KR101804224B1 - Small Igniter for Exploding Nanoscale Energetic Materials with Conductive Paper electrode and Method for Fabricating the same - Google Patents

Abstract

The present invention relates to a nano-high-energy material small-sized igniter having a conductive paper electrode capable of igniting nanoscale energetic materials (nEMs) using a conductive paper electrode using a carbon nanostructure as a heat generating and heat transfer medium, A conductive paper electrode including a paper on which a carbon nanostructure used as a heat generating and heat transfer medium is coated on a surface and which has a region where ignition starts, a nanoparticle material coated on the surface of the conductive paper electrode, (nEMs) thin film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a small-sized high-energy material small igniter having a conductive paper electrode and a manufacturing method thereof,

The present invention relates to a method of igniting nano-energy materials, and more particularly, to a method of igniting nanoscale energy materials (nEMs) using a conductive paper electrode using a carbon nanostructure as a heat generating and heat transfer medium, Electrode small igniter and a method of manufacturing the same.

Carbon nanotubes (CNTs) are attracting attention as the representative nanomaterials of nanotechnology. Their electronic structure changes depending on the tube diameter and symmetry, layer structure, bundle structure, bonding deformation, presence of impurities, Is a representative nanoscale carbon material which is expected to have various applications in fields of electronic information communication, environment, energy and medicine.

Nano-high energy materials (nEMs) are composite materials composed of nanoscale fuel materials and oxidizers. It is a composite material that contains internal energy of chemical energy when it is ignited by external energy input. And it has been widely applied to various thermal engineering as an igniter, a propellant and an explosive.

Traditional ignition methods for these nanoscopic high energy materials include mechanical impact, flame, and electric spark.

These traditional ignition methods are very effective for ignition of nanoscale high energy materials, but because of their complex mechanical and electrical circuit composition and their relatively large volume, they are a major limitation for various thermal applications as ignition and detonator components have.

To overcome these shortcomings of conventional ignition methods, it is necessary to develop new ignition methods for nano-high energy materials.

Korean Patent Publication No. 10-2014-0129828 Korean Patent Publication No. 10-2009-0041637

The present invention relates to a method of manufacturing a nano-high-energy material small-sized igniter having a conductive paper electrode using a carbon nano-structure as a heat generating and heat transfer medium and a method of manufacturing the same, The purpose is to provide.

The present invention relates to a nano-high-energy material small-sized igniter having a conductive paper electrode capable of igniting nanoscale energetic materials (nEMs) using a conductive paper electrode using a carbon nanostructure as a heat generating and heat transfer medium, And a manufacturing method thereof.

The present invention relates to a small-sized igniter capable of igniting a carbon nano-structure coated conductive paper by depositing nEMs thin film on a paper electrode coated with a carbon nanostructure, And to provide a method of manufacturing the same.

The present invention relates to a method of manufacturing a small igniter by coating a carbon nanostructure on a paper to produce a conductive flexible substrate and forming and attaching a nanoscopic energy material in a thin film form to form a small igniter, And a conductive paper electrode for inducing an ignition / combustion / explosion phenomenon of a nano-high energy material with generated heat energy after generating resistance heat, and a method for manufacturing the nano-high energy material small igniter.

The objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

In order to accomplish the above object, the present invention provides a miniature nano-energy material small igniter having a conductive paper electrode, comprising a paper on which a carbon nanostructure used as a heat generating and heat transfer medium is coated on a surface, And a nano-sized high energy material (nEMs) thin film coated on the surface of the conductive paper electrode.

Here, the region where the ignition starts is a neck portion of a butterfly ribbon having a first width at both ends and a second width smaller than the first width at the center.

And the ignition temperature of the paper on which the carbon nanostructure is coated is lower than the ignition temperature of the paper before the carbon nanostructure is coated on the surface.

The carbon nanostructure may be any one of Fullerene, single wall carbon nanotube (SWCNT), multiwall carbon nanotube (MWCNT), and graphene, or a combination thereof.

In addition, the ignition delay time of the conductive paper electrode is controlled by the thickness of the nano-sized high-energy material (nEMs) thin film, and as the thickness of the nano-high energy material (nEMs) And an increase in time occurs.

A method for fabricating a small-sized nano-high-energy material igniter having a conductive paper electrode according to the present invention includes the steps of: preparing a conductive paper electrode using a carbon nanostructure; preparing a nano-sized high energy material (nEMs) (NEMs) thin film using a spin coating process on a conductive paper electrode coated with a conductive metal electrode.

The step of fabricating the conductive paper electrode using the carbon nanostructure includes the steps of: preparing a carbon nanostructure solution; coating the carbon nanostructure on the surface of the paper by using a vacuum deposition method; And producing a conductive paper electrode having a region having a first width at both ends so as to be ignited and having a second width smaller than the first width at the center, wherein ignition is initiated.

The carbon nanostructure is characterized by using any one of Fullerene, single wall carbon nanotube (SWCNT), multiwall carbon nanotube (MWCNT), and graphene, or a combination thereof.

