CN103272490B - A kind of fiber reinforcement flat carbon film and preparation method thereof - Google Patents
A kind of fiber reinforcement flat carbon film and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 86
- 239000000835 fiber Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000002787 reinforcement Effects 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 238000012216 screening Methods 0.000 claims abstract description 11
- 238000007493 shaping process Methods 0.000 claims abstract description 10
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims abstract description 3
- 239000003245 coal Substances 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 235000012054 meals Nutrition 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000002802 bituminous coal Substances 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003830 anthracite Substances 0.000 claims description 2
- 239000003077 lignite Substances 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 46
- 239000008187 granular material Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 210000004379 membrane Anatomy 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229940099259 vaseline Drugs 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000036244 malformation Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a kind of fiber reinforcement flat carbon film and preparation method thereof.Described fiber reinforcement flat carbon film is made up of carbon matrix and the fibre reinforced materials being full of carbon matrix, and it is characterized in that, carbon matrix is continuous phase, has flourishing pore structure; Fibre reinforced materials is decentralized photo, combines together with carbon matrix.This fiber reinforcement flat carbon film intensity is high, resistance to corrosion is strong.Described preparation method comprises following processing step: the persursor material taking carbonaceous material as flat carbon film, pulverized rear and additive mix, the mould that inner side scribbles releasing agent is put into after ball milling, screening, fibre reinforced materials is added in material simultaneously, through shaping, open film, drying and carbonization and obtain fiber reinforcement flat carbon film.The method achieve siccative direct pressing and prepare high strength flat carbon film, have that preparation technology is simple, low production cost, the advantage such as with short production cycle.
Description
Technical field
The invention belongs to technical field of membrane separation, particularly relate to a kind of fiber reinforcement flat carbon film and preparation method thereof.
Background technology
Carbon membrane is a kind of novel charcoal basement membrane parting material, the advantage (efficient, energy-conservation) of Carbon Materials excellent structural characteristic (abundant pore structure, homogeneous pore-size distribution) and membrane material, organically blending is integrated for it, shows good application prospect in gas separaion, fluid separation applications etc.Carbon membrane normally by carbonaceous material under vacuum or inert gas shielding, be prepared from through high temperature pyrolysis.According to the difference of structure, carbon membrane can be divided into homogeneous carbon membrane and compound carbon membrane, and homogeneous carbon membrane can be divided into again flat carbon film, tubulose carbon membrane, hollow fiber carbon membrane and capillary carbon membrane.
The homogeneous carbon membrane middle plateform reported at present and the preparation method of tubulose carbon membrane mainly adopt the extruded rear charing of wet method to be prepared from (such as: CN1490076A, CN102527257A, CN101733001A, CN01147847A, CN1415406A and CN1569316A).In shaping film-forming process, this method needs to introduce solvent (as organic solvent or water) and binding agent, and prepare former film through mixing, refining, ageing and the technique such as shaping, then former film needs after long-time drying at room temperature, just can carry out charing and be prepared into carbon membrane.Therefore, adopt this legal system for carbon membrane, not only need to spend very long drying time, simultaneously prevent former film bend or the generation in crack in the dry run temperature and humidity that will meticulously control environment, add the complexity of preparation process and control difficulty, improve production cost.In addition, because the charcoal skeleton structure of carbon membrane at high temperature merges formation with the form of carbon and pulverized coal particle through certain polycondensation reaction mutually primarily of undecomposed binding agent, its intensity is not very high usually, and in actual application, as in the separation process of membrane module assembling and feed liquid, all to bear certain External Force Acting, and the circulation impact will resisting feed liquid with wash away, therefore, the requirement of large-scale commercial can't be met in mechanical strength according to the carbon membrane that this legal system is standby.
Fiber reinforcement flat carbon film, on the basis ensureing the original excellent machinability of carbon membrane and hole structural property, is significantly strengthened the mechanical strength of existing carbon membrane, can meet the application of multiple occasion by the fibrous material adding high strength.Therefore, development of new fiber reinforcement flat carbon film, will expand the application of existing carbon membrane further, accelerates the industrialization process of carbon membrane.
