CN113683423B - Reticular glassy state porous carbon thin-wall special-shaped part and preparation method thereof - Google Patents
Reticular glassy state porous carbon thin-wall special-shaped part and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a reticular glassy state porous carbon thin-wall special-shaped piece, which comprises the following steps: firstly, laying polyethylene wax powder on the upper part of a precursor polyurethane sponge, and carrying out vacuum heating and heat preservation to obtain a blank; secondly, machining; thirdly, immersing the blank into the sealed mixed solution for heating and heat preservation to obtain a dewaxing blank; fourthly, drying after repeated cleaning; fifthly, dipping, coating the slurry and drying in the shade in sequence, and then curing at high temperature to obtain a cured part; and sixthly, embedding the solidified part in graphite powder for high-temperature carbonization to obtain the reticular glassy state porous carbon thin-wall special-shaped part. According to the invention, the precursor polyurethane sponge is adopted for filling and processing and combined with the solidified piece powder embedding and sintering process, so that the blank machinability is improved, the volume shrinkage uniformity of the solidified piece in the glassy carbon forming process is ensured, and the dimensional precision of the product thin-wall special-shaped piece is improved, thereby realizing the smooth forming of the high-dimensional precision reticular glassy carbon thin-wall special-shaped piece and solving the problem that the reticular glassy carbon thin-wall special-shaped piece is difficult to prepare.
Description
Technical Field
The invention belongs to the technical field of porous carbon material preparation, and particularly relates to a reticular glassy state porous carbon thin-wall special-shaped piece and a preparation method thereof.
Background
The reticular glassy carbon is a three-dimensional reticular microporous material consisting of glassy carbon foam, the aperture ratio is up to 90-97%, and the density is small (0.03 g/cm)3) The composite material has the characteristics of high chemical stability, high specific surface area, high electric conductivity, low thermal conductivity and thermal expansion coefficient, high structural strength, low resistance to fluid, low production cost and the like, and is widely applied to the fields of aviation (such as thermal insulation layers of spacecrafts), electrochemistry, biomedicine, environmental protection and the like.
At present, great progress is made in research and application of reticular glassy porous carbon materials abroad. The porous tantalum orthopedic implant material developed by Zimmer company is successfully applied in clinic, so that the reticular glassy porous carbon stent becomes one of the materials widely applied in the medical field. Czerwinski et al electrodeposit Pb and PbO on reticulated vitreous porous carbon surface2The lead-acid battery is used as the current collectors of positive and negative grids of the lead-acid battery. Czerwinski et al use platinized reticulated vitreous porous carbon electrode for CO in acidic solution2The adsorption of (2) was investigated. T.schoetz et al use the unique properties of conductive polymers to prepare conductive polymer nano/microporous films as energy storage materials with reticulated vitreous porous carbon as the substrate, improving electrode capacity. The domestic research on the reticular glassy porous carbon mainly stays in the preparation and application stage of simple shapes. Chinese patent publication No. CN1907914A discloses the production of medical porous tantalum from three-dimensional reticulated graphite foam or reticulated vitreous carbon. The self-made reticulated vitreous carbon and the canine bone marrow stromal stem cells are cultured by Yu Yi and the like, and research shows that the porous vitreous carbon support can promote the adhesion and proliferation of the bone marrow stromal stem cells in vitro and has good bone induction characteristics in vivo.
