CN116715524A - Preparation method of high-carbon siliconized graphite based on nano carbon black and resin impregnation - Google Patents
Preparation method of high-carbon siliconized graphite based on nano carbon black and resin impregnation Download PDFInfo
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- CN116715524A CN116715524A CN202310698196.5A CN202310698196A CN116715524A CN 116715524 A CN116715524 A CN 116715524A CN 202310698196 A CN202310698196 A CN 202310698196A CN 116715524 A CN116715524 A CN 116715524A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 71
- 239000010439 graphite Substances 0.000 title claims abstract description 71
- 239000006229 carbon black Substances 0.000 title claims abstract description 47
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 title claims abstract description 25
- 239000011347 resin Substances 0.000 title claims abstract description 25
- 238000005470 impregnation Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 230000008595 infiltration Effects 0.000 claims abstract description 44
- 238000001764 infiltration Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000007770 graphite material Substances 0.000 claims abstract description 22
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005011 phenolic resin Substances 0.000 claims abstract description 18
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000011856 silicon-based particle Substances 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000009702 powder compression Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 20
- 229910052710 silicon Inorganic materials 0.000 abstract description 15
- 239000010703 silicon Substances 0.000 abstract description 15
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005475 siliconizing Methods 0.000 description 3
- 239000003738 black carbon Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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Abstract
The application discloses a method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation, which comprises the steps of mixing spherical graphite with nano carbon black, pressing and forming by a hydraulic press after uniform mixing, pressing and impregnating a formed blank body in phenolic resin, taking out the blank body after impregnation, cleaning and drying, then carbonizing at high temperature, and placing a carbonized sample into a vacuum resistance furnace for reaction infiltration, thus obtaining the siliconized graphite material with high carbon content. According to the application, the compact nano carbon black layer is formed on the surface of the graphite particles, and the compact nano carbon black layer is preferentially reacted with silicon in the reaction infiltration process to form a compact thinner silicon carbide layer, so that further reaction of carbon and silicon is prevented, the coated graphite particles are effectively protected, and the prepared siliconized graphite material is compact, high in carbon phase content, simple in preparation process, low in energy consumption and short in production period.
Description
Technical Field
The application belongs to the technical field of inorganic nonmetallic material preparation, and particularly relates to a method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation.
Background
The siliconized graphite material is a composite material formed by compounding carbon, silicon carbide and silicon after siliconizing graphite, combines the advantages of the graphite and the silicon carbide material, has the advantages of good self-lubricating performance, lower thermal expansion coefficient, excellent high-temperature strength, good thermal shock resistance and the like, has a series of characteristics of high strength, high hardness, oxidation resistance, corrosion resistance and the like, and is an ideal structural material. Therefore, the siliconized graphite material is widely applied to the fields of bearing bushes, thermal structural materials, thermocouple protection pipes and the like, and is suitable for the bushes of mechanical seal friction pairs and thrust bearings used in canned pumps, centrifugal pumps, compressors and the like in harsh environments. The current method for preparing the siliconized graphite composite material mainly comprises the following steps: chemical vapor infiltration, chemical vapor reaction, precursor impregnation and pyrolysis, reaction infiltration, and the like. Compared with the former three methods, the method for preparing the siliconized graphite ceramic by the reaction infiltration method has the advantages of simple molding, low cost, low sintering temperature, compact primary sintering, high sintering speed, near net size and the like. The silicon-carbon contact angle is small at high temperature, the reaction is very intense, and the carbon source in the common porous blank body is easy to react with liquid silicon to generate silicon carbide, so that the content of carbon phase in the siliconized graphite material is low. Therefore, how to prepare the siliconized graphite material with high carbon content by a reaction infiltration method so as to exert excellent self-lubricating performance is a key preparation technology.
In the Chinese patent (the method for preparing the siliconized graphite by modifying a carbon source and performing reaction infiltration and the siliconized graphite, 202111249322.6), the siliconized graphite material is prepared by mixing graphite particles with resin, solidifying, carbonizing and crushing to obtain composite particles and performing the reaction infiltration.
In the chinese patent (graphite modification method and prepared modified graphite, 200610119250.2), graphite and high molecular polymer are fully mixed, and the graphite material with high molecular polymer coated on the surface is obtained by sectional heating and curing, but in the present application, the high molecular polymer coated on the surface of graphite is used for solving the problems of peeling and pulverization of graphite layer caused by co-intercalation of lithium ions and electrolyte, thereby reducing the capacity attenuation caused by the peeling and pulverization, prolonging the cycle life of the electrode, and is not used for obtaining the siliconized graphite material with high carbon content.
