CN107892582B - Preparation method of carbon fiber reinforced nanoporous carbon heat-insulation composite material - Google Patents
Preparation method of carbon fiber reinforced nanoporous carbon heat-insulation composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon fiber reinforced nano-pore carbon heat-insulation composite material, and aims to provide a preparation method of a carbon fiber reinforced nano-pore carbon heat-insulation composite material which is short in period, safe and reliable and small in volume shrinkage in a carbonization process. The technical scheme is that phenols and aldehydes are used as reaction monomers, methanol is used as a solvent, hexamethylenetetramine is used as a catalyst, zinc chloride is used as a molten salt to play a role of a pore-forming agent and a supporting role, carbon fibers are used as a reinforcement, firstly, raw materials are mixed to prepare phenolic sol, the phenolic sol is used for impregnating a carbon fiber prefabricated part, the sol becomes gel, the gel is aged at room temperature and then carbonized and cracked, and finally, the carbon fiber reinforced nano-pore carbon heat insulation composite material is obtained through water washing, desalting and normal pressure drying. The method has the advantages of short period, safety, reliability, small volume shrinkage in the carbonization process, small density of the material prepared by the method, temperature resistance of 2000 ℃, no cracking phenomenon and contribution to preparing special-shaped components.
Description
Technical Field
The invention relates to a preparation method of a novel heat-insulation composite material, in particular to a preparation method of a carbon fiber reinforced nano-pore carbon heat-insulation composite material resistant to ultra-high temperature (under inert or anaerobic conditions).
Background
The novel high-speed aircraft (generally over 5 times of sound velocity) can generate pneumatic heating problem during high-speed flight, the pneumatic heating on the surface of the aircraft body is extremely serious, and the temperature of a local ultrahigh-temperature part even reaches 2000 ℃. In order to effectively prevent the heat on the surface or the ultrahigh-temperature part of the fuselage from being transmitted to the interior of the fuselage, a high-performance heat-insulating material with ultrahigh temperature resistance, light weight and low heat conductivity is urgently needed by a heat protection system. The nano-porous carbon material has intrinsic characteristics of carbon material, and can resist ultra-high temperature (more than 2000 ℃ under inert or vacuum atmosphere) [ Mater Lett, 2011, 65: 3454-And because of the unique nano-pore structure and nano-particles, the gas phase heat conduction and the solid phase heat conduction are effectively reduced, the carbon nano-particles have good infrared radiation absorption function, the high-temperature heat conductivity is low, and the carbon nano-particles are an ultrahigh-temperature-resistant high-performance heat-insulating material which has great potential and becomes the requirement of a high-speed aircraft heat protection system; common preparation methods of the nanoporous carbon materials are roughly divided into a template carbonization method and a sol-gel method; the template carbonization method faces two major problems: firstly, the technology of uniformly filling an organic carbon source into a nano-pore of an inorganic template is still not mature; and secondly, complicated template removal procedures are required, silica compounds are mostly adopted for the inorganic template, and a hydrofluoric acid or strong alkali corrosion method is mainly adopted for removing the template, so that the environment is polluted, and the method is also a key problem for determining the template carbonization law to produce the multilevel porous carbon material in a modeling manner. The sol-gel process for producing nanoporous carbon materials is generally combined with a supercritical drying process, wherein supercritical drying consumes a large amount of liquid CO2Or ethanol, increases the production cost, improves the risk of the process, and has small yield [ rare metal materials and engineering, 2009,38(2):1034-1036 ]. The pure nano-pore carbon aerogel has low strength and large brittleness, limits the application of the pure nano-pore carbon aerogel in the field of ultra-high temperature resistance, and has great potential to become a novel high-efficiency heat insulation material of a high-speed aircraft if the pure nano-pore carbon aerogel can be made into a composite material by fiber reinforcement to improve the mechanical property of the composite material. However, the traditional sol-gel method for preparing the nano-porous carbon material has long preparation period; a large amount of volatile and flammable organic solvents are used in the solvent replacement and supercritical drying processes, so that the production cost and potential safety hazards are increased [ J.Sol-Gel Sci.Technol., 2008, 45: 9-15; AIAA, 2012, 5945:1-13 ], and the industrial production is limited; the preparation and performance research of carbon aerogel and a heat insulation composite material thereof, doctor