KR20170059671A - Dielectric based on nanoring structure carbon nanotube and polymer and method for fabricating the same - Google Patents
Dielectric based on nanoring structure carbon nanotube and polymer and method for fabricating the same Download PDFInfo
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Abstract
The present invention relates to a method of manufacturing a dielectric material using a polymer material such as PVDF, which comprises dispersing a carbon nanotube having a nanorning structure excellent in dispersibility in a polymer material, thereby dispersing the carbon nanotube in a dispersed nanorning structure into a conductive pillar, The present invention relates to a nano-ring-type carbon nanotube and a polymer-based dielectric material capable of increasing the capacitance of a dielectric material by performing a role of the nano- The method comprising: dispersing a polymer material and a carbon nanotube having a nanor ring structure in a dispersion solution; Molding a dispersion solution in which carbon nanotubes of a polymer material and a nano ring structure are dispersed; And evaporating the dispersion solution to prepare a dielectric material comprising a polymer material and a carbon nanotube having a nano ring structure, wherein the carbon nanotube having the nanor ring structure has a non-covalent bond with the polymer for bonding And the coupling polymer is any one of π-conjugated liquid polymer, aromatic polymer, and non-aromatic polymer, or a combination thereof.
Description
The present invention relates to a nano-ring-structured carbon nanotube and a dielectric material based on a polymer material and a method of manufacturing the same. More particularly, the present invention relates to a dielectric material having excellent dispersibility in a polymer material, A carbon nanotube having a nano ring structure capable of increasing the capacitance of a dielectric by allowing a carbon nanotube having a dispersed nanorring structure to act as a conductive piller by dispersing a ring carbon nanotube, And a method of manufacturing the same.
Studies on dielectrics based on poly (vinylidenedifluoride) (PVDF) have been underway (see Korean Patent No. 1152463). PVDF has excellent mechanical and chemical properties and has excellent dielectric properties among polymeric materials due to C-F dipole.
In addition, PVDF has piezoelectric properties that convert electrical energy into mechanical energy. Electron donors are required to increase the dielectric properties of PVDF. Recently, techniques for improving dielectric properties by dispersing carbon nanotubes (CNTs) having many electrons in PVDF have been proposed. However, the nano-scale effect of carbon nanotubes is not exhibited due to the low dispersibility of carbon nanotubes, which limits the improvement of PVDF dielectric properties.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a method of manufacturing a dielectric material by using a polymer material such as PVDF by dispersing carbon nanotubes having nano ring structure, The present invention provides a carbon nanotube having a nano ring structure and a polymer material based dielectric material capable of increasing the capacitance of the dielectric material by allowing the carbon nanotube structure to act as a conductive piller, .
According to another aspect of the present invention, there is provided a method of fabricating a nano-ring-structured carbon nanotube and a polymer-based dielectric material, the method including: dispersing a polymer material and a nanorring carbon nanotube in a dispersion solution; Molding a dispersion solution in which carbon nanotubes of a polymer material and a nano ring structure are dispersed; And evaporating the dispersion solution to prepare a dielectric material comprising a polymer material and a carbon nanotube having a nano ring structure, wherein the carbon nanotube having the nanor ring structure has a non-covalent bond with the polymer for bonding And the coupling polymer is any one of π-conjugated liquid polymer, aromatic polymer, and non-aromatic polymer, or a combination thereof.
(PVDF-TrFE) copolymer of polyvinylidene fluoride (PVDF), polyvinylidene fluoride (PVDF) and trifluoroethylene (TrFE), and the polymeric material is a piezoelectric polymer material or a dielectric polymer material. (PD), polypropylene (PP), polymethylmethacrylate (PMMA), polycarbonate (PC), polyamide (PA)), polystyrene (PS) , And polyimide (PI).
The nano-ring carbon nanotubes may be mixed at a content of 11 wt% or less based on the total weight of the polymer material and the nano-ring carbon nanotubes.
The nano-ring carbon nanotubes are prepared by reacting a metal oxide precursor solution with an acid-treated carbon nanotube to prepare a metal oxide-carbon nanotube composite in which carbon nanotubes are bound around the metal oxide particles And introducing the metal oxide-carbon nanotube composite into a polymer solution for bonding to induce the non-covalent bonding of the binding polymer and the carbon nanotube, and a step of immersing the metal oxide- And removing the metal oxide particles to form a carbon nanotube having a nanor ring structure.
