KR101867905B1 - Apparatus for manufacturing boron nitride nanotubes and method of manufacturing boron nitride nanotubes using the same - Google Patents

Apparatus for manufacturing boron nitride nanotubes and method of manufacturing boron nitride nanotubes using the same Download PDF

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KR101867905B1
KR101867905B1 KR1020160150965A KR20160150965A KR101867905B1 KR 101867905 B1 KR101867905 B1 KR 101867905B1 KR 1020160150965 A KR1020160150965 A KR 1020160150965A KR 20160150965 A KR20160150965 A KR 20160150965A KR 101867905 B1 KR101867905 B1 KR 101867905B1
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boron
metal layer
reaction chamber
fiber
anode electrode
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KR20180053874A (en
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김명종
김준희
조현진
안석훈
장세규
김수민
손동익
서태훈
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한국과학기술연구원
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    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C01B21/06Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
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    • C23C14/0021Reactive sputtering or evaporation
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    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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    • C01P2004/00Particle morphology
    • C01P2004/10Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13Nanotubes

Abstract

A reaction chamber; A cathode electrode rod positioned in the reaction chamber; A cathode electrode rod including a boron fiber and a metal layer as a cathode electrode rod for causing arc discharge with the cathode electrode rod; And a gas injection port for injecting a buffer gas and a nitrogen supply gas into the reaction chamber.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a boron nitride nanotube production apparatus, and a boron nitride nanotube production method using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to an apparatus for producing boron nitride nanotube (BNNT) and a method for manufacturing boron nitride nanotubes using the same, and more particularly, to a boron nitride nanotube A boron nitride nanotube production apparatus, and a method of manufacturing a boron nitride nanotube.

Since the discovery of carbon nanotubes (CNTs), boron nitride nanotubes (BNNTs) have received much attention due to their structural similarity to CNTs. Boron nitride nanotubes have high mechanical strength compared to low density and have high thermal conductivity, electrical insulation, and piezoelectricity. They have been found by theoretical computational studies and also have excellent resistance to radiation shielding and thermal or chemical stress Has proven to have the same excellent properties. Particularly, some of these properties of boron nitride nanotubes are expected to be similar to or better than the characteristics of carbon nanotubes.

However, despite these anticipated potentials, studies on the synthesis of substantial boron nitride nanotubes are only being conducted by few, and the results are also limited. In particular, boron nitride nanotubes having a small diameter (< 10 nm) are preferred for boron nitride nanotubes for characterization and application. Also, for industrialization through mass production, production costs are low and manufacturing time is short This study should be made possible.

On the other hand, an initial method of synthesizing boron nitride nanotubes has been used in a similar manner to the synthesis of CNTs. The first boron nitride nanotubes were prepared by evaporating the electrodes by charging the boron powder to the tungsten rod by arc discharge. However, there is a problem that the yield (mg / day) is very low. In addition, although a manufacturing method of evaporating a boron target in a nitrogen gas atmosphere using a high thermal energy of a laser has been developed, boron nitride nanotubes of high purity can be obtained. However, in the case of a laser, And it is found that a lot of electric power is used, which is not suitable for mass production in terms of energy. In addition, although boron nitride nanotubes were successfully produced at low temperature by the catalyst by supplying heat to a boron powder containing a metal catalyst using a chemical vapor deposition (CVD) method, the diameter of the boron nitride nanotubes was largely largely manufactured And so on.

Therefore, there is a growing interest in a manufacturing method capable of efficiently producing small-diameter boron nitride nanotubes in a short time.

KR 10-2015-0143798 A KR 10-2016-0019559 A

Embodiments of the present invention provide a boron nitride manufacturing apparatus capable of producing a boron nitride nanotube having a fine diameter for a short time.

In another embodiment of the present invention, a method for producing boron nitride nanotubes using the apparatus is provided.

In an embodiment of the present invention, a reaction chamber; A cathode electrode rod positioned in the reaction chamber; An anode electrode rod including a boron fiber and a metal layer as an anode electrode rod for causing an arc discharge with the cathode electrode electrode; And a gas injection port for injecting a buffer gas and a nitrogen supply gas into the reaction chamber.

In an exemplary embodiment, the boron fiber may include at least one selected from the group consisting of boron, boron nitride, boron oxide, boric acid, metal boride, ammonia borane, and mixtures thereof.