Compared with foreign researches, the reticular glassy state porous carbon material prepared in China has the advantages of low strength, easiness in slag falling and high processing difficulty, and especially has great difficulty in preparation of special-shaped parts, so that the application of the material under the requirement of complex-shaped environment is limited.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a reticular vitreous porous carbon thin-wall special-shaped member, aiming at the defects of the prior art. The method adopts the combination of the filling and processing of the precursor polyurethane sponge and the powder embedding and sintering process of the solidified piece, improves the machinability of the blank, ensures the uniform volume shrinkage of the solidified piece in the process of forming the glassy carbon, and improves the dimensional precision of the product thin-wall special-shaped piece, thereby realizing the smooth molding of the high-dimensional precision reticular glassy carbon thin-wall special-shaped piece and solving the problem that the reticular glassy carbon thin-wall special-shaped piece is difficult to prepare.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of a reticular glassy porous carbon thin-wall special-shaped piece is characterized by comprising the following steps:
placing a precursor polyurethane sponge in a container, laying polyethylene wax powder on the upper part of the precursor polyurethane sponge, transferring the precursor polyurethane sponge into a vacuum drying box, carrying out vacuum heating and heat preservation, cooling to room temperature, unloading vacuum, and taking out to obtain a blank;
step two, machining the blank obtained in the step one;
step three, immersing the blank machined in the step two into a closed mixed solution for heating and heat preservation, repeating the steps for multiple times, and taking out the blank to obtain a de-waxing blank;
step four, repeatedly cleaning the dewaxing blank obtained in the step three, and then drying;
step five, dipping and coating slurry on the dried dewaxing blank in the step four, removing redundant slurry, drying in the shade, and then curing at high temperature to obtain a cured piece;
and step six, burying the solidified part obtained in the step five in graphite powder for high-temperature carbonization to obtain the reticular glassy state porous carbon thin-wall special-shaped part.
According to the invention, polyurethane sponge is adopted as a precursor, polyethylene wax powder is laid on the upper part of the polyurethane sponge, then vacuum heating and heat preservation are carried out, the polyethylene wax powder is melted and permeates into pores of the precursor polyurethane sponge under the action of gravity through heating and heat preservation, air in the pores is effectively removed by combining with the vacuum condition, the filling efficiency of the polyethylene wax powder is improved, a blank is obtained, and a polyurethane sponge thin-wall special-shaped piece is obtained through mechanical processing; heating and insulating the mechanically processed blank to fully remove polyethylene wax powder in pores, repeatedly cleaning and drying, then impregnating and coating slurry, drying in the shade and curing at high temperature, introducing resin carbide into the dried dewaxing blank through the impregnating and coating slurry, and being beneficial to improving the carbon content in the reticular glassy state porous carbon thin-wall special-shaped piece; after drying in the shade, removing the solvent in the slurry, and then curing at high temperature to enable the resin carbide to generate chemical change and gradually harden and form, so that the strength of the product thin-wall special-shaped piece is improved, and a cured piece is obtained; the solidified piece is buried in graphite powder for high-temperature carbonization, so that resin carbide and precursor polyurethane sponge in the solidified piece are subjected to micromolecule separation in the high-temperature carbonization process, macromolecule chain pyrolysis fracture and dehydration are converted into glassy carbon, a reticular glassy porous carbon structure is formed, the solid carbon material graphite powder is used for burying, space constraint is formed on the solidified piece buried in the graphite powder, the volume shrinkage uniformity of the solidified piece in the high-temperature carbonization process is ensured, the deformation of a product thin-wall special-shaped piece is avoided, the smooth molding of the reticular porous carbon thin-wall special-shaped piece is ensured, and the size precision of the product thin-wall special-shaped piece is improved.
The preparation method of the reticular glassy state porous carbon thin-wall special-shaped piece is characterized in that the molecular weight of the polyethylene wax powder in the step one is 1500. The melting point of the polymer is reduced along with the reduction of the molecular weight, and the low molecular weight polyethylene wax powder is preferably selected for filling, so that the heating temperature for removing the polyethylene wax powder by subsequent heating and heat preservation is favorably reduced, and the removing effect is improved.
The preparation method of the reticular glassy state porous carbon thin-wall special-shaped piece is characterized in that in the step one, the vacuum degree of vacuum heating and heat preservation is not more than 100Pa, the temperature is 90-110 ℃, and the heat preservation time is 1-2 h. The optimized technological parameters of vacuum heating and heat preservation ensure that the polyethylene wax powder is fully melted and filled into the pores of the polyurethane sponge, and simultaneously, the performance of the polyurethane sponge is not influenced.
The preparation method of the reticular glassy state porous carbon thin-wall special-shaped piece is characterized in that 10% -20% of machining allowance is reserved in the machining process of the blank in the step two to compensate for size shrinkage caused by subsequent sintering. The measure of reserving the machining allowance is favorable for eliminating the adverse effect error of the process on the product, ensures the smooth forming of the special-shaped piece and improves the dimensional precision of the product thin-wall special-shaped piece.
