method using the same, and completed the present invention.

Republic of Korea Patent Publication No. 10-2014-0006420 Republic of Korea Patent Publication No. 10-2014-0128645 Republic of Korea Patent Publication No. 10-2015-0008667 Republic of Korea Public Utility Model Publication No. 20-2016-0004136

An object of the present invention is an atomic layer evaporator for functional coating of low-density glass bubble fine particles, capable of forming a coating thin film having a thickness of uniform number or tens of nanometers (nm) on light and low-density glass bubble fine particles, and It is to provide a coating method used.

Another object of the present invention is a double shell, characterized in that a coating layer capable of minimizing the loss of light and low density glass bubble microparticles and exhibiting uniform functionality is formed on the surface of the glass bubble microparticles having a shell structure. To provide an atomic layer evaporator for functional coating of low-density glass bubble fine particles capable of mass-producing shell) structure fine particles and a coating method using the same.

In order to achieve the above object, the present invention provides an atomic layer evaporator for functional coating of low-density glass bubble fine particles, and a coating method using the same.

Hereinafter, the present specification will be described in more detail.

The present invention is a fluidized bed reactor in which a reactant is supplied through a lower surface and a process passage through which the supplied reactant can be discharged through an upper surface is formed; A reactant supply unit for supplying a reactant into the fluidized bed reactor; A gas supply unit for supplying a reaction gas and a purge gas into the fluidized bed reactor; And a pressure control unit for controlling the pressure in the fluidized bed reactor; and an atomic layer evaporator for functional coating of fine particles of low-density glass bubbles.

In the present invention, the fluidized bed reactor comprises: a reactor case formed in a shape corresponding to the outer shape of the fluidized bed reactor in order to attach and attach the fluidized bed reactor; An upper mesh for preventing loss of the glass bubble fine particles; And a lower mesh for uniformly supplying the reactive gas supplied through the gas supply unit.

In the present invention, circular beads in the form of beads integrally formed inside the lower mesh ^{and having a density of 1 to 10 g/cm 3} and a particle size of 0.1 to 5 millimeters (mm); And a vibration supply unit for supplying regular vibrations to desorb the glass bubble fine particles attached to the upper mesh in the fluidized bed reactor, wherein the vibration supply unit may further include mechanical vibration, pneumatic vibration, electromagnetic vibration, or ultrasonic vibration. It is characterized in that to supply.

In the present invention, in the fluidized bed reactor, the width of the lower surface of the fluidized bed reactor is relatively narrower than the width of the upper surface in order to induce a pressure drop in the fluidized bed reactor (downwards tapering), and the lower surface is the When lowering the glass bubble fine particles flowing in the fluidized bed reactor due to a space gap between the upper and lower surfaces that are formed with a relatively narrow width on the upper surface and inclined downward based on a vertical cross-section. It is characterized in that it can fall.

In the present invention, the reactant supply unit includes a reactant supply unit for supplying a metal reactant to the fluidized bed reactor; And a precursor supply unit supplying a precursor for oxidizing the metal reactant in order to chemically adsorb the glass bubble fine particles.

In the present invention, the gas supply unit comprises: a first gas supply unit for supplying a reaction gas for coating the shell portion of the glass bubble fine particles; And a second gas supply unit for supplying a purge gas for transporting the reaction gas to the process passage, wherein the first gas supply unit and the second gas supply unit control the flow of the reaction gas and the purge gas. It characterized in that it includes; MFC (Mass Flow Controller, mass flow controller).

In the present invention, the pressure control unit includes a rotary pump for controlling the pressure inside the fluidized bed reactor to a ground state; And a throttle valve for adjusting the pressure inside the fluidized bed reaction in order to uniformly flow the glass bubble fine particles present in the fluidized bed reactor.

In addition, the present invention comprises the steps of: (S1) supplying fine glass bubble particles and a metal precursor using the atomic layer evaporator; (S2) supplying a purge gas; (S3) supplying a reaction gas; And (S4) supplying a purge gas to form a functional coating layer on the fine glass bubble particles; providing a coating method using an atomic layer evaporator for functional coating of the low-density glass bubble fine particles.

In the present invention, the coating method is characterized in that the atomic layer deposition cycle consisting of the steps (S1) to (S4) is repeated one or more times through the atomic layer deposition method.