In an exemplary embodiment, the boron fiber is a fiber bundle comprising a plurality of boron fiber strands, and the metal layer may be laminated on each of the boron fiber strands.

In an exemplary embodiment, the metal layer may be a laminate of the boron fiber strands through a chemical vapor deposition process or a physical vapor deposition process.

In an exemplary embodiment, the boron fiber is a fiber bundle comprising a plurality of boron fiber strands, and the metal layer may be a metal thin film surrounding the fiber bundle.

In an exemplary embodiment, the boron fiber is a fiber bundle comprising a plurality of boron fiber strands, and the metal layer may be a plated thin film plated on the fiber bundle.

In an exemplary embodiment, the metal layer may be a plated thin film plated on a fiber bundle through an electroless plating or electroplating process.

In an exemplary embodiment, the boron fiber has a diameter of 0.1 to 1 cm and may have a length of 1 cm to 1 m.

In an exemplary embodiment, the metal layer may comprise at least one of Ni, Cu, Fe, Cr, Mo, Si, Ti, U, Zr, Pt, Au, Al, Mg, Mn, Rh, Ta, W, Ge, White brass, brass, and an alloy thereof.

In an exemplary embodiment, the metal layer may have a thickness of 1 nm to 1 mm.

In an exemplary embodiment, the metal layer may be a synthesis catalyst of boron nitride nanotubes.

In an exemplary embodiment, the boron nitride nanotubes prepared through the boron nitride nanotube production apparatus may have an average diameter of 10 nm or less.

In an exemplary embodiment, the nitrogen feed gas may include one or more selected from the group consisting of nitrogen (N 2 ), ammonia (NH 3 ), and borazine (B 3 N 3 H 6 ) carried by the carrier gas have.

In another embodiment of the present invention, there is provided a method comprising: injecting a buffer gas and a nitrogen feed gas into a reaction chamber; And generating an arc discharge between a cathode electrode disposed in the reaction chamber and an anode electrode including a metal layer and a boron fiber to produce a boron nitride nanotube; The present invention also provides a method for producing a boron nitride nanotube.

In an exemplary embodiment, the method further comprises forming an anode electrode rod, wherein the boron fiber is a fiber bundle comprising a plurality of boron fiber strands, wherein each of the boron fiber strands is subjected to a chemical or physical vapor deposition process And the metal layer may be laminated to form the anode electrode.

In an exemplary embodiment, the method further comprises forming an anode electrode bar, wherein the boron fiber is a fiber bundle comprising a plurality of boron fiber strands, the metal layer is a metal thin film, And then forming the anode electrode by coating.

In an exemplary embodiment, the method includes forming an anode electrode bar; Wherein the boron fiber is a fiber bundle comprising a plurality of boron fiber strands and the metal layer is a plated thin film and the electroless plating process or the electrolytic plating process is performed on the fiber bundle to form the plated thin film on the fiber bundle, To form the anode electrode bar.

 In an exemplary embodiment, power can be applied between the cathode electrode and the anode electrode to have a potential difference of 10 V to 100 V in a current range of 10A to 180A.

In an exemplary embodiment, the reaction chamber may have a temperature of 2,000 to 5,000 占 폚.

In an exemplary embodiment, the pressure inside the reaction chamber may be in the range of 1 mTorr to 5000 Torr.

The apparatus for producing boron nitride according to an embodiment of the present invention may include a metal layer and a cathode electrode including boron fiber. In this case, the conductivity in the process chamber is improved and the metal layer functions as a synthesis catalyst, so that the boron nitride nanotube having a fine diameter can be produced in a short time.

In other words. Due to the catalytic action of the anode electrode of the present invention, the boron fiber and the nitrogen feed gas are effectively decomposed into boron and nitrogen in the process chamber, and they can be bonded together to efficiently produce the boron nitride nanotubes.

In addition, the anode bar of the boron nitride producing apparatus includes boron fiber, and the boron fiber can continuously supply the boron precursor. Accordingly, the efficiency of the boron nitride nanotubes can be increased in the manufacturing process.

1 is a schematic view showing an apparatus for manufacturing boron nitride nanotubes according to an embodiment of the present invention.
2A and 2B show transmission electron microscope (TEM) photographs of boron nitride nanotubes prepared according to an embodiment of the present invention. 2C shows electron energy loss spectroscopy (EELS) results of boron nitride nanotubes prepared according to an embodiment of the present invention.
FIGS. 3A and 3B show the results of X-ray photoelectron spectroscopy (XPS) analysis of boron nitride nanotubes prepared according to an embodiment of the present invention. FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention.