The preparation method of the reticular glassy state porous carbon thin-wall special-shaped part is characterized in that in the third step, the mixed solution is composed of xylene and n-heptane according to the mass ratio of 1: 4-1: 8; the heating and heat preservation device is a glass bottle with a reflux condensing device. The optimized mixed solution composition is favorable for fully dissolving the polyethylene wax, and the removal effect of the polyethylene wax is improved; meanwhile, as the xylene and the n-heptane are volatile and toxic chemical reagents, the glass bottle with the reflux condensing device is used as heating and heat-preserving equipment, so that the mixed solution enters the reflux condensing device after being heated and volatilized to be liquefied when meeting cold and flows back to the mixed solution, the toxic gas is prevented from being volatilized to endanger health, the components of the mixed solution are ensured to be in a dynamic balance state, and the heating and heat-preserving process is accompanied with a condensation and reflux process.
The preparation method of the reticular glassy state porous carbon thin-wall special-shaped piece is characterized in that in the third step, the heating and heat preservation temperature is 90-110 ℃, the time is 30-60 min, and the repetition frequency is 3-5 times. The polyethylene wax powder with low molecular weight, such as molecular weight 1500, is a non-polar crystalline polymer, and is fully dissolved in the mixed solution under the preferable heating and heat preservation conditions, so that the polyethylene wax powder is completely removed.
The preparation method of the reticular glassy state porous carbon thin-wall special-shaped part is characterized in that in the fourth step, the reagent adopted for repeated cleaning is ethanol, ether or chloroform, and the number of times of repeated cleaning is 2-4; the drying temperature is 60 ℃ and the drying time is 1 h. The preferred reagent is effective in removing residual xylene and n-heptane from the dewaxed blanks, preferably using safer ethanol; the preferred drying temperature facilitates the complete volatilization of the reagents, in particular ethanol, so as to obtain dewaxed blanks free from any contamination by impurities.
The preparation method of the reticular glassy state porous carbon thin-wall special-shaped piece is characterized in that the slurry adopted by the dipping and sizing in the step five is an alcoholic solution of ammonia-phenolic resin/furfuryl alcohol resin or a mixture of the alcoholic solution of ammonia-phenolic resin/furfuryl alcohol resin and asphalt powder. The optimized slurry contains thermosetting resin, and through subsequent drying in the shade and high-temperature curing processes, the cured part is ensured to have certain hardness, cannot be easily deformed, the carbon content of the product is improved, the strength of the product is further improved, collapse caused by low strength is avoided, and therefore the molding of the reticular glass state porous carbon thin-wall special-shaped part is ensured.
The preparation method of the reticular glassy state porous carbon thin-wall special-shaped piece is characterized in that the high-temperature carbonization temperature in the sixth step is 800-1000 ℃, and the heating rate is 1 ℃/min.
In addition, the invention also provides a reticular glassy state porous carbon thin-wall special-shaped piece prepared by the method.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the precursor polyurethane sponge is filled with polyethylene wax powder to prepare the blank, and then the blank is mechanically processed, so that the processability of the blank is improved by improving the strength of the precursor polyurethane sponge, the dimensional precision of the product thin-wall special-shaped piece is improved, the volume shrinkage uniformity of the solidified piece in the process of forming glassy carbon is ensured by combining the powder embedding and sintering process of the solidified piece, and the deformation of the product thin-wall special-shaped piece is avoided, thereby realizing the smooth molding of the high-dimensional precision reticular porous carbon glassy carbon thin-wall special-shaped piece, and solving the problem that the reticular porous carbon thin-wall special-shaped piece is difficult to prepare.
2. The invention adopts the low molecular weight polyethylene wax powder to fill the polyurethane sponge precursor, which is beneficial to fully filling at lower temperature to improve the strength of the precursor polyurethane sponge, reduces the heating temperature during the subsequent wax removal, and reduces the bad residue in the product thin-wall special-shaped piece.
3. The resin carbide is introduced into the dried dewaxing blank by dipping and sizing, so that the carbon content in the product reticular glassy state porous carbon thin-wall special-shaped piece is favorably improved, the strength of the product thin-wall special-shaped piece is further improved, and the shape collapse of the product thin-wall special-shaped piece is avoided.
