CN108101025B - Method for reinforcing tube wall structure of carbon nano tube - Google Patents
Method for reinforcing tube wall structure of carbon nano tube Download PDFInfo
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- CN108101025B CN108101025B CN201711220581.XA CN201711220581A CN108101025B CN 108101025 B CN108101025 B CN 108101025B CN 201711220581 A CN201711220581 A CN 201711220581A CN 108101025 B CN108101025 B CN 108101025B
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Abstract
The invention relates to a method for reinforcing the wall structure of a carbon nano tube, which comprises the steps of pretreating the carbon nano tube prepared by a chemical vapor deposition method; heating the pretreated carbon nano tube, introducing growth gas for providing reinforcing atoms and protective gas for controlling reaction rate, and keeping the temperature for t to obtain the carbon nano tube after secondary deposition; and graphitizing the carbon nano tube after the secondary deposition. The method comprises the steps of depositing an amorphous carbon layer on the wall of the traditional carbon nanotube, then inducing amorphous carbon into the rearrangement process of an original carbon layer through a post-stage high-temperature treatment process, finally forming a uniform and controllable carbon layer structure with high graphitization degree on the surface of a target carbon nanotube, and finally repairing and reinforcing the wall structure of the carbon nanotube from a nanoscale, thereby providing important guarantee for improving the comprehensive performance of the carbon nanotube composite material.
Description
Technical Field
The invention relates to a method for reinforcing a carbon nanotube wall structure, and belongs to the field of nano carbon materials.
Background
With the rapid development of manufacturing industrial technologies, the demand of advanced manufacturing industries represented by aerospace, electric vehicles, intelligent electronic products and the like for new materials is higher and higher, and greater challenges are certainly provided for the material field. Since the 90 s, carbon nanotubes have attracted much attention due to their excellent physical and chemical properties, and have been a subject of attention by researchers in various countries for over 20 years, so that the advantages of the carbon nanotube material have been fully demonstrated. One of the challenges that is the main focus of the future carbon era is how to convert monomeric carbon nanotubes into macroscopic materials and achieve the excellent performance at the macroscopic scale while maintaining their excellent performance at the nanoscale. Most of the existing carbon nanotube materials are applied in a monomer form as a main material, and the excellent performance of the existing carbon nanotube materials under the nanoscale is difficult to show in a macroscopic guest material. One of the performance-limiting factors is that carbon nanotubes prepared by a vapor deposition (CVD) method usually have bamboo-like carbon layer structural defects after graphitization treatment, and the structural defects introduced by the periodic growth mechanism of the carbon nanotubes are almost unavoidable. After the initial growth is finished, the structural node naturally exists in the carbon tube wall structure, carbon atoms on the tube wall are purified and rearranged in the subsequent high-temperature treatment process, and carbon atoms shrink and are lost at the node of the growth period, so that the mutual complementary internal connection of the carbon atoms of the adjacent two side nodes is formed. The bamboo-like structure destroys the continuity of the carbon layer, and influences the overall heat conduction, electric conduction and axial mechanical properties of the carbon tube, and the influences can be kept in the composite material all the time. Eventually, the performance of the carbon nanotubes in practical applications is greatly compromised.
How to complement the inherent structural defects in the tube wall structure of the carbon nano tube prepared by a Chemical Vapor Deposition (CVD) method is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for reinforcing the wall structure of a carbon nanotube, which can effectively supplement sufficient carbon atoms on the surface of the wall of the carbon nanotube so as to reinforce the structural defects and maintain the ideal continuous structure and axial performance of the carbon nanotube.
The purpose of the invention is realized by the following technical scheme:
the method for reinforcing the wall structure of the carbon nanotube comprises the following steps:
(1) pretreating the carbon nano tube prepared by adopting a chemical vapor deposition method;
(2) heating the pretreated carbon nano tube to the decomposition temperature of growth gas, introducing the growth gas for providing reinforcing atoms and protective gas for controlling the reaction rate, and keeping the temperature for t to obtain the carbon nano tube subjected to secondary deposition;
(3) and graphitizing the carbon nano tube after the secondary deposition.
Preferably, the pretreatment in step (1) is surface cleaning.