The acid-treated carbon nanotube is a carbon nanotube having either or both of a hydroxyl group (-OH) and a carboxyl group (-COOH) on its surface. Also, the metal oxide precursor solution is a solution containing a metal oxide precursor, and the metal oxide precursor is zinc acetate hydrate (Zn (CH 3 COO) 2 .2H 2 O).
Wherein the metal oxide precursor of the metal oxide precursor solution is selected from zinc acetate hydrate, tin acetate hydrate, aluminum acetate hydrate, titanium acetate hydrate, ferrous acetate hydrate, copper acetate hydrate, sodium acetate hydrate, cobalt acetate hydrate, lanthanum acetate hydrate, cerium acetate hydrate , Silver acetate hydrate, manganese acetate hydrate, molylacetate hydrate, nickel acetate hydrate, or a combination thereof.
The OH component of the hydroxyl group (-OH) or the carboxyl group (-COOH) of the acid-treated carbon nanotube binds to the metal particles of the metal oxide.
In the process of introducing the metal oxide-carbon nanotube composite into the polymer solution for bonding and inducing the non-covalent bonding between the polymer for bonding and the carbon nanotube, the metal oxide-carbon nanotube complex and the binding polymer are mixed at a ratio of 1: 1 to 1: 3. ≪ / RTI >
The binding polymer of the binding polymer solution may be any one of a π-conjugated polymer, an aromatic polymer, and a non-aromatic polymer, or a combination thereof. The π-conjugated polymer is any one or combination of poly (phenylenevinylene), polypyrrole, polyaniline, and poly (3-alkylthiophenes) The aromatic polymer is a polyimide. The non-aromatic polymer includes poly (vinylpyrrolidone), poly (vinyl alcohol), polybutadiene, polyisoprene, , Poly (methyl methacrylate), and polyethylene oxide (poly (ethylene oxide)), or a combination thereof.
(-OH) or carboxyl group (--OH) present on the surface of the carbon nanotube in the course of introducing the metal oxide-carbon nanotube complex into the polymer solution for bonding and inducing the non-covalent bond between the binding polymer and the carbon nanotube, COOH) is non-covalently bonded with the oxygen (O) component present in the binding polymer.
The nano-ring structure and the polymer-based dielectric material according to the present invention are composed of nano-ring carbon nanotubes and polymer materials, and the nano-ring carbon nanotubes include up to 11 wt% The carbon nanotubes of the structure have a non-covalent bond with the binding polymer, and the binding polymer is any one of a π-conjugated polymer, an aromatic polymer, and a non-aromatic polymer, or a combination thereof.
The carbon nanotubes and the polymer-based dielectric material according to the present invention and their fabrication methods have the following effects.
Since the carbon nanotubes having excellent dispersibility are combined with the polymer material to form a dielectric, the dielectric constant and capacitance characteristics are increased by the dispersed carbon nanotubes.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart illustrating a method of manufacturing a nanotube-based dielectric material according to an embodiment of the present invention. FIG.
2 is a schematic view showing a bonding reaction between a hydroxyl group (-OH) of a carbon nanotube and oxygen (O) of polyvinylpyrrolidone (PVP).
FIG. 3 is a photograph of a nanotube-based carbon nanotube and a polymer-based dielectric prepared through Experimental Example 2. FIG.
FIG. 4 is a graph showing the polarization characteristics of the dielectric material prepared in Experimental Example 2. FIG.
FIGS. 5 and 6 are experimental results showing the dielectric constant characteristics according to the frequency of the dielectric prepared through Experimental Example 2. FIG.
7 shows the XRD results of the dielectrics and the PVDF-TrFE dielectrics prepared in Example 2. Fig.
Disclosed herein is a technique for improving the dielectric properties of a dielectric material by dispersing carbon nanotubes having a nano ring structure having excellent dispersibility in a polymer material in producing a dielectric material using a polymer material having dielectric properties. Carbon nanotubes of nano-ring structure dispersed in a polymer material are conductive pillars, and the distance d between the dielectric electrodes is reduced by uniform dispersion. Ultimately, the capacitance C of the dielectric material Increase.