4. The method has the advantages of low cost, strong operability, good process stability and the like, and can be widely applied to the preparation technology of the porous carbon material thin-wall special-shaped piece.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is a picture of a reticulated vitreous porous carbon thin-walled profile prepared in example 3 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
placing a precursor polyurethane sponge in a container, laying polyethylene wax powder on the upper part of the precursor polyurethane sponge, transferring the precursor polyurethane sponge into a vacuum drying box, vacuumizing until the vacuum degree is not more than 100Pa, heating to 90 ℃, preserving the heat for 1h, carrying out vacuum heating and heat preservation, cooling to room temperature, unloading the vacuum, and taking out to obtain a blank; the precursor polyurethane sponge is a block with a three-dimensional reticular open-pore structure, and the porosity of the precursor polyurethane sponge is not less than 98%; the molecular weight of the polyethylene wax powder is 1500;
step two, machining the blank obtained in the step one, and reserving 10% of machining allowance to compensate for size shrinkage caused by subsequent sintering;
step three, immersing the blank machined in the step two into a closed mixed solution, heating to 90 ℃, preserving heat for 40min, repeating for 3 times, and taking out to obtain a de-waxing blank; the mixed solution consists of dimethylbenzene and n-heptane according to the mass ratio of 1:8, and equipment adopted for heating and heat preservation is a glass bottle with a reflux condensing device;
step four, repeatedly cleaning the dewaxing blank obtained in the step three by adopting ethanol for 2 times, and then drying for 1h at the temperature of 60 ℃;
step five, dipping and coating slurry on the dried dewaxing blank in the step four, removing redundant slurry, drying in the shade, and then curing at high temperature of 150 ℃ to obtain a cured piece; the slurry adopted by the dipping and slurry hanging is an alcoholic solution of furfuryl alcohol resin, the mass ratio of the furfuryl alcohol resin to the ethanol in the slurry is 1:1, and the slurry contains 5 wt% of 1mol/L phosphoric acid solution curing agent;
and step six, burying the solidified part obtained in the step five in graphite powder for high-temperature carbonization, and heating to 800 ℃ at a heating rate of 1 ℃/min for high-temperature carbonization to obtain the reticular glassy state porous carbon thin-wall special-shaped part.
The solvent used for the repeated washing in the fourth step of this example may also be diethyl ether or chloroform.
Example 2
The embodiment comprises the following steps:
placing a precursor polyurethane sponge in a container, laying polyethylene wax powder on the upper part of the precursor polyurethane sponge, transferring the precursor polyurethane sponge into a vacuum drying box, vacuumizing until the vacuum degree is not more than 100Pa, heating to 100 ℃, preserving heat for 1.5h, carrying out vacuum heating and heat preservation, cooling to room temperature, unloading vacuum, and taking out to obtain a blank; the precursor polyurethane sponge is a block with a three-dimensional reticular open pore structure, and the porosity of the precursor polyurethane sponge is not less than 98%; the molecular weight of the polyethylene wax powder is 1500;
step two, machining the blank obtained in the step one, and reserving 15% of machining allowance to compensate for size shrinkage caused by subsequent sintering;
step three, immersing the blank machined in the step two into a sealed mixed solution, heating to 110 ℃, preserving heat for 60min, repeating for 4 times, and taking out to obtain a de-waxing blank; the mixed solution consists of dimethylbenzene and n-heptane according to the mass ratio of 1:6, and equipment adopted for heating and heat preservation is a glass bottle with a reflux condensing device;
step four, repeatedly cleaning the dewaxing blank obtained in the step three by adopting ethanol for 3 times, and then drying for 1h at the temperature of 60 ℃;
step five, dipping and coating slurry on the dried dewaxing blank in the step four, removing redundant slurry, drying in the shade, and then curing at a high temperature of 170 ℃ to obtain a cured piece; the slurry adopted by the dipping and sizing is an alcoholic solution of ammonia phenolic resin, and the mass ratio of the ammonia phenolic resin to the ethanol in the slurry is 1: 1;
and step six, burying the solidified part obtained in the step five in graphite powder for high-temperature carbonization, and heating to 900 ℃ at a heating rate of 1 ℃/min for high-temperature carbonization to obtain the reticular glassy state porous carbon thin-wall special-shaped part.