Summary of the invention
The present invention aims to provide simple, with low cost, corrosion resistant high strength flat carbon film of a kind of preparation technology and preparation method thereof, needs meticulous control, production cycle length, intensity to be difficult to meet the deficiencies such as demand of industrial production to solve and to make up in existing carbon membrane material preparation process.
Fiber reinforcement flat carbon film of the present invention is made up of carbon matrix and the fibre reinforced materials being full of carbon matrix, and it is characterized in that, carbon matrix is continuous phase, has flourishing pore structure; Fibre reinforced materials is decentralized photo, combines together with carbon matrix.The compression strength of fiber reinforcement flat carbon film of the present invention is preferably 65-140kg/cm
2, the average pore size of pore structure is preferably 0.14 – 0.60 μm, and porosity is preferably 30-50%.
The present invention comprises following processing step for the preparation of the method for above-mentioned fiber reinforcement flat carbon film: the persursor material taking carbonaceous material as flat carbon film, pulverized rear and additive mix, the mould that inner side scribbles releasing agent is put into after ball milling, screening, fibre reinforced materials is added in material simultaneously, through shaping, open film, drying and carbonization and obtain fiber reinforcement flat carbon film.
Carbonaceous material is generally the coal of different rank, as anthracite, coking coal, bottle coal, rich coal, lean coal, bituminous coal, brown coal, plant base charcoal, resin-based charcoal, petroleum coke, MCMB, phenolic resins etc., one or more mixture wherein can be used.In addition, carbonaceous material preferred powder is broken to 200-500 μm.
Additive generally selects one or more the mixture in carboxymethyl cellulose, starch, phenolic resins, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral resin, polystyrene, and its addition is generally the 5%-40% of persursor material and additive gross mass.
Ball milling refers to that batch mixing is put into ball mill carries out milled processed, and the processing time, general control was at 0.5-4h.
Screening refers to that control raw meal particle size is at 5-50 μm with screen cloth by large granular materials screening removal.
One or more the mixture in oleic acid, silicone oil, methyl-silicone oil, paraffin, glycerine, vaseline generally selected by releasing agent.
Fibre reinforced materials can use ceramic fibre net, shortly cut ceramic fibre, silicon carbide fibre net, boron fibre net, Al
2o
3one or more mixture in fleece, carbon fibre web, short carbon fiber, stainless steel cloth, nickel screen, the consumption of fibre reinforced materials is generally the 3-10% of persursor material quality.
Condition of molding is preferably as follows: briquetting pressure controls at 60-200MPa, and the dwell time controls at 10-20min.
Open film and refer to that opening mould takes out film, now preferably the board-like carbon membrane plate jig pressed is clamped, to prevent Flat Membrane malformation.
The complete Flat Membrane of preparation is carried out drying process, and baking temperature controls usually between room temperature is to 100 DEG C, and drying time is generally 1-12h.
Dried former film is put into temperature programming and control retort, heat up under vacuum or inert gas shielding and carry out charing process, just prepare fiber reinforcement flat carbon film.Wherein inert gas selects nitrogen or argon gas usually, and heating rate general control is at 0.5-10 DEG C/min, and charing final temperature selects 600-1000 DEG C usually, and general constant temperature 30-120min at this temperature.
The invention has the beneficial effects as follows:
Fiber reinforcement flat carbon film intensity of the present invention is high, resistance to corrosion strong, has broad application prospects in gas, fluid separation applications field.In addition, the preparation method of the flat carbon film that the present invention develops achieves siccative direct pressing and prepares high strength flat carbon film, there is the advantages such as preparation technology is simple, low production cost, and due in preparation process without the need to introducing liquid flux, thus significantly shorten the production cycle.
