On-line continuous spinning device and method for carbon nanotube array

Abstract

The present invention relates to an online continuous spinning device and method for a carbon nanotube array, wherein the online continuous spinning device comprises a three-temperature zone tubular furnace and a tubular furnace quartz tube installed in the three-temperature zone tubular furnace, a pair of rotating motors are arranged in parallel at both ends of the tubular furnace quartz tube, a graphite paper with a magnetron sputtering catalyst is wound on a pair of rotating motors so that the graphite paper passes through the tubular furnace quartz tube and unwinds and rewinds, a carbon source and a mixed gas are passed through a gas flow controller through an air inlet quartz tube into the tubular furnace quartz tube to react and generate a carbon nanotube array, the carbon nanotube array is pulled to a labyrinth seal outlet at the end of the tubular furnace quartz tube and the carbon nanotube fibers are collected by a collecting motor; wherein the mixed gas comprises hydrogen and argon. The present invention continuously generates a carbon nanotube array by fully automatic roll-to-roll, and pulls the carbon nanotube array without cooling to achieve large-scale continuous production and collection of carbon nanotube fibers, thereby improving efficiency.

Description

Technical Field

[0001] The invention belongs to the technical field of continuous spinning of carbon nanotube arrays, and in particular relates to an online continuous spinning device and method for a carbon nanotube array. Background Art

[0002] Carbon nanotube fiber is a one-dimensional continuous assembly of carbon nanotubes. It has many advantages such as high tensile strength, high flexibility, light weight, excellent electrical properties and high thermal conductivity. Therefore, carbon nanotube fiber has very broad application prospects in many fields, such as aerospace, wind power blades, automotive structural parts, and sports goods. Carbon nanotube arrays are formed by the growth of carbon nanotubes perpendicular to the substrate. Carbon nanotube arrays have good orientation, large aspect ratio and regular three-dimensional arrangement structure, which can be processed into many functional devices. Among them, some carbon nanotube arrays are spinnable, and carbon nanotube fibers with excellent performance can be obtained; and carbon nanotube fibers spun from carbon nanotube arrays have the advantages of high carbon nanotube orientation, few fiber impurities and stable mechanical properties. It has now become an important technology for preparing high-performance carbon nanotube fibers.

[0003] However, the current process of preparing carbon nanotube fibers by array spinning mostly uses a hard substrate to grow the carbon nanotube array, and the furnace and substrate are limited in size, which makes it impossible to achieve continuous spinning and collection of carbon nanotube fibers, limiting the large-scale production of carbon nanotube fibers. Therefore, based on the current situation that carbon nanotube arrays cannot achieve continuous spinning in the prior art, it is necessary to improve the existing carbon nanotube array spinning method. Summary of the invention

[0004] Based on the above-mentioned shortcomings and deficiencies in the prior art, one of the objects of the present invention is to at least solve one or more of the above-mentioned problems in the prior art. In other words, one of the objects of the present invention is to provide an online continuous spinning device and method for a carbon nanotube array that meets one or more of the above-mentioned needs.

[0005] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0006] An online continuous spinning device for a carbon nanotube array comprises a three-temperature zone tubular furnace and a tubular furnace quartz tube installed in the three-temperature zone tubular furnace, two ends of the tubular furnace quartz tube respectively extend outside the three-temperature zone tubular furnace, a pair of rotating motors are arranged in parallel at two ends of the tubular furnace quartz tube, graphite paper with a magnetron sputtering catalyst is wound on the pair of rotating motors so that the graphite paper passes through the tubular furnace quartz tube and is unwound and rewound, a carbon source and a mixed gas are passed into the tubular furnace quartz tube through an air inlet quartz tube through a gas flow controller to react and generate a carbon nanotube array, the carbon nanotube array is pulled to a labyrinth seal outlet at the end of the tubular furnace quartz tube and the carbon nanotube fibers are collected by a collecting motor;

[0007] The mixed gas includes hydrogen and argon.

[0008] As a preferred embodiment, the catalyst is nano-iron ions.