As used herein, "fine diameter" means a diameter of 10 nm or less, and means a diameter in the range of 0.0001 nm to 10 nm.

As used herein, &quot; boron fiber &quot; means a fiber bundle comprising a plurality of boron fiber strands.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing an apparatus for producing a boron nitride nanotube. FIG.

Referring to FIG. 1, an arc discharge device is used as an apparatus for producing boron nitride nanotubes, which includes a reaction chamber 100, a cathode electrode rod 120 located in the reaction chamber 100, And includes gas injection holes 151 and 152 for injecting a buffer gas and a nitrogen supply gas into the anode electrode rod 130 and the reaction chamber 100.

Meanwhile, in the reaction chamber 100, an inner space is defined. In the inner space, a buffer gas and a nitrogen supply gas are injected to synthesize boron nitride nanotubes (BNNT) by arc discharge, arc discharge is generated to form boron nitride nanotubes And the synthesized boron nitride nanotubes are formed in the process chamber 100. After the synthesis of the boron nitride nanotubes is completed, the boron nitride nanotubes formed therein are collected.

In the process chamber 100, a cathode electrode rod 120 and an anode electrode rod 130 where an arc discharge occurs in the synthesis of boron nitride nanotubes are disposed.

The cathode electrode rod 120 and the anode electrode rod 130 may be arranged such that their lengths are aligned with each other and their ends are opposite to each other.

The anode electrode rod 130 may include a boron fiber and a metal layer.

On the other hand, the boron fiber may serve as a source of boron in the arc discharge and may contain at least one fibrous material selected from the group consisting of boron, boron nitride, boron oxide, boric acid, metal boride, ammonia borane, .

The boron fiber may be a fiber bundle comprising a plurality of boron fiber strands. For example, the boron fiber may comprise 10 to 10,000 boron fiber strands.

The boron fiber (i.e., the boron fiber bundle) may have a diameter of 0.1 to 1 cm, and may preferably have a diameter of 0.5 to 0.7 cm. When the boron fiber has a diameter of less than 0.1 cm, the productivity of the boron nitride nanotube may deteriorate, and when the boron fiber exceeds 1 cm, the purity of the boron nitride nanotube to be produced may be much lower.

In the anode electrode rod 130, the metal layer and the boron fiber can be bonded in various forms.

In an exemplary embodiment, a metal layer may be deposited on each of the boron fiber strands. That is, a metal layer may be laminated on each of the boron fiber strands constituting the bundle of boron fibers. In this case, the metal layer may always be formed by a chemical vapor deposition process or physical vapor deposition process on the boron strand.

Alternatively, the boron fiber is a fiber bundle including a plurality of boron fiber strands, and the metal layer may be a plated thin film plated on the fiber bundle. In this case, the metal layer may be formed by performing an electroless plating process or an electrolytic plating process on the fiber bundle.

In one embodiment, in order to perform the plating process smoothly, a first metal layer is formed on boron fiber (i.e., a fiber bundle), and an electroless plating process or an electrolytic plating process is performed on the fiber bundle, And a boron fiber coated with a plated thin film which is a metal layer.

Alternatively, the metal layer may simply be a thin metal film surrounding the boron fiber (i.e., the boron fiber bundle).

In an exemplary embodiment, the metal layer may comprise at least one of Ni, Cu, Fe, Cr, Mo, Si, Ti, U, Zr, Pt, Au, Al, Mg, Mn, Rh, Ta, W, Ge, White brass, brass, and an alloy thereof, and may preferably include Ni.

The metal layer may be made to have a thickness of 1 nm to 1 mm, preferably 10 nm to 500 μm. Catalyst performance may be poor if the metal layer has a thickness of less than 1 nm, and boron may be difficult to evaporate from the boron fiber if the metal layer has a thickness greater than 1 mm.

The material that can be used as the cathode electrode rod 120 is not particularly limited as long as it is a material capable of causing arc discharge with the anode electrode rod 130, but it is preferable to include a carbon material (for example, graphite) and / or a metal Do.

