KR101726823B1 - Production method of high performance carbon nano tube/carbon composite fiber and cabon nanotube/carbon composite fiber thereby - Google Patents
Production method of high performance carbon nano tube/carbon composite fiber and cabon nanotube/carbon composite fiber thereby Download PDFInfo
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
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Abstract
The present invention relates to a method for producing a carbon nanotube / carbon composite fiber having high strength and high conductivity, and a carbon nanotube / carbon composite fiber produced therefrom, and more particularly, to a method for producing carbon nanotube fibers step; A step of densifying the carbon nanotube fibers to densify the carbon nanotube fibers; And a carbon deposition step of depositing carbon on the densified carbon nanotube fiber. The method of producing a carbon nanotube / carbon composite fiber according to claim 1, wherein the carbon nanotube is carbon nanotube oriented in the fiber axis direction. And carbon which connects between the carbon nanotubes and the carbon nanotubes. The present invention also relates to a carbon nanotube / carbon composite fiber.
Description
The present invention relates to a method for producing a carbon nanotube / carbon composite fiber having high strength and high conductivity, and a carbon nanotube / carbon composite fiber produced therefrom.
More specifically, the present invention relates to a carbon nanotube fiber manufacturing process for manufacturing and fiberizing carbon nanotubes; A step of densifying the carbon nanotube fibers to densify the carbon nanotube fibers; And a carbon deposition step of depositing carbon on the densified carbon nanotube fiber. The method of producing a carbon nanotube / carbon composite fiber according to claim 1, wherein the carbon nanotube is carbon nanotube oriented in the fiber axis direction. And carbon which connects between the carbon nanotubes and the carbon nanotubes. The present invention also relates to a carbon nanotube / carbon composite fiber.
Carbon nanotubes (CNTs) are a kind of carbon isotope, a graphene cylinder-shaped structure with a diameter of several nanometers. Due to its excellent mechanical and physical properties, it has been actively studied in academia. Its tensile strength is tens GPa, electrical conductivity is 10,000 S / cm, and thermal conductivity is 6,600 W / mK. However, since the carbon nanotubes have a short length, the performance of the composite material is difficult to manifest, it is difficult to directly handle the carbon nanotubes, and the carbon nanotubes are difficult to be dispersed. The possibility of various applications has been suggested. Carbon nanotube fiber (CNT fiber) means that carbon nanotubes are physically woven into a spun yarn or carbon nanotubes are chemically connected to form a fiber.
Among the methods of producing carbon nanotube fibers, the closest approach to industrialization is continuous continuous spinning. When carbon nanotubes are synthesized in the gas phase, they are extracted in the form of fibers just as cotton candy is produced. It is a continuous process and has the advantage of being able to make fibers of high quality and long carbon nanotubes. However, the physical properties of carbon nanotubes are far below the physical properties of carbon nanotubes themselves and do not meet the properties of competitive carbon fibers. The reason for this is largely due to the existence of empty spaces inside the carbon nanotube fibers. The hollow space can be irregularly distributed in the course of compacting the carbon nanotubes in the form of fibers, which makes it difficult to obtain carbon nanotube fibers having uniform physical properties. Second, carbon nanotube fibers are mainly composed of physical bonds between carbon nanotubes. The third reason is that the degree of orientation or alignment of carbon nanotubes is not good. If the carbon nanotubes are well aligned, the attraction between the carbon nanotubes can be maximized and the properties of the carbon nanotube fibers can be improved.
On the other hand, carbon fibers are generally produced by carbonization of polymer fibers at a high temperature. The sp2 chemical bonds are increased and the crystallinity is increased, resulting in high strength properties. Since carbon nanotube fibers are composed of carbon nanotubes composed only of sp2 bonds, theoretically, the physical properties of carbon nanotube fibers are likely to exceed that of carbon fibers. Recently, studies for improving the properties of carbon nanotube fibers Is actively proceeding.
