KR102241509B1 - Manufacturing process of nono-particles using flowable substrates and manufacturing device therefor - Google Patents

Abstract

The present invention is a method for producing nanoparticles on the surface of a material to create a new deposition surface using the principle of heterogeneous nucleation by providing a new deposition surface continuously in a limited space in a physical evaporation deposition method. , A method of continuously forming various kinds of nanoparticles on the surface of a material by forming a nucleus on the surface of a fluid substrate made of a material and continuously creating a deposition surface so that the generated nucleus does not grow into a thin film, and It relates to a device for.

Description

TECHNICAL FIELD The manufacturing process of nono-particles using flowable substrates and manufacturing device therefor.

The present invention relates to a method of manufacturing nanoparticles directly on the surface of a material used as a raw material for an existing product in a physical manner using the principle of heterogeneous nucleation. More specifically, it is a method of forming nanoparticles on the surface of a material by making vapor of a metal or a metal compound using a physical vapor deposition method. Here, "constituent material" is a material that has the shape of a solid powder or chip used in existing products and does not volatilize in a vacuum. In the present invention, it continuously flows to form nanoparticles within a limited space. It means a material that makes a fluid substrate.

In the present invention, vapors of a metal or a metal compound made by a physical method are solidified again on the surface of the material at a relatively low temperature to form a nucleus, which is the initial stage of thin film growth on the surface of the material. Subsequently, the core material formed on the surface of the material disappears from the region where the metal or metal compound vapor is supplied, so that no more metal vapors can access the nucleus. The resulting nuclei can no longer grow and are stabilized at room temperature into a nanoparticle-sized solid.

In the present invention, the flowable substrate can be obtained by continuously flowing solid powder or chip-shaped material in a limited space (hereinafter referred to as “constituent material container”). In other words, if a device that can flow powder or chip-shaped material in the material container (hereinafter referred to as “flow device”) is provided and the material is continuously moved, the material material in the material container is continuously fluid. It will cycle while having. At this time, the moment the vapor supplied from the device that provides metal or metal compound vapor reaches the surface of the member material (hereinafter referred to as “deposition surface”) located at the top of the material container, a nucleus, which is the smallest unit of solid, is formed. It is done. In this way, the nucleated member materials are moved away from the deposition surface by the continuous flow of the member materials by the flow device, and the nuclei are stabilized and become nanoparticles. In this continuous process, the material under the material container moves to the top to form a new deposition surface, and after forming a new nucleus by the vapor of a metal or metal compound on the surface, it leaves the deposition area and moves into the material. While the nucleus is stabilized, it becomes nanoparticles continuously. Since this process is repeated by the continuous flow of raw materials, the surfaces of new flowable substrates can be continuously provided on the deposition surface, and other nanoparticles can be continuously formed on the surface of the new flowable substrate. As a result, the present invention can efficiently mass-produce high-quality nanoparticles while creating a new deposition surface with only a simple flow of material passing through the material. In addition, the flowable substrate made of powder or chip-shaped material has many nucleation sites compared to the planar structure, so that it is possible to form a smaller and more stable nucleus compared to a deposition substrate such as a conventional fixed and smooth solid film.

Nano-sized materials exhibit new electrical, chemical, optical, and magnetic properties different from bulk materials due to their large specific surface area. Since nano-ized materials can give new functions by adding a small amount to existing products, various applications of nano-powder are being attempted in various industrial fields.

Methods of manufacturing nanopowder are generally classified into a chemical method and a physical method.

The method of manufacturing nanoparticles by a chemical method is to manufacture through oxidation/reduction methods using chemical materials such as metal salts, reducing agents, dispersants, surfactants, and organic solvents. It is a distributed form. Nanopowder manufactured by a chemical manufacturing method has problems such as agglomeration of nanoparticles by ionic particles or reaggregation of nanoparticles during drying. The effect may be reduced. In addition, it includes pollution problems and environmental pollution problems due to residual chemicals in nanoparticles.

Methods of manufacturing nanoparticles by conventional physical methods include mechanical grinding, electric explosion, and inert gas condensation. These physical methods of manufacturing nanoparticles have disadvantages in that impurities are easily mixed, or it is difficult to obtain nanoparticles having a uniform size, and it is difficult to obtain nanoparticles having a small size.

As an example of a method of manufacturing nanoparticles by a conventional physical method, there is an example of manufacturing nanoparticles using silicone oil within a limited space. In this method, a container is filled with silicone oil in a vacuum chamber, and a part of the drum is immersed in silicone oil and rotated. When a metal vapor is produced and supplied physically to the surface where the silicone oil of the drum is applied, nuclei are generated on the surface of the silicone oil. It will grow into particles. Nanoparticles formed on the silicone oil by continuously supplied metal vapors are mixed and stabilized by moving into the silicone oil by the continuous rotation of the drum. Such a method is an example of using a liquid-flowable substrate and uses the principle of non-uniform nucleation, but there are many problems in application to the industry because there is a problem that silicone oil must be removed when applied to a product.