In order to form a nano-ring structure carbon nanotube, the present invention uses nano-sized oxide particles and arranges carbon nanotubes around nano-sized oxide particles to form a nano ring shape of carbon nanotubes The proposed method is based on In addition, in order to strengthen the nanorning structure of carbon nanotubes in the production of nano-ring carbon nanotubes, the present invention provides a nano-ring structure that induces non-covalent bonding between a nanotube- We present a technology that can improve the yield for carbon nanotubes.
Hereinafter, a carbon nanotube having a nano ring structure according to an embodiment of the present invention, a dielectric material based on a polymer material, and a method of manufacturing the same will be described in detail.
Referring to FIG. 1, a method of fabricating a nano-ring-structured carbon nanotube and a polymer-based dielectric according to an embodiment of the present invention includes 1) a step of preparing a composite of a metal oxide and a carbon nanotube, 2) (3) removing the metal oxide to prepare a carbon nanotube having a nano ring structure, (4) dispersing a carbon nanotube having a nanor ring structure in the polymer material, (5) And forming a dielectric material by molding a polymer material in which carbon nanotubes are dispersed.
1) The step of producing a composite of a metal oxide and a carbon nanotube is as follows.
First, an acid-treated carbon nanotube and a metal oxide precursor solution are prepared (S101). The acid-treated carbon nanotube refers to a carbon nanotube having either or both of a hydroxyl group (-OH) and a carboxyl group (-COOH) on its surface, and the carbon nanotubes are added to the acid solution, Carbon nanotubes can be obtained. As the acid solution, a mixed solution of sulfuric acid and nitric acid can be used. The hydroxyl groups (-OH) or carboxyl groups (-COOH) provided on the surfaces of the acid-treated carbon nanotubes are dispersed in the solvent of the carbon nanotubes (a solvent of the metal oxide precursor solution described later) And reacts with the metal oxide precursor to convert the metal oxide precursor to a metal oxide and to mediate the bond between the metal oxide and the carbon nanotube.
The metal oxide precursor solution is a mixture of a metal oxide precursor and a solvent and the solvent of the metal oxide precursor solution is selected from the group consisting of dimethylformamide (DMF), tetrahydrofuran (THF), chlorobenzene (CB), dichlorobenzene (DCB) , Trichlorobenzene (TCB), or a combination thereof. Preferably, dimethylformamide (DMF) may be used.
The metal oxide precursor may be zinc acetate hydrate, tin acetate hydrate, aluminum acetate hydrate, titanium acetate hydrate, iron acetate hydrate, copper acetate hydrate, sodium acetate hydrate, cobalt acetate hydrate, lanthanum acetate hydrate, cerium acetate hydrate, (Zn (CH 3 COO) 2 .2H 2 O) may be used as the organic solvent, and the organic solvent may be any one or a combination of acetate hydrate, manganese acetate hydrate, molylacetate hydrate and nickel acetate hydrate, preferably zinc acetylacetate hydrate .
When a metal oxide precursor solution and an acid-treated carbon nanotube are prepared, an acid-treated carbon nanotube is added to a metal oxide precursor solution and heated to a predetermined temperature to form a metal oxide, and a ring- Nanotubes are provided (S102). A case where zinc acetate hydrate (Zn (CH 3 COO) 2 .2H 2 O) is used as the metal oxide precursor will be described as an example.
When the acid-treated carbon nanotubes are introduced into the metal oxide precursor solution, that is, zinc acetate hydrate (Zn (CH 3 COO) 2 .2H 2 O) and heated to a predetermined temperature, zinc oxide hydrate (Zn (CH 3 COO) 2 · 2H 2 O is decomposed into zinc hydroxide (Zn (OH) 2 ) and acetic acid (CH 3 COOH) and zinc hydroxide (Zn (OH) 2 ) is further decomposed into ZnO and H 2 O And the metal oxide precursor (Zn (CH 3 COO) 2 .2H 2 O) is converted into a metal oxide (ZnO) by a series of such continuous reactions.
