KR101864513B1 - Manufacturing device of composite metal particle and method of preparing the same - Google Patents

Abstract

Provided are a metal composite particle production apparatus and a manufacturing method thereof. The present invention can produce the metal composite particle of uniform size by using microwaves and microwaves which are classified according to the size of a hybrid droplet. Further, the present invention is widely applicable to bio-functional materials which can be applied in a medical health field, including production of catalyst particles for energy synthesis or for environmental purification.

Description

TECHNICAL FIELD [0001] The present invention relates to a metal composite particle manufacturing apparatus and a manufacturing method thereof. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

The present invention relates to an apparatus and a method for manufacturing a metal composite particle.

The core-shell nanoparticles consist of the core material in the center and the shell-forming material surrounding it. The core-shell nanoparticles having such a structure are distinguished from the case where two or more materials are simply mixed or existing as an alloy, and depending on whether a material having a specific property is used for each core and shell, at least two The research and development of nanoparticles of core-shell structure by various combinations including metal-metal, metal-ceramic, metal-organic, organic-organic structure can be provided. .

In general, nano metal complexes can be widely used in the fields of energy environment and medical health, and the demand is increasing. Accordingly, various manufacturing methods have been developed, but most of them are limited to physicochemical process under critical operating condition or liquid chemical process.

Conventionally, there is a problem that the process is complicated, the cost is high, the harmful components such as wastewater and waste are generated due to the necessity of the liquid chemical process or the process based on the critical condition, have.

KR Registration No. 10-0860590

INDUSTRIAL APPLICABILITY The present invention can produce metal composite particles of uniform size using micro flow paths and microwaves classified according to the size of the hybrid droplet and can be applied to the medical health field including the production of catalyst particles for energy synthesis or environmental purification The present invention provides an apparatus and a method for manufacturing a metal composite particle which can be widely used for bio-functional materials.

According to an embodiment of the present invention, there is provided a core particle generator comprising: a core particle generator for generating core metal particles; A droplet generation unit configured to generate a hybrid droplet by jetting a liquid containing a metal precursor material into the flow of the core metal particles; A sorting unit arranged to classify the hybrid droplets generated by the droplet generating unit according to sizes and to discharge hybrid droplets within a predetermined size range; And a microwave heating unit for applying a microwave to the hybrid droplet discharged from the separating unit.

The core metal particle generating unit may be any one selected from the group consisting of spark ablation, flame, high temperature furnace, and spray drying apparatus.

The core metal particles may be formed of transition metals including rare earth metals such as gold (Au), palladium (Pd), platinum (Pt), silver (Ag) (Non-Metals).

The droplet generating unit may spray the liquid with the core metal particles by a spraying or droplet atomization method.

In addition, the liquid may comprise a reducing agent and a solvent of the metal precursor material.

In addition, the solvent may include at least one member selected from the group consisting of water, alcohol, hydrocarbon, acid-base and oil.

In addition, the hybrid droplet may have a structure in which the core metal particles are formed inside and the liquid surrounds the outside.

In addition, the metal precursor material may be a metal other than the core metal particles.

In addition, the classifier may include a plurality of micro flow paths in different directions in which the flow of the hybrid droplet is classified according to the size.

The microwave heating unit may include a flow channel through which the hybrid droplet flows, and air, nitrogen (N2), hydrogen (H2), helium (He) At least one selected from the group consisting of argon (Ar), oxygen (O2), and a mixture thereof may be implanted.

Also, the frequency of the microwave heating unit may be 0.5 to 500 MHz.

In addition, the microwave heating unit may be arranged to control microwave irradiation concentration in the flow channel.

According to another embodiment of the present invention, there is provided a method of manufacturing a core metal particle, Spraying a liquid comprising a metal precursor material into the stream of core metal particles to produce a hybrid droplet; Passing the hybrid droplet by size and passing through a separator arranged to discharge the hybrid droplet within a predetermined size range; Applying a microwave to the hybrid droplet discharged from the separator; And a metal complex particle.

The step of forming the core metal particles may be performed using any one selected from the group consisting of spark ablation, flame, high temperature furnace, and spray drying apparatus.

In addition, the step of generating the hybrid droplet may be performed by spraying a liquid containing the core metal particles and the metal precursor material by spraying or droplet atomization.