In the present invention, the glass bubble microparticles are in the form of a shell in which the inside of the microparticles is empty, the inner (core) part of the shell is empty, and the shell part is 50 nanometers (nm) to 300 millimeters ( mm) is characterized in that it is formed of thick soda lime borosilicate glass (Soda Lime Borosilicate Glass) or silica (SiO _{2 ).}

All matters mentioned in the atomic layer evaporator of the present invention and the coating method using the same are applied equally unless contradictory to each other.

The atomic layer evaporator for functional coating of low-density glass bubble fine particles of the present invention and a coating method using the same can adjust the thickness of the functional coating on the surface of the glass bubble fine particles having a light and low density, and the reaction gas is directed from the bottom to the top. It is possible to more easily form a functional coating layer having a uniform thickness on the low-density glass bubble microparticles by adding it, and with reference to the accompanying drawings, embodiments of the present invention will be described. The same reference numerals shown in each drawing indicate the same member. In describing the present invention, detailed descriptions of related known functions or configurations are omitted so as not to obscure the subject matter of the present invention. A uniform coating layer may be formed by allowing the gas to flow evenly through control of pressure, temperature, vibration, etc. by flowing the glass bubble fine particles.

In addition, the atomic layer evaporator for functional coating of low-density glass bubble fine particles of the present invention and a coating method using the same can increase the final yield by minimizing loss of glass bubble fine particles having a low density, and are complex different from the existing wet process. Since the process and time are reduced and batch-type reactors are manufactured and used, the production of fine particles of a double shell structure in large quantities, characterized in that the functional coating layer is formed on the surface of the glass bubble fine particles of the shell structure, is possible. It is possible.

1 is an overall device configuration diagram of an atomic layer evaporator for functional coating of low-density glass bubble fine particles of the present invention.
2 is a schematic diagram of a fluidized bed reactor, which is a configuration of the atomic layer deposition apparatus of the present invention.
3 is a scanning electron microscopy (SEM) image of glass bubble microparticles on which a coating layer is formed using the atomic layer deposition machine of the present invention.
4 is a Transmission Electron Microscopy (TEM) image confirming the composition distribution of fine particles of glass bubbles on which a coating layer is formed using the atomic layer evaporator of the present invention.

The present invention provides an atomic layer evaporator for functional coating of low-density glass bubble fine particles and a coating method using the same.

In order to fully understand the present invention, operational advantages of the present invention, and objects achieved by the implementation of the present invention, reference should be made to the accompanying drawings illustrating preferred embodiments of the present invention and the contents described in the accompanying drawings.

Hereinafter, the present invention will be described in detail by describing a preferred embodiment of the present invention with reference to the accompanying drawings. However, in describing the present invention, a description of a function or configuration that is already known will be omitted in order to clarify the gist of the present invention.

Hereinafter, the present specification will be described in more detail.

Atomic Layer Evaporator for Functional Coating of Low Density Glass Bubble Fine Particles

FIG. 1 is an overall apparatus configuration diagram of an atomic layer evaporator for functional coating of low-density glass bubble fine particles of the present invention, and FIG. 2 is a schematic diagram of a fluidized bed reactor that is a configuration of an atomic layer evaporator of the present invention.

The present invention provides an atomic layer evaporator for functional coating of low-density glass bubble fine particles.

More specifically, the atomic layer evaporator 100 for functional coating of low-density glass bubble fine particles of the present invention has a process passage through which a reactant is supplied through a lower surface, and the supplied reactant can be discharged through an upper surface. The formed fluidized bed reactor 110; A reactant supply unit 120 for supplying a reactant into the fluidized bed reactor 110; A gas supply unit 130 for supplying a reaction gas and a purge gas into the fluidized bed reactor 110; And a pressure control unit 140 for controlling the pressure in the fluidized bed reactor 110; and an atomic layer deposition machine 100 for functional coating of fine particles of low-density glass bubbles.

In the present invention, the fluidized bed reactor 110 may be formed in a shape extending in the longitudinal direction, a reactant and gas are supplied through a lower surface, and the supplied reactant and gas can be discharged through an upper surface. It can be formed as a process passage. In addition, the fluidized bed reactor 110 may serve as a process chamber in which a coating process using an atomic layer deposition method is performed.

In the present invention, in the fluidized bed reactor 110, the width of the lower surface of the fluidized bed reactor 110 is relatively narrower than the width of the upper surface in order to induce a pressure drop in the fluidized bed reactor 110 (downwards tapering). More specifically, according to Bernoulli's theorem, when the width is relatively narrow, like the lower surface of the fluidized bed reactor 110, the glass bubble fine particles having high fluidity at a low pressure have a relatively wide width. It is directed to the upper surface of the fluidized bed reactor 110, and at this time, as the pressure increases, the flow rate is lowered so that the glass bubble fine particles sink again, so that the glass bubble fine particles have excellent fluidity without loss or loss of the glass bubble fine particles. Can be obtained.

