KR101481346B1 - Method of fabricating metal-ceramic nano particle - Google Patents

Abstract

The present invention relates to a metal-ceramic nanoparticle manufacturing method. The method comprises: a step of preparing a base solution; a step of arranging multiple electrodes in the base solution; a step of forming colloid containing metal particles by ionizing metal elements contained in the multiple electrodes by applying voltage to the multiple electrodes and reducing ionized metal elements; a step of preparing ceramic particles; a step of mixing the ceramic particles in the colloid containing the metal particles; and a step of drying and heating the colloid containing the metal particles and the ceramic particles.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a metal-ceramic nano particle,

The present invention relates to a method of manufacturing metal-ceramic nanoparticles, and more particularly, to a method of manufacturing metal-ceramic nanoparticles in which ceramic particles are mixed with a colloid including metal particles produced by an electrolysis method.

Nanoparticles mean particles with a large surface area ranging in size from a few nanometers to a few hundred nanometers. Since nanoparticles manipulate and control materials on nano-stales, reference materials and new physical / chemical properties can be expected, making them the next-generation material that can overcome the limitations of existing materials.

Accordingly, nanoparticles are a key new material required for commercialization of various technologies such as biosensors, light emitting materials for next-generation displays, terra-bit class hard drives, solar cells, ink-jet materials for inkjet fritting, catalysts, medicine and biotechnology.

In order to improve and improve the properties of these nanoparticles, studies are underway to manufacture nanoparticles mixed with metals and ceramics.

For example, as disclosed in Korean Patent Registration No. 10-0819418 (Application No. 10-2007-0107590), transition metals and their alloy particle powders, ceramic particle powders, and synthetic polymers are dissolved in a polar solvent, Various methods for utilizing metal and ceramic powders have been developed.

For example, in Korean Patent Registration No. 10-0823487 (Application No. 10-2006-0107331), a mixed solution is prepared by mixing a metal precursor and a solvent, and the metal precursor is reduced by examining the mixed solution, Nanoparticles are prepared and used as catalysts.

SUMMARY OF THE INVENTION The present invention provides a method for producing metal-ceramic nanoparticles having improved catalytic properties.

Another object of the present invention is to provide a method for manufacturing metal-ceramic nanoparticles which can be mass-produced easily.

Another object of the present invention is to provide a method for manufacturing a highly reliable metal-ceramic nano-particle.

Another object of the present invention is to provide a method for manufacturing porous metal-ceramic nanoparticles.

In order to solve the above-mentioned technical problems, the present invention provides a method for manufacturing metal-ceramic nanoparticles.

The method of manufacturing a metal-ceramic nanoparticle according to the present invention includes the steps of preparing a base solution, disposing a plurality of electrodes in the base solution, applying a voltage to the plurality of electrodes, Ionizing the element and reducing the ionized metal element to form a colloid containing the metal particle; preparing ceramic particles; mixing the ceramic particles with a colloid containing the metal particles; And drying and heat-treating the colloid including the particles and the metal particles.

The step of preparing the colloid containing the metal particle may further include dispersing the produced metal particle in the base solution while ionizing the metal element and reducing the metal ion.

The step of preparing the ceramic particles comprises the steps of: preparing a source solution; spraying the source solution in a droplet state; and heat treating the source solution in a droplet state to form a ceramic particle Lt; / RTI >

The source solution may comprise a water soluble polymer added.

The water-soluble polymer may include at least one of poly ethylene glycol (PEG), poly acrylic acid (PAA), polyvinylpyrrolidone (PVA), and polyvinyl alcohol (PVA).

The source solution contains at least one of aluminum hydroxide (Al (OH) ₃ ), aluminum sulfite (Al ₂ (SO ₄ ) ₃ ), aluminum chloride (ALCl ₃ ), or aluminum isopropyl manganate .

According to an embodiment of the present invention, a source solution is sprayed in a droplet state, and a source solution in a sprayed droplet state is heat-treated to produce ceramic particles. The ceramic particles may be mixed with colloids containing metal particles prepared by an electrolysis method to produce metal-ceramic nanoparticles. Thus, the catalytic properties of the metal-ceramic particles can be improved. In addition, a metal-ceramic nanoparticle manufacturing method which can be mass-produced easily by a simplified manufacturing process can be provided.