In addition, the hybrid droplet may have a structure in which the core particles are formed inside and the liquid surrounds the outside.

Further, in the step of applying the microwave, the microwave irradiation concentration can be adjusted.

Exemplary embodiments of the apparatus and method for producing a metal composite particle of the present invention can produce metal composite particles of uniform size and can be used for bio- It is possible to produce widely available metal composite particles.

1 is a view schematically showing an apparatus for manufacturing a metal composite particle according to an embodiment of the present invention.
2 is a view showing a spark discharge which is an embodiment of the core particle generator of the present invention.
3 is a schematic diagram showing an apparatus for manufacturing a hybrid droplet according to an embodiment of the present invention.
FIGS. 4 and 5 are schematic views illustrating a micro-channel distributor according to an embodiment of the present invention.
6 is a schematic view illustrating a microchannel channel 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. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

In addition, the same or corresponding reference numerals are given to the same or corresponding reference numerals regardless of the reference numerals, and redundant description thereof will be omitted. For convenience of explanation, the size and shape of each constituent member shown in the drawings are exaggerated or reduced .

Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

TECHNICAL FIELD The present invention relates to an apparatus for producing metal composite particles and a manufacturing method thereof. According to the exemplary metal composite particle production apparatus of the present invention, it is possible to produce metal composite particles of uniform size, and it is possible to produce a metal composite particle of uniform size, which can be used for energy synthesis or environmental purification, Widely available metal composite particles can be produced.

The term " spark discharge " used in the present application means a high-frequency discharge method performed in the kV-mA mode at atmospheric pressure. For example, the spark discharge may be applied at 0.5 to 500 kHz, but is not limited thereto. The term " nano " in this application is meant to indicate a size in nanometers (nm), for example, a size of 1 nm to 1000 nm, but is not limited thereto. The term " aerosol particles " or " core metal particles ", " nanoparticles " in the present application may mean particles having a size in nanometers (nm), for example, an average particle size of 1 nm to 1000 nm , But is not limited thereto.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of an exemplary metal composite particle production apparatus of the present invention

1, the apparatus 10 for producing a metal composite particle of the present invention comprises a core particle producing portion 100 for producing core metal particles, A droplet generating unit 200 configured to jet the liquid 520 to generate a hybrid droplet 530, a classifying unit 300 configured to discharge the hybrid droplet generated in the droplet generating unit, And a microwave heating unit 400 for applying a microwave to the hybrid droplet.

The metal composite particle of the present invention is characterized in that the interior generated through the core particle generator 100 and the droplet generator 200 is composed of metal particles 510 and a metal precursor material 521, The metal droplet 530 composed of the solvent 522 containing the metal precursor 530 is reduced by the microwave to produce the metal composite particles 500 in which the inside and the outside are made of different metals.

The core particle generator 100 is a part for generating the core metal particles 510 which are internal particles of the hybrid droplet 530 of the present invention and has an aerosol metal particle 510 ) Can be formed.

More specifically, the aerosol metal particles 510 may be produced by spark discharge, flame, high temperature furnace, and spray-drying apparatus, but are not limited thereto.

Referring to FIG. 2, the core particle generator 100 may generate core particles by spark ablation. The core particle generator 100 generates air, nitrogen (N 2), hydrogen (H 2 ), Helium (He), argon (Ar), oxygen (O2), and a mixture thereof. Here, the compressed gas may further contain oxygen (O 2) to produce metal oxide particles at the time of producing the metal composite particles to be described later.

In addition, the core particle generation unit 100 includes a pair of metal electrodes 121 spaced apart at a predetermined interval, and generates core metal particles from a gap of the metal electrode by a spark discharge And a power supply unit 130 for applying power to the metal electrode.

More specifically, in the core particle generator 100, a spark discharge may be generated in the metal electrode 121 by a power source applied from the power source 130 in an atmosphere where the compressed gas is supplied.

Here, due to the spark discharge, molecules are ionized in a high electric field to generate ions or radicals, and electrons and ions move at high speed in the electric field and collide with the surface of the metal electrode. At this time, if the temperature of the surface of the metal electrode is locally higher than the melting point of the surface of the metal electrode, a part of the metal electrode is vaporized and condensed immediately after vaporization, thereby forming aerosol metal particles, that is, core metal particles.