Korean Patent Application Publication 10-2007-0044879

The present invention is to provide a method and apparatus for manufacturing nanoparticles in a physical manner using the principle of heterogeneous nucleation. An object of the present invention is to provide a physical method of making a metal or a metal compound into a vapor and forming it into nanoparticles on the surface of a raw material using the principle of heterogeneous nucleation. As a result, it is intended to solve the problems of non-uniform particle size, agglomeration between nanoparticles, residual chemicals, low dispersibility, impurity mixing, and low productivity of existing nanoparticle manufacturing methods.

In order to achieve the above object, the present invention

As a method of producing nanoparticles in a vacuum bath,

1) providing a material constituting a flowable substrate in a limited space;

2) providing at least one evaporation source selected from the group consisting of metals, metal compounds and alloys

3) continuously creating a new deposition surface by flowing raw materials;

*4) depositing the vapor generated from the evaporation source on the new deposition surface to form a nucleus of a metal, a metal compound or an alloy;

5) moving the core material formed thereon to move away from the deposition surface, and cooling the core material into nanoparticles; And

6) including the step of repeating steps 3) to 5), and

The material is in the form of powder or chips in a solid state, and

It provides a method of forming nanoparticles on the surface of the material constituting the flowable substrate, characterized in that the retention time of the material constituting the flowable substrate on the deposition surface is less than 1 second on average.

In addition, the present invention is a device for forming nanoparticles on the surface of a raw material.

Vacuum bath;

A member feed container provided in the lower part of the vacuum tank;

A flow device provided in the raw material container and provided with blades for stirring the raw material constituting the flowable substrate;

A cooling device for cooling the raw materials constituting the fluid substrate; And

It is provided on the top of the material container in the vacuum tank and includes an evaporation source capable of generating steam

It provides an apparatus for forming nanoparticles on the surface of a material constituting a flowable substrate.

The nanoparticle manufacturing method according to the present invention is a method of forming nanoparticles on the surface of a fluid solid substrate based on the principle of non-uniform nucleation. By controlling the time when the raw material forms the deposition surface, that is, the time that the material is exposed to the deposition area, it is possible to manufacture nanoparticles of small uniform size and high purity on the surface of the material. In addition, the size of the nanoparticles can be controlled by controlling the process conditions such as the deposition rate, the flow rate of the material, and the size of the material.

Unlike the conventional chemical manufacturing process, the nanoparticle manufacturing method according to the present invention does not use any chemicals during the process. Therefore, the nanoparticles formed in the process and the material forming the flowable substrate do not contain additional by-products. There is an effect that can produce nanoparticles. In addition, it has the advantage of being able to use the product itself to be produced. That is, in the present invention, nanoparticles are formed on the surface by using a raw material used as a raw material of an existing product as a substrate, and thus, there is an advantage that the final product can be manufactured by using it as it is in the existing product manufacturing process. In addition, it is very easy to impart functionality to a product due to the excellent dispersibility of the prepared nanoparticles.

In a chemical manufacturing method, since chemicals such as an oxidizing agent, a reducing agent, and a dispersing agent to be used are determined according to the type of nanoparticles to be produced, it is difficult to simultaneously prepare and disperse heterogeneous nanoparticles in the same solvent. In addition, in order to add nanoparticles to a product, the solvent used for the nanoparticle and the solvent used for the product must be the same or well mixed, but in most cases, it is difficult to find an appropriate solvent because different solvents are used. On the other hand, when the present invention is used, various kinds of nanoparticles can be produced by replacing only the material of the evaporation source that is the raw material of the nanoparticles in the same device, so that various nanoparticles are simultaneously formed on the surface of the flowable substrate, which is the same material. Because it is easy to form nanoparticles in the form of an alloy or an alloy, it is very easy to develop a multifunctional or special functional application material.

The apparatus for manufacturing nanoparticles according to the present invention can be manufactured by batch-type or continuous-type equipment, and it is easy to manufacture equipment for mass production by using a high-productivity evaporation source and applying a large-capacity raw material flow system.