On the other hand, the anode electrode rod 130 has a cylindrical rod shape and can be configured to move linearly in the longitudinal direction, and the cathode electrode rod 120 can be fixed. To this end, a motor may be connected to the anode electrode rod 130. When the anode electrode rod 130 is moved in the longitudinal direction, the distance to the anode electrode rod 120 can be adjusted, and the intensity of the arc discharge can be controlled.

In an exemplary embodiment, in the synthesis of boron nitride nanotubes, it is desirable that power is applied between the cathode and anode electrode rods 120 and 130 to have a potential difference of 10 V to 100 V in a current range of approximately 10 A to 180 A , But is not limited thereto.

On the other hand, a heating device may be further added to the outer wall or the inside of the reaction chamber 100 (not shown). When a heating device is added, the temperature of the inner space is maintained at a certain level in the process of synthesizing the boron nitride nanotubes, thereby lengthening the growth time of the boron nitride nanotubes. Thus, the generation of impurities such as amorphous carbon and nanoparticles can be suppressed as much as possible, and the yield and purity of the boron nitride nanotubes can be improved.

In addition, the process chamber 100 is provided with gas injection ports 151 and 152 for injecting gas into the inner space.

Although two gas injection ports are shown in FIG. 1, a plurality of gas injection ports 151 and 152 may be provided. For example, a first gas injection port 151 for injecting the buffer gas G1, And a second gas inlet 152 for injecting the gas G2 may be provided.

Further, although two gas injection openings are shown in Fig. 1, if necessary, the reaction chamber 100 may be provided with one gas injection opening, and the buffer gas and the nitrogen supply gas may be injected together through the gas injection opening .

Here, the buffer gas (G1) may contain hydrogen (H 2), nitrogen (N 2), helium (He) gas, etc., but are not nitrogen feed gas (G2) is restricted so long as it contains nitrogen, nitrogen ( N 2 ), ammonia (NH 3 ), liquid state borazine transported by a carrier gas (B 3 N 3 H 6 ), and the like.

Meanwhile, a voltage is applied to the cathode electrode and the anode electrode bar to generate an arc discharge to generate a boron nitride nanotube. A voltage between 10 V and 100 V is applied between the cathode electrode and the anode electrode, Can be applied.

On the other hand, as the power source is applied, thermoelectrons are emitted from the cathode electrode bar to generate thermal plasma. At this time, the reaction chamber may have a temperature of 2,000 to 5,000 ° C

As thermal electrons are emitted from the cathode electrode rod 120 to generate thermal plasma, boron is evaporated from the boron fiber in the anode electrode rod 130 and functions as a boron supplying body. At this time, the metal layer in contact with the boron fiber enhances the conductivity of the anode electrode rod 130 and serves as a catalyst, so that the boron fiber can be more smoothly decomposed.

Further, the nitrogen supply gas is decomposed to form nitrogen (N 2) according to the high temperature of the reaction chamber, and nitrogen (N 2) and boron react with each other to form boron nitride nanotubes.

At this time, the metal layer in the anode electrode rod 130 may be designed so that the nitrogen supply gas is decomposed at a lower energy, so that the metal layer of the anode electrode rod 130 finally assists the breakdown of the boron fiber and the nitrogen supply gas in a short time .

 The metal layer promotes the reaction between nitrogen (N 2) and boron to promote the formation of boron nitride nanotubes in a short period of time. As the boron nitride nanotubes are formed in a short time, the boron nitride nanotubes .

Generally, when the reaction time of the boron nitride nanotubes is prolonged, boron nitride nanotubes having multiple layers can be produced while the boron nitride nanotubes grow more. this? The diameter of the boron nitride nanotubes increases with an increase in the number of layers, and the characteristics of the boron nitride nanotubes decrease as the diameter increases. Meanwhile, according to the method for producing a boron nitride nanotube according to an embodiment of the present invention, since boron nitride nanotubes are formed in a short period of time, boron nitride nanotubes having a small number of layers and small diameters can be manufactured.

The boron nitride nanotubes prepared according to one embodiment of the present invention may be prepared to have an average diameter of 10 nm or less, preferably, an average diameter of 1 nm to 10 nm.

On the other hand, a method for producing boron nitride nanotubes by using the above-described apparatus for producing boron nitride nanotubes will be described. Meanwhile, the method for manufacturing the present boron nitride nanotube includes the same or similar structure as the above-described boron nitride nanotube production apparatus, and thus a detailed description thereof will be omitted.