In the present invention, the lower surface of the fluidized bed reactor 110 is formed with a relatively narrow width on the upper surface, and may be formed to be inclined downward based on a vertical cross section.

In the present invention, when the glass bubble fine particles flowing in the fluidized bed reactor 110 are lowered due to the gap in the space width between the upper surface and the lower surface, the glass bubble fine particles are desorbed. When it sinks again, it is possible to recover the fluidity toward the bottom again through the downwardly inclined portion of the lower surface of the fluidized bed reactor 110.

In the present invention, the fluidized bed reactor 110 includes a reactor case 116 formed in a shape corresponding to the outer shape of the fluidized bed reactor 110 in order to attach and attach the fluidized bed reactor 110; An upper mesh 111 for preventing loss of the fine glass bubble particles; And a lower mesh 112 for uniformly supplying the reactive gas supplied through the gas supply unit 130.

In the present invention, the reactor case 116 may be formed in a shape corresponding to the outer shape of the fluidized bed reactor 110 in order to easily attach and detach the fluidized bed reactor 110. More specifically, when the glass bubble fine particles are manufactured, the fluidized bed reactor 110 is attached to the reactor case 116 to fix the fluidized bed reactor 110, and when the glass bubble is injected or removed, the fluidized bed reactor 110 is attached to the reactor case ( 116) can be easily removed.

In the present invention, the upper mesh 111 and the lower mesh 112 have a pore size of 10 to 100 micrometers (um), and can be adjusted according to the weight, density or size of the glass bubble fine particles, It is not limited thereto.

In the present invention, the fluidized bed reactor 110 is integrally formed inside the lower mesh 112, ^{and has a density of 1 to 10 g/cm 3} and a particle size of 0.1 to 5 millimeters (mm). Beads 113; And a vibration supply unit 114 for supplying regular vibrations to desorb the glass bubble fine particles attached to the upper mesh 111 in the fluidized bed reactor 110.

In the present invention, the circular beads 113 have a higher density and a larger particle size than the glass bubble fine particles, the circular beads 113 is 0.5 to 3 centimeters (cm) than the length of the lower mesh 112 It is formed long and can be introduced. In addition, the circular beads 113 may have a uniform gas flow path for the reaction gas supplied through the lower mesh 112.

In the present invention, the vibration supply unit 114 is integrally attached to the upper surface of the fluidized bed reactor 110 to apply vibration during the coating process by the atomic layer deposition method. By mixing, fluidity may be increased, and the fine glass bubble particles that may be attached to the upper mesh 111 may be temporarily desorbed.

In the present invention, the vibration supply unit 114 may supply mechanical vibration, pneumatic vibration, electromagnetic vibration, or ultrasonic vibration, and regular vibration supplied to detach the glass bubble fine particles attached to the upper mesh 111 If so, it is not limited thereto.

In the present invention, the fluidized bed reactor 110 may additionally include a temperature controller 115 capable of controlling and controlling a process temperature during a coating process by an atomic layer deposition method.

In the present invention, the temperature control unit 115 may be formed in a form in which a heat wire exists in the center to surround the heat wire to surround the heat insulating material, and more specifically, may be a form to wrap around the heat wire with an insulating plate.

In the present invention, the upper mesh 111 of the fluidized bed reactor 110 may be integrally formed with the centering 117, and the lower mesh 112 may be integrally formed with the fluidized bed reactor 110. .

More specifically, the general centering is formed in a hollow shape to connect the passage between the tube and the tube, but the centering 117 of the present invention is the upper mesh 111 and the centering to prevent loss of the glass bubble. (117) is formed in one piece.

In the present invention, the center ring 117 is wrapped with an O-ring 118, and the O-ring 118 has a circular shape and may be made of a material having elasticity, and may be preferably a viton.

In the present invention, the reactant supply unit 120 includes a reactant supply unit 121 for supplying a metal reactant to the fluidized bed reactor 110; And a precursor supply unit 122 supplying a precursor for oxidizing the metal reactant in order to chemically adsorb the glass bubble fine particles.

More specifically, when a metal precursor is to be coated on the low-density glass bubble, a metal oxide is formed by supplying a precursor from the precursor supply unit 122 to oxidize the metal reactant supplied from the reactant supply unit 121, The metal oxide may form a coating layer on the low-density glass to form the low-density glass bubble fine particles.