academic papers of national defense science and technology university, 2012.06, the volume shrinkage rate is up to more than 50%, and when the composite material is prepared, the shrinkage of the reinforcement fiber is small, the shrinkage of the reinforcement and the matrix is mismatched, so that the cracking of the composite material is caused. Literature [ Zhi-Long Yu, Guan-Cheng Li, NinaFechler, NingYang, Zhi-Yuan Ma, XinWang, Markus Antonietti, and Shu-Hong Yulymerizationunder Hypersaline Conditions:A Robust Routeto Phenolic Polymer-Derived CarbonAerogels[J]Angew. chem. int.Ed.2016,55, 1-6. the bulk nanoporous carbon material is prepared by using phenol and formaldehyde as reaction monomers by a molten salt method, and the process has the defects that the thermal reaction of a solvent is needed, and the product expands several times, which is not beneficial to preparing the composite material. Patent document CN201510004277.6 discloses a method for preparing porous carbon, which comprises reacting polycarboxylic acid and diamine or acetic anhydride and diamine as reactants in a metal salt solution to form a three-dimensional network prepolymer, and then performing pyrolysis to obtain porous carbon, but the porous carbon has more micron-sized macropores and poor heat insulation performance; patent document CN201310748841.6 discloses a method for preparing carbon aerogel, in which water-soluble saccharide compounds and water-soluble polymers are dissolved in water in a closed container, and under the catalysis of acid or alkali, a cross-linked network structure is formed through high-temperature hydrothermal reaction, and then the nano-pore carbon aerogel is obtained through supercritical drying and carbonization, but the use of supercritical drying is not avoided in the process; in the above patent documents, different raw materials and processes are selected to shorten the period for preparing the porous carbon material to a certain extent and avoid solvent replacement, but the limitations of the conventional process methods cannot be broken through, and the problems existing in the conventional process methods cannot be solved. Therefore, a novel method with short preparation period, safety and reliability is needed to be developed for preparing the carbon fiber reinforced nanopore carbon composite material with excellent heat insulation performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a carbon fiber reinforced nano-pore carbon heat-insulation composite material which has the highest temperature resistance of 2000 ℃, short preparation period, safety, reliability and small volume shrinkage in the carbonization process.
The problems of long preparation period, large potential safety hazard, large volume shrinkage in the carbonization process and the like in the traditional technology are solved, and particularly the problems of high risk, high cost and difficulty in large-scale production in the process are caused by using supercritical drying; the invention provides a new method, which is characterized in that zinc chloride is added into phenolic sol to inhibit the shrinkage of a nano-pore carbon material, so as to prepare a carbon fiber reinforced nano-pore carbon heat-insulation composite material; phenols and aldehydes are used as reaction monomers, alcohols are used as solvents, hexamethylenetetramine is used as a catalyst, zinc chloride is used as molten salt to play a role of a pore-forming agent and a supporting role, carbon fibers are used as reinforcements, firstly, raw materials are mixed to prepare phenolic sol, the phenolic sol is used for impregnating a carbon fiber prefabricated part, the sol becomes gel, and then the gel is aged at room temperature, so that the carbon fiber reinforced nano-pore carbon heat-insulating composite material can be directly carbonized and cracked. The matrix nano-porous carbon material generated by the supporting action of the salt does not have larger volume shrinkage, is well matched with the carbon fiber reinforcement, and does not crack the composite material.
The ultrahigh temperature resistant carbon fiber reinforced nano-pore carbon heat insulation composite material consists of a carbon fiber prefabricated part and a nano-pore carbon material substrate, wherein the carbon fiber refers to inorganic carbon fiber capable of resisting temperature of more than 2000 ℃, the carbon fiber prefabricated part is formed by chopping carbon fiber (3 ~ 10 cm) and then laying or weaving fiber bundles, and the apparent density of the carbon fiber prefabricated part is 0.06 ~ 0.20.20 g/cm3The nano-pore carbon material matrix is prepared by taking phenolic resin generated by phenols and aldehydes as a carbon precursor, zinc chloride as a pore-forming agent and alcohol as a solvent through heating carbonization, washing desalting with water and drying under normal pressure, the phenolic sol is used for impregnating a carbon fiber prefabricated member, and the ultrahigh-temperature-resistant carbon fiber reinforced nano-pore carbon heat-insulation composite material is obtained through gel aging, heating carbonization, washing desalting with water and drying under normal pressure, wherein the density is 0.16 ~ 0.57.57 g/cm3The temperature can reach 2000 ℃.