The solvent used for the repeated washing in the fourth step of this example may also be diethyl ether or chloroform.
Example 3
The embodiment comprises the following steps:
placing a precursor polyurethane sponge in a container, laying polyethylene wax powder on the upper part of the precursor polyurethane sponge, transferring the precursor polyurethane sponge into a vacuum drying box, vacuumizing until the vacuum degree is not more than 100Pa, heating to 90 ℃, preserving the heat for 2 hours, carrying out vacuum heating and heat preservation, cooling to room temperature, unloading the vacuum, and taking out to obtain a blank; the precursor polyurethane sponge is a block with a three-dimensional reticular open pore structure, and the porosity of the precursor polyurethane sponge is not less than 98%; the molecular weight of the polyethylene wax powder is 1500;
step two, machining the blank obtained in the step one, and reserving 20% of machining allowance to compensate for size shrinkage caused by subsequent sintering;
step three, immersing the blank machined in the step two into a closed mixed solution, heating to 90 ℃, preserving heat for 30min, repeating for 5 times, and taking out to obtain a de-waxing blank; the mixed solution consists of dimethylbenzene and n-heptane according to the mass ratio of 1:4, and equipment adopted for heating and heat preservation is a glass bottle with a reflux condensing device;
step four, repeatedly cleaning the dewaxing blank obtained in the step three by using ethanol for 4 times, and then drying the blank at 60 ℃ for 1 hour;
step five, dipping and coating slurry on the dried dewaxing blank in the step four, removing redundant slurry, drying in the shade, and then curing at high temperature of 150 ℃ to obtain a cured piece; the slurry adopted by the dipping and pulp hanging is an alcoholic solution of ammonia phenolic resin, the mass ratio of the ammonia phenolic resin to the ethanol in the slurry is 1:1, and the slurry contains 10 wt% of asphalt powder;
and step six, burying the solidified part obtained in the step five in graphite powder for high-temperature carbonization, and heating to 900 ℃ at a heating rate of 1 ℃/min for high-temperature carbonization to obtain the reticular glassy state porous carbon thin-wall special-shaped part.
Fig. 1 is a picture of the reticulated vitreous carbon thin-wall special-shaped piece prepared in this embodiment, and as can be seen from fig. 1, the reticulated vitreous carbon thin-wall special-shaped piece is a porous carbon acetabular support with a cavity hemisphere shape, the wall thickness is 3mm, the diameter is 50mm, and the aperture ratio is not less than 96%.
The solvent used for the repeated washing in the fourth step of this example may also be diethyl ether or chloroform.
Example 4
The embodiment comprises the following steps:
placing a precursor polyurethane sponge in a container, laying polyethylene wax powder on the upper part of the precursor polyurethane sponge, transferring the precursor polyurethane sponge into a vacuum drying box, vacuumizing until the vacuum degree is not more than 100Pa, heating to 110 ℃, preserving heat for 1h, carrying out vacuum heating and heat preservation, cooling to room temperature, unloading vacuum, and taking out to obtain a blank; the precursor polyurethane sponge is a block with a three-dimensional reticular open pore structure, and the porosity of the precursor polyurethane sponge is not less than 98%; the molecular weight of the polyethylene wax powder is 1500;
step two, machining the blank obtained in the step one, and reserving 15% of machining allowance to compensate for size shrinkage caused by subsequent sintering;
step three, immersing the blank machined in the step two into a sealed mixed solution, heating to 100 ℃, preserving heat for 50min, repeating for 4 times, and taking out to obtain a de-waxing blank; the mixed solution consists of dimethylbenzene and n-heptane according to the mass ratio of 1:6, and equipment adopted for heating and heat preservation is a glass bottle with a reflux condensing device;
step four, repeatedly cleaning the dewaxing blank obtained in the step three by using ethanol for 3 times, and then drying the blank at 60 ℃ for 1 h;
step five, dipping and coating slurry on the dried dewaxing blank in the step four, removing redundant slurry, drying in the shade, and then curing at high temperature of 150 ℃ to obtain a cured piece; the slurry adopted by the dipping and pulp hanging is an alcoholic solution of furfuryl alcohol resin, the mass ratio of the furfuryl alcohol resin to the ethanol in the slurry is 1:1, and the slurry contains 5 wt% of 1mol/L phosphoric acid solution and 10 wt% of asphalt powder;
and step six, burying the solidified part obtained in the step five in graphite powder for high-temperature carbonization, and heating to 1000 ℃ at a heating rate of 1 ℃/min for high-temperature carbonization to obtain the reticular glassy state porous carbon thin-wall special-shaped part.