In the process of converting a metal oxide precursor (Zn (CH 3 COO) 2 .2H 2 O) into a metal oxide (ZnO), carbon nanotubes treated with acid are present in the metal oxide precursor solution, (Zn) in the zinc acetate hydrate (Zn (CH 3 COO) 2 .2H 2 O) is bonded to the -OH of the carbon nanotube due to the presence of the hydroxyl group (-OH) and the carboxyl group (-COOH) To form zinc hydroxide (Zn (OH) 2 ). That is, the -OH of the hydroxyl group (-OH) or carboxyl group (-COOH) of the carbon nanotube zinc acetate hydrate (Zn (CH 3 COO) 2 · 2H 2 O) reacts with Zn to Zn (OH) 2 of . At this time, OH component is generated Zn (OH) 2 is the type that is, Zn (OH) combined with carbon nanotubes according to -OH being in the carbon nanotubes in the resulting Zn (OH) 2 2 · CNT ( carbon nanotubes (see
ZnO particles can be formed by thermal decomposition of Zn (CH 3 COO) 2 .2H 2 O. In this case, the ZnO particles formed in this case form a nanorod, and ZnO particles form a nanorod It is impossible to manufacture ring-shaped carbon nanotubes. On the other hand, as described above, when a carbon nanotube having a hydroxyl group (-OH) or a carboxyl group (-COOH) on its surface is reacted with Zn (CH 3 COO) 2 .2H 2 O, the ZnO particles react with the nanorod ) Quantum dots instead of the carbon nanotubes, thereby making it possible to manufacture carbon nanotubes having a ring structure, and it is possible to realize carbon nanotubes having a ring structure having a size of 20 to 30 nm.
On the other hand, the composite in which the metal oxide and the carbon nanotube are combined is precipitated in the metal oxide precursor solution, and the precipitated bound complex can be separated by using a centrifuge. In the following description, a composite in which a metal oxide and a carbon nanotube are combined will be referred to as a " metal oxide-carbon nanotube composite ".
The above reaction can be summarized as follows.
(Scheme 1)
Zn (CH 3 COO) 2 .2H 2 O + CNT-OH (or CNT-COOH)? Zn (OH) 2 .CNT + 2CH 3 COOH
(Scheme 2)
Zn (OH) 2 · CNT → ZnO + H 2 O
The metal oxide precursor is reacted with the acid-treated carbon nanotube to form a metal oxide-carbon nanotube composite, and (2) the bonding reaction step of the carbon nanotube and the binding polymer proceeds.
Specifically, a polymer solution for bonding is prepared, and a reaction between the carbon nanotubes and the binding polymer is induced by introducing a metal oxide-carbon nanotube complex into the polymer solution for bonding (S103). At this time, a dispersant may be added to improve the dispersibility of the metal oxide-carbon nanotube composite in the polymer solution for bonding, and sodium dodecyl sulfate, sodium dodecylbenzene sulfonate ( sodium dodecyl benzenesulfonate, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, and octyl phenol ethoxylate, or a combination thereof may be used.
When the metal oxide-carbon nanotube composite and the binding polymer are reacted, the metal oxide-carbon nanotube composite and the binding polymer should be mixed in a mass ratio of 1: 1 to 1: 3. When the binding polymer is mixed with less than the above ratio, the reaction with the carbon nanotubes is not performed. When the mixing ratio is higher than the above ratio, unreacted polymer is generated and it is difficult to purify. In addition, the temperature of the solution during the reaction is preferably about 60 to 80 DEG C, and the reaction time can be 5 to 24 hours.
The coupling polymer serves to maintain the shape of the ring carbon nanotubes through chemical bonding with the carbon nanotubes, and a π-conjugated polymer, an aromatic polymer, and a non-aromatic polymer may be used. As the π-conjugated polymer, any one of poly (phenylenevinylene), polypyrrole, polyaniline, and poly (3-alkylthiophenes) or a combination thereof may be used Polyimide may be used as the aromatic polymer. Examples of the non-aromatic polymer include poly (vinylpyrrolidone), poly (vinyl alcohol), polybutadiene (poly polybutadiene, polyisoprene, poly (methyl methacrylate), and polyethylene oxide (poly (ethylene oxide)), or a combination thereof. As the solvent for the polymer solution for binding, any one of water, methanol, ethanol, methylene chloride, and dimethylformamide may be used.