The Chinese patent (a method for preparing C/SiC composite material by low-cost fused silica infiltration method, 201310290077.2) refers to a sintered body which is impregnated with phenolic resin for one time of siliconizing and then subjected to secondary siliconizing after carbonization, but the phenolic resin is used as a carbon source for reacting with silicon to generate silicon carbide after carbonization so as to improve the compactness of the carbon/silicon carbide material and reduce the air hole content and the free silicon content, and the siliconized graphite with high carbon content cannot be obtained.
Therefore, how to provide a method for preparing graphite silicide with high carbon phase content is a technical problem to be solved.
Disclosure of Invention
In order to solve the defects in the prior art, the application aims to provide a method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation, which is characterized in that a compact nano carbon black layer is formed on the surface of graphite particles, and a compact and thinner silicon carbide layer is formed by preferentially reacting with silicon in reaction infiltration to prevent further reaction of carbon silicon, so that coated graphite particles are effectively protected, and the preparation of high-carbon siliconized graphite is realized.
The application is realized by the following technical scheme.
According to one aspect of the application, there is provided a method for preparing high carbon siliconized graphite based on nano carbon black and resin impregnation, comprising the steps of:
(1) Mechanically mixing spherical graphite and nano carbon black, and pressing and forming uniformly mixed powder to obtain a blank;
(2) Immersing the blank body in phenolic resin, pressurizing and immersing, cleaning the surface and drying;
(3) Carbonizing the impregnated and dried blank at high temperature in a protective atmosphere to obtain porous carbon;
(4) And placing the porous carbon on a crucible with the bottom fully paved with silicon particles, adding a layer of silicon particles on the upper surface of the porous carbon, completely embedding the porous carbon by the silicon particles, performing reaction infiltration at a vacuum high temperature, sintering, preserving heat, and cooling to obtain the siliconized graphite material.
As a preferable scheme, the spherical graphite and the nano carbon black are mechanically mixed according to the mass ratio of 80-95 percent and 5-20 percent.
Preferably, the pressure of powder compression molding is 30-40 MPa, and the pressure maintaining time is 20-40 s.
As a preferable scheme, the blank is immersed in the phenolic resin, the pressurizing and impregnating pressure is 0.6-0.8 MPa, and the pressure maintaining time is 2-6 h.
Preferably, the protective atmosphere is nitrogen or argon.
As a preferable scheme, the heating rate during carbonization is 1 ℃/min, the carbonization temperature is 800-1200 ℃, the heat preservation time is 2-4 h,
as a preferable scheme, the reaction infiltration sintering temperature is 1450-1650 ℃ and the heat preservation time is 10-60 min.
Preferably, the reaction infiltration vacuum degree is 10Pa or less.
According to another aspect of the application, there is provided a method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation.
Due to the adoption of the technical scheme, the application has the following beneficial effects:
by controlling the mechanical mixing proportion of the nano carbon black particles and the spherical graphite and the pressure of powder compression molding, a layer of compact nano carbon black coating layer with high purity, small particle size and large specific surface area is formed on the surface of the graphite particles; the molded green body is immersed in resin, and the particles can be well bonded by immersing in the resin under high pressure, so that the green body becomes very compact through high-temperature carbonization. The compact nano carbon black layer on the surface of the graphite particles preferentially reacts with silicon in reaction infiltration to form a compact thinner silicon carbide layer to prevent further reaction of carbon and silicon, so that the coated graphite particles are effectively protected, the carbon phase content in the siliconized graphite is improved, and the self-lubricating performance of the material is further improved.
The carbon content of the siliconized graphite composite material prepared by the preparation method can reach 39.25vol.% and the density is 2.6-2.8 g.cm -3 The open porosity is less than 1%.
In addition, the graphite silicide material prepared by the application is compact, has high carbon phase content, simple preparation process, low energy consumption and short production period, and has wide application prospect in the fields of chemical industry, metallurgy, environmental protection, national defense, aerospace, nuclear energy and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and constitute a part of this specification, are incorporated in and constitute a part of this specification and do not limit the application in any way, and in which:
FIG. 1 is an SEM image of siliconized graphite prepared in example 3 of the application;
fig. 2 is an SEM image of graphite silicide prepared in comparative example 1 of the present application.
Detailed Description
The present application will now be described in detail with reference to the drawings and the specific embodiments thereof, wherein the exemplary embodiments and descriptions of the present application are provided for illustration of the application and are not intended to be limiting.