Preferably, the specific method of the pretreatment in step (1) is: putting a certain amount of carbon nano tubes into a dilute hydrochloric acid solution, stirring and cleaning, pouring out supernatant, then cleaning with distilled water, and drying in a drying oven.
Preferably, the relationship between the constant temperature time t and the secondary deposition thickness h is as follows: h is t 60.
Preferably, the constant temperature time t is 1-3 hours.
Preferably, the growth gas is methane, the protective gas is hydrogen, and the volume ratio of the growth gas to the protective gas is 8: 2.
Preferably, the growth gas is acetylene, the protective gas is hydrogen, and the volume ratio of the growth gas to the protective gas is 8: 2.
Preferably, the step (2) further comprises introducing helium gas to cool to room temperature after the constant temperature time t.
Preferably, the graphitization treatment in the step (3) is carried out at 2600-2800 ℃ for 10-20 minutes.
Preferably, the method for preparing the carbon nanotubes by the chemical vapor deposition method in the step (1) is as follows: placing an iron-nickel alloy catalyst in the middle area of a quartz tube furnace, introducing helium and hydrogen into the furnace by using carbon source gas as carbon monoxide, heating to 700 ℃, then introducing mixed gas of the carbon monoxide and the hydrogen, keeping the temperature for 1 hour, and naturally cooling to room temperature under the protection of the helium.
Preferably, the method further comprises the step (4) of observing whether the graphitized carbon nanotube wall carbon layer is uniform and continuous by adopting a Transmission Electron Microscope (TEM), and if so, finishing carbon nanotube reinforcement; otherwise, selecting the carbon nano tube prepared by the chemical vapor deposition method again, and returning to the step (1).
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, an amorphous carbon layer is deposited on the wall of the traditional carbon nanotube, and then the amorphous carbon is induced into the rearrangement process of the original carbon layer through a post-stage high-temperature treatment process, and finally a uniform and controllable carbon layer structure with high graphitization degree is formed on the surface of the target carbon nanotube, so that the carbon tube carbon layer structure is repaired and reinforced in a nanoscale manner, and an important guarantee is provided for improving the comprehensive performance of the carbon nanotube composite material. The method for repairing and reinforcing the wall structure of the carbon tube from the nanometer scale provides important guarantee for improving the comprehensive performance of the carbon nanotube composite material.
(2) The reinforcement method of the invention maintains the ideal continuous structure and axial performance of the carbon nano tube. The method has simple process and is suitable for engineering application.
(3) The invention is suitable for carbon nanotubes with any size and structure, can effectively reinforce the tube wall structure of the carbon nanotubes, controls the tube diameter, has quick and effective secondary deposition method and lower cost, and has continuous and stable structure after graphitizing and shaping.
Drawings
FIG. 1 is a flow chart of the carbon nanotube wall structure reinforcement of the present invention;
FIG. 2(a) is a low magnification photomicrograph of the original carbon nanotube structure; FIG. 2(b) is a high magnification photomicrograph of the original carbon nanotube structure; fig. 2(c) is a low magnification photomicrograph of the reinforced structure, and fig. 2(d) is a high magnification photomicrograph of the reinforced structure.
Detailed Description
The invention provides a reinforcing method of a carbon nanotube wall structure, which is characterized in that a certain amount of amorphous carbon atomic layers are deposited on the surface of the tube wall of a target carbon nanotube, the average tube wall thickness is in the range of 20-40 nm, the carbon nanotube after secondary deposition is subjected to high-temperature graphitization treatment at the treatment temperature of 2600-2800 ℃, the rearrangement and reinforcement of the carbon layer structure of the tube wall of the carbon nanotube are completed, and an ideal continuous and uniform carbon layer structure is obtained.
In a quartz tube furnace, heating to 700 ℃ in carbon monoxide (CO) atmosphere, and preparing a plurality of grams of carbon nano tubes for later use by utilizing iron-nickel alloy catalytic reaction. The reinforcement method combined with the figure 1 specifically comprises the following steps:
(1) pretreating the carbon nano tube prepared by adopting a chemical vapor deposition method;
(2) heating the pretreated carbon nano tube to the decomposition temperature of growth gas, introducing the growth gas for providing reinforcing atoms and protective gas for controlling the reaction rate, and keeping the temperature for t to obtain the carbon nano tube subjected to secondary deposition;
(3) and graphitizing the carbon nano tube after the secondary deposition.