In the present invention, the reactant supply unit 120 is connected to the fluidized bed reactor 110 through a connection pipe, and the connection pipe is a central part to maintain a higher temperature than the reactant, that is, glass bubble fine particles or metal precursors. The heating wire may be formed in a form surrounding the heating wire to surround the heat-insulating material, and more specifically, may be configured to surround the heating wire with a heat-insulating plate. In addition, the heating wire of the connection pipe may additionally include a temperature control device that raises a temperature or maintains a cool temperature with a cooler.

In the present invention, the gas supply unit 130 includes a first gas supply unit 131 for supplying a reaction gas for coating the shell portion of the glass bubble fine particles; And a second gas supply unit 132 for supplying a purge gas for transporting the reaction gas to the process passage, wherein the first gas supply unit 131 and the second gas supply unit 132 are the reaction gas And a Mass Flow Controller (MFC) 133 for controlling the flow of the purge gas.

In the present invention, the pressure control unit 140 includes a rotary pump 141 for controlling the pressure inside the fluidized bed reactor 110 to a ground state; And a throttle valve 142 for adjusting the pressure inside the fluidized bed reaction in order to uniformly flow the glass bubble fine particles present in the fluidized bed reactor 110.

In the present invention, the rotary pump 141 performs initial vacuum and can maintain a constant vacuum degree of the operating pressure even during the coating process.

In the present invention, the throttle valve 142 may be located in the middle of a connection pipe to which the fluidized bed reactor 110 and the rotary pump 141 are connected.

In the present invention, when the reaction gas is injected through the lower surface of the fluidized bed reactor 110 and the flow rate decreases, the glass bubble fine particles stop, and when the flow rate increases again, the glass bubble fine particles are applied. The resistance and gravity become the same to have fluidity, but when the pressure inside the fluidized bed reactor 110 is lowered and the flow rate is slightly increased during the pumping process, the glass bubble fine particles are sucked and lost in the pumping direction. A coating film may be formed by controlling the pressure through the throttle valve 142 to minimize loss of glass bubble fine particles of various sizes.

Coating Method Using Atomic Layer Evaporator for Functional Coating of Low Density Glass Bubble Fine Particles

The present invention provides a coating method using an atomic layer evaporator for functional coating of the low-density glass bubble fine particles.

FIG. 3 is a SEM image of fine glass bubble particles having a coating layer formed using the atomic layer evaporator of the present invention, and FIG. 4 is a TEM image confirming the composition distribution of fine glass bubble particles having a coating layer formed using the atomic layer vapor deposition device of the present invention.

The present invention comprises the steps of: (S1) supplying fine glass bubble particles and a metal precursor using the atomic layer deposition machine; (S2) supplying a purge gas; (S3) supplying a reaction gas; And (S4) supplying a purge gas to form a functional coating layer on the fine glass bubble particles; provides a coating method using an atomic layer evaporator for functional coating of the low-density glass bubble fine particles comprising.

In the present invention, the coating method may be to repeat the atomic layer deposition cycle consisting of the steps (S1) to (S4) one or more times through the atomic layer deposition method.

The term "purge gas" used in the present invention means a gas for efficiently removing unreacted metal precursors, reaction gases or by-products in the above manufacturing method, and Ar or N2 gas may be used.

The term "reactive gas" used in the present invention means a gas capable of forming a TiZnO coating thin film by reacting with the Zn and Ti precursors.

The term “atomic layer deposition (ALD)” used in the present invention means a deposition method capable of controlling each atomic layer.

In the present invention, the atomic layer evaporator for functional coating of the low-density glass bubble fine particles is as described above.

In the present invention, the glass bubble fine particles are in the form of a shell, the inner (core) portion of the shell is empty, and the shell portion is a soda lime borough having a thickness of 50 nanometers (nm) to 300 millimeters (mm). It may be silicate glass (Soda Lime Borosilicate Glass) or silica (SiO ₂ ).

All matters mentioned in the atomic layer evaporator of the present invention and the coating method using the same are applied equally unless contradictory to each other.

From the above description, it will be understood that those skilled in the art belonging to the present invention may be implemented in other specific forms without changing the technical spirit or essential features of the present invention. In this regard, the embodiments described above are illustrative in all respects, and should be understood as non-limiting.