The step of preparing the nano-high-energy material (nEMs) solution comprises the steps of: mixing the Al nanoparticles and the CuO nanoparticles in a ratio of Al: CuO = 30: 70 wt% And mixing the Al / CuO composite powder with an ethanol solution by using ultrasonic energy.

The step of coating the carbon nanostructure on the surface of the paper includes steps of raising a filter support on a vacuum flask, placing a paper on the filter support, fixing a filtration device thereon and forming a vacuum at the bottom with a vacuum pump, In the ethanol solution in which the carbon nano structure poured onto the paper is dispersed with a vacuum pump connected to the vacuum flask, only the carbon nanostructure remains on the paper, and the ethanol solution passing through the paper is transferred to the lower flask , And drying the paper coated with the carbon nanostructure.

The small nano-energy material small igniter having the conductive paper electrode according to the present invention and the manufacturing method thereof have the following effects.

First, it is possible to manufacture a conductive paper electrode using a carbon nanostructure as a heat generation and heat transfer medium, and a nano-high energy material small igniter having the same.

Second, nanoscale energetic materials (nEMs) can be ignited using conductive paper electrodes that utilize carbon nanostructures as heat generation and heat transfer media.

Third, the use of conductive paper electrodes using carbon nanostructure as a heat generation and heat transfer medium enables various thermal applications as ignition and detonator parts due to their small volume characteristics.

Fourth, carbon nanostructures are coated on ordinary paper to produce conductive flexible substrates, and nano-high-energy materials are formed and adhered to thin films to form a small-sized igniter, thereby realizing an efficient manufacturing process.

Fifth, various types of electrodes can be realized by generating resistance heat by applying voltage to a paper-based small igniter coated with carbon nanostructure and inducing ignition / combustion / explosion phenomenon of nano-high energy material by generated heat energy And efficient control of remote ignition is possible.

FIGS. 1A and 1B are a process flow diagram and a flow chart for manufacturing a conductive paper electrode using a carbon nanostructure.
FIGS. 2A and 2B are a flow chart and a flowchart of a process for manufacturing a small-sized high-energy material small igniter using a conductive paper electrode
FIG. 3 is a graph showing the results of resistance measurement of a paper electrode according to an initial concentration of a carbon nanotube solution and a photograph of a carbon nanotube thin film formed on the carbon nanotube thin film, (b) a neck width of a butterfly ribbon electrode coated with a carbon nanotube thin film, ) Of the resistance measurement result
FIG. 4 shows (a) a butterfly-shaped photo of a paper electrode coated with a carbon nanotube thin film, (b) a planar and lateral SEM image of the MWCNT thin film deposited on the paper, and (c) an enlarged view of the MWCNT thin film- High magnification SEM image of the part
FIG. 5 is a graph showing a comparison of resistance values of a paper electrode coated with a carbon nanotube thin film according to various curvature radii (b) Repeated bending of a paper electrode coated with a carbon nanotube thin film having a radius of curvature of R2.5 mm Change of resistance value according to test and photograph before and after bending test
FIG. 6 is a graph showing the results of photographing and resistance measurement after (a) attaching / detaching 3M tape to / from a paper electrode coated with a carbon nanotube thin film, (b) Change photograph and resistance value measurement result
FIG. 7 is a graph showing the results of measurement of maximum exothermic temperature according to various applied voltages of a paper electrode coated with a carbon nanotube thin film, (b) a butterfly-shaped paper electrode under a fixed applied voltage of about 15 V, And video-based still image analysis results
(B) a SEM image of the nEMs / MWCNT / paper thin section, (c) the MWCNT and the nEMs thin film, SEM image enlarged paper electrode interface
9 is a graph showing the results of an analysis of ignition and explosion phenomena of nEMs thin films by ignition of a paper electrode coated with a carbon nanotube thin film
FIG. 10 is a graph showing an explosion pressure measurement result after ignition of a nEMs thin film in a pressure cell by ignition of a paper electrode coated with a carbon nanotube thin film
FIG. 11 shows the results of the ignition and explosion phenomena of nEMs thin films by voltage application on paper electrodes coated with Fullerene / MWCNT, SWCNT, and Graphene thin films
FIG. 12 shows a remote ignition and explosion door blowing technique using a small-sized igniter based on a carbon nanotube paper in which an nEMs thin film is formed.

Hereinafter, a preferred embodiment of a miniature nano-energy material small igniter having a conductive paper electrode according to the present invention and a method of manufacturing the same will be described in detail.

The features and advantages of a nano-high energy material miniature igniter having a conductive paper electrode according to the present invention and its manufacturing method will be apparent from the following detailed description of each embodiment.

FIGS. 1A and 1B are a process flow diagram and a flowchart for manufacturing a conductive paper electrode using a carbon nanostructure.

The present invention relates to a method of manufacturing a small igniter by coating a carbon nanostructure on a paper to produce a conductive flexible substrate and forming and attaching a nanoscopic energy material in a thin film form to form a small igniter, And generate heat of resistance to generate ignition / combustion / explosion phenomenon of nano-high energy material by the generated thermal energy.