Methods for manufacturing carbon nanotube fibers by physically focusing carbon nanotubes include a method of focusing fibers by passing water or an organic solvent through the produced carbon nanotubes, a method of twisting carbon nanotubes to orient the carbon nanotubes And a method of chemically connecting the carbon nanotubes by chemically bonding the carbon nanotubes by introducing crosslinking between the carbon nanotubes to increase the bonding force between the carbon nanotubes. US Patent No. 7993620B discloses a technique for manufacturing carbon nanotubes by spinning using a spindle to form fibers or nonwoven fabrics. After forming a carbon nanotube aggregate, the carbon nanotubes are coated with a polymer solution after passing through a bathtub Korean Unexamined Patent Publication No. 2002-0090383, which discloses a technique for producing carbon nanotube fibers through a step of applying a twist, and a carbon nanotube array fabricated by a CVD method, is coated with a carbon nanotube yarn using an organic solvent, U.S. Patent No. US 7,704,480, which is a technology for producing carbon nanotubes, is disclosed in U.S. Patent Publication No. US2013-0028830A which discloses a technique for increasing the density of carbon nanotubes by using divinylbenzene.
Carbon nanotubes are extremely difficult to dissolve or disperse in liquids. Recently, however, it has become known that super acids can be used to make thermodynamic pure solutions. In 2009, Matteo Pasquali of Rice University developed chlorosulfuric acid ) Was used to dissolve the carbon nanotubes. Chlorinated sulfuric acid is the only solvent known to dissolve carbon nanotubes to date. Chemical vapor infiltration (CVI) was developed by Bickerdike in 1962 to increase the density of porous carbon materials. The precursor is supplied to the gas and penetrates to the surface of the porous material, causing a chemical reaction on the surface. Lt; / RTI > It can be seen as a special application of chemical vapor deposition (CVD), which is widely used in the past, in that the gas can be penetrated into the porous material and deposited uniformly.
As described above, in order to produce carbon nanotube fibers, carbon nanotube focusing technology using various physical or chemical methods, spinning technique after dissolving carbon nanotubes, and carbon nanotubes deposited by carbon nanotube to improve physical properties Efforts have been underway. However, in the conventional technology developed so far, only individual and fractional solutions have been proposed, and the physical properties of the carbon nanotube fibers produced have not yet reached high strength and high conductivity. Therefore, it is required to develop a manufacturing method of carbon nanotube fibers which can be more economical and mass-producible by a simple two step process than the conventional process, and also to develop a carbon nanotube fiber having more improved mechanical, electrical and thermal properties .
The present invention was developed to solve the above problems. It is an object of the present invention to improve the orientation of the carbon nanotubes in the fiber axis direction by reducing the irregularly distributed voids in the fibers when carbon nanotubes are bundled and made into carbon nanotube fibers The present invention also provides a method for producing carbon nanotube fibers capable of increasing the bonding force between carbon nanotubes.
In addition, the present invention relates to a method for manufacturing a carbon nanotube, a physical or chemical focusing method, and an individual method for increasing the bonding force between carbon nanotubes by a single two-step process, thereby achieving a more economical and mass- To provide a method for producing nanotube fibers.
In addition, the present invention provides a carbon nanotube / carbon composite fiber having excellent mechanical, thermal and electrical properties by using carbon nanotubes with high focusing and high orientation.
In order to solve the above-described problems, the present invention provides a method of manufacturing a carbon nanotube, A step of densifying the carbon nanotube fibers to densify the carbon nanotube fibers; And a carbon deposition step of depositing carbon on the densified carbon nanotube fiber. The present invention also provides a method for producing a carbon nanotube / carbon composite fiber.
In the present invention, the step of manufacturing the carbon nanotube fibers may use a direct air spinning method using a gas phase airgel.
In the present invention, the gas phase aerogel direct spinning method may be to produce carbon nanotubes from a carbon nanotube manufacturer including a carbon source, a catalyst, and an activator using a fluidized bed reactor.
In the present invention, the carbon source is at least one selected from the group consisting of C2 to C10 saturated or unsaturated hydrocarbons, alcohols or ketones, and the catalyst is at least one selected from the group consisting of copper (Cu), chromium (Cr), molybdenum (Mo) Tungsten, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, And ferrocene, and the activator may be any one of thiophene and carbon disulfide.
In the present invention, the step of densifying the carbon nanotube fibers may include the steps of: swelling the carbon nanotube fibers to swell the carbon nanotube fibers using super strong acid; And a carbon nanotube fiber refocusing step of washing and removing the super strong acid with water.