In the case where poly (vinylpyrrolidone) is used as the binding polymer, the binding reaction between the binding polymer and the carbon nanotube will be described as an example. In the case of the hydroxyl group present on the surface of the carbon nanotube The hydrogen (H) component of the carboxyl group (-COOH) or the hydrogen (H) component of the carboxyl group (-COOH) becomes noncovalent bond with the oxygen (O) component present in the polyvinylpyrrolidone (See FIG. 2). At this time, the carbon nanotube forms a non-covalent bond with the binding polymer in the state that the metal oxide-carbon nanotube complex is formed. Here, the non-covalent bond means a chemical bond that is not a covalent bond, and may specifically denote a π-π bond, a CH-π bond, a cation-π bond, or a hydrogen bond.
On the other hand, if the metal oxide-carbon nanotube composite is not bound to the binding polymer, and the metal oxide particle removal process using a subsequent acid solution is performed, the ring structure of the carbon nanotube is solved.
The metal oxide-carbon nanotube composite bonded through the non-covalent bond with the binding polymer is precipitated in the polymer solution for bonding, and the metal oxide-carbon nanotube composite having the binding polymer bonded thereto can be recovered by using a centrifugal separator .
In the state where the carbon nanotubes and the binding polymer are bonded through noncovalent bonding, 3) the step of removing the metal oxide proceeds.
When the metal oxide-carbon nanotube composite nanotubes are not covalently bonded to the binding polymer, only the ring carbon nanotubes remain when the metal oxide is removed. Thus, the production of the ring carbon nanotubes Is completed. More precisely, when the metal oxide is removed, only the binding polymer linked to the carbon nanotube remains so that the ring carbon nanotube and the carbon nanotube are maintained in the ring structure.
Specifically, when the metal oxide-carbon nanotube composite having the binding polymer bonded thereto is added to the hydrochloric acid solution as an acid solution in one embodiment, the metal oxide of the metal oxide-carbon nanotube composite is dissolved in hydrochloric acid, and the ring- Only the tube (combined with the binding polymer) remains (S104). At this time, ultrasound can be applied to the hydrochloric acid solution to minimize the metal oxide remaining in the ring-shaped carbon nanotubes. When the ring-shaped carbon nanotubes from which the metal oxide is removed are diluted with water and purified, the production of the carbon nanotubes having the nano ring structure is completed.
4) dispersing the carbon nanotubes having the nano ring structure in the polymer material, and 5) forming the polymer material in which the carbon nanotubes having the nano ring structure are dispersed to produce a dielectric material. Proceed to step.
In a state in which the nano ring structure carbon nanotubes are prepared, a dispersion solution is prepared, and the polymer material and the nanorring carbon nanotubes are put into the dispersion solution and then kneaded (S105). In the case of kneading, ultrasound may be applied to the dispersion solution to sufficiently disperse the polymer material and the nanorring carbon nanotubes.
The polymeric material may be a piezoelectric polymeric material or a dielectric polymeric material, which is the body of the completed dielectric body, that is, the substrate. As the piezoelectric polymer material, a polymer material including polyvinylidene fluoride (PVDF), more specifically, a copolymer of polyvinylidene fluoride (PVDF), polyvinylidene fluoride (PVDF) and trifluoroethylene (TrFE) PVDF-TrFE) may be used. Examples of the dielectric polymer material include polydimethylsiloxane (PDMS), polypropylene (PP), polymethylmethacrylate (PMMA), polycarbonate (PC), polyamide (PA), polystyrene (PS), polyimide ) May be used. As the dispersion solution, a dimethylformamide (DMF) solution may be used.
As described above, the present invention is characterized in that a carbon nanotube having a nanorning structure excellent in dispersibility is dispersed in a polymer material to improve a dielectric property of a dielectric material.
When the nano-ring carbon nanotubes and the polymer material are injected into the dispersion solution and kneaded, the polar groups of the binding polymer and the polymer material bonded to the carbon nanotubes having the nanor ring structure are homogeneous, Of the carbon nanotubes are uniformly dispersed in the polymer material. Here, the binding polymer is any one of a π-conjugated polymer, an aromatic polymer, and a non-aromatic polymer as described above.
In the mixing of the nano ring carbon nanotubes and the polymer material in the dispersion solution, the nano ring carbon nanotubes should be mixed with the polymer material and the nano ring carbon nanotubes in a total amount of 11 wt% or less. When the content of the conductive filler is higher than 11 wt%, the dielectric constant decreases and the loss value increases due to the network of carbon nanotubes.