In the following description, a carbon nanotube is used as a carbon nanostructure while explaining a small-sized high-energy material small igniter having a conductive paper electrode and a method for manufacturing the same. However, the carbon nanostructure used in the technology implementation of the present invention, It is of course possible to use various materials such as Fullerene, MWCNT, SWCNT, and Graphene thin film.

The present invention is to develop a small-sized igniter capable of igniting a carbon nanotube-coated conductive paper as a new ignition method of nano-high-energy materials and using them as an electrode to generate heat according to voltage application.

When using conductive paper substrates coated with carbon nanotubes for ignition of nano-high energy materials,

(i) In general, the characteristics of paper are that the substrate is very flexible,

(ii) Paper is very cheap and very easy to handle compared to metal or semiconductor substrates,

(iii) a user can easily cut the electrode to realize various shapes of electrodes and is highly portable,

(iv) have a variety of advantages that may be combined with electrical circuitry to implement remote ignition.

Therefore, a miniature igniter based on a conductive paper substrate coated with such a carbon nanotube can maximize the application range of nanograhydro-energetic materials to thermo-electric civil materials.

For this purpose, the present invention relates to a method of manufacturing a conductive flexible substrate by coating carbon nanotubes on a commonly used ordinary paper, manufacturing and attaching a nanofiber energy material in the form of a thin film on a paper substrate coated with the carbon nanotube, .

In order to achieve this goal, we have developed a new paper-based compact igniter with carbon nanotubes coated with aluminum (Al, fuel metal) and copper oxide (CuO) nanoparticles (NPs) To generate resistance heat, and then to induce the ignition / combustion / explosion phenomenon of the nano-high energy material with the generated thermal energy.

In order to observe the combustion characteristics of nano-high-energy materials and small-sized igniters, the flame propagation, combustion speed and explosion pressure were measured at high speed camera ) And a pressure cell tester.

First, a process for manufacturing a conductive paper electrode using a carbon nanostructure will be described.

The conductive paper electrode using the carbon nanostructure according to the present invention is composed of a paper on which a carbon nano structure used as a heat generating and heat transfer medium is coated on a surface, Having an electrode shape.

Here, the region where the ignition is started is preferably a neck portion of a butterfly ribbon having a first width at both ends and a second width smaller than the first width at the center, but the shape is not limited thereto.

With this structure, the firing temperature of the paper on which the carbon nanostructure is coated is lower than the firing temperature of the paper before the carbon nanostructure is coated on the surface.

The process for preparing a conductive paper electrode using the carbon nanostructure according to the present invention includes the steps of preparing a multi-walled carbon nanotube nano solution, preparing a carbon nanotube-coated paper electrode using a vacuum deposition method, And a step of manufacturing a nanotube paper electrode.

In one embodiment of the present invention, multi-walled carbon nanotubes (MWCNTs) manufactured by thermal & chemical vapor deposition method, CNT Co. Ltd, Korea) are used.

They have a purity of about 95%, an average diameter of about 20 nm, a length of about 1 to 25 μm, and a specific surface area of about 250 m ² / g.

FIGS. 1A and 1B illustrate a process for coating a multi-walled carbon nanotube (MWCNTs) solution on a nonconductive paper using a vacuum adsorption process and fabricating a small electrode substrate.

First, 0.3 wt% of CNTs are added to an ethanol solution, and ultrasonic energy (ultrasonic output = 750 W, ultrasonic frequency = 20 kHz) is dispersed for 25 minutes (S101)

The filter support is placed on a vacuum flask, and a plain paper (circular shape: about 4.5 cm in diameter) is placed thereon. Then, a filtration apparatus is fixed on the upper side and a vacuum is formed in the lower side by a vacuum pump.

About 3 ml of the ethanol solution in which the prepared MWCNTs are dispersed is poured into a beaker using a micropipette (100-1,000 μl), and then slowly poured into the filtration apparatus (S103)

At this time, only the MWCNTs remain on the paper while the ethanol in the ethanol solution in which the MWCNTs dispersed on the paper is poured onto the paper by the vacuum pump connected to the vacuum flask, and the ethanol solution passing through the paper is collected in the lower flask. S104)

After the MWCNTs-coated paper was dried at room temperature (25 ° C, 30 minutes), it was cut into an electrode shape having a specific shape and size and connected to a DC power supply (0 to 30 V) And a temperature change is measured while supplying a specific voltage (S105)

A process for fabricating a small nano-energy material small igniter using a conductive paper electrode using a carbon nanostructure will be described below.

FIGS. 2A and 2B are a process flow diagram and a flowchart for manufacturing a miniature nano-energy material small igniter using a conductive paper electrode.

The process for fabricating a small-sized nano-high-energy material igniter using a conductive paper electrode according to the present invention includes a step of preparing a conductive paper electrode using a carbon nanostructure, a step of preparing a nano-sized high energy material (nEMs) (NEMs) thin film using a spin coating process on conductive paper electrodes.

A small nano-energy material small igniter having a conductive paper electrode according to the present invention includes a conductive paper electrode having a region where a carbon nanostructure used as a heat generating and heat transfer medium is coated on a surface and in which ignition starts, (NEMs) thin film coated on the surface of a conductive paper electrode.