1 is a flowchart illustrating a method for fabricating metal-ceramic nanoparticles according to an embodiment of the present invention.
FIG. 2 is a view for explaining an apparatus for producing ceramic particles according to a method of manufacturing a metal-ceramic nanoparticle according to an embodiment of the present invention.
FIG. 3 is a flowchart illustrating a method of manufacturing a colloid including metal particles according to an embodiment of the present invention. Referring to FIG.
FIG. 4 is a view for explaining an apparatus for producing a colloid containing metal particles according to a method of manufacturing metal-ceramic nanoparticles according to an embodiment of the present invention.
FIG. 5 is a graph for explaining heat generation characteristics of metal-ceramic nanoparticles produced according to the method of manufacturing metal-ceramic nanoparticles according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

Also, in various embodiments of the present specification, the terms first, second, third, etc. are used to describe various elements and the like, but should not be limited by such terms. These terms have only been used to distinguish one component from another. Each embodiment described and exemplified herein also includes its complementary embodiment.

FIG. 1 is a flow chart for explaining a method of manufacturing a metal-ceramic nanoparticle according to an embodiment of the present invention. FIG. 2 is a cross-sectional view illustrating a method of fabricating a metal-ceramic nanoparticle according to an embodiment of the present invention. Fig. 2 is a view for explaining an apparatus for manufacturing.

Referring to FIGS. 1 and 2, a base solution 110 is prepared in a container 100 (S110). The base solution 110 may be a DI water to which a reducing agent is added. The reducing agent may include at least one of sodium citrate, citric acid, trisodium citrate monosodium citrate, or alcohol.

A plurality of electrodes 121 and 122 are disposed in the base solution 110 (S120). The size and surface area of the first electrodes 121 and 122 spaced apart from each other in the base solution 110 may be different from each other. The size / surface area of the first electrode 121 may be smaller than the size / surface area of the second electrode 122.

A voltage is applied to the electrodes 121 and 122 by using the power source 230 to ionize the metal element included in the electrodes 121 and 122 and to reduce the ionized metal element to generate a colloid containing metal particles (S130).

A first voltage V1 is applied to the first electrode 121 having a relatively small surface area and a second voltage V2 of a level lower than the first voltage V1 is applied to the second electrode 122 having a relatively small surface area, (V2) may be applied. Accordingly, a plurality of sites are provided in which the ionized metal elements can be reduced by receiving electrons from the surface of the second electrode 122, so that metal particles can be easily formed.

The stirrer 142 and / or the ultrasonic disperser 144 may be disposed in the container 100 filled with the base solution 110. The base solution 110 is stirred by the stirrer 142 and / or the ultrasonic disperser 144 while the metal elements constituting the first electrode 121 are ionized and the ionized metal elements are reduced. . As a result, the precipitated metal particles can be dispersed in the base solution 110.

According to one embodiment, as the amount of metal particles to be deposited increases, the speed at which the base solution 110 is stirred by the stirrer 142 and / or the ultrasonic disperser 144 may be increased. Thus, agglomeration of the metal particles is minimized, and colloids having metal particles of uniform size can be provided.

Ceramic particles are prepared (S140). The step of preparing the ceramic particles will be described with reference to Figs. 3 and 4. Fig.

FIG. 3 is a flowchart illustrating a method of manufacturing ceramic particles according to an exemplary embodiment of the present invention. FIG. 4 is a cross-sectional view illustrating a method of manufacturing a metal-ceramic nanoparticle according to an exemplary embodiment of the present invention. Fig. 3 is a view for explaining an apparatus for producing ceramic particles according to the present invention.

3 and 4, a source solution (SS) is prepared (S210). The source solution SS may include a raw material for ceramics. For example, the source solution SS can be prepared by adding aluminum hydroxide (Al (OH) ₃ ), aluminum sulfite (Al ₂ (SO ₄ ) ₃ ), aluminum chloride (ALCI ₃ ) to a solvent such as DI water or alcohol ), Or aluminum isopropoxide oxide (AIP) may be added. In this case, the produced ceramic particles may be aluminum oxide powder. In another example, the source solution SS may comprise a metal salt.

The source solution (SS) may further comprise a water-soluble polymer. For example, the water-soluble polymer may include at least one of poly ethylene glycol (PEG), poly acrylic acid (PAA), polyvinylpyrrolidone (PVA), and polyvinyl alcohol (PVA). By the water-soluble polymer added to the source solution (SS), the porosity of the produced ceramic powder can be increased.

The source solution SS may be stored in the source solution supply unit 210. The source solution supply unit 210 may supply the source solution SS to the atomizer.

The source solution SS may be sprayed in a droplet state by the ultrasonic vibrator 212 installed in the sprayer S220. For example, the ultrasonic vibrator 212 may be sprayed in a droplet state So that the source solution SS can be sprayed in a droplet state.