[0009] As a preferred solution, before magnetron sputtering, a buffer layer is magnetron sputtered on graphite paper, and the buffer layer is aluminum oxide.

[0010] As a preferred solution, the magnetron sputtering thickness of the catalyst is 2-3 nm, and the thickness of the buffer layer is 20-30 nm.

[0011] As a preferred solution, the width of the graphite paper is 60-80% of the diameter of the quartz tube of the tubular furnace.

[0012] As a preferred solution, the volume percentage of the carbon source is 25-45%, the volume percentage of hydrogen is 7-23%, and the volume percentage of argon is 45-60%.

[0013] As a preferred embodiment, the carbon source is ethylene.

[0014] As a preferred solution, the labyrinth seal air outlet adopts a straight-through labyrinth seal structure.

[0015] As a preferred solution, the rotating motor adopts a winding characteristic torque motor to achieve constant tension transmission.

[0016] The present invention also provides an online continuous spinning method of the online continuous spinning device as described in any of the above schemes, comprising the following steps:

[0017] (1) Setting the temperature control program of the three-zone tubular furnace: 20-300°C heating rate 5°C / min, 300-750°C heating rate 10°C / min, 500°C insulation for 15 minutes, 750°C insulation for 30-50 minutes;

[0018] (2) Turn on the gas flow controller, first introduce protective gas argon at room temperature, and when the temperature of the three-zone tubular furnace rises to the reaction temperature, introduce the mixed gas for a period of time, and then introduce the carbon source after the gas in the furnace is stable; 20-30 minutes after the carbon source is introduced, turn on a pair of rotating motors at the same time to drive the graphite paper;

[0019] (3) Turn on the collection motor and adjust the collection motor speed so that the collection speed is less than the graphite paper transmission speed, and pull the carbon nanotube array through the labyrinth seal outlet to the collection motor.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The online continuous spinning device and method of the carbon nanotube array of the present invention can generate the carbon nanotube array continuously by fully automatic roll-to-roll, and can also pull the carbon nanotube array without cooling to realize large-scale continuous production and collection of carbon nanotube fibers, thereby improving the production efficiency of carbon nanotube fibers, reducing energy loss in the repeated heating process of the prior art, reducing production costs, and realizing continuous spinning of carbon nanotube arrays. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a schematic structural diagram of an online continuous spinning device for a carbon nanotube array according to an embodiment of the present invention;

[0023] In the figure: 1. front support plate, 2. labyrinth seal air outlet, 3. carbon nanotube fiber, 4. collecting motor, 5. rear rotating motor, 6. tubular furnace quartz tube, 7. three-temperature zone tubular furnace, 8. tubular furnace control console, 9. rear support plate, 10. carbon nanotube array, 11. inlet quartz tube, 12. gas flow controller, 13. gas control valve, 14. inlet pipe, 15. argon gas cylinder, 16. hydrogen gas cylinder, 17. ethylene gas cylinder, 18. graphite paper, 19. front rotating motor. DETAILED DESCRIPTION

[0024] In order to more clearly illustrate the embodiments of the present invention, the specific implementation methods of the present invention will be described below with reference to the accompanying drawings. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, other accompanying drawings and other implementation methods can be obtained based on these accompanying drawings without creative work.

[0025] Embodiment 1:

[0026] like Figure 1As shown, the online continuous spinning device of the carbon nanotube array of this embodiment includes a three-zone tubular furnace 7, a tubular furnace quartz tube 6 installed in the three-zone tubular furnace 7, both ends of the tubular furnace quartz tube 6 extend outside the three-zone tubular furnace 7 respectively, a front support plate 1 and a rear support plate 9 are installed under the tubular furnace quartz tube 6, a front rotating motor 19 and a rear rotating motor 5 are arranged in parallel at both ends of the tubular furnace quartz tube 6, a graphite paper 18 is wound on the front rotating motor 19, and one end is pulled out and passed through the tubular furnace quartz tube 6 and wound on the rear rotating motor 5; an argon gas cylinder 15, a hydrogen gas cylinder 16, and an ethylene gas cylinder 17 enter the gas inlet quartz tube 11 through the gas inlet pipe 14 and the gas flow controller 12, thereby passing into the tubular furnace quartz tube 6, and the end of the tubular furnace quartz tube 6 has a labyrinth seal outlet 2, and a collecting motor 4 is arranged outside the labyrinth seal outlet 2. In addition, the tubular furnace control console 8 is used to set the temperature control program of the three-zone tubular furnace 7.