Here, it is preferable that aluminum (Al) nanoparticles are used as a fuel metal material and copper oxide (CuO) nanoparticles are used as a metal oxide material in a nano-sized high energy material (nEMs) thin film. It does not.

The total burning time is controlled by the absolute mass of nano-high energy materials (nEMs) according to the thickness of the nano-sized high-energy material (nEMs).

In addition, the ignition delay time of the conductive paper electrode is controlled by the thickness of the nano-sized high-energy material (nEMs) thin film, and as the thickness of the nano-high energy material (nEMs) And an increase in time occurs.

The maximum pressure generated during the ignition and explosion of the nano-high-energy material (nEMs) film increases as the thickness of the nano-high energy material (nEMs) increases.

(Al, NT base, Korea) nanoparticles having an average diameter of ~ 80 nm were used as the fuel metal materials and nanoparticles of aluminum (Al) were used as the fuel metal materials in order to produce nano-sized high- Copper oxide (CuO, NT base, Korea) nanoparticles having an average diameter of ~ 100 nm are used as the metal oxide material, respectively.

It is to be understood that the fuel metal material and the metal oxide material are not limited thereto.

First, in order to prepare a nano-high energy material (nEMs) composite powder, Al nanoparticles and CuO nanoparticles are mixed in a ratio of Al: CuO = 30: 70 wt% (S201) And mixed for 30 minutes using ultrasonic energy (ultrasonic wave output = 170 W, ultrasonic frequency = 40 kHz) (S202)

Next, the conductive paper electrode coated with MWCNTs was placed on a spin coater, and about 10 μL of the nEMs solution was dropped using a micropipette (3-25 μL), and the solution was then dried at about 300 rpm for about 30 seconds Thereby forming a nano-high energy material thin film (S203)

The combustion characteristics of the nano-high energy material and the small igniter according to the present invention will be described below.

Ignition and explosion reactions were induced in a small - sized, conductive paper - based igniter with nEMs composite thin films deposited at atmospheric air and photographed at a frame rate of 30 kHz using a high - speed camera (FASTCAM SA3 120K).

The high speed camera used has a maximum frame rate of 1,200,000 fps, a minimum frame rate of 60 fps, a sensor size of 17.4 mm x 17.4 mm, a CMOS image sensor, Pixel size) 17 um x 17 um, operating voltage and current conditions are DC: 22-32 V, 100 VA, AC: 100-240 V, 10-60 Hz, 60 VA respectively.

FIG. 3 is a graph showing the results of resistance measurement of a paper electrode according to an initial concentration of a carbon nanotube solution and a photograph of a carbon nanotube thin film formed on the carbon nanotube thin film, (b) a neck width of a butterfly ribbon electrode coated with a carbon nanotube thin film, ). ≪ / RTI >

First, in order to determine an initial concentration of a carbon nanotube nanofluid suitable for manufacturing a small igniter and a wire size for ignition of the paper, the resistance of the carbon nanotube electrode formed on the paper according to the initial concentration of the nanofluid solution ) And the resistance (Fig. 3 (b)) according to the width of the narrow portion of the paper electrode in the form of a butterfly ribbon is measured.

FIG. 3 (a) shows the resistance value and the shape of the paper electrode formed with the carbon nanotube thin film after pouring them onto paper according to the initial concentration of the carbon nanotube nanofluid and removing the solution by vacuum.

At this time, the resistance value of the paper electrode was measured by a multimeter and the distance between the measurement probes was fixed to about 0.5 cm.

As shown in FIG. 3 (a), as the initial concentration of carbon nanotubes (MWCNTs) nanofluids increases, finally, the MWCNT thin film coated on the paper substrate is gradually severely cracked and a part of the MWCNT thin film is separated I could see.

When the initial concentration of the MWCNT solution was about 0.1 wt%, the resistance value of the MWCNT thin film formed on the paper was somewhat higher. However, when the initial concentration of the MWCNT solution increased to about 0.7 wt% The resistance was the lowest.

When the initial concentration of the MWCNT solution was increased to 0.3 wt% or more, the resistance value decreased, but the MWCNT concentration was increased and a lot of cracks were observed after drying on the paper.

As can be seen from the image of the paper electrode where the carbon nanotube thin film of FIG. 3 (a) was formed, the initial concentration of the MWCNT solution was increased, and the MWCNT thin film produced by the strong binding and coagulation phenomenon between the MWCNTs Seems to have occurred.

Therefore, it is preferable to fix the initial concentration of the MWCNT solution to 0.3 wt% in order to allow the MWCNT thin film to be uniformly coated with little cracks on the paper electrode while maintaining a low resistance value.

In the present invention, the paper substrate coated with carbon nanotubes is made to have a uniform width as a butterfly ribbon shape, and a width of only a central portion is narrowed to intensively generate resistance heat in a narrow neck portion, Ignition.

The paper electrode coated with such a butterfly-shaped carbon nanotube was actually designed and manufactured, The resistance value according to the length of the narrow neck portion at the center was measured and shown in FIG. 3 (b).