In one embodiment of the present invention, there is provided a method comprising: injecting a buffer gas and a nitrogen feed gas into a reaction chamber; And generating an arc discharge between a cathode electrode disposed in the reaction chamber and an anode electrode including a metal layer and a boron fiber to produce a boron nitride nanotube; The present invention also provides a method for producing a boron nitride nanotube.

First, a method for manufacturing the positive electrode electrode will be described.

In an exemplary embodiment, the anode electrode rod comprises a metal layer and a boron fiber, and the boron fiber may be a fiber bundle comprising a plurality of boron fiber strands. The anode electrode rod can be manufactured, for example, by three methods.

For example, a metal layer may be laminated to each of the boron fiber strands through a chemical vapor deposition (CVD) process or a physical vapor deposition process (PVD) process to produce a positive electrode electrode including a metal layer laminated on each of the boron fiber strands. That is, the boron fiber in the anode electrode rod may include a plurality of boron fiber strands in which a plurality of metal layers are laminated.

At this time, as a metal source of the CVD process or the PVD process, a metal such as Ni, Cu, Fe, Cr, Mo, Si, Ti, U, Zr, Pt, Au, Al, Mg, Mn, Rh, Ta, W, Ge, Steel, white brass, brass, and alloys thereof may be used.

Alternatively, an electroless plating process or an electrolytic plating process is performed on the boron fiber (that is, the fiber bundle including the boron fiber strand) including the boron fiber strand to laminate the plating thin film on the fiber bundle to manufacture the anode electrode rod It is possible. In this case, the metal layer may be a plated thin film, and the anode electrode rod may comprise a fiber bundle of boron fibers and a plated thin film (metal layer) surrounding the bundle.

Alternatively, the anode electrode rod may be formed by simply coating a metal thin film on a fiber bundle including a boron fiber strand. In this case, the metal layer may be a metal thin film coated on the boron fiber.

On the other hand, after the anode electrode is formed, an annealing process may be further performed. By performing the annealing process, the surface of the metal layer can be cleaned, and the size and density of the metal layer on the crystal plane can be controlled.

In an exemplary embodiment, the annealing process may be performed in a furnace, the furnace interior is maintained at a pressure of 1 to 2 bar, and may be performed at a temperature of 800 to 1,500 ° C. Also, the annealing process may be performed for 30 minutes to 2 hours.

Thereafter, arc discharge is generated between the cathode electrode rod disposed in the reaction chamber and the anode electrode rod including the boron fiber and the metal layer to produce the boron nitride nanotube.

Specifically, after the anode electrode rod is disposed in the reaction chamber, a buffer gas and a nitrogen supply gas are injected into the reaction chamber, and an arc discharge is generated between the anode electrode rod disposed in the reaction chamber and the anode electrode rod including the boron fiber and the metal layer To produce a boron nitride nanotube.

In an exemplary embodiment, the gases injected into the reaction chamber may each be supplied at a flow rate of 1 to 10,000 cm 3 / min, and the pressure inside the reaction chamber may be maintained at 1 mTorr to 5,000 Torr.

Meanwhile, a voltage is applied to the cathode electrode and the anode electrode bar to generate an arc discharge to generate a boron nitride nanotube. A voltage between 10 V and 100 V is applied between the cathode electrode and the anode electrode, Can be applied.

In addition, as the power source is applied, thermal electrons are emitted from the cathode electrode to generate thermal plasma, and the reaction chamber may have a temperature of 2,000 to 5,000 ° C. If the temperature is out of the above temperature range, the production efficiency of the boron nitride nanotubes may be inadequate.

As the arc discharge is performed and the thermoelectrons are led out from the cathode electrode rod, the boron fiber is decomposed to form boron, which reacts with the nitrogen formed by the decomposition of the nitrogen supply gas to produce the boron nitride nanotubes. At this time, the metal layer existing in the anode electrode rod functions as a catalyst in the production of the boron nitride nanotubes, so that the boron nitride nanotubes having a finer diameter can be manufactured in a shorter time.

After the boron nitride nanotubes are manufactured, a heating apparatus connected to the reaction chamber may be operated to additionally perform a heat treatment. Accordingly, the purity of the boron nitride nanotubes can be improved by removing impurities in the reaction chamber.