Next, a dispersion solution in which carbon nanotubes having a nano ring structure and a polymer substance are dispersed is injected into a molding mold. Then, the dispersion solution is evaporated and removed by heating at a temperature of 80 to 90 DEG C, thereby completing the method of manufacturing a dielectric material based on a CNT and a polymer material according to an embodiment of the present invention (S106).
On the other hand, when the carbon nanotubes of the nano-ring structure are uniformly dispersed in the polymer material in the above-described process, the capacitance of the finally completed dielectric increases. The carbon nanotubes of the nano ring structure dispersed in the polymer material act as a conductive pillar to increase the conductive path and thereby reduce the thickness d of the dielectric, The decrease in the thickness d of the dielectric is directly related to the increase in the capacitance C of the dielectric. That is, the nano-ring carbon nanotubes having the polymer for bonding are homogeneously homogeneous with the polymer material, and are uniformly dispersed in the polymer material. When the carbon nanotubes are evenly dispersed, each carbon nanotube acts as a conductive filler It is possible to improve the dielectric properties of the finished dielectric material.
Hereinabove, the carbon nanotube having the nanor ring structure according to an embodiment of the present invention and the dielectric material based on the polymer material and the method of manufacturing the same are described. Hereinafter, the present invention will be described in more detail with reference to experimental examples.
EXPERIMENTAL EXAMPLE 1: Preparation of Carbon Nanotubes Having a Nanor Ring Structure [
An acid solution was prepared by mixing sulfuric acid (H 2 SO 4 ) and nitric acid (HNO 3 ) in a volume ratio of 3: 1. Then, carbon nanotubes (CNT) The reaction was carried out at about 20 캜 or less. Carboxyl groups (-COOH) were formed on the surfaces of acid-treated carbon nanotubes (CNTs).
A metal oxide precursor solution was prepared by dissolving 8.4 mM zinc acetate dihydrate (Zn (CH 3 COO) 2 .2H 2 O) in dimethylformamide (DMF). Then, 40 mg of the acid-treated carbon nanotube was added to the metal oxide precursor solution and stirred. ZnO-CNT complexes were formed and precipitated due to the reaction of zinc acetate hydrate (Zn (CH 3 COO) 2 .2H 2 O) with acid-treated carbon nanotubes. After diluting with water and ethanol, the precipitated ZnO-CNT complex was recovered using a centrifugal separator.
100 mg of the prepared ZnO-CNT complex was added to water together with sodium dodecyl sulfate (SDS) and dispersed using ultrasonic waves. Then, polyvinylpyrrolidone (PVP) was added thereto and stirred. An aqueous solution containing ZnO-CNT complex, sodium dodecyl sulfate (SDS) and polyvinylpyrrolidone (PVP) was placed in an oven at 70 ° C and reacted for 12 hours. As a result, polyvinylpyrrolidone (PVP) was bound to the CNT of the ZnO-CNT complex and precipitated in the aqueous solution. The polyvinylpyrrolidone (PVP) -bonded ZnO-CNT complex precipitated in the aqueous solution was recovered using a centrifuge.
The prepared polyvinylpyrrolidone (PVP) -bonded ZnO-CNT complex (100 mg) was added to 300 mL of hydrochloric acid. ZnO particles were removed due to the reaction of hydrochloric acid and ZnO-CNT complex, and nanorring carbon nanotubes were formed.
Experimental Example 2: Preparation of nano-ring carbon nanotubes and polymer-based dielectrics
The carbon nanotubes of the nanorring structure prepared in Experimental Example 1 were added to a dimethylformamide (DMF) solution in which PVDF was dispersed at a mixing ratio of 1, 3, 5, 7, 9, 11, 13 and 15 wt% Ultrasonic waves were irradiated and mixed. A DMF solution containing nano ring carbon nanotubes and PVDF dispersed therein was injected into a molding mold and heated at 80 ° C to remove the DMF solution to prepare a dielectric film. FIG. 3 is a photograph of the nanorring carbon nanotube and the polymer-based dielectric prepared through Experimental Example 2. FIG.
≪ Experimental Example 3: Polarization characteristics &
FIG. 4 shows experimental results showing the polarization characteristics of the dielectric prepared in Experimental Example 2. FIG. In FIG. 4, the black line shows the polarization characteristic of the dielectric made of PVDF-TrFE, and the red line shows the polarization characteristic of the dielectric made of PVDF-TrFE and 3 wt% nano ring structure carbon nanotubes. For the experiment of FIG. 4, gold (Au) was deposited on both surfaces of each dielectric using a thermal evaporator and an electric field of ± 150 MV / m was applied.