The embodiment of the application provides a method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation, which comprises the following steps:
step 1, mechanically mixing 80-95% of spherical graphite and 5-20% of nano carbon black according to the mass ratio, putting the uniformly mixed powder into a die, and adopting a hydraulic press to press and shape, wherein the pressure of the press and shape is 30-40 MPa, and the pressure maintaining time is 20-40 s.
In the step 1, the nano carbon black has high purity and small particle size, and after mechanical mixing, the nano carbon black is uniformly adsorbed on the surface of the spherical graphite to form a continuous and relatively compact nano carbon black layer. The nano carbon black layer can react with silicon preferentially in the reaction infiltration process, so that the coated graphite particles are effectively protected. By further optimizing the proportion of the spherical graphite to the nano carbon black, the attaching effect of the nano carbon black on the surface of the spherical graphite is improved, and the protection effect is improved.
In the step 1, a blank body with certain strength and porosity can be manufactured by compression molding under certain pressure, so that the smooth proceeding of reaction infiltration is ensured. By optimizing the pressure and the pressure maintaining time of the compression molding, a better infiltration effect can be achieved, and the successful infiltration of liquid silicon is ensured.
Step 2, adopting phenolic resin as an impregnant, placing the blank in an autoclave with the temperature of 25-35 ℃, pressurizing to 0.6-0.8 MPa, sucking the phenolic resin into the autoclave by utilizing negative pressure, maintaining the pressure, immersing for 2-6 h, releasing pressure, taking out the blank, cleaning the surface, and drying to obtain an immersed and dried blank;
step 3, the impregnated and dried blank is placed in a tube furnace to be carbonized under the condition that the protective atmosphere is nitrogen or argon, the heating rate during carbonization is 1 ℃/min, the carbonization temperature is 800-1200 ℃, and the heat preservation time is 2-4 hours, so that porous carbon is obtained;
in the steps 2 and 3, phenolic resin is adopted as an impregnant, and the resin is immersed under high pressure to well adhere particles, so that the green body becomes very compact after high-temperature carbonization. The resin impregnation can be made more complete by optimizing the pressure and dwell time of the pressurization in the autoclave.
And 4, placing the porous carbon on a crucible with the bottom fully paved with silicon particles, adding a layer of silicon particles on the upper surface of the porous carbon to enable the porous carbon to be fully embedded by the silicon particles, placing the crucible into a vacuum resistance furnace for reaction infiltration, wherein the vacuum degree of the reaction infiltration is below 10Pa, the sintering temperature of the reaction infiltration is 1450-1650 ℃, the heat preservation time is 10-60 min, and cooling to room temperature along with the furnace to obtain the siliconized graphite material.
In the step 4, the porous carbon is embedded by the silicon particles, so that the infiltration of liquid silicon is facilitated, the reaction infiltration vacuum degree is controlled below 10Pa, the infiltration of the liquid silicon can be effectively promoted by optimizing the reaction infiltration sintering temperature, and the high-density graphite silicide is prepared.
The preparation of the siliconized graphite by reaction infiltration has the advantages of simple process, low sintering temperature, high sintering speed and short preparation period, and can effectively reduce the preparation cost.
In the method, spherical graphite is mixed with nano carbon black, and as the nano carbon black particles have high purity, small particle size and large specific surface area, the spherical graphite can be well coated, and a compact nano carbon black layer is formed on the particle surface. Because the silicon-carbon reaction is very intense, the spherical graphite without the nano carbon black is difficult to be reserved in the reaction infiltration, the carbon phase content is low, and the carbon source with the nano carbon black is more reserved after the reaction infiltration.
The molded green body is immersed in resin, and the particles can be well bonded by immersing the green body in the resin under high pressure, so that the green body becomes very compact after high-temperature carbonization. The compact nano carbon black layer on the surface of the graphite particles preferentially reacts with silicon in reaction infiltration to form a compact and thinner silicon carbide layer to prevent further reaction of carbon and silicon, so that the coated graphite particles are effectively protected, and the preparation of the siliconized graphite with high carbon phase content is realized.
The carbon content of the obtained siliconized graphite is 32.30-39.25 vol.% and the density is 2.6-2.8 g.cm -3 The open porosity is less than 1%.
The application is further illustrated by the following specific examples.