In the present invention, the super acid is selected from the group consisting of sulfuric acid (HSO 3 Cl), fluorosulfonic acid (FSO 3 H), trifluoroacetic acid (CF 3 COOH), trifluoromethanesulfonic acid (CF 3 SO 3 H) (HSbF 6 ), carborane acid, and the like.
In the present invention, the carbon deposition step may include filling the space between the carbon nanotubes with pyrolytic carbon using a chemical vapor deposition method.
In the present invention, the chemical vapor deposition may include heating a carbon nanotube fiber to 600 to 1,000 ° C in a heating furnace; And a carbon source supplying step of supplying a mixed gas of a hydrocarbon gas and an inert gas or a mixed gas of a hydrocarbon gas and hydrogen into the heating furnace.
Also, in the present invention, a plurality of carbon nanotubes oriented in the direction of the fiber axis produced by the above-mentioned production method; And carbon which connects between the carbon nanotubes and the carbon nanotubes.
Also, in the present invention, carbon nanotube fibers are prepared by direct aerosol gas phase spinning method, the carbon nanotube fibers are densified into super strong acid, and carbon is deposited in a hollow space inside the carbon nanotube fibers by chemical vapor deposition, The present invention provides a carbon nanotube / carbon composite fiber having electrical and thermal performance.
According to the manufacturing method of the present invention, it is possible to produce carbon nanotube / carbon composite fiber having more uniform, excellent mechanical, electrical and thermal properties.
The carbon nanotube / carbon composite fiber according to the present invention has an increased bonding force between carbon nanotubes and thus has excellent mechanical strength. Young's modulus also increases as slip between carbon nanotubes decreases when a tensile load is applied .
In addition, the carbon nanotube / carbon composite fiber according to the present invention is improved in electrical conductivity and thermal conductivity as the defects are reduced by filling carbon vacancies inside the carbon nanotube fibers with carbon.
In addition, according to the manufacturing method of the present invention, it is possible to manufacture the conventional carbon nanotubes, physical or chemical focusing, and individual methods for increasing the bonding force between the carbon nanotubes to two simple steps to achieve more economical and mass productivity There is an advantage that it can be provided.
FIG. 1 is a conceptual view illustrating a carbon nanotube fiber densification step in a process of manufacturing a carbon nanotube / carbon composite fiber according to an embodiment of the present invention.
FIG. 2 is a graphical representation of changes in cross-section and side surface of carbon nanotube fibers according to one embodiment of the present invention.
3 (a) is a force-elongation curve curve of a carbon nanotube fiber according to an embodiment of the present invention, and FIG. 3 (b) is a graph showing a force- elongation curve ) Curve.
FIG. 4 (a) is a specific stress-strain curve curve of carbon nanotube fibers according to an embodiment of the present invention, (b) is a specific stress-strain curve of the carbon nanotube / specific stress-strain curve.
FIG. 5 (a) is a photograph of a carbon nanotube fiber according to an embodiment of the present invention, and FIG. 5 (b) is a photograph of a sintered electron microscope of a carbon nanotube fiber.
6 (a) is a photograph of a scanning electron microscope of a carbon nanotube fiber according to an embodiment of the present invention, and (b) is a photograph of a scanning electron microscope of a carbon nanotube / carbon composite fiber.
Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
As used throughout this specification, the term " carbon nano tube fiber (CNT fiber) " means that carbon nanotubes are physically bound to form a spun yarn, or carbon nanotubes are chemically connected to form a fiber .
Also, the term "carbon nano tube (CNT)" is meant to include a single wall, a double wall, and a multi wall carbon nanotube (CNT).
&Quot; Fiber " refers to a thin, long thread-like shape, meaning filament or yarn.
Also, the " carbon nanotube / carbon composite fiber " includes a carbon-based composite material in which voids inside the carbon nanotube fiber are filled with carbon, or carbon is deposited in a space or a bonding site between carbon nanotubes, It means.
BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. In particular, the technical idea of the present invention and its core structure and action are not limited by this. In addition, the content of the present invention can be implemented by various other types of equipment, and is not limited to the embodiments and examples described herein.
The method for producing a carbon nanotube / carbon composite fiber according to the present invention comprises the steps of: preparing a carbon nanotube fiber and fabricating the carbon nanotube fiber; A step of densifying the carbon nanotube fibers to densify the carbon nanotube fibers; And a carbon deposition step of depositing carbon on the densified carbon nanotube fibers.