The preparation method comprises the following steps:
the first step, preparing carbon fiber prefabricated member, the method is:
the apparent density is in the range of 0.06 ~ 0.20.20 g/cm according to the required volume size of the carbon fiber preform and the apparent density of the carbon fiber preform3Calculating the mass of the required carbon fiber by adopting mass = density multiplied by volume, laying or weaving the weighed carbon fiber (required to be chopped (3 ~ 10 cm)) by using a mould, clamping and fixing the carbon fiber, and enabling the arrangement direction of the carbon fiber to be vertical to heat insulation so as to ensure that the carbon fiber is not damagedThe direction of heat flow in use, a carbon fiber preform is obtained.
Secondly, preparing a phenolic sol/salt mixture, wherein the method comprises the following steps:
using phenols and aldehydes as raw materials, alcohols as solvent, zinc chloride (ZnCl)2) As a molten salt, hexamethylenetetramine (C)6H12N4) Weighing the raw materials and phenols according to a certain molar ratio, wherein the molar ratio of the aldehydes to the phenols is 2: 1, the molar ratio of the alcohols to the phenols is 2 ~ 12: 1, the molar ratio of the zinc chloride to the phenols is 0.5 ~ 5:1, and the molar ratio of the hexamethylenetetramine to the phenols is 0.0075 ~ 0.015.015: 1, mixing and stirring to prepare a phenolic sol/salt mixture;
the above-mentioned phenols mean phenol (C)6H5OH), resorcinol (C)6H6O2) And hydroquinone (C)6H6O2) Any of the above;
the aldehyde is furfural (C)5H4O2) And formaldehyde (HCHO), and the like;
the alcohol refers to methanol (CH)3OH), ethanol (C)2H5OH) and isopropanol (C)3H8O) and the like or a mixed alcohol of any of them;
thirdly, preparing a carbon fiber reinforced phenolic gel/salt complex, which comprises the following steps:
putting the carbon fiber prefabricated member into a vacuum impregnation tank, and performing sol impregnation by vacuumizing (-0.1 Mpa) and then adding normal pressure (1 atmosphere), namely firstly, infiltrating phenolic sol into the carbon fiber prefabricated member by adopting a vacuum impregnation mode, opening a valve of the vacuum impregnation tank after the phenolic sol infiltrates into the carbon fiber prefabricated member to change the pressure in the vacuum impregnation tank to the normal pressure, and aging for 3 ~ 48 hours under the normal pressure to change the phenolic sol in the carbon fiber prefabricated member into phenolic gel, thereby obtaining the carbon fiber reinforced phenolic gel/salt composite.
Fourthly, carbonization and cracking, the method comprises the following steps:
putting the carbon fiber reinforced phenolic gel/salt composite into a tubular furnace, vacuumizing, then filling argon or nitrogen into the tubular furnace, replacing a small amount of air remained in the tubular furnace for 1 ~ 5 times, heating to 650 ~ 2000 ℃ at the heating rate of 1.0 ~ 5.0.0 ℃/min, preserving the heat for 1 ~ 5 hours at the temperature, naturally cooling, and filling argon or nitrogen at the flow rate of 20 ~ 200ml/min in the whole process to obtain the carbon fiber reinforced nanopore carbon/salt composite.
Fifthly, washing with water to remove salt, wherein the method comprises the following steps:
soaking the carbon fiber reinforced nanopore carbon/salt complex in dilute hydrochloric acid with the mass concentration of 10% for 2 ~ 6 hours, removing a small amount of zinc oxide (ZnO) in the carbon fiber reinforced nanopore carbon/salt complex, soaking in water again, changing water every 3 ~ 12 hours, and circularly replacing the water for 4 ~ 8 times to remove zinc chloride (ZnCl) in the water2) To obtain a carbon fiber reinforced nanopore carbon/water complex;
sixthly, drying under normal pressure, which comprises the following steps:
and (3) placing the carbon fiber reinforced nanoporous carbon/water composite in an oven or a muffle furnace, heating to 100 ~ 200 ℃, preserving heat for 1 ~ 24 hours, and cooling to obtain the carbon fiber reinforced nanoporous carbon heat-insulating composite.