According to the method for producing a boron nitride nanotube according to one embodiment of the present invention, the boron fiber and the nitrogen supply gas are effectively decomposed into boron and nitrogen in the reaction chamber due to the catalytic action of the anode electrode, The boron nitride nanotubes can be efficiently produced in a short time. In addition, boron nitride nanotubes having a fine diameter can be produced. The boron nitride nanotubes may be prepared to have an average diameter of 10 nm or less, and preferably have an average diameter of 1 nm to 10 nm.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Example

Example 1: Manufacturing method of anode electrode using physical vapor deposition method

Physical vapor deposition (PVD) was used to coat nickel metal on the boron fiber strand. Boron fiber strands having a diameter of 100 mu m were cut into 400 pieces each having a length of 20 cm, fixed on a wafer substrate, and then installed in an E-beam evaporator chamber. The metal target was Ni metal, the coating speed was 1.5 A / s, and the final thickness of the coating was 1 um. After the boron fiber strand using the electron beam evaporator, 400 boron fiber strands were gathered to have an electrode rod shape, and a cathode electrode was manufactured.

Example 2: A method for producing a positive electrode including a metal thin film

Aluminum (Al) thin films were used to wrap the bundles of fibers containing boron fiber strands to produce anode electrodes with improved conductivity. Boron fiber strands having a diameter of 100 .mu.m are cut into 400 pieces each having a length of 20 cm and then bundled into one bundle to form a bundle of boron fibers at the ends of a 20 cm.times.20 cm aluminum film. The anode electrode rod was fabricated by slowly wrapping a bundle of boron fibers located at the end of the aluminum thin film and maintaining the shape of a single cylindrical bar.

Example 3: A method for producing a positive electrode including a plated thin film

Copper metal was coated on the surface of the boron fiber bundle using electroless plating. The boron fiber bundles used for the electroless plating were coated with 50 nm of copper on the boron fiber bundles using an electron beam evaporator (E-beam evaporator) to utilize the self-catalytic properties of the copper plating. The copper salt used for plating is copper sulfate (CuSO 4 ) and the copper ion concentration is maintained at 3.0 g / L. The pH adjuster is sodium hydroxide (NaOH) and maintains pH = 12.5. Formaldehyde (HCHO) is used as the reducing agent and the concentration is maintained at 16 mL / L. This plating solution is placed in a plating bath, and the plating bath is maintained at a temperature of 40 DEG C and a stirring speed of 50 rpm using a heating stirrer. Thereafter, plating is performed by immersing the substrate in a boron fiber bundle plating solution coated with a copper metal using an electron beam evaporator. The total plating time is 60 minutes. Thus, a positive electrode electrode including a plated thin film formed on a bundle of boron fibers was produced.

Example 4: Manufacturing method of boron nitride nanotubes by arc discharge

The positive electrode electrode prepared in Example 1 was used. At this time, the boron fiber of the anode electrode rod is used as a source of boron, and the nickel metal coated on the surface serves to improve the conductivity.

The prepared positive electrode was installed in the space inside the reaction chamber, and the inside pressure was kept at a vacuum of 5.0 X 10 &lt; -3 &gt; Torr or less.

On the other hand, the cathode electrode rod was made of graphite and fixed inside the chamber. When the anode electrode was moved toward the cathode electrode, thermoelectrons were emitted at a certain distance and collided with the plasma gas in the chamber to generate thermal plasma. In Example 4, a voltage of 30 V and a current of 40 A were used, and helium gas was used to generate a stable plasma. That is, 400 SCCM of helium gas as buffer gas and 400 SCCM of ammonia gas as nitrogen feed gas were fed into the reaction chamber through one or more inlets at a ratio of 1: 1. The pressure inside the chamber was maintained at 760 Torr as helium gas and ammonia gas were continuously discharged into the at least one other inlet.

A thermal plasma was generated from the cathode electrode rod by the release of the thermal electrons, and the temperature at this time was maintained at 3500 ° C. Due to the high temperature of the thermoelectrons and plasma, the boron fibers in the anode electrode were evaporated to supply boron. In addition, the nickel metal on the surface of the boron fiber serves also as a catalyst to decompose ammonia gas, which is a nitrogen supply source, at a lower energy level, thereby further promoting the formation of boron nitride nanotubes. The ammonia gas inside the chamber was decomposed by the catalytic action of high heat and nickel to supply nitrogen. The decomposed boron and nitrogen combine with each other to form boron nitride nanotubes. The formed boron nitride nanotubes were collected on the inner surface of the chamber.