FIG. 1 is a conceptual view illustrating a step of densifying a carbon nanotube fiber in a process of producing a carbon nanotube / carbon composite fiber according to an embodiment of the present invention. Referring to FIG. 1, a carbon nanotube- Carbon nanotubes are formed while moving to the lower part of the reactor, and the carbon nanotubes formed are focused on each other to form the
First, the step of manufacturing the carbon nanotube fibers according to the present invention will be described.
In the present invention, the carbon nanotube fiber manufacturing step may be a direct aerial aerosol spinning method, and the direct aerial aerosol spinning method may be carried out by using a fluidized bed reactor, from a carbon nanotube manufacturer including a carbon source, a catalyst and an activator, Lt; / RTI >
In the present invention, the carbon source is at least one selected from the group consisting of C2 to C10 saturated or unsaturated hydrocarbons, alcohols or ketones, and the catalyst is at least one selected from the group consisting of copper (Cu), chromium (Cr), molybdenum (Mo) Tungsten, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, And ferrocene, and the activator may be any one of thiophene and carbon disulfide.
In the present invention, at least one carbon source selected from the group consisting of saturated or unsaturated hydrocarbon, an alcohol or a ketone of the C2 to C10 is methanol (CH 3 OH), ethanol (C 2 H 5 OH), formaldehyde (CH 2 O), acetaldehyde (C 2 H 4 O), diethyl ether ((C 2 H 5 ) 2 O), 1-propanol (CH 3 CH 2 CH 2 OH), acetone (CH 3 OCH 3 ) C 6 H 6), toluene (C 7 H 8), xylene (C 6 H 4 (CH 3 ) 2), cumene (C 9 H 12), methane (CH 4), ethane (C 2 H 6), propane (C 3 H 8), butane (C 4 H 10), pentane (C 5 H 12), hexane (C 6 H 14), cyclohexane (C 6 H 12), ethylene (C 2 H 4), propylene (C 3 H 6 ) and acetylene (C 2 H 2 ), but are not limited thereto. In the present invention, the carbon source is acetone, the catalyst is ferrocene, and the activator is thiophene.
According to one embodiment of the present invention, a carbon nanotube manufacturing solution composed of acetone, ferrocene and thiophene is injected into a fluidized bed reactor heated at a temperature of 1,000 ° C. or higher at a constant rate to form a carbon nanotube aerogel, To produce a carbon nanotube fiber.
Next, the carbon nanotube fiber densification step in the present invention will be described.
In the present invention, the step of densifying the carbon nanotube fibers may include the steps of: swelling the carbon nanotube fibers to swell the carbon nanotube fibers using super strong acid; (HSO 3 Cl), fluorosulfonic acid (FSO 3 H), trifluoroacetic acid (CF 3 COOH), and carbon nanotube fiber re-concentration step of washing and removing super strong acid with water. , Trifluoromethanesulfonic acid (CF 3 SO 3 H), antimonic acid fluoride (HSbF 6 ), and carborane acid. In the present invention, sulfuric acid (HSO 3 Cl) is more preferable as super acid.
In the present invention, once the carbon nanotubes produced from the fluidized bed reactor are in the form of fibers, the movement of the carbon nanotubes is greatly restricted. Therefore, it is difficult to eliminate the voids that are unevenly distributed inside the fibers by re-focusing the carbon nanotubes. As previously discussed in the prior art, carbon nanotubes found in Rice University in the United States are thermodynamically dissolved in sulfuric acid, which is melted and melted. In this case, if tension is applied to the carbon nanotube fibers, the carbon nanotubes inside the fibers can be rearranged and focused and densified.
According to one embodiment of the present invention, the carbon nanotube fibers emitted from the fluidized bed reactor are passed through a sulfuric acid bath, which is a strong acid, and are then collected and washed in a water bath, and then the fibers are wound through a final winding apparatus. When carbon nanotube fibers pass through sulfuric acid, they swell due to solvent swelling. At this time, due to the tensile force of the fibers, the orientation of the carbon nanotubes in the fibers increases in the axial direction. It happens.