The invention can achieve the following beneficial effects
The invention is based on a sol-gel technology and a molten salt method, takes phenolic resin generated by the reaction of phenols and aldehydes as a carbon precursor, alcohols as a solvent, hexamethylenetetramine as a catalyst and zinc chloride as a pore-forming agent, and the phenolic resin, the alcohols, the hexamethylenetetramine and the zinc chloride are firstly mixed to prepare sol, then the sol is mixed with a carbon fiber prefabricated part, and the carbon fiber reinforced nano-pore carbon heat-insulating composite material is obtained after gel aging, carbonization and cracking, water washing desalting and normal pressure drying treatment.
Therefore, the invention has the following advantages compared with the prior art:
(1) the invention has simple preparation process and short period, and the carbon fiber is used for preparing the fiber prefabricated member, wherein the apparent density range of the carbon fiber prefabricated member is 0.06 ~ 0.20.20 g/cm3And clamping and fixing the weighed carbon fibers by using a mold, and enabling the arrangement direction of the carbon fibers to be perpendicular to the heat flow direction in the heat insulation use process to obtain the carbon fiber prefabricated member. With phenols and aldehydesThe method comprises the following steps of preparing a sol by mixing reaction monomers, alcohols as a solvent, hexamethylenetetramine as a catalyst and zinc chloride as a pore-forming agent, impregnating a carbon fiber prefabricated member under vacuum and normal pressure, and performing gel aging, carbonization cracking, water washing desalting and normal pressure drying to obtain the carbon fiber reinforced nano-pore carbon heat-insulation composite material, wherein the main time-consuming steps of the fourth carbonization cracking step, the fifth washing desalting step and the sixth drying step are carried out for one day, the whole process is simple, the total time is about 3 ~ 4 days, compared with the traditional sol-gel method which consumes more than 20 days, the production period is short, compared with the template carbonization method, a template is not used, a complicated template removing procedure is not used, although zinc chloride is used as the pore-forming agent, the zinc chloride is extremely soluble in water, the zinc chloride in the product can be removed by soaking in water, and the zinc chloride can be recycled by evaporating water, so that the environment is not polluted.
(2) The invention has small potential safety hazard and low cost. The method adopts cheap phenols and aldehydes as reaction monomers, raw materials are easy to obtain, and the whole process avoids solvent replacement and supercritical drying which are commonly adopted in the traditional process, wherein the solvent replacement needs to consume a large amount of organic solvent, and the supercritical drying needs high-temperature and high-pressure equipment (such as ethanol, the critical temperature is 243 ℃, and the critical pressure is 6.30 MPa), so that the method has high danger, small yield and difficulty in large-scale production; in the sixth step, the water in the product can be removed only by normal pressure drying, so that the energy consumption is low, the production cost is greatly reduced, the potential safety hazard is small, and the large-scale production is easy. Furthermore, the process compares the documents [ Zhi-Long Yu, Guan-Cheng Li, NinaFechler, NingYang, Zhi-Yuan Ma, XinWang, Markus Antonietti, and Shu-Hong Yu.polymerization under Conditions of Hypersaline Conditions: A Robust Routto polymeric Polymer-Derived Carbon Aerogels [ J ]. Angew.Chem.int.Ed.2016,55,1-6 in Shilong, Li crown, Nina Fechler, Yanning, Majorang, Wanxin, Markus Antonietti, and Shushu Macro ] polymerization under high salt Conditions: a simple preparation method [ J ] of carbon aerogel derived from phenolic polymer, German applied chemical society, 2016,55,1-6 ] is adopted to prepare the nanoporous carbon material, no solvothermal reaction is needed, and the product does not expand.
(3) By usingThe carbon fiber reinforced nano-pore carbon heat-insulation composite material prepared by the method has low thermal conductivity and high temperature resistance, zinc chloride plays a role of a pore-forming agent in the fourth step of carbonization and cracking process, so that more nano-pore structures are formed in a matrix carbon material, and the nano-pore structures can still be maintained after water washing, desalting and normal pressure drying because the carbon skeleton has certain strength, the pore diameters of the nano-pore structures are mainly distributed between 0.6 ~ 25nm, and the specific surface area is as high as 1300m2The thermal conductivity of the prepared carbon fiber reinforced nano-pore carbon heat insulation composite material at 2000 ℃ is 0.122 ~ 0.478W/mK, the prepared carbon fiber reinforced nano-pore carbon heat insulation composite material has the inherent intrinsic characteristic of the carbon material (can resist the temperature of 2000 ℃ in an anaerobic environment), and the nano-pore structure can not collapse or shrink obviously at 2000 ℃ in the anaerobic environment.