Referring to FIG. 4, the Pr value of the PVDF-TrFE (black line) is 63, while the Pr value of the dielectric (red) of the present invention is 79.16, . This result can be deduced from the fact that the nano-ring carbon nanotubes are uniformly dispersed in the PVDF-TrFE to multiply the polarization phenomenon, and polyvinylpyrrolidone (PVP) bonded to the nano- This means that there is resistance to high magnetic fields.
EXPERIMENTAL EXAMPLE 4: Permittivity Characteristics According to Frequency
FIGS. 5 and 6 are experimental results showing the dielectric constant characteristics according to the frequency of the dielectric prepared through Experimental Example 2. FIG. 5 and 6 are graphs showing the results of experiments for the dielectric materials containing carbon nanotubes of 1, 3, 5, 7, 9, 11, 13 and 15 wt% of nano ring structure at 100 Hz, 1 kHz, 10 kHz, 500, And the dielectric constant was measured. For the comparison, the same experiment was also performed on the dielectric made of PVDF-TrFE.
5 and 6, dielectric constants (dielectric constants of about 19 to 37) of dielectrics including nano-ring carbon nanotubes in all frequency ranges are higher than dielectric constants (dielectric constants of about 8.8 to 13) made of PVDF-TrFE . In particular, it can be seen that the dielectric constant having the maximum value in the case of the dielectric material containing 11 wt% of carbon nanotubes is shown. However, when the weight ratio of carbon nanotubes exceeds 11 wt%, the dielectric constant tends to decrease.
<Experimental Example 5: XRD results>
7 shows the XRD results of the dielectric made of Experimental Example 2 and the dielectric made of PVDF-TrFE. Referring to FIG. 6, PVDF is a material having α and β phases. Most PVDFs are present in the alpha phase, which has low physical and electrical properties. Therefore, it is possible to obtain high electrical and physical properties by switching to β phase through polling and drawing. To secure this, a copolymer of PVDF-TrFE was used. This material was analyzed to confirm the presence of α and β by measuring XRD. In the present invention, 1 to 15 wt% of nano-ring carbon nanotubes were added, but it was confirmed that there was no phase change, and it can be seen that the reason for increasing the dielectric constant does not include the factor of phase change.
Claims (15)
Molding a dispersion solution in which carbon nanotubes of a polymer material and a nano ring structure are dispersed; And
And evaporating the dispersion solution to prepare a dielectric material comprising a polymer material and a carbon nanotube having a nanor ring structure,
The nano-ring structure carbon nanotubes may be formed by a method comprising the steps of:
The carbon nanotubes are non-covalently bonded to the binding polymer,
Wherein the coupling polymer is any one of a π-conjugated polymer, an aromatic polymer, and a non-aromatic polymer, or a combination thereof.
The piezoelectric polymer material is any one of polyvinylidene fluoride (PVDF), a copolymer of polyvinylidene fluoride (PVDF) and trifluoroethylene (TrFE) (PVDF-TrFE)
The dielectric polymer material may be selected from the group consisting of polydimethylsiloxane (PDMS), polypropylene (PP), polymethylmethacrylate (PMMA), polycarbonate (PC), polyamide (PA)), polystyrene (PS), polyimide Wherein the carbon nanotube is a carbon nanotube or a polymer material.
Wherein the carbon nanotube is mixed with the polymer material in an amount of up to 11 wt% based on the total weight of the polymer nanomaterial and the nanot ring carbon nanotubes.
A process for producing a metal oxide-carbon nanotube composite in which carbon nanotubes are bound to metal oxide particles by reacting a metal oxide precursor solution with an acid-treated carbon nanotube,
Introducing the metal oxide-carbon nanotube composite into a polymer solution for bonding to induce non-covalent bonding of the polymer for bonding and carbon nanotube;
Wherein the carbon nanotube composite is produced through a process of reacting a metal oxide-carbon nanotube composite having a binding polymer bonded thereto with an acid solution to remove metal oxide particles to form a carbon nanotube having a nano ring structure (METHOD FOR MANUFACTURING DIELECTANE BASED ON.