[0027] The width of the graphite paper 18 in this embodiment is 30-40 mm. Aluminum oxide with a thickness of 20 nm is magnetron sputtered on one side surface as a buffer layer, and nano-iron ions with a thickness of 2 nm are magnetron sputtered on the surface as a catalyst.

[0028] The online continuous spinning method of the online continuous spinning device of the carbon nanotube array of this embodiment includes:

[0029] (1) The graphite paper 18 is rolled onto the front rotating motor 19, and the front rotating motor 15 is started to pull out the graphite paper 18 on which the catalyst has been magnetron sputtered. The pulled-out part passes through the tubular furnace quartz tube and is wound onto the rear rotating motor 5, and the front rotating motor 15 is turned off;

[0030] (2) Open the gas flow controller 12, introduce 500 SCCM of protective gas argon for 30 minutes, and exhaust the air in the tube furnace;

[0031] (3) Setting the temperature control program of the three-temperature zone tubular furnace 7 by the tubular furnace control console 8: 20-300°C heating rate 5°C / min, 300-750°C heating rate 10°C / min, 500°C insulation for 15 minutes, 750°C insulation for 30 minutes, and introducing 500 SCCM of protective gas argon during the heating process; after the temperature of 750°C stabilizes, continue to maintain 750°C for 2 hours, introduce 300 SCCM of argon, 40 SCCM of hydrogen, and after the mixed gas stabilizes, introduce 160 SCCM of ethylene. After 30 minutes of introduction, the carbon source (i.e., ethylene) is cracked and combined with the catalyst to generate a carbon nanotube array 10, and the generated carbon nanotube array 10 is pulled through the labyrinth seal outlet 2 to the collection motor 4;

[0032] (4) Start the collecting motor. After 10 minutes, start the front and rear rotating motors to ensure that the graphite paper 18 continuously passes through the tubular furnace and continuously generates the carbon nanotube array 10. After the reaction, the graphite paper 18 is collected by the rear rotating motor 5. The collecting motor 4 continuously pulls the carbon nanotube array 10 to complete the collection of the array carbon nanotube fibers 3.

[0033] Embodiment 2:

[0034] The structure of the online continuous spinning device of the carbon nanotube array of this embodiment is the same as that of the embodiment 1, except that:

[0035] The width of the graphite paper in this embodiment is 30-40 mm. Aluminum oxide with a thickness of 20 nm is magnetron sputtered on one side surface, and nano-iron ions with a thickness of 3 nm are magnetron sputtered on the surface.

[0036] The online continuous spinning method of the online continuous spinning device of the carbon nanotube array of this embodiment includes:

[0037] (1) The graphite paper roll is mounted on the front rotating motor, the front rotating motor is started to pull out the graphite paper with the catalyst after magnetron sputtering, the pulled-out part passes through the quartz tube of the tubular furnace and is wound on the rear rotating motor, and the front rotating motor is turned off;

[0038] (2) Open the gas flow controller and introduce 500 SCCM of protective gas argon for 30 minutes to exhaust the air in the tube furnace;

[0039] (3) Setting the temperature control program of the three-zone tubular furnace: 20-300°C heating rate of 5°C / min, 300-750°C heating rate of 10°C / min, 500°C insulation for 15 minutes, 750°C insulation for 30 minutes, and introducing 500 SCCM of protective gas argon during the heating process; after the temperature at 750°C stabilizes, continue to maintain 750°C for 1.7 hours, and introduce 250 SCCM of argon and 50 SCCM of hydrogen at the same time. After the mixed gas stabilizes, introduce 200 SCCM of ethylene. After 30 minutes of introduction, the carbon source is cracked and combined with the catalyst to generate a carbon nanotube array, and the generated carbon nanotube array is pulled through the labyrinth seal outlet to the collection motor;

[0040] (4) Start the collection motor, and after 10 minutes, start the front and rear rotating motors to ensure that the graphite paper continuously passes through the tubular furnace and continuously generates a carbon nanotube array. After the reaction, the graphite paper is collected by the rear rotating motor, and the collection motor continuously pulls the carbon nanoarray to complete the collection of the array carbon nanotube fibers.