(4) The carbon fiber reinforced nano-pore carbon heat-insulating composite material prepared by the method has no surface cracking, and is more beneficial to preparing special-shaped components. In the fourth step of carbonization and cracking, the phenolic resin generated by the reaction of phenols and aldehydes substances can not shrink in volume due to the support of salt, and has good matching property and consistency with carbon fiber, so that the surface of the carbon fiber reinforced nano-pore carbon heat-insulation composite material can not crack; solves the problem of volume shrinkage of more than 50 percent generated in the process of carbonizing the organogel in the traditional method, and is more beneficial to preparing composite materials and special-shaped components.
Drawings
FIG. 1 is a general flow diagram of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
(1) preparing a carbon fiber prefabricated part: the apparent density of the carbon fiber preform designed in example 1 was 0.10g/cm, depending on the volume size of the carbon fiber preform and the apparent density of the carbon fiber preform3Using a mold to weigh the weighed carbonClamping and fixing the fibers, and enabling the arrangement direction of the carbon fibers to be perpendicular to the heat flow direction during heat insulation use to obtain a carbon fiber prefabricated part;
(2) preparation of a phenolic sol/salt blend: resorcinol and furfural are used as reaction monomers, methanol is used as a solvent, and zinc chloride is used as a molten salt as a pore-foaming agent, and the method comprises the following specific steps: firstly, zinc chloride is placed in a beaker, methanol and furfural are sequentially added, stirring and mixing are carried out for 25 minutes, then resorcinol and hexamethylenetetramine are added, stirring is carried out for 20 minutes, and resorcinol is fully dissolved to obtain a phenolic sol/salt mixture; wherein, the mass ratio of furfural: methanol: zinc chloride: hexamethylenetetramine: the molar ratio of resorcinol is 2: 12: 5: 0.015: 1;
(3) preparing a carbon fiber reinforced phenolic gel/salt complex: placing the prepared carbon fiber prefabricated member in a vacuum impregnation tank, and performing sol impregnation by adopting a mode of vacuumizing and then adding normal pressure: firstly, phenolic sol is infiltrated into a carbon fiber prefabricated member in a vacuum impregnation mode, after the phenolic sol is infiltrated into the carbon fiber prefabricated member, a valve is opened to change the pressure in an impregnation tank to normal pressure, and the phenolic sol is aged for 24 hours under the normal pressure to change the sol in the carbon fiber prefabricated member into gel, so that a carbon fiber reinforced phenolic gel/salt composite is obtained;
(4) heating and carbonizing: putting the carbon fiber reinforced phenolic gel/salt composite into a tubular furnace, vacuumizing, filling argon, replacing air in the tubular furnace for 2 times, heating to 650 ℃ at the speed of 2 ℃/min, preserving the temperature at 650 ℃ for 2 hours, naturally cooling, and filling argon at the ventilation rate of 50mL/min in the whole process; obtaining a carbon fiber reinforced nanopore carbon/salt complex;
(5) and (3) water washing desalting: soaking the carbon fiber reinforced nano-pore carbon/salt complex in dilute hydrochloric acid with the mass concentration of 10% for 4 hours to remove a small amount of zinc oxide (ZnO) in the carbon fiber reinforced nano-pore carbon/salt complex, then soaking the carbon fiber reinforced nano-pore carbon/salt complex in deionized water, and replacing the water once for 4 hours, wherein the water is replaced for 6 times in a circulating way to remove zinc chloride (ZnCl) in the water2) To obtain a carbon fiber reinforced nanopore carbon/water complex;
(6) drying under normal pressure: placing the carbon fiber reinforced nano-pore carbon/water complexAnd (3) heating to 120 ℃ in a normal-pressure oven, preserving the temperature for 24 hours, and cooling to obtain the carbon fiber reinforced nano-pore carbon heat-insulating composite material. The density of the carbon fiber reinforced nanoporous carbon heat-insulating composite material prepared by the embodiment is 0.19g/cm3And a thermal conductivity of 0.152W/mK at 2000 ℃.