The sprayed source solution (DSS) in the droplet state can be transferred to the reactor by the carrier gas 222 supplied from a carrier gas supplier 220. The carrier gas 222 may include at least one of air, oxygen gas, nitrogen gas, inert gas, and mixed gas.

The source solution (DSS) in the droplet state can be filtered by the filter unit 230 before moving to the reactor. The filter 230 may filter droplets larger than the reference size among the droplet source solution (DSS). Thus, droplets larger than the reference size may not enter the reactor. Droplets having a reference size or smaller can be introduced into the reactor by the filtering unit 130, and the uniformity of the size of the ceramic particles to be produced can be improved.

Also, the filter unit 230 can prevent the impurity particles from entering the reactor. Thus, ceramic particles of high purity can be produced.

Unlike the above-described and embodiments, the filter portion 230 may be omitted in order to simplify the manufacturing process of the ceramic particles.

The source solution (DSS) in the droplet state that has entered the reactor by the carrier gas 222 may be heat treated and ceramic particles may be collected at the collector 250. (S230) In the reactor, By the heat supplied to the solution (DSS), the source solution (DSS) in the droplet state can be thermally decomposed.

The reactor may include a first temperature sensor 242, a first heater 244, a second temperature sensor 246, a second heater 248, and a temperature controller 240. The first temperature sensor 242 and the first heater 244 are disposed at the lower end of the reactor adjacent to the filter unit 230 and the second temperature sensor 246 and the second heater 248 are disposed adjacent to the filter unit 230, May be disposed at the top of the reactor adjacent to the collecting unit 250.

The temperature controller 240 may receive the measured temperature from the first temperature sensor 242 and control the first heater 244 such that the lower end of the reactor has a first temperature. The temperature controller 240 may receive the measured temperature from the second temperature sensor 246 and control the second heater 248 such that the upper end of the reactor has a second temperature higher than the first temperature .

Thus, the droplet source solution (DSS) that has entered the reactor may be heat treated to the first temperature and then to a second temperature higher than the first temperature. If high-temperature heat is applied to the source solution (DSS) in the droplet state at once, the characteristics of the ceramic particles may be deteriorated. However, as described above, according to the embodiment of the present invention, after the source solution (DSS) is subjected to the heat treatment at a relatively low temperature in the droplet state, the heat treatment is performed at a relatively high temperature to minimize the deterioration of the characteristics of the ceramic particles .

In order to simplify the production process of the ceramic particles, unlike the above-described embodiment and the embodiment described above, one temperature sensor is provided in the reactor, and the temperature in the reactor can be kept constant.

In the reactor, the reaction gas 262 generated by thermally decomposing the source solution (DSS) in the droplet state may be collected by the pump 260 and discharged to the outside.

1, the ceramic particles may be mixed with the colloid containing the metal particles produced by the above-described method (S150). The ceramic particles may be mixed with the colloid containing the metal particles And then stirred for a certain period of time.

The colloid containing the ceramic particles and the metal particles may be dried and heat treated (S160). For example, the colloid containing the ceramic particles and the metal particles may be dried in an oven or the like at a temperature higher than room temperature Dried and heat treated.

According to the embodiment of the present invention, the ceramic particles produced by heat-treating the source solution in the droplet state are mixed with the colloid containing metal particles prepared by electrolyzing the metal electrode in the base solution to produce the metal-ceramic nanoparticles have. Thus, the catalyst characteristics of the metal-ceramic nanoparticles can be improved. In addition, it is possible to provide a metal / ceramic nanoparticle manufacturing method with high reliability, which simplifies the manufacturing process of the metal-ceramic nanoparticles, improves the production yield, and facilitates mass production.

Hereinafter, the characteristics of the Pt / Al ₂ O ₃ composite particles produced according to the method for producing metal-ceramic nanoparticles according to the embodiment of the present invention will be described.

≪ Example 1 >

Aluminum hydroxide (Al (OH) ₃ ) was added to distilled water and stirred for 1 hour, PEG was added as a water-soluble polymer, and stirring was performed again to prepare a source solution. The source solution was sprayed in a droplet state using an ultrasonic atomizer, and the source solution in a droplet state was introduced into a preheated reactor at 1000 캜 by using a carrier gas. The source solution in the droplet state was thermally decomposed in the reactor to collect Al ₂ O ₃ particles together with gases such as H ₂ O and CO ₂ .