(4) Observing whether the graphitized carbon nanotube wall carbon layer is uniform and continuous by adopting a Transmission Electron Microscope (TEM), and finishing carbon nanotube reinforcement if the graphitized carbon nanotube wall carbon layer is uniform and continuous; otherwise, selecting the carbon nano tube prepared by the chemical vapor deposition method again, and returning to the step (1).
Example 1:
uniformly laying about 1 g of iron-nickel alloy catalyst on a quartz substrate, placing the iron-nickel alloy catalyst in the middle area of a quartz tube furnace, introducing helium and hydrogen (2:8) into the furnace, raising the temperature to 700 ℃, introducing mixed gas of carbon monoxide and hydrogen (8:2), and keeping the temperature for 1 hour. And finally, naturally cooling to room temperature under the protection of helium to obtain the carbon nano tube prepared by the chemical vapor deposition method.
(1) The carbon nano tube prepared by the chemical vapor deposition method is pretreated, and the surface of the carbon nano tube is cleaned and decontaminated. Putting 1 g of the carbon nano tube obtained in the step 1 into 500ml of dilute hydrochloric acid (10%) solution, stirring and cleaning for 10 minutes, pouring out supernate, cleaning for 3 times by using distilled water, and drying for 4 hours in a drying oven (120 ℃) for later use;
(2) uniformly depositing amorphous carbon atoms with a certain thickness on the surface of the carbon nano tube by a secondary deposition method, wherein a secondary deposition gas source selects methane gas (CH)4) The temperature is 900 ℃ and 950 ℃ for decomposition and deposition on the surface of the carbon tube. Selection of deposition time, in accordance with CH4Determining the optimal balance point of the decomposition rate and the deposition rate which can be controlled by the characteristics of gas source decomposition and deposition rate, wherein the constant temperature time corresponding to the effective deposition thickness is 1-3 hours, the average diameter of the obtained product is 60-100nm, the deposition surface is smooth, and the pipe diameter is uniform; the method comprises the steps of depositing amorphous carbon atoms with a certain thickness on the surface by adopting a secondary deposition method, and inducing the amorphous carbon atoms into the defects of the original carbon layer structure through high-temperature graphitization treatment at the later stage. The secondary deposition thicknesses obtained in different constant temperature time are different, and the relationship between the constant temperature time t and the secondary deposition thickness h is as follows: h is t x 60(t is hour), the constant temperature time is selected according to the required deposition thickness, generally 1 to 3 hours, and the excessive deposition time can cause the occurrence of disordered layers and cause the surface to be in contact withIs discontinuous.
(3) Carrying out high-temperature graphitization treatment on the obtained carbon nano tube covered with amorphous carbon atoms with a certain thickness at the treatment temperature of 2600-2800 ℃ to obtain a carbon nano tube with a reinforced tube wall structure;
(4) and microcosmic observation and analysis are carried out on the pipe wall structure of the secondary deposition carbon nanotube material prepared by the method. If the carbon nano tube is uniform and continuous, the carbon nano tube after reinforcement meets the requirement, otherwise, the carbon nano tube is selected again for reinforcement.
Example 2: (1) the carbon nano tube prepared by the chemical vapor deposition method is pretreated, and the surface of the carbon nano tube is cleaned and decontaminated.
(2) Uniformly depositing amorphous carbon atoms with a certain thickness on the surface of the carbon nano tube by a secondary deposition method, wherein ethylene gas (C) is selected as a secondary deposition gas source2H4) The protective gas is hydrogen, and the volume ratio is 8:2, the temperature is selected to be 700 ℃ and 750 ℃ to decompose and deposit on the surface of the carbon tube. Selection of deposition time according to C2H4Determining the optimal balance point of the decomposition rate and the deposition rate which can be controlled by the characteristics of gas source decomposition and deposition rate, wherein the constant temperature time corresponding to the effective deposition thickness is 1-3 hours, the average diameter of the obtained product is 60-100nm, the deposition surface is smooth, and the pipe diameter is uniform; the method comprises the steps of depositing amorphous carbon atoms with a certain thickness on the surface by adopting a secondary deposition method, and inducing the amorphous carbon atoms into the defects of the original carbon layer structure through high-temperature graphitization treatment at the later stage. The secondary deposition thicknesses obtained in different constant temperature time are different, and the relationship between the constant temperature time t and the secondary deposition thickness h is as follows: and h is t × 40(t is in hours), the constant temperature time is selected according to the required deposition thickness, the constant temperature time is usually 1-3 hours, and the excessive deposition time can cause the occurrence of random layers and cause surface discontinuity.