The core metal particles 510 generated from the metal electrode 121 may be formed of transition metals including gold (Au), palladium (Pd), platinum (Pt), silver (Ag) Metals, Other Metals, and Non-Metals.

The voltage applied to the pair of metal electrodes 121 may be 0.5 to 20 kV, for example, 3 to 10 kV, and the amount of current may be controlled to be 0.5 to 50 mA.

Although not shown, the core particle generator 100 of the metal composite particle production apparatus 10 of the present invention includes a gas supply device such as a carrier air supply system, a mass flow controller (MFC) And the like. The carrier gas composed of air, nitrogen (N2), hydrogen (H2), helium (He), argon (Ar), oxygen (O2) And can be supplied quantitatively at the interval between the electrodes 121.

More specifically, when a voltage is applied to the metal electrode 121, the metal sublimates at an interval between the pair of metal electrodes 121 due to the high temperature generated by the spark, The metal is condensed out of the gap, thus forming the aerosol metal particles 510.

Here, when a certain amount of oxygen exists in the compressed gas, metal oxide particles may be generated.

The particle size of the aerosol metal particles 510 generated from the core particle generator 100 can be widely controlled from several nanometers to hundreds of nanometers in accordance with the flow rate or flow rate of the carrier gas.

For example, when the flow rate or the flow rate of the supplied carrier gas is increased, as the concentration of the aerosol metal particles is decreased, the phenomenon of agglomeration among the particles is also decreased. Through this process, the size of the metal aerosol particles can be reduced have. The particle size, shape, and density of the metal aerosol particles can be changed by spark generation conditions such as applied voltage, frequency, current, resistance, and capacitance, kind and flow rate of the inert gas, shape of the spark electrode, and the like .

As described above, the core metal particles 510 generated from the core particle generator 100 may be introduced into the droplet generator 200 while being suspended in the compressed gas.

In addition, the droplet generating portion 200 is a portion for generating an outer droplet 520 surrounding the core particle of the hybrid droplet 530, and the outer droplet 520 is a portion of the aerosol metal particle 510, And another metal precursor material 521 and a solvent 522 containing the reducing agent.

Here, the metal precursor material 521 may include one selected from the group consisting of a transition metal precursor, a rare-earth metal precursor, another metal precursor, and a non-metal precursor. Or more.

For example, the precursor may be selected from the group consisting of nitrate, chloride, bromide, acetate, acetylacetonate, and the like. And may include conventionally known deposition deposition precursors.

For example, gold (AuCN), silver nitrate (AgNO3), palladium chloride (PdCl2), palladium acetate (Palladium Acetate), silver acetate (Silver Acetate) and the like may be included.

In addition, the solvent 522 may include at least one member selected from the group consisting of water, alcohol, hydrocarbon, acid-base and oil.

More specifically, the droplet generating unit 200 may be a spray or an atomizing device, and the aerosol metal particles 510 may be suspended in the compressed gas to the spray or droplet atomizer And may be sprayed together with the solvent to generate the hybrid droplet 530.

As shown in FIG. 3, in one example, the first metal generated through the spark discharge floats the aerosol metal particles 510 in the compressed gas and moves to the droplet generating portion 200 according to the flow of the gas, A solvent 522 including a metal ion 521 and a reducing agent is sprayed together with the aerosol metal particles 510 in the droplet generating portion 200 to form an aerosol metal particle 510 made of a first metal And a solvent containing a second metal ion and a reducing agent externally forms a droplet 520 to generate a hybrid droplet 530. [ Here, the first metal and the second metal may be different metals.

Meanwhile, the hybrid droplet 530 generated as described above may pass through the classifier 300 including a plurality of microchannels in different directions in which the flow is classified depending on the size.

4, the classifier 300 may be a cruciform microchannel, and a hybrid droplet 530 having a polydisperse size distribution may be introduced into the microchannel inlet port 310, Can be discharged to the fine flow path port 320 selectively.

In addition, the hybrid droplet 532 that can not be sorted by the sorting unit 300 may be discharged through the subsidiary port 330.

Particles having a large size among the hybrid droplets 530 passing through the partition 300 maintain a linear motion due to a large inertia and move to the sub port 330. Particles having a small size are moved to the sub- So that the flow can be classified according to the size of the particles.