1 is a graph of free energy change according to a nuclear radius in homogeneous / heterogeneous nucleation.
2 is a graph showing a difference between a critical nuclear radius and a critical free energy according to temperature.
3 is an example of a nanoparticle manufacturing apparatus that has a horizontal rotating shaft and a pedal-type flow blade in the material container to flow the material material.
4 is an example of a nanoparticle manufacturing apparatus for flowing a material by providing a vertical rotating shaft and a pedal-type flow blade in the material container.
5 is an example of a nanoparticle manufacturing apparatus having a horizontal rotating shaft and a ribbon-shaped flow blade in a material container.
6 is an example in which a cooling device is provided in a raw material container, a rotating shaft, and a flow blade.
7 is a photograph of silver/glucose.
8 is a photograph of palladium/glucose.
9 is a picture of platinum/glucose.
10 is a photograph of gold/glucose.
11 is a photo of a nano-colloid of platinum and gold.
12 is a photograph of a silver/PET chip.
13 is a photograph of a yarn obtained by spinning with silver/PET.
14 is a photograph of an antibacterial food material container made of silver/ABS.
15 is a photograph of an antibacterial film for packaging material made of silver/LDPE.
16 is a photograph of an antibacterial nonwoven fabric made of silver/PP.
17 is a photograph of Ni/Fe/glucose and Ni/SUS/glucose in which two different types of nanoparticles are formed on the surface of glucose, which is a constituent material of the same flowable substrate.
18 is a result of preparing a colloid in which Fe, SUS, Ni nanoparticles and mixed metal Fe/Ni and SUS/Ni nanoparticles are dispersed in water, which is the same solvent, without a dispersant.
19 is a photograph of Cu/Zn/calcium carbonate powder formed by forming alloy nanoparticles Cu/Zn on the surface of calcium carbonate.

The method of forming nanoparticles on the surface of the material of the present invention is to form nanoparticles on the surface of the material using the material used in the final product. The final product can be made by using the raw material in which the nanoparticles are formed on the surface.

Here, the term "constituent material" is a material that has the shape of a solid powder or chip used in existing products and does not volatilize in a vacuum. In the present invention, it is continuously fluid to form nanoparticles in a limited space. It refers to the material that makes the substrate.

In order to form nanoparticles on the surface of the material of the present invention, the material is placed in a material container having a certain volume and equipped with a flow device, and the material is continuously flowed in the material container by a flow device. At this point, it is exposed to the deposition area to form a deposition surface. The deposition surface continuously repeats a process in which a new deposition surface containing a new material appears due to the flow of the material.

The vapor particles supplied from the evaporation source reach the surface of the material located on the deposition surface and instantaneously condense to generate nuclei.Before the nucleus grows, the material is released from the deposition area by flow, and the resulting nuclei are stable. It becomes a nanoparticle. As the material that generated the nucleus disappears from the deposition area, a new deposition surface containing the new material is formed in the deposition area by flow, and the process of generating new nuclei is continuously repeated.

In the present invention, the retention time of the material constituting the flowable substrate on the deposition surface is less than 1 second on average. If it is longer than 1 second, the nanoparticles become coarse, and thus nanoparticles of the desired size cannot be obtained.

The nanoparticle manufacturing method according to the present invention uses the principle of non-uniform nucleation to form nuclei on the surface of the substrate, and after growing to the size of nanoparticles, the environment of the substrate is controlled so that the nanoparticles are no longer grown and stabilized. It is to form nanoparticles. Homogeneous nucleation refers to a case in which a nucleus is formed by itself in a liquid or vapor phase under ambient temperature or pressure conditions, and non-uniform nucleation refers to a case where vapor particles reach the surface of a substrate or heterogeneous to form a nucleus.

Referring to Fig. 1, the principle of generating non-uniform rows according to the present invention will be described in detail.

1 is a graph of a change in free energy (ΔG) according to the size (r) of a nuclear radius according to the nucleation theory. _{ΔG hom} and _{ΔG het} mean free energy for homogeneous nucleation and homogeneous nucleation, respectively. Both uniform nucleation and non-uniform nucleation ^{exist in an unstable nucleus below the critical radius (r *} ), and grow into a stable nucleus above the critical size.

As shown in FIG. 1, the non-uniform nucleation is advantageous in nucleation because the energy barrier is lower than that of the uniform nucleation. In the case of supplying vapor particles to the surface of a fixed substrate, the nuclei are initially generated by the vapor reaching the surface of the substrate, and the nuclei continue to grow and combine with the adjacent nuclei to change into a thin film by the continuous supply of vapor. . However, in the heterogeneous nucleation method of the present invention, in order to form nanoparticles, the growth of the formed nuclei is stopped by rapidly moving the substrate to an area not exposed to the vapor so that the nuclei generated on the surface of the substrate by the vapor no longer grow. It is what makes it nanoparticles.

2 is a graph showing a difference between a critical nuclear radius and a critical free energy according to temperature. As the temperature decreases (T1 -> T2), the difference between the critical free energy and the critical nuclear radius decreases. That is, when the temperature of the substrate is lower, it is more advantageous to generate nuclei having a smaller size on the surface of the substrate.