Detailed description of the invention
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
After anchracite duff being broken to 200-500 μm, take 100g anchracite duff respectively and 20g starch puts into grinding in ball grinder 2h, with screen cloth, large granular materials screening is removed, control raw meal particle size between 20-30 μm.Material is put into inner side scribble the mould of silicone oil and add 6g ceramic fibre net, after paving when briquetting pressure is 80MPa shaping press mold, after pressurize 10min, open mould, the board-like carbon membrane plate jig pressed clamped at room temperature dry 5h.Dried former film is put into temperature programming and control retort, under argon shield, rise to 900 DEG C and constant temperature 30min with the heating rate of 3 DEG C/min, treat that it is cooled to less than 100 DEG C just can take out.Carbon membrane performance is as shown in table 1.
Embodiment 2-9
According to the step of embodiment 1, but reinforcing material adds by the type provided in table 1, and the carbon membrane performance obtained is as shown in table 1.
The carbon membrane performance that table 1 is prepared under using different reinforcing material condition
Embodiment 10
After coking coal powder being broken to 200-500 μm, take 100g coking coal powder respectively and grinding in ball grinder 3h put into by 25g polyvinyl alcohol, with screen cloth, large granular materials screening is removed, control raw meal particle size between 10-20 μm.Material is put into inner side scribble the mould of glycerine and add 3g boron fibre net, after paving when briquetting pressure is 100MPa shaping press mold, after pressurize 10min, open mould, the board-like carbon membrane plate jig pressed clamped at room temperature dry 3h.Dried former film is put into temperature programming and control retort, under argon shield, rise to 800 DEG C and constant temperature 60min with the heating rate of 5 DEG C/min, treat that it is cooled to less than 100 DEG C just can take out.Carbon membrane performance is shown in Table 2.
Embodiment 11-19
According to the step of embodiment 10, but add by the type provided in table 2 containing carbon matrix precursor, the carbon membrane performance obtained is as shown in table 2.
Table 2 uses the carbon membrane performance of different carbon containing precursor power
Embodiment 20
After bituminous coal powder being broken to 200-500 μm, take 100g bituminous coal respectively and 25g carboxymethyl cellulose puts into grinding in ball grinder 4h, with screen cloth, large granular materials screening is removed, control raw meal particle size between 5 and 15 mum.Material is put into inner side scribble the mould of vaseline and add 4g Carbon fibe net, after paving when briquetting pressure is 120MPa shaping press mold, after pressurize 20min, open mould, the board-like carbon membrane plate jig pressed clamped at room temperature dry 2h.Dried former film is put into temperature programming and control retort, under argon shield, rise to 950 DEG C and constant temperature 60min with the heating rate of 8 DEG C/min, treat that it is cooled to less than 100 DEG C just can take out.Carbon membrane performance is shown in Table 3.
Embodiment 21-26
According to the step of embodiment 20, but additive adds by the type provided in table 3, and the carbon membrane performance obtained is as shown in table 3.
The carbon membrane performance that table 3 uses different additive to prepare
Embodiment 27
After rich coal and lean coal are crushed to 200-500 μm, take 70g rich coal, 30g lean coal and 15g polyvinyl alcohol respectively and put into grinding in ball grinder 1h, with screen cloth, large granular materials screening is removed, control raw meal particle size between 25-35 μm.Material is put into inner side scribble the mould of paraffin and add 8g short carbon fiber, after paving when briquetting pressure is 150MPa shaping press mold, after pressurize 20min, open mould, the board-like carbon membrane plate jig pressed clamped at room temperature dry 2h.Dried former film is put into temperature programming and control retort, under argon shield, rise to 850 DEG C and constant temperature 30min with the heating rate of 6 DEG C/min, treat that it is cooled to less than 100 DEG C just can take out.Carbon membrane performance is shown in Table 4.
Embodiment 28-30
According to the step of embodiment 27, but add by the type provided in table 4 containing carbon matrix precursor, the carbon membrane performance obtained is as shown in table 4.
