CN112661134B - Method for preparing pyrolytic carbon from acetaldehyde precursor - Google Patents
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Abstract
The invention relates to a method for preparing pyrolytic carbon by using an acetaldehyde precursor, which is characterized by comprising the following steps: in the chemical vapor infiltration process, an acetaldehyde organic solution is used as a precursor, and nitrogen is used as a carrier gas and a diluent gas. The acetaldehyde organic solution is poured into a closed metal container, and the reaction can be participated by changing the acetaldehyde organic solution into vapor through a bubbling method. The invention uses chemical vapor deposition technology to prepare the pyrolytic carbon with good structure by taking acetaldehyde as a precursor for the first time. The preparation method is simple and reasonable, wide in process conditions and convenient to operate. Meanwhile, the invention widens the selection of a raw material system for preparing the pyrolytic carbon and also provides a new idea for the structural optimization of the pyrolytic carbon.
Description
Technical Field
The invention belongs to a method for preparing pyrolytic carbon, relates to a method for preparing pyrolytic carbon by using an acetaldehyde precursor, and particularly relates to a method for preparing a pyrolytic carbon film, a pyrolytic carbon substrate and a pyrolytic carbon interface by using acetaldehyde as a precursor.
Background
Carbon materials have been successfully used in the aerospace, military and civilian applications. The carbon/carbon composite material is widely applied to nozzles, throat linings, airplane brake discs and the like of rocket engines due to the excellent high-temperature properties of the carbon/carbon composite material, such as high specific strength, high specific modulus, high thermal conductivity, good wear resistance, excellent thermal shock resistance and the like. A carbon/carbon (C/C) composite material is composed of carbon fibers and pyrolytic carbon, and a method widely used to prepare pyrolytic carbon at present is a Chemical Vapor Infiltration (CVI) method. In recent decades, there has been much interest in the development of pyrolytic carbon precursors, the earliest and commonly used precursor for the preparation of pyrolytic carbon being methane. With further optimization of the CVI process, the selection of precursors is greater and includes ethane, propane, ethylene, propylene, acetylene, 1, 3-butadiene, benzene, cyclohexane, ethanol, etc. A pyrolytic carbon matrix was prepared in patent 1 (CN 200910023764.1) from a mixed precursor of natural gas and acetylene. In patent 2 (CN 2013102069401.1), an isotropic pyrolytic carbon with higher apparent density is prepared by using propylene as a precursor. Literature 1"Zhang WG, hu ZJ, huttinger KJ.chemical vapor injection of carbon fiber felt. Optimization of differentiation and carbon microstructure. Carbon 2002;40 (14): 2529-45, "it is reported that by controlling the methane pressure and deposition temperature, different kinds of pyrolytic carbons can be obtained. Document 2"Zhang SY, yan XF, li HJ, li W, guo LJ.Deposition of pyrolytic carbon using ethanol as precusor in chemical vapor injection. Journal of organic materials,2009;24 1073-6, the high texture pyrolytic carbon matrix is successfully prepared by using ethanol as a precursor.
Acetaldehyde has a strong pyrolysis reactivity due to the presence of aldehyde groups (-CHO), and tends to form oligomers and polymers easily. Acetaldehyde has the formula C 2 H 4 O, and ethanol (C) having the same number of carbon atoms 2 H 6 O) carries two less hydrogen atoms per carbon atom in a single molecule, and acetaldehyde is more reactive than ethanol in chemical composition. The method of acetaldehyde pyrolysis is a free radical mechanism decomposition method, wherein oxygen will participate in reaction in the form of free radicals, and trace oxygen can oxidize and decompose short and disordered chain hydrocarbon in the formation process of pyrolytic carbon to form large and regularly arranged fused ring aromatic hydrocarbon molecules, which is beneficial to ordering of the structure of pyrolytic carbon. However, there has been no report or patent mentioning of acetaldehyde as a precursor for preparing pyrolytic carbon. Therefore, the invention has the significance that acetaldehyde is selected as a precursor for preparing the pyrolytic carbon film, the pyrolytic carbon substrate and the pyrolytic carbon interface for the first time, the feasibility and the effect of the acetaldehyde as the precursor for preparing the pyrolytic carbon are proved, and the invention has very important significance on the organization structure design, the performance improvement and the industrial application of the carbon/carbon composite material.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for preparing pyrolytic carbon by using an acetaldehyde precursor, which adopts acetaldehyde as the precursor for preparing a pyrolytic carbon film, a pyrolytic carbon substrate and a pyrolytic carbon interface for the first time.