Example 2 ~ 243
In the second step of preparing phenolic sol, the molar ratio of furfural to resorcinol is 2: 1, the aldehyde and the phenolic substance are determined to be unchanged, the phenolic resin is generated by the reaction of the aldehyde and the phenolic substance and mainly used as a carbon source, under the condition of consistent dosage, the performance of the product is not obviously influenced by the aldehyde or the phenolic substance, in the fourth step of carbonization and cracking, argon or nitrogen is filled in a tube furnace, the phenolic gel/salt complex is in an inert atmosphere to prevent the phenolic gel/salt complex from being oxidized at high temperature, under the condition of ensuring the oxygen-free environment in the tube furnace, the times of filling argon or nitrogen, replacing air and the flow of filling argon or nitrogen do not obviously influence the performance of the product, according to differential scanning thermogravimetric analysis of the phenolic gel, a reasonable temperature rise program is set, so the violent degree of carbonization and cracking of the phenolic gel can be relieved, in the fifth step of washing and desalting, zinc oxide and zinc chloride in the product are mainly removed, the product is soaked in dilute hydrochloric acid, the product is soaked in water, the longer the soaking time or the more the times of water removal, the water removal can be reduced, the times of soaking in the drying process of drying the composite material can be completely removed, the drying process of 351, the drying process is not obviously influenced by adopting the drying process of the drying of the thermal insulation of the composite material, the thermal insulation of the thermal insulation material, the thermal insulation material is obviously improved by adopting the heat insulation process of the heat insulation material, the heat insulation process of the heat insulation material, the heatThe thermal conductivity of the carbon fiber reinforced nano-pore carbon heat-insulating composite material prepared by the invention at 2000 ℃ is 0.122 ~ 0.478W/m.K, and the lowest density is only 0.16g/cm3And the generated matrix nano-porous carbon material does not have large volume shrinkage due to the supporting effect of salt, is well matched with a carbon fiber reinforcement, and does not crack the composite material. Therefore, the composite material prepared by the method can resist high temperature, is light and is suitable for the field of high-temperature inert atmosphere furnaces or high-speed aircraft thermal protection systems.
TABLE 1 preparation Process parameters and Material Performance parameters of carbon fiber reinforced nanoporous carbon thermal insulation composite Material
Claims (10)
1. A preparation method of a carbon fiber reinforced nanopore carbon heat insulation composite material is characterized by comprising the following steps:
the first step, preparing carbon fiber prefabricated member, the method is:
according to the required volume of the carbon fiber prefabricated member and the apparent density of the carbon fiber prefabricated member, calculating the required carbon fiber mass by adopting mass (density multiplied by volume), laying or weaving the weighed carbon fibers by using a mold, clamping and fixing the carbon fibers, and enabling the arrangement direction of the carbon fibers to be vertical to the heat flow direction during heat insulation use to obtain the carbon fiber prefabricated member;
secondly, preparing the phenolic sol by the following steps:
takes phenols and aldehydes as raw materials, alcohols as solvent, and zinc chloride, namely ZnCl2As a molten salt, hexamethylenetetramine, i.e. C6H12N4The raw materials are weighed according to a certain molar ratio with phenols, and the molar ratio of aldehydes to phenols is 2: 1, the molar ratio of the alcohols to the phenols is in the range of 2-12: 1, the molar ratio of zinc chloride to phenols is in the range of 0.5-5: 1, the molar ratio of hexamethylene tetramine to phenols is in the range of 0.0075-0.015: 1; then mixing and stirring to prepare phenolic sol;
thirdly, preparing a carbon fiber reinforced phenolic gel/salt complex, which comprises the following steps:
placing the carbon fiber prefabricated member in a vacuum impregnation tank, and performing sol impregnation by adopting a mode of adding normal pressure after vacuumizing: firstly, phenolic sol is infiltrated into a carbon fiber prefabricated member in a vacuum impregnation mode, after the phenolic sol is infiltrated into the carbon fiber prefabricated member, a valve of a vacuum impregnation tank is opened to change the pressure in the vacuum impregnation tank into normal pressure, and the phenolic sol in the carbon fiber prefabricated member is aged under the normal pressure to change the phenolic sol in the carbon fiber prefabricated member into phenolic gel, so that a carbon fiber reinforced phenolic gel/salt composite is obtained;
fourthly, carbonizing and cracking the carbon fiber reinforced phenolic gel/salt complex to obtain a carbon fiber reinforced nanopore carbon/salt complex;
fifthly, washing the carbon fiber reinforced nanopore carbon/salt complex with water to remove salt to obtain a carbon fiber reinforced nanopore carbon/water complex;
and sixthly, drying the carbon fiber reinforced nanopore carbon/water complex at normal pressure to obtain the carbon fiber reinforced nanopore carbon heat insulation composite material.