The use of sulfuric acid can dissolve carbon nanotubes or carbon nanotube fibers. However, in the present invention, the carbon nanotube fibers can be swelled by chlorosulfuric acid treatment for a short period of time to induce swelling of the carbon nanotube fibers. In the swollen state Due to the tension of the fiber winding, the orientation of the carbon nanotubes in the fiber increases in the axial direction, and as the water passes, a certain kind of solidification occurs and the fiber is refocused and densified. In other words, the carbon nanotube fibers are swollen by using sulfuric acid chloride, and the carbon nanotubes are solidified in a swollen state by inducing the orientation by using tensile force, and then, by washing with water, again.
Next, a carbon deposition step in which carbon is deposited on the densified carbon nanotube fiber according to the present invention will be described.
In the present invention, the carbon deposition step fills the space between the carbon nanotubes by pyrolytic carbon deposition using a chemical vapor deposition method. In the chemical vapor deposition method, carbon nanotube fibers are heated to 600 to 1,000 ° C in a heating furnace Carbon nanotube fiber heating step; And a carbon source supplying step of supplying a mixed gas of a hydrocarbon gas and an inert gas or a mixed gas of a hydrocarbon gas and hydrogen into the heating furnace.
The hydrocarbon gas and at least one member selected from the group consisting of saturated or unsaturated hydrocarbon, an alcohol or a ketone of C2 to C10 preferably, the inert gas is a group consisting of argon (Ar), helium (He), nitrogen (N 2) , And acetylene as the hydrocarbon gas and argon (Ar) as the inert gas are more preferable.
According to the chemical vapor deposition method of the present invention, when a hydrocarbon material is supplied at a high temperature, carbon is decomposed and penetrates into gaps between the carbon nanotube fibers, and the infiltrated carbon is deposited on the carbon nanotubes. As the deposited carbon becomes thick, the void spaces between the carbon nanotubes are filled, and the carbon nanotubes are not separated and connected to carbon, resulting in a carbon nanotube / carbon composite fiber.
According to one embodiment of the present invention, carbon nanotube fibers are placed in a heating furnace and then heated to a high temperature of 600 to 1,000 ° C. in an inert gas atmosphere. When the temperature is reached, the hydrocarbon gas is supplied for 1 to 36 hours together with the inert gas and the hydrogen gas while maintaining the temperature. At this time, it is possible to use inert gas alone or only hydrogen gas. After the reaction is completed, the carbon nanotube fibers are taken out of the reactor after cooling in an inert gas atmosphere to room temperature.
FIG. 2 is a graphical representation of changes in cross-section and side surface of carbon nanotube fibers according to one embodiment of the present invention.
As described above, once the carbon nanotubes (CNTs) formed from the fluidized bed reactor are in the form of fibers, unevenly distributed voids exist inside the fibers, The orientation is not high. However, the carbon nanotube fiber swelling step of inflating the carbon nanotube fibers by using super strong acid (chlorosulfuric acid: CSA); And a carbon nanotube fiber re-focusing step for washing and removing super strong acid by water, the carbon nanotubes are aligned and reoriented in the fiber axis direction, and the void space inside the carbon nanotube is reduced to become a densified carbon nanotube fiber (densified CNT fiber) . Then, when the hydrocarbon material is supplied at a high temperature, the carbon is decomposed to permeate through the gaps of the carbon nanotube fibers, and the infiltrated carbon is deposited on the carbon nanotubes (CVI process). As the deposited carbon is thickened, the void spaces are filled and the carbon nanotubes are not separated, but they become carbon and become high performance carbon nanotube / carbon fiber.
Therefore, according to the manufacturing method of the present invention, a plurality of carbon nanotubes oriented in the fiber axis direction; And carbon which connects between the carbon nanotubes and the carbon nanotubes.
Further, carbon nanotube fibers prepared by direct aerial aerosol spinning according to the present invention are densified into super strong acid, and when carbon is deposited in the void space inside carbon nanotube fibers by chemical vapor deposition, , Carbon nanotube / carbon composite fibers having electrical and thermal performance are produced.