The carbon membrane performance that table 4 uses different presoma mixture to prepare
Embodiment 31
After rich coal being crushed to 200-500 μm, taking 100g rich coal, 15g phenolic resins and 5g polystyrene and put into grinding in ball grinder 1.5h, with screen cloth, large granular materials screening is removed, control raw meal particle size between 20-30 μm.Material is put into inner side scribble the mould of paraffin and add 10gAl
2o
3fleece, after paving when briquetting pressure is 80MPa shaping press mold, after pressurize 10min, open mould, the board-like carbon membrane plate jig pressed clamped at room temperature dry 6h.Dried former film is put into temperature programming and control retort, under argon shield, rise to 800 DEG C and constant temperature 60min with the heating rate of 5 DEG C/min, treat that it is cooled to less than 100 DEG C just can take out.Carbon membrane performance is shown in Table 5.
Embodiment 32-35
According to the step of embodiment 31, but additive adds by the type provided in table 5, and the carbon membrane performance obtained is as shown in table 5.
The carbon membrane performance that table 5 uses different additive mixture to prepare
Claims (5)
1. prepare the method for fiber reinforcement flat carbon film for one kind, it is characterized in that, comprise following processing step: the persursor material taking carbonaceous material as flat carbon film, pulverized rear and additive mix, the mould that inner side scribbles releasing agent is put into after ball milling, screening, fibre reinforced materials is added in material simultaneously, through shaping, open film, drying and carbonization and obtain fiber reinforcement flat carbon film;
Described fiber reinforcement flat carbon film, be made up of carbon matrix and the fibre reinforced materials being full of carbon matrix, carbon matrix is continuous phase, has flourishing pore structure; Fibre reinforced materials is decentralized photo, combines together with carbon matrix;
Carbonaceous material is one or more the mixture in anthracite, coking coal, bottle coal, rich coal, lean coal, bituminous coal, brown coal, plant base charcoal, resin-based charcoal, petroleum coke, MCMB, phenolic resins, and carbonaceous material is crushed to 200-500 μm;
Additive is one or more the mixture in carboxymethyl cellulose, starch, phenolic resins, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral resin, polystyrene;
Ball-milling treatment time controling is at 0.5-4h, and screening controls raw meal particle size at 5-50 μm;
Briquetting pressure controls at 60-200MPa, and the dwell time controls at 10-20min.
2. preparation method according to claim 1, is characterized in that, additive addition is the 5%-40% of persursor material and additive gross mass.
3. preparation method according to claim 1, is characterized in that, fibre reinforced materials is ceramic fibre net, shortly cuts ceramic fibre, silicon carbide fibre net, boron fibre net, Al
2o
3one or more mixture in fleece, carbon fibre web, short carbon fiber, stainless steel cloth, nickel screen, the consumption of fibre reinforced materials is the 3-10% of persursor material quality.
4. preparation method according to claim 1, is characterized in that, drying is carried out between room temperature is to 100 DEG C, and drying time controls at 1-12h.
5. preparation method according to claim 1, is characterized in that, carbonizes and carries out under vacuum or inert gas shielding; inert gas selects nitrogen or argon gas; heating rate controls at 0.5-10 DEG C/min, and charing final temperature is at 600-1000 DEG C, and constant temperature 30-120min at this temperature.
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CN110448958A (en) * | 2019-07-25 | 2019-11-15 | 天津大学 | The preparation method of fiber reinforcement type porous charcoal base electro-catalysis filtrate |
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CN114531925B (en) * | 2021-03-25 | 2024-07-12 | 宁德新能源科技有限公司 | Carbon current collector, electrochemical device and electronic device including the same |
CN114272758B (en) * | 2022-01-27 | 2022-10-28 | 南京新核复合材料有限公司 | Carbon fiber combined permeable membrane |
CN114984766B (en) * | 2022-05-25 | 2023-06-16 | 天津工业大学 | Preparation method of carbon film with self-adhesion performance and obtained carbon film |
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