When a material capable of imparting a new function to the final product is selected as the evaporation source by using the method of the present invention, a material having nanoparticles having a new function can be made easily. The raw materials made in this way can be put into the manufacturing process of existing products as they are to be commercialized.

The raw material of the present invention is a non-volatile metal, an organic polymer. It may be an organic compound or an inorganic compound.

The ingredients of the present invention are metals such as copper, aluminum, tungsten carbide, graphite, and organic compounds such as glucose, sugar polysaccharides, and sucrose, polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and ABS resin. Organic polymers such as (acrylonitrile-butadiene-styrene resine), polysulfone (PS), polymethyl methacrylate (PMMA), polyacrylate, polytetrafluoroethylene (PTFE), and polyvinylidene fluoride (PVDF) , Alumina, calcium carbonate, NaHCO3, TiO2, NaCl, zeolite, may be an inorganic compound such as carbon nanotube CNT.

The smaller the diameter of the raw material powder or chip, the better the nucleation can be formed for nanoparticle formation, but it may be preferably 1 μm to 5 mm. The diameter of the raw material powder or chips used in the present invention may be selected differently depending on the specific gravity.

When the material has a specific gravity of 2 or more, such as metal or alumina, the particle size may be small, and preferably 1 μm to 1 mm. When the raw material has a specific gravity of less than 2, such as an organic polymer, the particle size is preferably large and may be 1mm to 5mm. When the specific gravity and size of the particles are as described above, nucleation can be performed well without scattering out of the material container when the material material flows.

On the other hand, the size and degree of nucleation of the nanoparticles may vary depending on the surface characteristics of the material used as the flowable substrate. For example, vapor particles that have reached the surface of a crystalline substrate can grow into relatively coarse nanoparticles because they have good mobility on the surface of the crystalline substrate and are easy to bind with surrounding particles.

In the present invention, the flowable substrate formed by the material is a three-dimensional shape of the material in a general flat surface. In this case, when the particle size of the material ^{is reduced by (1/2) n} magnification, the deposition surface area is n ² times. It increases in proportion to and makes the nucleation easier to form exponentially compared to a flat substrate. As a result, nuclei formation for nanoparticles is well formed compared to a flat substrate.

The shorter the retention time for the material to stay on the deposition surface, the better. If the material is less than 1 second, the material does not escape to the outside and the formed nuclei do not grow, which is advantageous to become nanoparticles.

The nanoparticles made by the method of the present invention have a size of 2 to 30 nm, more preferably 2 to 10 nm.

The present invention may include a metal, a metal compound, or an alloy as an evaporation source. The metals are silver (Ag), copper (Cu), iron (Fe), titanium (Ti), zinc (Zn), zirconium (Zr), gold (Au), platinum (Pt), palladium (Pd), and rare earths ( Rare Earth Materials) and silicon (Si) may be one or more selected from the group consisting of. The alloy may be at least one selected from the group consisting of stainless steel (SUS), brass, and bronze. The metal compound may be at least one selected from the group consisting of metal oxides, metal nitrides, and metal oxynitrides.

The step of generating vapor from the evaporation source of the present invention includes DC sputtering, DC magnetron sputtering, RF sputtering, Ion Beam Sputtering, and Arc Discharge Process. ), Laser Ablation, Thermal Evaporation, E-beam Evaporation, Molecular Beam Epitaxy, or a combination thereof.

The present invention provides a material having nanoparticles on the surface prepared by the above method.

The present invention provides a product manufactured using a raw material having nanoparticles on the surface manufactured by the above method.

The present invention is a device for forming nanoparticles on the surface of the material

Vacuum bath;

A member feed container provided in the lower part of the vacuum tank;

A flow device provided in the raw material container and provided with blades for stirring the raw material constituting the flowable substrate;

A cooling device for cooling the raw materials constituting the fluid substrate; And

It is provided on the top of the material container in the vacuum tank and includes an evaporation source capable of generating steam

It provides an apparatus for forming nanoparticles on the surface of a material constituting a flowable substrate.

The apparatus of the present invention consists of a vacuum bath.

The device of the present invention minimizes the exposure time of the uppermost layer of the fluid substrate made by the efficient flow of the material to the deposition area, that is, the time to be exposed to the deposition surface by the flow device inside the material container. It disappears and then provides a new top layer of flowable substrate, and the process is repeated over and over again. While the raw materials in which the nanoparticles are formed are flowing so that they are not exposed to the deposition area for a relatively long period of time in the raw material container, a new material is provided to the deposition surface, and new nuclei are formed on the surface of the new material. The present invention is capable of mass-producing a material with high quality nanoparticles by continuously exposing a new material to the deposition surface by using a flow device that continuously flows the material and inserts the material into the material container, which is a limited space. have.