≪ Comparative Example 1 &
Carbon nanotube fibers were prepared by direct aerial aerosol method. A vertical electric furnace (Lenton 1500 ° C Tube Furnace, Quartz tube, diameter 7 cm, length 1 m) was heated to 1,170 ° C with 1,000 sccm of argon. After reaching the reaction temperature of 1,170 ° C, 1,000 sccm of hydrogen is flowed for about 10 minutes and the inside of the reactor is changed to a hydrogen atmosphere. Then, a solution (97.8 wt% of acetone, 1.6 wt% of ferrocene, and 0.8 wt% of thiophene) mixed with a carbon source, a catalyst and an activator was injected into the reactor at a constant rate (0.2 ml / min) The nanotubes are synthesized in large quantities and come down to the bottom of the reactor in the form of aerosols. The synthesized carbon nanotube aerogels were shrunk in the form of fibers through water and wound at a constant speed (3 m / min.) To produce carbon nanotube fibers.
≪ Comparative Example 2 &
Carbon nanotube fibers were prepared from carbon nanotube arrays. In order to form a carbon nanotube array on a substrate, a chemical vapor deposition method was used. Silicon (Siltron Inc. Korea, direction <100>, thickness: 660-690 μm) with 300 nm of SiO 2 deposited was used as the substrate, and Al 2 O 3 was deposited on the substrate in a 10 nm And 1 nm of iron was deposited thereon by e-beam deposition.
The substrate was placed in the center of a tubular furnace (Lindberg Blue M, HTF55322,
≪ Example 1 >
The carbon nanotube fibers radiated by a direct aerial aerosol method, which is the same method as in Comparative Example 1, are passed through chlorosulfuric acid (CSA) at a constant rate for 5 seconds, and water is passed through with tension. When the carbon nanotubes pass through the sulfuric acid, the swelling occurs, and the water is passed through and the focusing occurs. After passing the water, the carbon nanotubes were washed three times with water, and dried in a vacuum dryer at 60 ° C. to densify the carbon nanotube fibers.
≪ Example 2 >
The chemical vapor deposition method was carried out by using carbon nanotube fibers densified by the method of Example 1 above. The carbon nanotube fibers were placed in the center of a tube furnace having a diameter of 5 cm, and then 500 sccm of argon gas was supplied and heated to 650 ° C in 30 minutes. 360 sccm of argon, 120 sccm of hydrogen and 20 sccm of acetylene were flowed at 650 ° C, and the chemical vapor deposition process was carried out for 5 hours. Thereafter, 500 sccm of argon was flown and cooled to room temperature to prepare carbon nanotube / carbon composite fiber.
≪ Test Example 1 >
The non-tensile strength of the densified carbon nanotube fiber and the carbon nanotube / carbon composite fiber according to Example 1 and Example 2 was measured. FAVIMAT (Textechno) equipment was used for this purpose. The non-tensile strength was measured at a gauge length of 10 mm and a strain rate of 2.0 mm / min.
FIG. 3 (a) is a stress-elongation curve of carbon nanotube fibers according to Comparative Example 1, and FIG. 3 (b) is a graph showing the stress-elongation curves of carbon nanotube fibers according to Comparative Example 1, Stress-strain curve.
When the carbon nanotubes produced from the fluidized bed reactor are once formed into a fiber form, there is an uneven distribution space inside the fibers, and the carbon nanotubes themselves are not highly oriented in the fiber axis direction. Since the bonding force between the tubes is also weak, as shown in FIG. 3 (a), deformation is easily initiated by a small force and the bonding force between the carbon nanotubes is weak, so that cutting is performed after small elongation. On the other hand, the carbon nanotube fiber swelling step of inflating carbon nanotube fibers by using super strong acid; The carbon nanotubes are aligned and reoriented in the direction of the fiber axis, and the void spaces inside the carbon nanotubes are reduced to become the densified carbon nanotube fibers. the tensile strength is greatly increased as shown in FIG. 5B, and high-strength carbon nanotube fibers are not easily cut.
4 (a) is a specific stress-strain curve of three types of carbon nanotube fibers according to Comparative Example 1, and FIG. 4 (b) Of carbon nanotube / carbon composite fiber.
When the carbon nanotube fibers undergo swelling and re-focusing process and chemical vapor deposition step with super strong acid, the change of cross-sectional area or density changes, and the specific stress-strain curve reflecting such change is shown. The carbon nanotube / carbon composite fiber subjected to the swelling and re-focusing by the strong acid and the chemical vapor deposition step has a higher strength than the untreated carbon nanotube fiber.