A base solution was prepared by adding a dispersant and a reducing agent to ultrapure water and stirring. Two platinum (Pt) electrodes were placed facing the base solution, and then heat was applied at 60 DEG C and an alternating current of 2A was supplied for 60 minutes to perform electrolysis. During the electrolysis, the base solution was stirred and the cooling water was circulated to control the heat generated by the electrolysis reaction. Thus, a colloid containing platinum particles was prepared.

The colloid containing the platinum particles was loaded with Al ₂ O ₃ particles and dried at 100 ° C for 6 hours. Dried and then heat-treated at 600 ° C for 5 hours to prepare Pt / Al ₂ O ₃ composite particles according to the metal-ceramic nanoparticle manufacturing method according to the embodiment of the present invention.

≪ Comparative Example 1 &

Al ₂ O ₃ particles were produced according to the embodiment of the present invention described above.

Thereafter, distilled water maintained at pH 5 by adding 10 wt% nitric acid was heated to 60 ° C. Thereafter, chloroplatinic acid (H ₂ PtCl ₆ ) was added to perform oxidation-reduction reaction for one hour. A cooler was installed in the upper part of the reactor, and water vaporized was supplied into the reactor again to keep the volume of the aqueous solution constant. After the reaction was completed, the precipitation and washing processes were repeated to produce platinum particles.

Al ₂ O ₃ particles were supported on the colloid in which the platinum particles were dispersed and dried at 100 ° C for 6 hours. Dried and then heat-treated at 600 ° C for 5 hours to prepare Pt / Al ₂ O ₃ composite particles.

<Comparison of Characteristics of Pt / Al ₂ O ₃ Composite Particles According to Example 1 and Comparative Example 1>

FIG. 5 is a graph showing the exothermic characteristics of Pt / Al ₂ O ₃ composite particles of Example 1 and Pt / Al ₂ O ₃ composite particles of Comparative Example 1 produced according to the method of the present invention. FIG.

Referring to FIG. 5, the exothermic characteristics of Pt / Al ₂ O ₃ composite particles according to Example 1 and Comparative Example 1 were evaluated by hydrogen oxidation. In the case where Al ₂ O ₃ particles were dispersed in a colloid containing platinum particles produced by an electrolytic method according to Example 1 to prepare Pt / Al ₂ O ₃ composite particles, platinum prepared by a redox reaction according to Comparative Example 1 Al ₂ O ₃ particles were dispersed in the colloid containing the particles to produce Pt / Al ₂ O ₃ composite particles. Thus, it can be seen that the Pt / Al ₂ O ₃ composite particles produced according to Example 1 have improved catalytic properties for noxious gases (for example, CO, NO, NO _x, etc.).

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the scope of the present invention is not limited to the disclosed exemplary embodiments. It will also be appreciated that many modifications and variations will be apparent to those skilled in the art without departing from the scope of the present invention.

100: container
110: base solution
121 and 122: first and second electrodes
130: Power supply
142: stirrer
144: ultrasonic dispersing machine
SS: source solution
DSS: source solution in droplet state
210: source solution supply part
212: Ultrasonic vibrator
220: Carrier gas supply part
222: Carrier gas
230:
240: Temperature controller
242, 246: first and second temperature sensors
244, 248: first and second heaters
250: collection part
260: Pump
262: reaction gas

Claims (6)

Preparing a base solution;
Disposing a plurality of electrodes in the base solution;
Applying a voltage to the plurality of electrodes to ionize the metal element contained in the plurality of electrodes, and reducing the ionized metal element to form a colloid containing the metal particles;
Preparing ceramic particles;
Mixing the ceramic particles with a colloid containing the metal particles; And
Drying and heat treating the colloid comprising the ceramic particles and the metal particles,
Wherein preparing the ceramic particles comprises:
Preparing a source solution to which a water-soluble polymer is added;
Spraying the source solution in a droplet state; And
And heat treating the source solution in a droplet state to collect ceramic particles.
The method according to claim 1,
The step of preparing the colloid containing the metal particles may include:
Further comprising the step of ionizing the metal element and dispersing the produced metal particle in the base solution while reducing the metal ion.
delete delete The method according to claim 1,
Wherein the water-soluble polymer comprises at least one of poly ethylene glycol (PEG), poly acrylic acid (PAA), polyvinylpyrrolidone (PVP), and polyvinyl alcohol (PVA).
The method according to claim 1,
Wherein the source solution comprises at least one of aluminum hydroxide (Al (OH) ₃ ), aluminum sulfite (Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), or aluminum isopropoxide Method for manufacturing metal-ceramic nanoparticles.

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