The material container installed inside the vacuum tank of the present invention prevents the loaded material material from leaving the limited space during flow. Meanwhile, as the material flows up and down in the material container, the top layer of the material container continuously forms a new deposition surface, a fluid substrate. That is, the member materials located on the top surface of the material container are exposed to the deposition area to form the deposition surface, and the material materials located under the deposition surface are out of the deposition area. In order to form continuous nanoparticles, substrate materials must be continuously mixed and fluidized by a flow system. In addition, by having a device capable of cooling a solid substrate, nanoparticles can be formed more easily and nanoparticles having a smaller size can be efficiently produced.

The flow device for stirring the material constituting the fluid substrate is a screw type, a pedal type, a turbine type, a propeller type, an anchor type, or a ribbon to which a vertical or horizontal axis of rotation is applied. (ribbon) can be.

The stirring speed of the flow device is preferably 20 to 100 rpm. The stirring speed may be different depending on the material, but if the specific gravity of the material is less than 2, the speed may be lowered, and the greater the specific gravity of 2 or more may increase the speed. When agitating at the above speed, the deposition surface of the uppermost layer made of a material changes in proportion to the stirring speed.

On the other hand, the blades of the flow device of the present invention may be buried in raw materials. In this case, it is possible to prevent the material from scattering out of the material container and also to prevent vapor deposition on the wing.

The cooling device for cooling the raw material constituting the flowable substrate of the present invention is installed on the outer wall of the flow device, the outer wall of the raw material container, or inside the raw material container, and constitutes a cooling line capable of circulating a low-temperature liquid.

The apparatus of the present invention includes an evaporation source capable of generating steam and is provided on the top of the raw material container in the vacuum tank. The evaporation source is a metal, a metal compound, or an alloy to form a metal, a metal compound, or an alloy vapor by a physical method.

The vacuum degree of the vacuum tank of the present invention is controlled by including an inert gas, and the inert gas may be argon (Ar), neon (Ne), N2, O2, CH4, or the like. ^{The vacuum degree of the vacuum tank is preferably 1x10 -1} Torr when inert gas or reactive gas for a compound is injected. It is also possible in about degree, but in case of pure metal only, preferably 1x10 ^-5 Torr. It may be a high vacuum below.

The step of generating vapor from the evaporation source includes DC sputtering, DC magnetron sputtering, RF sputtering, Ion Beam Sputtering, Arc Discharge Process, and laser. It may be selected from laser ablation, thermal evaporation, e-beam evaporation, molecular beam epitaxy, or a combination thereof.

In the present invention, the deposition time is from 10 minutes until all the raw materials of the evaporation source are exhausted. In addition, when the raw material of the evaporation source is recharged and the raw material is continuously added, the concentration of the nanoparticles in the raw material can be controlled by controlling the time and can be produced at an infinite concentration.

The vacuum deposition can control the growth of nanoparticles by controlling the vacuum degree of the deposition tank, the flow rate of the flow device, the deposition time, and the deposition power, and thus the size and amount of nanoparticles deposited on the material.

Hereinafter, for example, a characteristic of a device for forming nanoparticles on the surface of a raw material will be described. In the example of various devices, methods for forming various deposition surfaces for manufacturing high-quality nanopowder are described, and a method for efficiently forming a deposition surface and a method for efficiently cooling a flowable substrate are described.

3 is an example of a nanoparticle manufacturing apparatus to which a method of flowing a material by providing a flow blade and a horizontal rotating shaft in a material container is applied. The configuration of the apparatus includes a raw material container 3 including a physical evaporation source 2 and a flow device 4 for flowing the raw material 5 in the vacuum bath 1. The member material 5 is put into the member material container that flows the material material within a limited space, and the material material is flowed using the horizontal rotation shaft 6 provided in the member material container. At this time, the flow blade 7 for flowing the raw material is attached to the rotating shaft 6, and the structure of the blade can be manufactured in a pedal-type structure. The apparatus for cooling the substrate may be installed on the outer wall of the material container, and may provide a cooling function to the rotating shaft 6.

At this time, the blades are buried in the material to prevent the material 5 from scattering out of the material container 3 when the material flows, and also prevents vapor deposition on the blade 7.

4 is an example of an apparatus for manufacturing nanoparticles on the surface of the material by providing a flow device for flowing the material using the vertical rotation axis (6). The device has a flow device 4 for flowing the evaporation source 2 and the raw material 5 in the vacuum bath. In the vacuum chamber, the physical evaporation source 2 is located at the top and the flow device 4 is located at the bottom. The flow blade 7 included in the flow device may be configured as a pedal type or a spiral.