Wherein the metal oxide-carbon nanotube composite and the binding polymer are mixed in a mass ratio of 1: 1 to 1: 3.
The aromatic polymer is a polyimide,
Examples of the non-aromatic polymer include poly (vinylpyrrolidone), poly (vinyl alcohol), polybutadiene, polyisoprene, poly (methyl (meth) methacrylate), and polyethylene oxide (poly (ethylene oxide)), or a combination thereof. The present invention also provides a method of manufacturing a dielectric material based on a nanorning structure of a carbon nanotube and a polymer material.
Wherein a hydrogen (H) component of a hydroxyl group (-OH) or a carboxyl group (-COOH) present on the surface of the carbon nanotube is noncovalently bonded to an oxygen (O) component present in the polymer for bonding Carbon nanotube and a polymer material based dielectric material.
Carbon nanotubes having a nano ring structure are contained in an amount of less than 11 wt%
The nano-ring structure carbon nanotubes may be formed by a method comprising the steps of:
The carbon nanotubes are non-covalently bonded to the binding polymer,
Wherein the binding polymer is any one of a π-conjugated polymer, an aromatic polymer, and a non-aromatic polymer or a combination thereof, and the nanotube-based carbon nanotube and the polymer-based dielectric material.
The piezoelectric polymer material is any one of polyvinylidene fluoride (PVDF), a copolymer of polyvinylidene fluoride (PVDF) and trifluoroethylene (TrFE) (PVDF-TrFE)
The dielectric polymer material may be selected from the group consisting of polydimethylsiloxane (PDMS), polypropylene (PP), polymethylmethacrylate (PMMA), polycarbonate (PC), polyamide (PA)), polystyrene (PS), polyimide ). The nanotube-based carbon nanotube and polymer-based dielectric material according to claim 1,
A process for producing a metal oxide-carbon nanotube composite in which carbon nanotubes are bound to metal oxide particles by reacting a metal oxide precursor solution with an acid-treated carbon nanotube,
Introducing the metal oxide-carbon nanotube composite into a polymer solution for bonding to induce non-covalent bonding of the polymer for bonding and carbon nanotube;
Wherein the carbon nanotube composite is produced through a process of reacting a metal oxide-carbon nanotube composite having a binding polymer bonded thereto with an acid solution to remove metal oxide particles to form a carbon nanotube having a nano ring structure Nanotubes and polymers based dielectrics.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190053450A (en) * | 2017-11-10 | 2019-05-20 | 한국과학기술연구원 | Dielectric having nanoring structure carbon nanotube and Energy harvesting device using the same |
| KR20200072934A (en) * | 2018-12-13 | 2020-06-23 | 주식회사 신우전자 | Humidity sensing film for humidity sensor including carbon doped with nano metal and method for manufacturing the same |
| CN111500001A (en) * | 2020-06-12 | 2020-08-07 | 南京工业大学 | Preparation method and application of carbon nanotube nano composite material |
| WO2020235847A1 (en) * | 2019-05-21 | 2020-11-26 | 성균관대학교산학협력단 | Piezoelectric nanomaterial |
| KR20200135172A (en) * | 2019-05-21 | 2020-12-02 | 성균관대학교산학협력단 | Piezo-electric nano-materials |
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| KR101297316B1 (en) * | 2011-08-23 | 2013-08-16 | 한국과학기술연구원 | A Complex of CNT-Polymer and a Method for Preparing the Same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190053450A (en) * | 2017-11-10 | 2019-05-20 | 한국과학기술연구원 | Dielectric having nanoring structure carbon nanotube and Energy harvesting device using the same |
| KR20200072934A (en) * | 2018-12-13 | 2020-06-23 | 주식회사 신우전자 | Humidity sensing film for humidity sensor including carbon doped with nano metal and method for manufacturing the same |
| WO2020235847A1 (en) * | 2019-05-21 | 2020-11-26 | 성균관대학교산학협력단 | Piezoelectric nanomaterial |
| KR20200135172A (en) * | 2019-05-21 | 2020-12-02 | 성균관대학교산학협력단 | Piezo-electric nano-materials |
| CN111500001A (en) * | 2020-06-12 | 2020-08-07 | 南京工业大学 | Preparation method and application of carbon nanotube nano composite material |
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