4 (A), the hybrid droplet 531 having passed through the main port 320 may have a quasi-monidisperse or monodisperse size distribution, and the sub port The distribution of the hybrid droplets 532 that have passed through the flow paths 330 and 330 is shown in FIG.

4C is a photograph of a hybrid droplet 530 having a polydisperse size distribution before passing through the dividing unit 300. FIG. 4D is a photograph of the hybrid droplet 530 after passing through the fine channel distributor 300 Figure 5 shows a photograph of a hybrid droplet 530 having a distribution of quasi-dispersed or monodisperse sizes.

5A, the size of the hybrid droplet 531 to be classified by the sorter 300 is determined by the width W of the inlet port 310 of the microchannel, the width S of the main port 320, Can be controlled by a combination of design factors of the fine channel thickness t.

As described above, the size of the hybrid droplet 530 can be adjusted by changing the design factors S, W, and t, and in the manufactured sorter 300, the hybrid droplet 530 can be divided into (B ). ≪ / RTI >

Meanwhile, the hybrid droplet 530 manufactured as described above usually has a Gaussian time distribution in a wide size range. Therefore, in order to make the sizes of the finally produced metal composite particles 500 more uniform, by passing a hybrid droplet through the classifier 300, that is, a cruciform microchannel capable of classifying a specific size, So that only a more uniform hybrid droplet can be selectively injected.

In addition, more uniform metal composite particles 500 can be generated by the microwave reaction applied from the microwave heating unit 400 including the flow channel, in the hybrid droplet 531 selected in the classifying unit 300 .

More specifically, referring to FIG. 6, the hybrid droplets 531 having a uniform size distribution may be connected in series to flow along with the sheath gas to the flow channel 410 to which the microwave is applied.

The sheath gas and the hybrid droplet pass through a flow channel 410 to which microwaves are locally irradiated. Under the condition of Irradiation at a certain frequency for a certain time, metal ions are adsorbed on the surface of the aerosol metal particles in the droplets by the reducing agent So that finally the metal composite particles 500 can be produced.

Here, the time for applying the microwaves may be 0.01 second to 15 seconds, and the turn-on state may be maintained for 5 seconds, for example, through ON / OFF operation of the microwave power The microwave can be irradiated by repeatedly performing the operation of maintaining the turn-off state for 3 seconds. By performing the above-described operation, it becomes possible to control the particle size distribution and shape of the particles to be produced.

The frequency of the microwave may be 0.5 to 500 MHz, but is not limited thereto.

Further, when a certain amount of oxygen is injected into the sheath gas, metal oxide particles may be generated.

The standard deviation of the size distribution of the metal composite particles can be controlled not only by uniformly applying a cross-shaped micro flow path, but also by the intensity of irradiation of the microwave (Irradiation Stiffness).

More specifically, the uniformity can be controlled by controlling the microwave irradiation intensity (Irradiation Stiffness) in the flow channel 410 of the microwave heating unit 400.

The present invention also provides a method for producing a metal composite particle.

For example, the metal composite particle production method relates to a method for producing metal composite particles through the above-described metal composite particle production apparatus. Therefore, details of the metal complex particles to be described later can be applied equally to those described in the metal complex particle production apparatus.

Exemplary methods for producing metal composite particles of the present invention include the steps of producing core metal particles, generating hybrid droplets, passing through a sorbent, and applying microwaves.

More specifically, the step of producing the core metal particles can produce core metal particles using any one of Spark Ablation, flame, high temperature furnace, and spray drying apparatus.

The step of generating the hybrid droplet may generate a hybrid droplet by spraying a liquid containing a metal precursor material to the stream of core metal particles produced in the step of producing the core metal particles.

Here, the hybrid droplet may be generated by spraying or droplet atomization.

More specifically, the hybrid droplet produced through the above process may be composed of core metal particles, and the solvent may include a metal precursor material other than the inner metal particles and a reducing agent.

The step of passing through the dividing section may include passing the hybrid droplet generated in the dividing section through the fine flow path of the dividing section and classifying the droplet according to the size to discharge a hybrid droplet of a uniform size within a predetermined size range.

The microwave application step may include a step of applying a microwave to a hybrid droplet of a uniform size that has passed through the separation section and is converted into metal particles by a reducing agent, So that particles can be generated.