2. The method of claim 1, wherein the first step comprises the step of forming a carbon fiber-reinforced nanoporous carbon thermal insulation compositeThe fiber is inorganic carbon fiber capable of resisting temperature of more than 2000 ℃, and is required to be chopped into 3-10 cm, and the apparent density of the carbon fiber prefabricated part is 0.06-0.20 g/cm3。
3. The method of claim 1, wherein the phenol in the second step is phenol C6H5OH, resorcinol and hydroquinone.
4. The method according to claim 1, wherein the aldehyde in the second step is furfural (C)5H4O2And formaldehyde, i.e., HCHO.
5. The method of claim 1, wherein the alcohol in the second step is methanol (CH)3OH, ethanol or C2H5One or a mixture of any of OH and isopropanol.
6. The method for preparing the carbon fiber reinforced nanoporous carbon thermal insulation composite material as claimed in claim 1, wherein the vacuum in the third step means an air pressure of-0.1 mpa, and the normal pressure means 1 atmosphere.
7. The method for preparing the carbon fiber reinforced nanoporous carbon thermal insulation composite material as claimed in claim 1, wherein the aging time in the third step is 3-48 hours.
8. The method for preparing the carbon fiber reinforced nanoporous carbon thermal insulation composite material as claimed in claim 1, wherein the carbonization and cracking method comprises the steps of putting the carbon fiber reinforced phenolic gel/salt composite into a tubular furnace, vacuumizing, filling argon or nitrogen into the tubular furnace, replacing air remained in the tubular furnace for 1-5 times, heating to 650-2000 ℃ at a heating rate of 1.0-5.0 ℃/min, preserving heat at the temperature for 1-5 hours, naturally cooling, and filling argon or nitrogen at a flow rate of 20-200 mL/min in the whole process to obtain the carbon fiber reinforced nanoporous carbon/salt composite material.
9. The method for preparing the carbon fiber reinforced nanoporous carbon thermal insulation composite material as claimed in claim 1, wherein the fifth step of the method for removing salt by washing with water is as follows: soaking the carbon fiber reinforced nanopore carbon/salt complex in dilute hydrochloric acid with the mass concentration of 10% for 2-6 hours, removing a small amount of zinc oxide (ZnO) in the carbon fiber reinforced nanopore carbon/salt complex, soaking in water, and replacing the water every 3-12 hours, so that the water is replaced for 4-8 times in a circulating manner, and removing zinc chloride in the water to obtain the carbon fiber reinforced nanopore carbon/water complex.
10. The method for preparing carbon fiber reinforced nanoporous carbon thermal insulation composite material as claimed in claim 1, wherein the sixth step of drying under normal pressure comprises: and (3) placing the carbon fiber reinforced nanopore carbon/water complex in an oven or a muffle furnace, heating to 100-200 ℃, preserving heat for 1-24 hours, and cooling to obtain the carbon fiber reinforced nanopore carbon heat insulation composite material.
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| DE102018132798A1 (en) * | 2018-12-19 | 2020-06-25 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Process for producing a porous fiber composite material, fiber composite material and use of a fiber composite material |
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| CN110698169B (en) * | 2019-11-21 | 2021-09-07 | 哈尔滨工业大学 | Preparation method of high-temperature-resistant quartz fiber needled felt/phenolic resin composite carbonized derivative |
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| CN111807852B (en) * | 2020-07-16 | 2022-10-04 | 北京中材人工晶体研究院有限公司 | Method for preparing high-porosity porous ceramic material |
| CN111876160B (en) * | 2020-08-19 | 2021-06-22 | 武汉大学 | Carbon aerogel material, preparation method thereof and application of carbon aerogel material as heavy metal contaminated soil remediation material |
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