5 is an example of a nanoparticle manufacturing equipment having a ribbon-type flow blade structure using a horizontal rotation axis. The device comprises a raw material container 3 having an evaporation source 2 at the top and a flow device 4 at the bottom in the vacuum bath.

The flow device 4 is composed of a horizontal rotating shaft 6 and a flow blade 7 for flowing the raw material 5. The flow wing (7) is a double flow wing and is composed of an inner flow wing (8) close to the rotation axis and an outer flow wing (9) far from the rotation axis, and each flow wing is composed of a spiral structure in the opposite direction from the center. Has been. By the rotation of the ribbon-type flow blade, the overall flow of the material is improved and the flow of the material is uniform. In the case of the forward rotation and the reverse rotation of the rotating shaft, the members move in opposite directions to each other. When rotating in the forward direction, the fluid substrates located near the center of the rotation axis are moved toward the center by receiving the force from the inner flow wing, and the fluid substrates far from the rotation axis are moved away from the center by the force of the outer flow wing. Even if it is rotated in the forward direction, the flowable substrate can be moved in the opposite direction according to the direction of the flow blades. The width or spacing of the ribbon-type flow blade can be changed according to the size and physical characteristics of the material selected as the flowable substrate material.

It is preferable to fill the level of the raw material above the maximum height of the outer flow blade in the device to which the horizontal rotating shaft type ribbon-type flow blade is applied. In this case, since there is almost no area in which the constituent materials are stagnant on the top surface, excellent flowability is obtained. The movement of the material in the vicinity of the rotation axis moves in the horizontal direction by the internal flow blades, so unlike the horizontal rotation axis, the movement of the material material in the vicinity of the rotation axis is excellent. This device has relatively high deposition efficiency because the flow blades are not exposed to the deposition area and can minimize the accumulation of heat in the deposition area. Due to the double ribbon-type flow blade, the overall flow of the material is good and the flow of the material is uniform, so that the nanoparticles formed on the surface of the substrate by the supplied metal vapor have a relatively uniform distribution. In addition, since damage to the substrate by heat is minimized, nanoparticles of excellent quality can be manufactured with high efficiency.

In the apparatus of the present invention, a device capable of cooling the raw material may be provided, and a water-cooled cooling device or other cooling device may be added as a cooling method. The location where the cooling device is attached may be a wall surface of a raw material container, a rotating shaft, a flow blade, or the like. The role of the cooling device is to discharge heat that may accumulate in the material by friction or heat in the deposition area to the outside, and it is advantageous in manufacturing high-quality nanoparticles as it can form a smaller and larger amount of nuclei when manufacturing nanopowder. .

6 shows an example in which a rotating shaft cooling device 10, a rotating blade cooling device 11, and a component fuel tank cooling device 12 are provided. In FIG. 6, only a part of the ribbon-type flow blade is shown, but it means that the same concept can be applied to the case of using a ribbon-type flow blade as in the apparatus shown in FIG. 6 and other various flow blades.

The cooling device cools the metal structures in which the material and the material in which the nanoparticles are formed in direct contact in order to effectively dissipate heat that may be generated by the material being exposed to the deposition area or friction caused by flow. You can control the temperature. The cooling device may be a cooling water circulation method, and the temperature of the cooling water supplied to the cooling device is preferably set within the range of 5 to 15 degrees.

Hereinafter, the present invention will be described with reference to one embodiment. However, the present invention is not limited to the following examples.

Example 1.

(1) Preparation of glucose powder in which silver, palladium, platinum, and gold nanoparticles are deposited, respectively

Using glucose powder as a material constituting a fluid substrate, and using metal ingots of silver, palladium, platinum, and gold, respectively, as a raw material for nanoparticles, nanoparticles on the surface of glucose by using the material flow device of FIG. The particles were deposited.

Specifically, after putting the glucose powder into the raw material container provided in the vacuum tank, vacuum evacuation was performed using a vacuum pump to finally achieve a ^{high vacuum of 1x10 -5} Torr or less. In that state, Ar gas was injected into the vacuum bath at a flow rate of 50 ~ 150 sccm, and the glucose powder as a component material was flowed at a speed of 60 rpm using a flow device to provide a continuous and repetitive deposition surface made of glucose powder. The metal ingot used as the evaporation source was a disk type having a diameter of 10 cm and a thickness of 1 cm, and was attached to the DC sputtering cathode. The metal atoms of the evaporation source were vaporized to form nanoparticles on the surface of glucose.