(3) Carrying out high-temperature graphitization treatment on the obtained carbon nano tube covered with amorphous carbon atoms with a certain thickness at the treatment temperature of 2600-2800 ℃ to obtain a carbon nano tube with a reinforced tube wall structure;
(4) and microcosmic observation and analysis are carried out on the pipe wall structure of the secondary deposition carbon nanotube material prepared by the method. If the carbon nano tube is uniform and continuous, the carbon nano tube after reinforcement meets the requirement, otherwise, the carbon nano tube is selected again for reinforcement.
The tube wall size distribution condition of the oriented high thermal conductivity carbon nanotube material prepared by the method is observed as follows: in fig. 2, (a) and (b), the thickness of the carbon nanotube wall is increased by about 30nm after reinforcement in the carbon nanotubes in fig. 2(c) and (d) without significant change; the diameter of the whole carbon nano tube is increased from 10nm to more than 60 nm.
According to the invention, an amorphous carbon layer is deposited on the wall of the traditional carbon nanotube, and then the amorphous carbon is induced into the rearrangement process of the original carbon layer through a post-stage high-temperature treatment process, and finally a uniform and controllable carbon layer structure with high graphitization degree is formed on the surface of the target carbon nanotube, so that the carbon tube carbon layer structure is repaired and reinforced in a nanoscale manner, and an important guarantee is provided for improving the comprehensive performance of the carbon nanotube composite material.
The above description is only for the best mode of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Those skilled in the art will appreciate that the invention may be practiced without these specific details.
Claims (5)
1. A method for reinforcing a carbon nanotube wall structure is characterized by comprising the following steps:
(1) the method comprises the following steps of pretreating the carbon nano tube prepared by a chemical vapor deposition method, wherein the pretreatment is surface cleaning, and the preparation method of the carbon nano tube comprises the following steps: placing an iron-nickel alloy catalyst in the middle area of a quartz tube furnace, introducing helium and hydrogen into the furnace by using carbon source gas which is carbon monoxide, heating to 700 ℃, then introducing mixed gas of the carbon monoxide and the hydrogen, keeping the temperature for 1 hour, and naturally cooling to room temperature under the protection of helium;
(2) heating the pretreated carbon nano tube to the decomposition temperature of growth gas, introducing growth gas for providing reinforcing atoms and protective gas for controlling reaction rate, and keeping the temperature for t to obtain the carbon nano tube after secondary deposition, wherein the growth gas is methane or acetylene, the protective gas is hydrogen, the volume ratio of the growth gas to the acetylene is 8:2, and the constant temperature for t is 1-3 hours;
(3) graphitizing the carbon nano tube after the secondary deposition, wherein the temperature of the graphitizing treatment is 2600-2800 ℃, and keeping the temperature for 10-20 minutes.
2. The method for reinforcing the wall structure of the carbon nanotube according to claim 1, wherein the pretreatment in step (1) comprises: putting a certain amount of carbon nano tubes into a dilute hydrochloric acid solution, stirring and cleaning, pouring out supernatant, then cleaning with distilled water, and drying in a drying oven.
3. The method for reinforcing the wall structure of the carbon nanotube according to claim 1 or 2, wherein the relationship between the constant temperature time t and the secondary deposition thickness h is as follows: h is t 60, t is in hours and h is in nm.
4. The method for reinforcing the wall structure of the carbon nanotube according to claim 1 or 2, wherein the step (2) further comprises introducing helium gas to cool the carbon nanotube to room temperature after the constant temperature time t.
5. The method for reinforcing the tube wall structure of the carbon nanotube according to claim 1 or 2, further comprising the step (4) of observing whether the carbon layer on the tube wall of the carbon nanotube after the graphitization treatment is uniform and continuous by using a Transmission Electron Microscope (TEM), and if so, finishing the carbon nanotube reinforcement; otherwise, selecting the carbon nano tube prepared by the chemical vapor deposition method again, and returning to the step (1).
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