Technical scheme
A method for preparing pyrolytic carbon by using acetaldehyde precursors is characterized by comprising the following steps: taking an acetaldehyde organic solution as a precursor, and taking nitrogen as a carrier gas and a diluent gas, the preparation steps are as follows:
step 1: pouring the acetaldehyde organic solution into a closed metal container, and changing the acetaldehyde organic solution into steam by a bubbling method so as to participate in the reaction;
step 2: placing the substrate in a reactor of a deposition furnace by adopting a chemical vapor infiltration process, and exhausting air in the deposition furnace; then raising the temperature from room temperature to 900-1200 ℃, wherein the temperature raising rate is less than 20 ℃/min; taking the acetaldehyde organic solution in the step (1) as a precursor, controlling the flow of acetaldehyde gas to be 80-200 sccm, and depositing the acetaldehyde gas at the temperature of 900-1200 ℃ for a set time; then, the temperature is gradually reduced from 900 ℃ to 1200 ℃ to 200 ℃, the power supply is turned off, and the material is taken out after natural cooling;
the whole deposition process is carried out under normal pressure and is always protected by nitrogen.
The substrate is a silicon wafer, a quartz glass sheet, a carbon fiber preform or a low-density C/C composite material.
The acetaldehyde purity was 40%.
The volume fraction of the nitrogen gas was 99.99%.
Advantageous effects
The method for preparing pyrolytic carbon by using the acetaldehyde precursor provided by the invention utilizes a chemical vapor deposition process technology to prepare the pyrolytic carbon with a good structure by using the acetaldehyde as the precursor for the first time. The preparation method is simple and reasonable, wide in process conditions and convenient to operate. Meanwhile, the invention widens the selection of a raw material system for preparing the pyrolytic carbon and also provides a new idea for the structural optimization of the pyrolytic carbon.
Acetaldehyde has a strong pyrolysis reactivity due to its aldehyde group (-CHO), and tends to form oligomers and polymers easily. Acetaldehyde has the formula C 2 H 4 O, and ethanol (C) having the same number of carbon atoms 2 H 6 O) carries two less hydrogen atoms per carbon atom in a single molecule, and acetaldehyde is more reactive than ethanol in chemical composition. High-temperature pyrolysis method for acetaldehydeThe method is a free radical mechanism decomposition method, wherein oxygen will participate in reaction in the form of free radicals, and trace oxygen can oxidize and decompose short and disordered chain hydrocarbon during the formation process of the pyrolytic carbon to form large and regularly arranged fused ring aromatic hydrocarbon molecules, which is beneficial to ordering of the structure of the pyrolytic carbon. The invention has the significance that acetaldehyde is selected as a precursor for preparing the pyrolytic carbon film, the pyrolytic carbon substrate and the pyrolytic carbon interface for the first time, the feasibility and the effect of the acetaldehyde as the precursor for preparing the pyrolytic carbon are proved, and the invention has very important significance on the organizational structure design, the performance improvement and the industrial application of the carbon/carbon composite material.
It can be observed from fig. 1 that the pyrolytic carbon prepared from acetaldehyde contains a large amount of carbon nano-flakes having a size of 100-200 nm. As can be seen from fig. 2, there are significant lattice stripes of carbon in these carbon nanoflakes. Fig. 3 and 4 are a raman spectrum and an XPS full spectrum of a pyrolytic carbon prepared with acetaldehyde, respectively, and it can be seen that the pyrolytic carbon prepared with acetaldehyde has a distinct characteristic peak of carbon and no other impurities. In conclusion, the acetaldehyde is adopted as the precursor, so that the pyrolytic carbon with a good structure can be successfully prepared.
Drawings
FIG. 1 is an SEM topography of pyrolytic carbon prepared with acetaldehyde
FIG. 2 is a TEM topography of pyrolytic carbon prepared with acetaldehyde
FIG. 3 is a Raman spectrum of pyrolytic carbon prepared with acetaldehyde
FIG. 4 is an XPS survey of pyrolytic carbon prepared with acetaldehyde
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1:
step 1: a quartz glass plate having a size of 10X 2mm was used as a substrate, and an acetaldehyde organic solution (purity: 40%) was used as a precursor. Nitrogen (N2, 99.99% by volume) was used as the carrier gas and the diluent gas.
Step 2: 4 bottles of acetaldehyde organic solution are poured into a closed metal container, and the acetaldehyde organic solution is changed into steam to participate in the reaction by a bubbling method.
And 3, step 3: the quartz glass substrate in step 1 was placed in a deposition reactor by isothermal chemical vapor infiltration, and the gases were passed through the quartz glass substrate in parallel from bottom to top. Then the temperature is raised from room temperature to 1050 ℃ at a rate of 8 ℃/min. Controlling the flow rate of acetaldehyde gas in the flow meter at 80sccm, depositing at 1050 ℃ for 5h, then gradually reducing the temperature from 1050 ℃ to 200 ℃, turning off the power supply, naturally cooling, and taking out the sample. The whole deposition process is carried out under normal pressure and is always protected by nitrogen.
Example 2:
step 1: the density is 0.47g/cm 3 The 2D carbon felt (size 50 × 25 × 10 mm) of (a) was used as a substrate, and an acetaldehyde organic solution (purity 40%) was used as a precursor. Nitrogen (N2, 99.99% by volume) was used as the carrier gas and the diluent gas.
And 2, step: 5 bottles of acetaldehyde organic solution are poured into a closed metal container, and the acetaldehyde organic solution is changed into steam to participate in the reaction by a bubbling method.