10: Metal composite particle manufacturing apparatus
100: Core particle generator
110:
120: discharge unit
121: metal electrode
130:
200:
300:
310: incoming port
320: Main port
330:
400: Microwave heating unit
500: metal composite particle
510: Core metal particles
520: Droplet
530: Hybrid droplet

Claims (17)

A core particle generator for generating core metal particles;
A droplet generation unit configured to generate a hybrid droplet by jetting a liquid containing a metal precursor material into the flow of the core metal particles;
A sorting unit arranged to classify the hybrid droplets generated by the droplet generating unit according to sizes and to discharge hybrid droplets within a predetermined size range; And
And a microwave heating unit for applying a microwave to the hybrid droplet discharged from the separation unit,
The core particle generation unit includes a pair of metal electrodes spaced apart at a predetermined interval, a part of the metal electrode is vaporized when the temperature of the surface of the metal electrode is locally increased by the spark discharge, and the condensed aerosol metal particles Core metal particles from the gap of the metal electrode, and a power supply unit for applying power to the metal electrode,
Wherein a hybrid droplet of the droplet generating portion forms droplets in which an aerosol metal particle is formed inside and a solvent containing a metal ion and a reducing agent on the outside,
The classifier includes a plurality of microchannels in different directions in which the flow of the hybrid droplet is classified depending on the size, and the hybrid droplet having the distribution of the polydispersion magnitudes generated by the droplet generating unit flows into the microchannel inlet port Only a droplet of a desired size flows out to the selected micro flow path port and flows into the microwave heating part, and the hybrid solution that can not be sorted by the fractionation part is discharged through the sub port,
Wherein the microwave heating unit includes a flow channel to which a microwave is applied, the sheath gas and the hybrid droplet pass through a flow channel, the microwave frequency is 0.5 to 500 MHz, and the microwave application time is in the range of 0.01 to 15 seconds. And repeatedly performing on / off operation of the power supply of the metal composite particles.
delete The method according to claim 1,
The core metal particles may be selected from the group consisting of transition metals including gold (Au), palladium (Pd), platinum (Pt), silver (Ag), rare earth metals (Rare-Earth Metals) (Non-Metals). ≪ / RTI > The method according to claim 1,
Wherein the droplet generating unit comprises:
Wherein the core metal particles and the liquid are sprayed by spraying or droplet atomization. delete The method according to claim 1,
Wherein the solvent comprises at least one selected from the group consisting of water, an alcohol, a hydrocarbon, an acid-base and an oil.
delete The method according to claim 1,
Wherein the metal precursor material is a metal different from the core metal particles. delete The method according to claim 1,
The microwave heating unit includes:
Wherein the flow channel is selected from the group consisting of air, nitrogen (N2), hydrogen (H2), helium (He), argon (Ar), oxygen (O2) Wherein at least one of the metal particles is injected.
delete delete A pair of metal electrodes which are spaced apart from each other at a predetermined interval, a part of the metal electrode is vaporized locally when the temperature of the surface of the metal electrode is raised by spark discharge, and the core metal particles, which are condensed aerosol metal particles, Generating core metal particles by a discharging portion generated from the gap of the metal electrode and a power supply portion applying power to the metal electrode; Spraying a liquid comprising a metal precursor material to the stream of core metal particles to produce a hybrid droplet wherein the aerosol metal particles are formed therein and the solvent comprising the metal ion and the reducing agent forms droplets; The hybrid droplet is classified according to its size so that the hybrid droplet flow is classified according to the size so as to discharge the hybrid droplet within a predetermined size range. The hybrid droplet having the distribution is introduced into the micro-channel inlet port, and only the droplet of the desired size flows out to the micro-channel port to be sorted, and the hybrid droplet that can not be sorted by the classification section is discharged through the sub- Passing through the part; And the microwave frequency is in a range of 0.5 to 500 MHz and the microwave application time is in a range of 0.01 second to 15 seconds, And applying a microwave to irradiate the microwave; ≪ / RTI >
delete 14. The method of claim 13,
Wherein the step of generating the hybrid droplet comprises:
Wherein the core metal particles and the metal precursor material are sprayed or atomized to form a liquid containing the metal precursor material.

delete delete

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