Glucose powder on which yellow silver nanoparticles are deposited (Ag/glucose), glucose powder on which black palladium nanoparticles are deposited (Pd/glucose), and glucose powder on which brown platinum nanoparticles are deposited (Pt/glucose) by the above method ) And gray gold nanoparticles were deposited to obtain a glucose powder (Au/glucose).

Pictures of the glucose powder on which the nanoparticles prepared by the above method are deposited are shown in FIGS. 7, 8, 9, and 10.

(2) Manufacture of platinum and gold colloids

When the glucose powder (a) on which the platinum nanoparticles are deposited and the glucose powder (b) on which the gold nanoparticles are deposited are mixed with water, the glucose is dissolved in water and the nanoparticles are evenly dispersed in water without a separate dispersant. It becomes a uniform colloidal state as shown in ((a) is a platinum nanoparticle colloid, (b) is a gold nanoparticle colloid.)

Example 2.

(1) Manufacture of PET chips with silver nanoparticles deposited

PET (polyethyleneterephthalate) chips, which are one of the polymer materials, were used as a raw material, and silver nanoparticles were deposited using a silver ingot as an evaporation source. The manufacturing sequence is to put the PET chip into the raw material container provided in the vacuum tank, and then perform vacuum evacuation using a vacuum pump, and vaporize the silver from the evaporation source provided in the upper part of the material container to form silver nanoparticles on the surface of the PET chip. Was deposited. A photograph of a PET chip on which silver nanoparticles are deposited is shown in FIG. 12.

(2) production of yarn

The silver/PET chip manufactured in this way was put into the existing spinning process to produce a yarn. A picture of the thread is shown in FIG. 13.

Example 3.

(1) Manufacture of ABS resin chips with silver nanoparticles deposited

Silver nanoparticles were deposited on the surface of the ABS chip by the method according to the present invention using an ABS resin (acrylonitrile-butadiene-styrene resine) chip as a material of the flowable substrate.

(2) plastic injection

The ABS resin chip on which the silver nanoparticles were deposited was injection-molded into a product in which the nanoparticles were evenly dispersed by using the existing injection molding process without additional additives or dispersants, and this was shown in FIG. 14.

Example 4.

(1) Manufacture of LDPE chips with silver nanoparticles deposited

Silver nanoparticles were formed on the surface of the LDPE chip by the method according to the present invention using LDPE (Low Density Polyethylene) chips as a material for the flowable substrate.

(2) Preparation of antibacterial film

An antimicrobial film in which the nanoparticles were evenly dispersed was prepared by using the existing film manufacturing process without any additional additives or dispersants using the LDPE chip on which the silver nanoparticles prepared by the above method were deposited, and is shown in FIG. 15.

Example 5.

(1) Manufacture of PP chips with silver nanoparticles deposited

A PP chip on which silver nanoparticles were deposited was manufactured by the method according to the present invention using a PP (polypropylene) chip as a material for a flowable substrate.

(2) Manufacture of nonwoven fabric

A PP chip on which the silver nanoparticles prepared by the above method were deposited, using the existing nonwoven fabric manufacturing process without any additional additives or dispersants, to prepare an antibacterial nonwoven fabric in which nanoparticles were evenly dispersed, and this was shown in FIG. 16.

Example 6.

(1) Preparation of Fe/glucose, SUS/glucose and Ni/glucose powder

Glucose powder on which Fe nanoparticles, SUS (stainless steel) nanoparticles, and Ni nanoparticles were deposited by the method according to the present invention was prepared by using glucose powder as a material of the flowable substrate.

(2) Preparation of Ni/Fe/glucose and Ni/SUS/glucose powder

Ni/Fe/glucose and Ni/SUS/glucose powder formed by sequentially forming two different kinds of metal nanoparticles on the surface of glucose as a component material by the method according to the present invention using glucose powder as a material for a fluid substrate Was prepared. The manufacturing sequence is a continuous and repetitive process consisting of glucose powder by injecting glucose powder into a material container provided in a vacuum tank and evacuating using a vacuum pump, and flowing the glucose powder as a material material using a flow device. It was made to provide a deposition surface. First, Ni nanoparticles were formed on the surface of the glucose powder using the Ni metal ingot as an evaporation source. In addition, by replacing the Ni metal ingot with the Fe metal ingot to form Fe nanoparticles on the surface of the glucose powder to which the Ni nanoparticles were attached, glucose powder (Ni/Fe/glucose) on which iron and nickel nanoparticles were deposited was prepared.

Glucose powder (Ni/SUS/glucose) on which stainless steel and nickel nanoparticles were deposited was prepared in the same process as the above method using a stainless steel (SUS) ingot and a Ni metal ingot. Fig. 17 shows photographs of Ni/Fe/glucose (a) and Ni/SUS/glucose (b) powder.