Atomic Layer Evaporator: 100
Fluidized bed reactor: 110
Upper mesh: 111
Lower mesh: 112
Round beads: 113
Vibration supply: 114
Temperature control unit: 115
Reactor Case: 116
Centering: 117
O-ring: 118
Reactant supply: 120
Reactant supply unit: 121
Precursor supply unit: 122
Gas supply: 130
First gas supply unit: 131
Second gas supply unit: 132
MFC: 133
Pressure control: 140
Rotary pump: 141
Throttle valve: 142

Claims (9)

A fluidized bed reactor in which a reactant is supplied through a lower surface and a process passage through which the supplied reactant can be discharged through an upper surface is formed;
A reactant supply unit for supplying a reactant into the fluidized bed reactor;
A gas supply unit for supplying a reaction gas and a purge gas into the fluidized bed reactor; And
Includes; a pressure control unit for adjusting the pressure in the fluidized bed reactor,
The fluidized bed reactor,
An upper mesh for preventing loss of fine glass bubble particles located inside the fluidized bed reactor;
A lower mesh for uniformly supplying the reactive gas supplied through the gas supply unit; And
Including; is injected so as to be formed to be 0.5 to 3 centimeters (cm) longer than the length of the lower mesh, ^{and having a density of 1 to 10 g/cm 3} and a particle size of 0.1 to 5 millimeters (mm); and,
The reactants are metal precursors Zn and Ti precursors,
The reactant is coated on the shell portion of the glass bubble fine particles to form a functional coating layer,
The functional coating layer is an atomic layer evaporator for functional coating of low-density glass bubble fine particles, characterized in that the TiZnO coating thin film. The method of claim 1,
The fluidized bed reactor,
A reactor case formed in a shape corresponding to the outer shape of the fluidized bed reactor in order to attach and detach the fluidized bed reactor; And
It may further include a vibration supply unit for supplying regular vibration to desorb the glass bubble fine particles attached to the upper mesh in the fluidized bed reactor,
The vibration supply unit,
Atomic layer deposition machine, characterized in that supplying mechanical vibration, pneumatic vibration, electromagnetic vibration, or ultrasonic vibration. The method of claim 1,
The fluidized bed reactor,
In order to induce a pressure drop inside the fluidized bed reactor, the width of the lower surface of the fluidized bed reactor is relatively narrower than the width of the upper surface (downwards tapering),
The lower surface is formed to have a relatively narrow width on the upper surface, and is formed to be inclined downward based on a vertical cross section,
An atomic layer evaporator, characterized in that when the glass bubble fine particles flowing in the fluidized bed reactor are lowered due to a space gap between the upper surface and the lower surface, the atomic layer deposition apparatus is characterized in that it can fall. The method of claim 1,
The reactant supply unit,
A reactant supply unit for supplying a metal reactant to the fluidized bed reactor; And
Atomic layer deposition apparatus comprising; a precursor supply unit for supplying a precursor for oxidizing the metal reactant in order to chemically adsorb the glass bubble fine particles. The method of claim 1,
The gas supply unit,
A first gas supply unit for supplying a reaction gas for coating the shell portion of the glass bubble fine particles; And
Consisting of; a second gas supply unit for supplying a purge gas for transporting the reaction gas to the process passage,
The first gas supply unit and the second gas supply unit,
Atomic layer deposition apparatus comprising a; MFC (Mass Flow Controller, mass flow controller) for controlling the flow of the reaction gas and the purge gas. The method of claim 1,
The pressure control unit,
A rotary pump for controlling the pressure inside the fluidized bed reactor to a ground state; And
And a throttle valve for adjusting the pressure inside the fluidized bed reaction in order to uniformly flow the glass bubble fine particles present in the fluidized bed reactor. Using the atomic layer deposition machine according to any one of claims 1 to 6,
(S1) supplying fine glass bubble particles and a metal precursor;
(S2) supplying a purge gas;
(S3) supplying a reaction gas; And
(S4) supplying a purge gas to form a functional coating layer on the fine glass bubble particles; Including,
The metal precursor is a Zn and Ti precursor,
The functional coating layer is a coating method using an atomic layer evaporator for functional coating of low-density glass bubble fine particles, characterized in that the TiZnO coating thin film. The method of claim 7,
The coating method,
A coating method, characterized in that repeating the atomic layer deposition cycle consisting of the steps (S1) to (S4) at least once through the atomic layer deposition method. The method of claim 7,
The glass bubble fine particles,
In the form of a shell,
The inner (core) portion of the shell is empty, and the shell portion is formed of Soda Lime Borosilicate Glass or silica (SiO ₂ ) having a thickness of 50 nanometers (nm) to 300 millimeters (mm). The coating method.

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