Experimental Example: Analysis of physical properties of the prepared boron nitride nanotubes (BNNT)

The composition of samples prepared according to the examples was measured by EDS (Energy Dispersive Spectroscopy), which is one of the optional functions in the SEM equipment, and is shown in Table 1.

As shown in Table 1, it was confirmed that the sample was composed of boron and nitrogen, and thus it was confirmed that "boron nitride nanotube" was produced.

Element Wt% Atomic% Net int. Error% BK 46.04 52.66 94.39 11.68 CK 6.46 6.65 39.96 14.72 NK 36.27 32.01 136.66 13.03 OK 11.23 8.68 58.74 15.27

The morphology of the boron nitride nanotube sample prepared according to the embodiment was analyzed using a TEM (transmission electron microscope), and it is shown in FIGS. 2A and 2B. Referring to FIGS. 2A and 2B, the boron nitride nanotube sample has a nanometer-unit tube shape and has an average diameter of 10 nm or less. In addition, in order to supplement the analysis results, the elements of the sample are analyzed using EELS (Electron Energy Loss Spectroscopy), which is one of the optional functions of the TEM, as shown in FIG. 2C. Also in FIG. 2C, the boron nitride nanotube sample, Nitrogen.

3A and 3B illustrate the state of chemical bonding between the boron nitride nanotube manufactured according to the embodiment and the element constituting the boron nitride nanotube by X-ray photoelectron spectroscopy. Figure 3a shows that boron was identified in boron nitride nanotubes and that boron is also bound to nitrogen. FIG. 3B shows that nitrogen was confirmed in the boron nitride nanotubes and nitrogen was bonded to the boron. It was confirmed that the boron nitride nanotube thus produced had a structure in which boron and nitrogen were bonded to each other.

The embodiments of the present invention described above should not be construed as limiting the technical idea of the present invention. The scope of protection of the present invention is limited only by the matters described in the claims, and those skilled in the art will be able to modify the technical idea of the present invention in various forms. Accordingly, such improvements and modifications will fall within the scope of protection of the present invention as long as it is obvious to those skilled in the art.

100: reaction chamber
120: cathode electrode rod
130: positive electrode
151: first gas inlet
152: second gas inlet

Claims (20)