And 3, step 3: and (3) placing the carbon felt substrate in the step (1) in a deposition reactor by adopting an isothermal chemical vapor infiltration method, and allowing gas to parallelly pass through the carbon felt substrate from bottom to top. Then the temperature is increased from room temperature to 1090 ℃, and the temperature increasing rate is 10 ℃/min. Controlling the flow rate of acetaldehyde gas in the flow meter at 100sccm, depositing at 1090 ℃ for 15h, then gradually reducing the temperature from 1090 ℃ to 200 ℃, turning off the power supply, naturally cooling, and taking out the sample. The whole deposition process is carried out under normal pressure and is always protected by nitrogen.
Example 3:
step 1: the density is 0.6g/cm 3 The 2D carbon felt (size 50 × 25 × 10 mm) of (b) was used as a substrate, and an acetaldehyde organic solution (purity 40%) was used as a precursor. Nitrogen (N2, 99.99% by volume) was used as the carrier gas and the diluent gas.
And 2, step: 5 bottles of acetaldehyde organic solution are poured into a closed metal container, and the acetaldehyde organic solution is changed into steam to participate in the reaction by a bubbling method.
And step 3: and (3) placing the carbon felt substrate in the step (1) in a deposition reactor by adopting an isothermal chemical vapor infiltration method, and allowing gas to parallelly pass through the carbon felt substrate from bottom to top. Then the temperature is raised from room temperature to 1120 ℃ with the temperature raising rate of 12 ℃/min. Controlling the flow rate of acetaldehyde gas in the flow meter at 110sccm, depositing at 1120 ℃ for 20h, then gradually reducing the temperature from 1120 ℃ to 200 ℃, turning off the power supply, naturally cooling, and taking out the sample. The whole deposition process is carried out under normal pressure and is always protected by nitrogen.
Example 4:
step 1: the density is 1.0g/cm 3 The low-density carbon/carbon composite material (size 50X 25X 12 mm) of (2) is used as a substrate, and an acetaldehyde organic solution (purity 40%) is used as a precursor. Nitrogen (N2, 99.99% by volume) was used as the carrier gas and the diluent gas.
And 2, step: 6 bottles of acetaldehyde organic solution are poured into a closed metal container, and the acetaldehyde organic solution is changed into steam to participate in the reaction by a bubbling method.
And step 3: the carbon/carbon composite material substrate in the step 1 is placed in a deposition reactor by using an isothermal chemical vapor infiltration method, and gas is enabled to pass through the substrate from bottom to top in parallel. The temperature was then raised from room temperature to 1170 ℃ at a rate of 12 ℃/min. Controlling the flow rate of acetaldehyde gas in the flow meter at 120sccm, depositing at 1170 ℃ for 30h, then gradually reducing the temperature from 1170 ℃ to 200 ℃, turning off the power supply, naturally cooling, and taking out the sample. The whole deposition process is carried out under normal pressure and is always protected by nitrogen.
Claims (3)
1. A method for preparing pyrolytic carbon by using acetaldehyde precursors, wherein the substrate is a silicon wafer, a quartz glass sheet, a carbon fiber preform or a low-density C/C composite material, and the method is characterized in that: taking an acetaldehyde organic solution as a precursor, and taking nitrogen as a carrier gas and a diluent gas, the preparation steps are as follows:
step 1: pouring the acetaldehyde organic solution into a closed metal container, and changing the acetaldehyde organic solution into steam by a bubbling method so as to participate in the reaction;
and 2, step: placing the substrate in a reactor of a deposition furnace by adopting a chemical vapor infiltration process, and exhausting air in the deposition furnace; then raising the temperature from room temperature to 900-1200 ℃, wherein the temperature raising rate is less than 20 ℃/min; taking the acetaldehyde organic solution in the step (1) as a precursor, controlling the flow of acetaldehyde gas to be 80-200 sccm, and depositing the acetaldehyde gas at the temperature of 900-1200 ℃ for a set time; then, the temperature is gradually reduced to 200 ℃ from 900-1200 ℃, the power supply is turned off, and the material is taken out after natural cooling;
the whole deposition process is carried out under normal pressure and is always protected by nitrogen.
2. The method of claim 1 for preparing pyrolytic carbon from acetaldehyde precursors, wherein: the acetaldehyde purity was 40%.
3. The method of claim 1 for preparing pyrolytic carbon from acetaldehyde precursors, wherein: the volume fraction of the nitrogen gas was 99.99%.
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| CN106132871A (en) * | 2015-03-09 | 2016-11-16 | Lg化学株式会社 | The preparation method of carbon nanostructure and the carbon nanostructure prepared by the method |
| CN111675209A (en) * | 2020-06-02 | 2020-09-18 | 天津理工大学 | Method for growing vertical graphene film by using nitrogen and ethanol |
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| CN106132871A (en) * | 2015-03-09 | 2016-11-16 | Lg化学株式会社 | The preparation method of carbon nanostructure and the carbon nanostructure prepared by the method |
| CN111675209A (en) * | 2020-06-02 | 2020-09-18 | 天津理工大学 | Method for growing vertical graphene film by using nitrogen and ethanol |
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