In FIG. 3 (b), the MWCNT thin film was formed on a paper substrate by fixing the initial concentration of the MWCNT solution at a reference level of 0.3 wt%, and a butterfly ribbon-shaped paper electrode was produced. The narrow width of the central part was 0.1 cm long It was observed that the resistance value changed every time.

As a result, the resistance value gradually increased as the length between the center electrode widths became longer.

FIG. 4 shows (a) a butterfly-shaped photo of a paper electrode coated with a carbon nanotube thin film, (b) a planar and lateral SEM image of the MWCNT thin film deposited on the paper, and (c) an enlarged view of the MWCNT thin film- High-magnification SEM image.

In order to examine the structure of the paper electrode formed with the carbon nanotube thin film, FE-SEM analysis is performed as follows.

As shown in FIG. 4 (a), 3 ml of the MWCNT solution having an initial concentration of 0.3 wt% was formed as a thin film on a paper electrode using a vacuum process, and a size of 3 cm x 1.5 cm (center neck: length 0.7 cm) .

In FIGS. 4 (b) and 4 (c), SEM photographs of cross sections of the MWCNT thin film are shown in the plan view of the MWCNT formed on the paper substrate. The thickness of the thin film is about 80 μm , Which is very similar to the paper substrate thickness of about 80 탆.

Here, the thickness of the carbon nanotube thin film is relatively easily adjustable depending on the amount of the MWCNT nanofluid solution supplied.

As shown in FIG. 4 (c), the MWCNT thin film was observed to be in a very uniform and strong contact with the paper substrate.

FIG. 5 is a graph showing a comparison of resistance values of a paper electrode coated with a carbon nanotube thin film according to various curvature radii (b) Repeated bending of a paper electrode coated with a carbon nanotube thin film having a radius of curvature of R2.5 mm And the change of the resistance value according to the test and before and after the bending test.

As described above, in order to measure the change of the resistance according to the degree of bending of the carbon electrode coated with the carbon nanotubes fabricated according to the present invention, the electrode was wound around a plastic tube having various radii of curvature, The change is measured as follows.

As shown in Fig. 5 (a), the radius of curvature was 33.5 Ω @ R 2.5 mm, 32.5 Ω @ R 5 mm, and 32.0 Ω @ R 10 mm.

As the radius of curvature decreases, the resistance value increases. As the radius of curvature decreases, the degree of bending of the carbon nanotube film increases. This is because the carbon nanotube layer, which is in close contact with the paper substrate, This is because the compressive stress acts on the surface of the carbon nanotube thin film and the tensile stress acts on the surface of the carbon nanotube thin film.

The relaxation between the MWCNTs near the surface layer of the carbon nanotube thin film and the occurrence of macroscopic microcracks cause a decrease in scattering and electrical mobility in the movement of the electrons. Therefore, when the radius of curvature becomes small, carbon nanotubes The surface resistance value of the coated paper electrode is slightly increased.

In addition, the paper coated with carbon nanotubes having the butterfly ribbon shape produced has a surface resistance value (i.e., 32.0) when the resistance value (i.e., 33.5?) In the case of R2.5 mm having a relatively small radius of curvature is flat Ω), showing a surface resistance value with no significant difference, and it can be seen that occurrence of microcracks in the inside is generally small.

This means that a paper electrode coated with a carbon nanotube having a butterfly ribbon shape can be used as a flexible small igniter.

FIG. 5 (b) shows the result of repeated bending test to measure the change of resistance according to the degree of repetitive bending at a radius of curvature of R2.5 mm in a paper electrode coated with carbon nanotubes.

As a result, it was confirmed that the MWCNT thin film was fabricated with coated electrode with high reliability, which showed the same value as the initial resistance value despite 250 repetitive bending at R2.5 mm having a large radius of curvature.

FIG. 6 is a graph showing the results of photographing and resistance measurement after (a) attaching / detaching 3M tape to / from a paper electrode coated with a carbon nanotube thin film, (b) Change photo and resistance value measurement result.

In order to evaluate the interfacial contact force for the paper electrode coated with the MWCNT thin film manufactured by the present invention, the separation test using the tape and the change of the resistance value before and after the wetting test were performed.

First, when the 3M tape is attached to a paper electrode coated with a prepared ribbon of a carbon nanotube film, how much carbon nanotube is visually separated from the tape, or when the carbon nanotube film is separated from the paper substrate And the like were visually compared with each other, and a photograph of the electrode immediately after tape contact and desorption was presented.

As shown in FIG. 6 (a), after the tape was contacted with the electrode surface, the amount of carbon nanotubes adhering to the tape was extremely small as a result of desorption, and it was observed that the resistance of the electrode was almost unchanged after desorption.

This is because the carbon nanotube thin film coating layer is very strongly bonded to the surface of the paper by the force of the van der Waals force.

6 (b) is a photograph before and after drying the paper electrode coated with the carbon nanotube thin film prepared in this study after dipping the beaker in water for one day, dipping it in water, and drying it.

It was difficult to find any trace of carbon nanotube thin film peeled or destroyed by water even when it was observed with the naked eye. As a result of measuring the resistance value before and after immersion in water, no noticeable change of resistance value was observed.

Therefore, it can be confirmed that the carbon nanotube thin film layer is strongly bonded to the paper electrode and is not easily separated or destroyed by external force.