  1. A reaction chamber;
    A cathode electrode rod positioned in the reaction chamber;
    An anode electrode rod including a boron fiber and a metal layer as an anode electrode rod for causing an arc discharge with the cathode electrode electrode; And
    And a gas injection port for injecting a buffer gas and a nitrogen supply gas into the reaction chamber,
    Wherein the boron fiber is a fiber bundle comprising a plurality of boron fiber strands,
    And the metal layer is laminated on each of the boron fiber strands.
  2. The method according to claim 1,
    Wherein the metal layer is laminated with the boron fiber strands through a chemical vapor deposition process or a physical vapor deposition process.
  3. A reaction chamber;
    A cathode electrode rod positioned in the reaction chamber;
    An anode electrode rod including a boron fiber and a metal layer as an anode electrode rod for causing an arc discharge with the cathode electrode electrode; And
    And a gas injection port for injecting a buffer gas and a nitrogen supply gas into the reaction chamber,
    Wherein the boron fiber is a fiber bundle comprising a plurality of boron fiber strands,
    Wherein the metal layer is a metal thin film surrounding the fiber bundle.
  4. A reaction chamber;
    A cathode electrode rod positioned in the reaction chamber;
    An anode electrode rod including a boron fiber and a metal layer as an anode electrode rod for causing an arc discharge with the cathode electrode electrode; And
    And a gas injection port for injecting a buffer gas and a nitrogen supply gas into the reaction chamber,
    Wherein the boron fiber is a fiber bundle comprising a plurality of boron fiber strands,
    Wherein the metal layer is a plated thin film plated on the fiber bundle.
  5. 5. The method of claim 4,
    Wherein the metal layer is a plated thin film plated on a fiber bundle through an electroless plating process or an electrolytic plating process.
  6. 6. The method according to any one of claims 1 to 5,
    Wherein the boron fiber comprises at least one selected from the group consisting of boron, boron nitride, boron oxide, boric acid, metal boride, ammonia borane, and mixtures thereof.
  7. 6. The method according to any one of claims 1 to 5,
    Wherein the boron fiber has a diameter of 0.1 to 1 cm and a length of 1 cm to 1 m.
  8. 6. The method according to any one of claims 1 to 5,
    The metal layer may be at least one of Ni, Cu, Fe, Cr, Mo, Si, Ti, U, Zr, Pt, Au, Al, Mg, Mn, Rh, Ta, W, Ge, bronze, stainless steel, At least one selected from the group consisting of brass and an alloy thereof.
  9. 6. The method according to any one of claims 1 to 5,
    Wherein the metal layer has a thickness of 1 nm to 1 mm.
  10. 6. The method according to any one of claims 1 to 5,
    Wherein the metal layer is a synthesis catalyst of boron nitride nanotubes.
  11. 6. The method according to any one of claims 1 to 5,
    Wherein the boron nitride nanotubes produced through the boron nitride nanotube production apparatus have an average diameter of 10 nm or less.
  12. 6. The method according to any one of claims 1 to 5,
    Wherein the nitrogen feed gas comprises at least one selected from the group consisting of nitrogen (N 2 ), ammonia (NH 3 ), and borazine (B 3 N 3 H 6 ) carried by the carrier gas.
  13. Injecting a buffer gas and a nitrogen feed gas into the reaction chamber;
    Generating arc discharge between a cathode electrode disposed in the reaction chamber and an anode electrode including a metal layer and a boron fiber to produce a boron nitride nanotube; And
    And forming an anode electrode rod,
    The boron fiber is a fiber bundle comprising a plurality of boron fiber strands,
    And laminating the metal layer on each of the boron fiber strands by a chemical vapor deposition process or a physical vapor deposition process to form the anode electrode bar.
  14. Injecting a buffer gas and a nitrogen feed gas into the reaction chamber;
    Generating arc discharge between a cathode electrode disposed in the reaction chamber and an anode electrode including a metal layer and a boron fiber to produce a boron nitride nanotube; And
    And forming an anode electrode rod,
    Wherein the boron fiber is a fiber bundle comprising a plurality of boron fiber strands and the metal layer is a metal thin film,
    And coating a metal thin film on the fiber bundle to form the anode electrode bar.
  15. Injecting a buffer gas and a nitrogen feed gas into the reaction chamber;
    Generating arc discharge between a cathode electrode disposed in the reaction chamber and an anode electrode including a metal layer and a boron fiber to produce a boron nitride nanotube; And
    And forming an anode electrode rod,
    Wherein the boron fiber is a fiber bundle comprising a plurality of boron fiber strands and the metal layer is a plated thin film,
    And performing an electroless plating process or an electrolytic plating process on the fiber bundle to form the plated thin film on the fiber bundle to form the positive electrode electrode.
  16. 16. The method according to any one of claims 13 to 15,
    And a power source is applied between the cathode electrode and the anode electrode to have a potential difference of 10V to 100V in a current range of 10A to 180A.
  17. 16. The method according to any one of claims 13 to 15,
    Wherein the reaction chamber has a temperature of 2,000 to 5,000 占 폚.
  18. 16. The method according to any one of claims 13 to 15,
    Wherein the pressure inside the reaction chamber is in the range of 1 mTorr to 5000 Torr.
  19. delete
  20. delete
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Citations (2)

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Publication number Priority date Publication date Assignee Title
JP3423639B2 (en) 1999-04-27 2003-07-07 キヤノン株式会社 Method and apparatus for producing carbon nanotube
JP3998241B2 (en) * 2002-10-18 2007-10-24 キヤノン株式会社 Manufacturing method of substrate on which carbon fiber is fixed

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US8206674B2 (en) 2007-05-15 2012-06-26 National Institute Of Aerospace Associates Boron nitride nanotubes
JP6359081B2 (en) 2013-04-18 2018-07-18 ナショナル リサーチ カウンシル オブ カナダ Boron nitride nanotube and method for producing the same

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
JP3423639B2 (en) 1999-04-27 2003-07-07 キヤノン株式会社 Method and apparatus for producing carbon nanotube
JP3998241B2 (en) * 2002-10-18 2007-10-24 キヤノン株式会社 Manufacturing method of substrate on which carbon fiber is fixed

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Title
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