Example 1:
1) Mechanically mixing spherical graphite and nano carbon black according to the weight ratio of 80:20, putting the mixed powder into a die, and adopting a hydraulic press to press and shape, wherein the pressure of the press and shape is 30MPa, and the pressure maintaining time is 30s;
2) Placing the green body in an autoclave with the temperature of 25 ℃ by adopting phenolic resin as an impregnant, pressurizing to 0.7MPa, sucking the phenolic resin into the autoclave by utilizing negative pressure, maintaining the pressure and immersing for 5 hours, releasing pressure, taking out the green body, cleaning the surface, and drying to obtain an immersed and dried green body;
3) Placing the impregnated and dried blank into an atmosphere tube furnace, and carbonizing at 800 ℃ for 3 hours under the protection of nitrogen;
4) Placing porous carbon on a crucible with silicon particles paved at the bottom, adding a layer of silicon particles on the upper surface of the porous carbon to enable the porous carbon to be completely embedded by the silicon particles, placing the crucible into a vacuum resistance furnace for reaction infiltration, wherein the vacuum degree of the reaction infiltration is below 10Pa, the sintering temperature of the reaction infiltration is 1500 ℃, the heat preservation time is 15min, the size of the silicon particles is 0.5-4 mm, and the weight of the silicon particles is 2 times of the total weight of the green compact.
The siliconized graphite material prepared by this process had a carbon content of 34.36vol.% and a density of 2.75g cm -3 The open porosity is less than 1%.
Example 2:
1) Mechanically mixing spherical graphite and nano carbon black according to the weight ratio of 85:15, putting the mixed powder into a die, and adopting a hydraulic press to press and shape, wherein the pressure of the press and shape is 35MPa, and the pressure maintaining time is 40s;
2) Placing the green body in an autoclave with the temperature of 25 ℃ by adopting phenolic resin as an impregnant, pressurizing to 0.8MPa, sucking the phenolic resin into the autoclave by utilizing negative pressure, maintaining the pressure and immersing for 4 hours, releasing pressure, taking out the green body, cleaning the surface, and drying to obtain an immersed and dried green body;
3) Placing the impregnated and dried blank into an atmosphere tube furnace, and carbonizing at 1100 ℃ for 4 hours under the protection of nitrogen;
4) Placing porous carbon on a crucible with silicon particles fully paved at the bottom, adding a layer of silicon particles on the upper surface of the porous carbon to enable the porous carbon to be fully embedded by the silicon particles, placing the crucible into a vacuum resistance furnace for reaction infiltration, wherein the vacuum degree of the reaction infiltration is below 10Pa, the sintering temperature of the reaction infiltration is 1550 ℃, the heat preservation time is 10min, the size of the silicon particles is 0.5-4 mm, and the weight of the silicon particles is 2 times of the total weight of the green compact.
The siliconized graphite material prepared by this process had a carbon content of 36.45vol.% and a density of 2.73g cm -3 The open porosity is less than 1%.
Example 3:
1) Mechanically mixing spherical graphite and nano carbon black according to the weight ratio of 90:10, putting the mixed powder into a die, and adopting a hydraulic press to press and shape, wherein the pressure of the press and shape is 40MPa, and the pressure maintaining time is 30s;
2) Placing the green body in an autoclave with the temperature of 25 ℃ by adopting phenolic resin as an impregnant, pressurizing to 0.8MPa, sucking the phenolic resin into the autoclave by utilizing negative pressure, maintaining the pressure and immersing for 5 hours, releasing pressure, taking out the green body, cleaning the surface, and drying to obtain an immersed and dried green body;
3) Placing the impregnated and dried blank into an atmosphere tube furnace, and carbonizing at 1000 ℃ for 3 hours under the protection of argon;
4) Placing porous carbon on a crucible with silicon particles fully paved at the bottom, adding a layer of silicon particles on the upper surface of the porous carbon to enable the porous carbon to be fully embedded by the silicon particles, placing the crucible into a vacuum resistance furnace for reaction infiltration, wherein the vacuum degree of the reaction infiltration is below 10Pa, the sintering temperature of the reaction infiltration is 1450 ℃, the heat preservation time is 35min, the size of the silicon particles is 0.5-4 mm, and the weight of the silicon particles is 2 times of the total weight of the green compact.
The siliconized graphite material prepared by this process had a carbon content of 39.25vol.% and a density of 2.68g cm -3 The open porosity is less than 1%.
The resulting product was characterized using a Field Emission Scanning Electron Microscope (FESEM). FIG. 1 is a back-scattered photograph of the product, and it is clear that a large amount of black carbon phase is preserved, no obvious pores are found in the sample, and the sample is very dense.