[0041] In view of the large number of embodiments of the scheme of the present invention, each embodiment can be determined according to actual application requirements within the limited range of each parameter. The experimental data is huge and numerous, and it is not suitable to list them one by one here. However, the content that needs to be verified in each embodiment and the final conclusion obtained are similar.

[0042] The above description is only a detailed description of the preferred embodiments and principles of the present invention. For ordinary technicians in this field, according to the ideas provided by the present invention, there will be changes in the specific implementation methods, and these changes should also be regarded as the protection scope of the present invention.

Claims

1. An online continuous spinning device for a carbon nanotube array, characterized in that: It comprises a three-temperature zone tubular furnace and a tubular furnace quartz tube installed in the three-temperature zone tubular furnace, two ends of the tubular furnace quartz tube respectively extend outside the three-temperature zone tubular furnace, a pair of rotating motors are arranged in parallel at two ends of the tubular furnace quartz tube, graphite paper with magnetron sputtering catalyst is wound on the pair of rotating motors so that the graphite paper passes through the tubular furnace quartz tube and is unwound and rewound, a carbon source and a mixed gas are passed into the tubular furnace quartz tube through an air inlet quartz tube through a gas flow controller to react and generate a carbon nanotube array, the carbon nanotube array is pulled to a labyrinth seal outlet at the end of the tubular furnace quartz tube and the carbon nanotube fibers are collected through a collecting motor; The mixed gas includes hydrogen and argon, and the labyrinth seal outlet adopts a straight-through labyrinth seal structure.

2. The online continuous spinning device of a carbon nanotube array according to claim 1, characterized in that: The catalyst is nano iron ions.

3. The online continuous spinning device of a carbon nanotube array according to claim 2, characterized in that: Before magnetron sputtering, the catalyst is magnetron sputtered on graphite paper to form a buffer layer, wherein the buffer layer is aluminum oxide.

4. The online continuous spinning device of a carbon nanotube array according to claim 3, characterized in that: The magnetron sputtering thickness of the catalyst is 2-3 nm, and the thickness of the buffer layer is 20-30 nm.

5. An online continuous spinning device for a carbon nanotube array according to any one of claims 1 to 4, characterized in that: The width of the graphite paper is 60-80% of the diameter of the tubular furnace quartz tube.

6. An online continuous spinning device for a carbon nanotube array according to any one of claims 1 to 4, characterized in that: The volume percentage of the carbon source is 25-45%, the volume percentage of hydrogen is 7-23%, and the volume percentage of argon is 45-60%.

7. An online continuous spinning device for a carbon nanotube array according to any one of claims 1 to 4, characterized in that: The carbon source is ethylene.

8. An online continuous spinning device for a carbon nanotube array according to any one of claims 1 to 4, characterized in that: The rotating motor adopts a winding characteristic torque motor to realize constant tension transmission.

9. The online continuous spinning method of the online continuous spinning device according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Set the temperature control program of the three-zone tubular furnace: 20-300℃ heating rate 5℃ / min, 300-750℃ heating rate 10℃ / min, 500℃ insulation for 15 minutes, 750℃ insulation for 30-50 minutes; (2) Turn on the gas flow controller, first introduce protective gas argon at room temperature, and when the temperature of the three-zone tubular furnace rises to the reaction temperature, introduce the mixed gas for a period of time, and then introduce the carbon source after the gas in the furnace is stable; 20-30 minutes after the carbon source is introduced, turn on a pair of rotating motors at the same time to drive the graphite paper; (3) Turn on the collection motor and adjust the collection motor speed so that the collection speed is less than the graphite paper transmission speed, and pull the carbon nanotube array through the labyrinth seal outlet to the collection motor.

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