FIG. 7 is a graph showing the results of measurement of maximum exothermic temperature according to various applied voltages of a paper electrode coated with a carbon nanotube thin film, (b) a butterfly-shaped paper electrode under a fixed applied voltage of about 15 V, And video-based still image analysis results.

FIG. 7 shows the results of measuring the maximum heating temperature and the ignition behavior according to various applied voltages on a paper electrode coated with a carbon nanotube thin film.

Specifically, an electrode of a DC power supply (DC power supply, 0 to 30 V) was connected to the end of a conductive carbon electrode coated with a carbon nanotube, and a voltage was applied to the resistance heat generated in the narrow neck portion of the butterfly- It was measured using an optical pyrometer and a conventional camera.

As shown in FIG. 7 (a), as the applied voltage increases with 5 V, 10 V, 12 V, 14 V, 15 V, etc., the resistance heat generated in the narrow neck portion of the butterfly- , 180 ° C, 260 ° C, 370 ° C and 430 ° C, respectively.

As a result of increasing the applied voltage, the resistance heat of the carbon nanotube thin-film paper electrode is relatively constantly increased. In general, when the voltage value is increased in the Ohm's law (V = IR) Which is a linear device.

The paper is generally known to ignite at a temperature of about 400 to 450 ° C. The paper electrode coated with the carbon nanotube thin film has a thickness of about 430 It is confirmed that ignition starts at about the temperature of about 캜.

Fig. 7 (b) shows the firing phenomenon in the neck of the butterfly ribbon of a paper electrode coated with a thin film of carbon nanotubes by resistance heat generated at an applied voltage of 15 V, A snapshot was shown.

A voltage of about 15 V was applied to the conductive paper electrode, and after one second, the ignition started at one end of the narrow neck of the butterfly paper electrode and propagated to the opposite end.

It can be seen that as the time passes, the firing range spreads widely from the central part of the neck, and after about 6 seconds, the firing phenomenon is stopped by the paper electrode short circuit.

That is, it is confirmed that the paper electrode coated with the carbon nanotube thin film according to the present invention has characteristics of a linear device, and the application range can be diversified by suitably controlling the resistance heat generated according to the magnitude of the applied voltage Able to know.

(B) a SEM image of the nEMs / MWCNT / paper thin section, (c) the MWCNT and the nEMs thin film, This is an SEM image in which the paper electrode interface is enlarged.

8 (a) shows an image of a nEMs thin film formed on a conductive paper electrode placed on a spin coater.

It was confirmed that the formed nEMs had a circular shape with a diameter of about 5 mm and were fixed to the center of the conductive paper electrode neck.

8 (b) is a SEM photograph of a cross section taken after the formation of the nEMs thin film. The thickness of the nEMs thin film on the paper substrate is about 150 μm, and cracks exist in the thin film, .

As shown in FIG. 8 (c), it was observed that the interface between the carbon nanotube thin film and the nEMs thin film was strongly in contact with each other.

In addition, it can be seen that the nEMs thin films prepared by the spin coating method have a relatively dense structure with high degree of filling, because the bonding force between the metal and the oxidizing agent nanoparticles constituting the nEMs is very strong due to the van der Waals force .

In order to analyze the influence of the change in the thickness of the nano-sized high-energy material (nEMs) on the paper electrode coated with the carbon nanotube thin film according to the present invention on the degree of explosion upon ignition, a voltage was applied to the paper electrode, The explosion experiment is as follows.

FIG. 9 is a graph showing the relationship between the ignition delay time, the burn rate, and the total burning time of the high-speed camera for the ignition and explosion phenomenon of the nEMs thin films having various lamination thicknesses by the ignition of the carbon nanotube thin- (Total burning time).

The nEMs thin films with various lamination thicknesses were analyzed by static image analysis of the explosion phenomenon during ignition using conductive paper electrodes. The nEMs thin films with various lamination thicknesses were ignited by the resistance heat according to the applied voltage of the conductive paper electrode, It can be seen that the explosion reaction is successfully induced.

As the lamination thickness of the nEMs thin films became thicker, the burning rate of the conductive paper electrode due to the resistance thermal ignition was determined to be about 70 m / s according to the applied voltage. The total burning time was 5.30 ms, 5.56 ms, 5.86 ms, 6.00 ms, and 6.26 ms, respectively.

That is, the total burning time was increased as the thickness of the nEMs was increased, but the burn rate was about 70 m / s.

This means that the increase in the absolute mass of nEMs with the thickness of the nEMs increases the total burning time, which is basically the same reactant material, which means that the effect on the burning rate is not significant.

The ignition delay time was influenced by the time of heating depending on the applied voltage of the carbon nanotube paper electrodes. As the thickness of the nEMs increased, the thermal resistance increased and the fine ignition delay time increased.

FIG. 10 is a graph showing the explosion pressure measured after ignition of a pressure cell in an nEMs thin film having various lamination thicknesses by ignition of a carbon nanotube thin film-coated paper electrode. (A) (B) change in pressure rise rate with thickness of nEMs thin film laminate.