The solvent used for the repeated washing in the fourth step of this example may also be diethyl ether or chloroform.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (10)
1. A preparation method of a reticular glassy porous carbon thin-wall special-shaped piece is characterized by comprising the following steps:
placing a precursor polyurethane sponge in a container, laying low-molecular-weight polyethylene wax powder on the upper part of the precursor polyurethane sponge, transferring the precursor polyurethane sponge into a vacuum drying oven, carrying out vacuum heating and heat preservation, cooling to room temperature, unloading vacuum, and taking out to obtain a blank;
step two, machining the blank obtained in the step one;
step three, immersing the blank machined in the step two into a closed mixed solution for heating and heat preservation, repeating the steps for multiple times, and taking out the blank to obtain a de-waxing blank;
step four, repeatedly cleaning the dewaxing blank obtained in the step three, and then drying;
step five, dipping and coating slurry on the dried dewaxing blank in the step four, removing redundant slurry, drying in the shade, and then curing at high temperature to obtain a cured piece; the slurry for dipping and hanging the slurry adopts resin carbide as a raw material;
and step six, burying the solidified part obtained in the step five in graphite powder for high-temperature carbonization to obtain the reticular glassy state porous carbon thin-wall special-shaped part.
2. The method for preparing the reticulated vitreous porous carbon thin-wall special-shaped piece according to claim 1, wherein the molecular weight of the polyethylene wax powder in the first step is 1500.
3. The method for preparing the reticulated vitreous porous carbon thin-wall special-shaped piece according to claim 1, wherein in the first step, the vacuum heating and heat preservation is carried out under the vacuum degree of not more than 100Pa, the temperature is 90-110 ℃, and the heat preservation time is 1-2 h.
4. The method for preparing the reticulated vitreous porous carbon thin-wall special-shaped piece according to claim 1, wherein in the second step, 10% -20% of machining allowance is reserved in the machining process of the blank to compensate for dimensional shrinkage caused by subsequent sintering.
5. The method for preparing the reticulated vitreous porous carbon thin-wall special-shaped piece according to claim 1, wherein the mixed solution in the third step is composed of xylene and n-heptane according to a mass ratio of 1: 4-1: 8; the heating and heat preservation device is a glass bottle with a reflux condensing device.
6. The method for preparing the reticular glassy porous carbon thin-wall special-shaped piece according to claim 1, wherein the heating and heat preservation in the third step are carried out at a temperature of 90-110 ℃ for 30-60 min, and the repetition times are 3-5 times.
7. The method for preparing the reticulated vitreous porous carbon thin-wall special-shaped piece according to claim 1, wherein the reagent adopted in the repeated cleaning in the step four is ethanol, ether or chloroform, and the number of the repeated cleaning is 2-4; the drying temperature is 60 ℃, and the drying time is 1 h.
8. The method for preparing the reticulated vitreous porous carbon thin-wall special-shaped piece according to claim 1, wherein the slurry used for dipping and sizing in the fifth step is an alcoholic solution of ammonia-phenol resin/furfuryl alcohol resin or a mixture of the alcoholic solution of ammonia-phenol resin/furfuryl alcohol resin and asphalt powder.
9. The method for preparing the reticulated vitreous porous carbon thin-wall special-shaped piece according to claim 1, wherein the temperature of the high-temperature carbonization in the sixth step is 800 ℃ to 1000 ℃, and the heating rate is 1 ℃/min.
10. A reticulated vitreous porous carbon thin-walled profile produced by the method of any one of claims 1 to 9.
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| JP2022571159A JP2023541749A (en) | 2021-08-19 | 2021-10-26 | Reticulated glass-like porous carbon thin-walled irregularly shaped parts and manufacturing method thereof |
| PCT/CN2021/126258 WO2023019726A1 (en) | 2021-08-19 | 2021-10-26 | Reticular glassy porous carbon thin-walled special-shaped part and preparation method therefor |
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