≪ Test Example 2 &
The carbon nanotube fibers according to Examples 1 and 2 were observed with a scanning electron microscope (FEI), and they were shown in Fig. 5 (a) is a scanning electron microscope (SEM) image of carbon nanotube fibers according to Comparative Example 1, and FIG. 5 (b) is a scanning electron micrograph of a carbon nanotube fiber according to Example 1. In Comparative Example 1, the diameter of the fiber was 40.7 mu, but the diameter of the fiber decreased to 19.5 mu in Example 1 through the sulfuric acid.
FIG. 6 is a scanning electron micrograph of the carbon nanotube fibers according to Example 2 and Comparative Example 2. FIG. 6 (a) is a scanning electron micrograph of the carbon nanotube fiber according to Comparative Example 2, and FIG. 6 (b) is a scanning electron micrograph of the carbon nanotube / carbon composite fiber according to Example 2 . According to FIG. 6, individual carbon nanotubes or thin carbon nanotube bundles are observed in Comparative Example 2, while individual carbon nanotubes are not observed in Example 2, and coarse bundles and coarse bundles are observed.
That is, when the hydrocarbon material is supplied at a high temperature after the carbon nanotube fiber is subjected to the densification process of swelling and refocusing by super strong acid, the carbon is decomposed and penetrates into the gaps of the carbon nanotube fibers, Deposition is achieved. As the deposited carbon becomes thick, the void spaces are filled and the carbon nanotubes are not separated and connected to the carbon to become the carbon nanotube / carbon composite fiber. Therefore, it can be seen that individual carbon nanotubes are not observed and a coarse bundle and a coarse bundle are connected to each other.
As described above, the carbon nanotube / carbon composite fiber according to the present invention has excellent mechanical strength due to an increased bonding force between the carbon nanotubes. As the slip between the carbon nanotubes decreases when the tensile load is applied, Young's modulus) increased. The carbon nanotube / carbon composite fiber produced according to the present invention can improve electrical conductivity and thermal conductivity as the defective portion is reduced by filling carbon vacancies in the carbon nanotube fibers with carbon.
10: Gaseous fluidized bed reactor
20: Manufacturers of carbon nanotubes
30: Carbon nanotube fiber
40: Super strong acid tank
50: Washing water tank
60: densified carbon nanotube fiber
Claims (9)
A step of swelling the carbon nanotube fibers to inflate the carbon nanotube fibers by applying a tensile force to the carbon nanotube fibers and using a super strong acid as a continuous process and a step of collecting carbon nanotube fibers to wash and remove the superacid A step of densifying the carbon nanotube fibers to densify the carbon nanotube fibers;
A carbon nanotube fiber heating step of heating the densified carbon nanotube fibers to 600 to 1,000 DEG C in a heating furnace;
A carbon source supplying step of supplying a mixed gas of a hydrocarbon gas and an inert gas or a mixed gas of a hydrocarbon gas and hydrogen into the heating furnace; And
And a carbon deposition step of depositing carbon on the densified carbon nanotube fibers by using a chemical vapor infiltration method in which a space between the carbon nanotubes is filled with pyrolytic carbon produced by pyrolysis of the supplied carbon source Wherein the carbon nanotube / carbon composite fiber is a carbon nanotube.
Wherein the step of preparing the carbon nanotube fibers comprises forming the carbon nanotubes at the same time as the production of carbon nanotubes by using a direct aerial aerosol method.
Wherein the gas phase aerogel direct spinning method comprises producing a carbon nanotube from a carbon nanotube manufacturing source containing a carbon source, a catalyst and an activator by using a fluidized bed reactor.
Wherein the carbon source is at least one selected from the group consisting of C2 to C10 saturated or unsaturated hydrocarbons, alcohols or ketones, and the catalyst is at least one of Cu, Cr, Iron, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and ferrocene, Wherein the activator is at least one selected from the group consisting of thiophene and carbon disulfide. The method for producing a carbon nanotube / carbon composite fiber according to claim 1, wherein the activator is one of thiophene and carbon disulfide.
The super acid is selected from the group consisting of sulfuric acid (HSO 3 Cl), fluorosulfonic acid (FSO 3 H), trifluoroacetic acid (CF 3 COOH), trifluoromethanesulfonic acid (CF 3 SO 3 H), antimonic acid (HSbF 6 ) Wherein the carbon nanotube / carbon composite fiber is selected from the group consisting of carborane and carborane.
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