The results of measuring the pressure change and the rate of pressure increase during the explosion reaction are shown in Fig. 1 (a). The nano-sized carbon nanotubes are coated with a thin film of nano-particles by using a pressure cell tester (PCT).

As shown in FIG. 10 (a), the maximum pressure generated upon ignition and explosion of the nEMs thin film formed on the carbon nanotube paper electrode shows a tendency to increase as the lamination thickness of the nEMs thin film increases, As the thickness of the thin film becomes thicker, the explosion pressure increases because the mass of the nano-high energy material increases.

10 (b), as the thickness of the nEMs thin film is increased, the pressure increasing rate is defined as a value obtained by dividing the maximum pressure value by the time taken to reach the maximum pressure, which is 0.52 kPa · μs ^-1 @ nEMs = 150 μm, 0.53 kPa μs ^-1 @ nEMs = 200 μm, 0.57 kPa μs ^-1 @ nEMs = 250 μm, 0.67 kPa μs ^-1 @ nEMs = 300 μm, 0.7 kPa μs ^{- 1} @ nEMs = 350 μm.

This means that when the mass of the nEMs thin film is increased, the explosion reaction can be controlled and the explosion reaction can be controlled when the nEMs thin film is ignited on the paper electrode coated with the carbon nanotube thin film.

FIG. 11 shows the results of analysis of ignition and explosion phenomena of nEMs thin films by voltage application on paper electrodes coated with Fullerene / MWCNT, SWCNT, and Graphene thin films.

The conductive paper electrode according to the present invention, a small nano-energy material small igniter having the same, and a method of manufacturing the same have a zero-dimensional, one-dimensional and two-dimensional (three-dimensional) one-dimensional carbon nanotubes (MWCNTs) The present invention can be applied to a paper electrode using various carbon nanostructures having a structure of a carbon nanostructure.

Fullerene (0D), Single Wall Carbon Nanotubes (SWCNTs), and Graphene (2D) were used as carbon nanostructures in this study. (MWCNT) - coated paper electrode was fabricated using the same manufacturing process as that of the paper electrode.

In the case of fullerene, a 0-dimensional nanomaterial of multidimensional carbon nanostructure, the cohesive force between the particles is stronger but the contact force with the paper substrate is weak, Respectively.

In other words, it was confirmed that it is difficult to produce a stable conductive paper electrode based only on 0-dimensional fullerene particles. As a result, a multi-walled carbon nanotube (MWCNT), which is a one-dimensional carbon nanotube (MWCNT), was added to the pulpal nanoparticles to produce a conductive paper electrode. As a result, And the Fullerene / MWCNT thin film was formed strongly in contact with the paper substrate.

In the production of paper electrodes based on the remaining SWCNTs and Graphen films, the contact force between the interfaces was weak and no separation occurred. Therefore, the paper electrode is fabricated on the basis of each carbon nanostructure composed of Fullerene / MWCNT, SWCNT, and Graphene, and the following experiment is carried out for the ignition and explosion of the nanenergetic materials (nEMs).

Fig. 11 shows the result of analyzing the static image of the explosion phenomenon generated when the nEMs are coated on the conductive paper electrode coated with various carbon nanostructures such as Fullerene / MWCNT, SWCNT, and Graphene, and the voltage is applied to the paper electrode.

Both the ignition and the instantaneous explosive reaction were successfully induced by the resistance heat generated by applying the voltage to the conductive nano-structured conductive paper electrode coated with various nEMs thin films.

For the conductive paper electrode with carbon nanostructure applied, the burn rate by resistive thermal ignition is ~ 3.4 m / s @ Fullerene / MWCNT, ~ 6.2 m / s @ SWCNT, ~ 3.3 m / s @ Graphene And total combustion time was ~ 54.5 ms @ Fullerene / MWCNT, ~ 65.3 ms @ SWCNT, ~ 68.4 ms @ Graphene value.

In all cases, it was observed that the burning rate was several m / s and the total burning time was not significantly different to the order of tens of ms, since the nEMs were basically the same reactant material and were hardly affected by the conductive material on the paper electrode to be.

Finally, it was confirmed that various carbon nanomaterials such as Fullerene, SWCNT, MWCNT, and Graphene were formed as thin films and used as small igniters for nEMs materials after manufacturing conductive paper electrodes, which showed stable ignition and explosion characteristics.

From the above results, it can be seen that the nEMs thin film is laminated on a paper electrode coated with a carbon nanotube thin film, so that it can be applied to a small igniter for a small armature.

A door breaching test was conducted to confirm the applicability of the carbon nanotube-coated conductive paper-based small igniter manufactured in the present invention.

Door briquetting technology is a technology for forcibly opening a locked door. It is used to enter the building in case of an emergency in order to protect life structures or equipment in civilian technology field.

12 is a moving image and still image of a door briquing technique using a remote ignition and explosion using a small igniter based on a carbon nanotube paper in which an nEMs thin film is formed.

(B) ignition and explosion of nEMs-on-a-paper by remote signaling; (c) (D) separation and detachment of the door hinge due to the explosive force, and (d) successful detachment of the door hinge portion.