(3) nanoparticle colloid preparation

The Fe/glucose, Ni/glucose and SUS/glucose powders prepared above were used to prepare a colloid of Fe, Ni, and SUS nanoparticles dispersed in the same solvent (water) without a dispersant. In addition, Fe/Ni/SUS/Ni mixed metal nanoparticle colloid was prepared in the same manner using Fe/Ni/glucose and SUS/Ni/glucose powder. This is shown in Figure 18. In FIG. 18, it can be seen that Fe, SUS, and Ni nanoparticles, which are single materials, are well dispersed in the solvent, and in the sample in which two types of nanoparticles are formed, Ni/Fe and Ni/SUS mixed metal nanoparticles are respectively It can be seen that it is well dispersed without a dispersant in the same solvent ((a) is a Fe nanoparticle colloid, (b) is a SUS nanoparticle colloid, (c) is a Ni nanoparticle colloid, and (d) is a Ni/Fe Nanoparticle colloid, (e) is a Ni/SUS nanoparticle colloid.)

Example 7. Preparation of Cu/Zn/Calcium Carbonate Powder

A Cu/Zn/calcium carbonate powder was prepared in which Cu and Zn nanoparticles were simultaneously formed on the surface of calcium carbonate as a member material by the method according to the present invention using _{calcium carbonate (CaCO 3} ) powder as a material for a fluid substrate. In this case, an alloy of Cu:Zn = 6:4 was used as the metal ingot used for the evaporation source. As a result, a photograph is shown in FIG. 19.

As described in the above embodiments, various member materials on which nanoparticles manufactured by the method according to the present invention are deposited have an advantage that they can be used as they are in manufacturing a final product. Since the nanoparticles formed on the surface of the raw material exhibit high dispersibility without a dispersant, they can be used as it is in the existing application product manufacturing process and included in various types of products such as fibers, films, nonwoven fabrics, and three-dimensional shapes. In addition, since various nanoparticles in the form of single, mixed, and alloy, which were difficult to manufacture in conventional chemical processes, can be formed on the surface of the material, it is very easy to impart various functions to existing applications.

1. Vacuum tank 2. Evaporation source 3. Raw material container 4. Flow device 5. Fluid substrate (constituent material) 6. Rotation shaft 7. Flow blade 8. Ribbon type inner flow blade 9. Ribbon type outer flow blade 10. Rotary shaft cooling device , 11. Rotating blade cooling device 12. Constituent fuel tank cooling device 101. Evaporation surface

Claims (12)

As a method of producing nanoparticles in a vacuum bath,
1) providing a material constituting a flowable substrate in a limited space;
2) providing at least one evaporation source selected from the group consisting of metals, metal compounds and alloys
3) continuously creating a new deposition surface by flowing raw materials;
4) depositing the vapor generated from the evaporation source on the new deposition surface to form a nucleus of a metal, a metal compound, or an alloy;
5) moving the core material formed thereon to move away from the deposition surface, and cooling the core material into nanoparticles; And
6) including the step of repeating steps 3) to 5), and
The member materials constituting the flowable substrate have an average retention time of less than 1 second on the deposition surface,
The raw material powder or chip has a diameter of 1 μm to 5 mm, and is a material that does not volatilize in a vacuum,
The diameter of the raw material powder or chip shape varies depending on the specific gravity.
When the specific gravity of the material is 2 or more, the diameter is 1 μm to 1 mm, and when the specific gravity is less than 2, the diameter is 1 mm to 5 mm.
When the particle size of the material ^{is reduced by (1/2) n} magnification of the fluid substrate formed by the material, the deposition surface area increases in proportion to ^{n 2 times.}
A stirring blade is provided in the flow device to flow the cored material, the stirring blade is buried in the material, and the stirring speed of the stirring blade is 20-100rpm, and the stirring speed is adjusted according to the specific gravity of the material. Method of forming nanoparticles on the surface of a material constituting a fluid substrate, characterized in that The method of claim 1, wherein the material is a nonvolatile metal, an organic polymer, an organic compound, or an inorganic compound. delete delete delete The method according to claim 1, wherein the metal is silver (Ag), copper (Cu), iron (Fe), titanium (Ti), zinc (Zn), zirconium (Zr), gold (Au), platinum (Pt), palladium ( At least one selected from the group consisting of Pd), rare earth materials, and silicon (Si), and the alloy is at least one selected from the group consisting of stainless steel (SUS), brass, and bronze And, the metal compound is at least one selected from the group consisting of metal oxides, metal nitrides, and metal oxynitrides; a method of forming nanoparticles on the surface of a member material constituting a fluid substrate delete A product manufactured by the method of claim 1 and made of a material with nanoparticles deposited on the surface delete delete delete delete

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