Example 4:
1) Mechanically mixing spherical graphite and nano carbon black according to the weight ratio of 95:5, putting the mixed powder into a die, and adopting a hydraulic press to press and form, wherein the pressure of the press and the forming is 40MPa, and the pressure maintaining time is 20s;
2) Placing the green body in an autoclave with the temperature of 35 ℃ by adopting phenolic resin as an impregnant, pressurizing to 0.6MPa, sucking the phenolic resin into the autoclave by utilizing negative pressure, maintaining the pressure and immersing for 2 hours, releasing pressure, taking out the green body, cleaning the surface, and drying to obtain an immersed and dried green body;
3) Placing the impregnated and dried blank into an atmosphere tube furnace, and carbonizing at 1200 ℃ for 2 hours under the protection of argon;
4) Placing porous carbon on a crucible with silicon particles fully paved at the bottom, adding a layer of silicon particles on the upper surface of the porous carbon to enable the porous carbon to be fully embedded by the silicon particles, placing the crucible into a vacuum resistance furnace for reaction infiltration, wherein the vacuum degree of the reaction infiltration is below 10Pa, the sintering temperature of the reaction infiltration is 1650 ℃, the heat preservation time is 40min, the size of the silicon particles is 0.5-4 mm, and the weight of the silicon particles is 2 times of the total weight of the green compact.
The siliconized graphite material prepared by this process had a carbon content of 32.30vol.% and a density of 2.76g cm -3 The open porosity is less than 1%.
Comparative example 1
Spherical graphite is directly used as a carbon source for reaction, no nano carbon black is added, other process parameters are the same as in example 1, and the carbon content of the finally obtained siliconized graphite material is 24.10vol.%.
The resulting product was characterized using a Field Emission Scanning Electron Microscope (FESEM). Fig. 2 is a back-scattered photograph of the product, and it is clearly seen that the black carbon phase remains not much. In comparison to fig. 1, it can be seen that the siliconized graphite composite material of comparative example 1 has significantly less carbon phase content than example 3.
As can be seen from the comparison of the above examples 1 to 4 with comparative example 1, the siliconized graphite material prepared by the present application is very dense with a density of 2.6 to 2.8g cm -3 The open porosity is less than 1%. The carbon content of the siliconized graphite material was not less than 32.30vol.%, the carbon content of the siliconized graphite material was significantly increased over that of comparative example 1, wherein example 1 was increased by 42.57% over comparative example 1; example 2 increased 51.24% compared to comparative example 1; example 3 increased 62.86% compared to comparative example 1; example 4 increased by 34.02% compared to comparative example 1. The siliconized graphite material prepared by the application is a graphite material with high carbon content and excellent performance, and can be widely applied to chemical industryThe fields of metallurgy, environmental protection, national defense, aerospace, nuclear energy and the like.
The application is not limited to the above embodiments, and based on the technical solution disclosed in the application, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the application.
Claims (10)
1. The method for preparing the high-carbon siliconized graphite based on nano carbon black and resin impregnation is characterized by comprising the following steps of:
(1) Mechanically mixing spherical graphite and nano carbon black, and pressing and forming uniformly mixed powder to obtain a blank;
(2) Immersing the blank body in phenolic resin, pressurizing and immersing, cleaning the surface and drying;
(3) Carbonizing the impregnated and dried blank at high temperature in a protective atmosphere to obtain porous carbon;
(4) And placing the porous carbon on a crucible with the bottom fully paved with silicon particles, adding a layer of silicon particles on the upper surface of the porous carbon, completely embedding the porous carbon by the silicon particles, performing reaction infiltration at a vacuum high temperature, sintering, preserving heat, and cooling to obtain the siliconized graphite material.
2. The method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation according to claim 1, wherein the spherical graphite and the nano carbon black are mechanically mixed according to the mass ratio of 80-95% to 5-20%.
3. The method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation according to claim 1, wherein the pressure of powder compression molding is 30-40 MPa and the dwell time is 20-40 s.
4. The method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation according to claim 1, wherein the blank is immersed in the phenolic resin under the pressure of 0.6-0.8 MPa and the dwell time of 2-6 h.
5. The method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation according to claim 1, wherein the protective atmosphere is nitrogen or argon.
6. The method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation according to claim 1, wherein the heating rate during carbonization is 1 ℃/min, the carbonization temperature is 800-1200 ℃, and the heat preservation time is 2-4 h.
7. The method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation according to claim 1, wherein the reaction infiltration sintering temperature is 1450-1650 ℃ and the heat preservation time is 10-60 min.
8. The method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation according to claim 1, wherein the vacuum degree of reaction infiltration is 10Pa or less.
9. A process for preparing high carbon siliconized graphite based on nano carbon black and resin impregnation prepared by the process of any one of claims 1-8.
10. The method for preparing high-carbon siliconized graphite based on nano carbon black and resin impregnation according to claim 9, wherein the carbon content of the siliconized graphite is 32.30-39.25 vol.% and the density is 2.6-2.8 g-cm -3 The open porosity is less than 1%.
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