The door bricking test performed in the present invention is prepared by connecting a remote voltage device and a carbon nanotube paper electrode-based small igniter as shown in FIG.

A safety distance of about 15 m was secured and a small ignition was applied remotely to test whether it could be ignited.

As a result, as shown in the continuous still image of FIG. 12, a signal was sent to the remote voltage pore device using a remote controller, and a small-sized igniter based on carbon nanotube paper in which an nEMs thin film (thickness: 150 μm) And the door hinge can be reliably removed by remote ignition and explosion.

Accordingly, the conductive paper-based remote small igniter coated with carbon nanotubes according to the present invention,

(i) no separate detonation line for door briquetting is required,

(ii) rod-shaped / plate-like explosives, and the like,

(iii) Because it is a small igniter, the manufacturing cost is low, it is very easy to carry and handle,

(iv) Because it is paper-based, it is flexible and can be applied to a narrow space. Therefore, it is expected that it is highly applicable in practical civilian technology field application.

As described above, it will be understood that the present invention is implemented in a modified form without departing from the essential characteristics of the present invention.

It is therefore to be understood that the specified embodiments are to be considered in an illustrative rather than a restrictive sense and that the scope of the invention is indicated by the appended claims rather than by the foregoing description and that all such differences falling within the scope of equivalents thereof are intended to be embraced therein It should be interpreted.

Claims (10)

A conductive paper electrode including a paper on which a carbon nanostructure used as a heat generation and heat transfer medium is coated, the conductive paper electrode having a region where ignition starts;
And a nano-sized high energy material (nEMs) thin film coated on the surface of the conductive paper electrode,
Wherein a region of the conductive paper electrode in which ignition is initiated is generated when a voltage is applied to generate a resistance heat to ignite a nano-high energy material at a specific position. Igniter. 2. The conductive paper electrode as claimed in claim 1, wherein the region where the ignition is started is a neck portion of a butterfly ribbon having a first width at both ends and a second width smaller than the first width at the center. High energy substance small igniter. The nano-high-energy material having a conductive paper electrode according to claim 1, characterized in that the ignition temperature of the paper on which the carbon nanostructure is coated is lower than the ignition temperature of the paper before the carbon nanostructure is coated on the surface Igniter. The carbon nanostructure according to claim 1,
A nanowhigh energy material having a conductive paper electrode, characterized in that the nanoparticle material is any one of Fullerene, single wall carbon nanotube (SWCNT), multiwall carbon nanotube (MWCNT), graphene, Small igniter. The method of claim 1, wherein the ignition delay time of the conductive paper electrode is controlled according to the thickness of the nano-sized high-energy material (nEMs)
Characterized in that as the layer thickness of the nano-high energy material (nEMs) thin film increases, the thermal resistance increases and the ignition delay time increases. A step of preparing a conductive paper electrode using a carbon nanostructure;
Nano-high-energy material (nEMs) solution;
(NEMs) thin film using a spin coating process on a conductive paper electrode coated with a carbon nanostructure,
The conductive paper electrode fabricated in the step of manufacturing the conductive paper electrode using the carbon nanostructure has a region where the ignition is started. When the voltage is applied, the resistance heat is concentrated and the ignition is performed. Wherein the energy material is ignited. ≪ RTI ID = 0.0 > 11. < / RTI > 7. The method of claim 6, wherein the step of preparing the conductive paper electrode using the carbon nanostructure comprises:
Preparing a carbon nanostructure solution,
Coating a carbon nanostructure on the surface of the paper by using a vacuum deposition method,
Fabricating a conductive paper electrode having a region in which a resistive heat is concentrated when the voltage is applied to initiate ignition having a first width at both ends and a second width less than the first width so that ignition occurs, ≪ / RTI > wherein the conductive material is a conductive material. 8. The method according to claim 6 or 7,
Characterized by using any one of a fullerene, a single wall carbon nanotube (SWCNT), a multiwall carbon nanotube (MWCNT), a graphene, or a combination thereof. (METHOD FOR MANUFACTURING ENERGY MATERIALS) 7. The method of claim 6, wherein the step of preparing the nano-energetic material (nEMs)
Al nanoparticles and CuO nanoparticles are mixed in a ratio of Al: CuO = 30: 70 wt% to prepare a nano-sized high energy material (nEMs) composite powder,
Al / CuO composite powders in an ethanol solution and mixing them using ultrasonic energy. The method of manufacturing a miniature nano-energy material small igniter having conductive paper electrodes according to claim 1, 8. The method of claim 7, wherein the step of coating the carbon nanostructure on the paper surface comprises:
Placing the filter support in a vacuum flask, raising the paper thereon, fixing the filtration device on the top and forming a vacuum in the bottom with a vacuum pump,
Introducing an ethanol solution in which a carbon nanostructure is dispersed into a filtration apparatus,
A step of allowing the carbon nanostructure to remain on the paper in the ethanol solution in which the carbon nano structure poured onto the paper is dispersed with the vacuum pump connected to the pressure reducing flask and the ethanol solution passing through the paper is collected in the lower flask,
And drying the carbon nanostructure-coated paper. ≪ RTI ID = 0.0 > 8. < / RTI >

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