CN100365178C - Preparation method of polyacrylonitrile-based carbon core - Google Patents
Preparation method of polyacrylonitrile-based carbon core Download PDFInfo
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- CN100365178C CN100365178C CNB2005100880835A CN200510088083A CN100365178C CN 100365178 C CN100365178 C CN 100365178C CN B2005100880835 A CNB2005100880835 A CN B2005100880835A CN 200510088083 A CN200510088083 A CN 200510088083A CN 100365178 C CN100365178 C CN 100365178C
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Abstract
The invention relates to a method for producing polyacrylonitrile-based carbon core, with high conductivity, via chemical deposition method, wherein the invention has high strength, high conductivity and controllable diameter; and the method is CVD method. The production comprises: preparing the PAN spinning solution with one-dimension high-conductivity carbon; preparing original fiber with spinning solution; crosslinking in oxygen gas, to prepare the pre-oxidized fiber; carbonizing in inertia gas, to prepare the carbonized fiber; graphitizing in inertia gas, to prepare the graphitized carbon corn. The invention can improve the conductivity of PAN-based carbon fiber; and since the anti-tension strength and flexible modulus of one-dimension high-conductivity carbon are higher than PAN-based carbon fiber, it can improve the strength of PAN-based carbon fiber to improve the treatment property of CVD method.
Description
Technical field
The present invention relates to a kind of polyacrylonitrile-based carbon core (polyacrylonitrile, be called for short PAN), especially relate to the method that a kind of employing chemical vapour deposition (CVD) (Chemical Vapor Deposition, be called for short CVD) legal system is equipped with the high conductivity polyacrylonitrile-based carbon core that continuous fibers uses.This carbon core is especially suitable for use as the core of CVD method carborundum (silicon carbide is called for short SiC) fiber.
Background technology
It is to adopt the conduction continuous monofilament as core (or being called the deposition carrier) that the CVD legal system is equipped with the SiC fiber, make core at the tubular reactor uniform motion, and apply voltage at two ends and carry out resistance heated (or radio frequency heating), core is heated to certain temperature, the silane of will vaporizing simultaneously is (as CH
3SiCl
3, CH
3HSiCl
2Deng) mix back importing reactor with hydrogen, make it form the SiC layer in scorching hot surface cracking of core silk and deposition.The domestic and international core of reporting has two kinds at present, thin tungsten filament (the about 12.5 μ m of diameter are called tungsten core SiC fiber) or major diameter mesophase pitch-based carbon fibers (the about 33 μ m of diameter are called carbon core SiC fiber).The advantage of tungsten is resistivity low (about 0.06 μ Ω m), so the tungsten core diameter can be very little.The shortcoming of tungsten is density height (about 19g/cm
3), the also higher (3.4g/cm of the SiC fibre density that obtains
3).Tungsten generates the intermediate layer (as WC etc.) of fragility with SiC reaction under hot conditions in addition, cause final CVD method SiC fiber decreased performance (look into the celebrating virtue, Liu Lang, the wing is brave, Zhu Xingming. Chinese patent, publication number: CN1103904A; Lindley M.W., Jones B.F..Nature, 1975,255:474-475).The advantage of mesophase pitch (mesophase pitch) based carbon core is low (the about 2.1g/cm of density
3), also lower (the about 3.0g/cm of the SiC fibre density that obtains
3).And at high temperature, carbon does not react with SiC, so the serviceability temperature of carbon core SiC fiber is higher than tungsten core SiC fiber.The shortcoming of mesophase pitch carbon core is a raw material modulation process complexity, the spinning temperature height, precursor fragility is big, continuous spinning and preoxidation technique difficulty are big, and lower (700～900MPa) (the Edie D.D..Carbon of carbon core intensity, 1998,36 (4): 345-362:Shilin Lu, Clara Blanco, Brian Rand.Carbon, 2002,40:2109-2116:Charles A.L., Lucille A.G., Charles E.B., Richard E.T..J.Amer.Ceram.Soc., 1999,82 (2): 407413).With the tungsten core relatively, mesophase pitch carbon core resistivity higher (2～8 μ Ω m), therefore in order to reach the identical thermal effect that adds, the carbon core diameter is more much bigger than tungsten core diameter.
In the small diameter high performance carbon fiber, the PAN base carbon fibre accounts for 85%, and asphalt base carbon fiber accounts for 15%, and main cause is a PAN base carbon fibre manufacturing technology maturation, and fibre property height and production cost are low.Do not adopt the report of PAN base carbon fibre but have as yet at present as CVD method SiC fiber core.This is because the mesophase pitch-based carbon fibers ratio is easier to graphitization, form the graphite crystal of high-crystallinity, fabricating low-defect-density, so resistivity is lower.By contrast, the PAN base carbon fibre forms random lamellar graphite after handling through high temperature graphitization, and degree of crystallinity is relatively poor, thereby resistivity higher (about 14 μ Ω m).In order to reach the same resistance of mesophase pitch based carbon core, just need to strengthen the diameter of PAN based carbon core fiber, thereby cause the diameter of final SiC fiber excessive, can't reel in the production process, can not produce continuously.
Summary of the invention
The objective of the invention is to shortcoming at the method for preparing the high conductivity polyacrylonitrile-based carbon core in the prior art, with PAN base carbon fibre favorable manufacturability can and the electric conductivity of mechanical property and one dimension high conductivity carbon excellence combine, the employing CVD legal system of providing a kind of and have that processing performance is good, intensity is high, electric conductivity and diameter being controlled easily is equipped with the method for continuous SiC fiber usefulness carbon core.The resistivity of carbon core provided by the invention can be adjusted by the addition of one dimension high conductivity carbon and the preparation technology of carbon core.Because the resistivity of carbon core provided by the invention is controlled, therefore can provide the core that satisfies the different-diameter that CVD method SiC fiber uses.
Step of the present invention is:
(1) preparation contains the PAN spinning solution of one dimension high conductivity carbon;
(2) prepare precursor by the spinning solution spinning;
(3) crosslinked in oxidizing atmosphere, the preparation preoxided thread;
(4) carbonization in inert atmosphere, the preparation carbon fibre;
(5) graphitization under inert atmosphere, preparation graphitized carbon core.
In step (1), described one dimension high conductivity carbon is meant that carbon content is greater than 95% The Fiber Shape Carbon Material, one dimension high conductivity carbon can be CNT (axially resistivity is about 0.4 μ Ω m), can be gas-phase growth of carbon fibre (axially resistivity is about 1.3 μ Ω m), also can be graphite whisker (axially resistivity is about 0.7 μ Ω m).The smoothly spinning in order not stop up spinnerets, the diameter that requires one dimension high conductivity carbon between 0.005～10 μ m, 0.01～1 μ m preferably; Length between 0.1～50 μ m, 1～20 μ m preferably; Draw ratio (L/D) is greater than 5.If length not in above-mentioned scope, can adopt ball-milling technology to reduce length.The method that preparation contains the PAN spinning solution of one dimension high conductivity carbon is, can adopt the method that one dimension high conductivity carbon is directly disperseed to sneak in the PAN solution to prepare, also PAN/ one dimension high conductivity carbon composition polymer can be dissolved in the solvent and prepare all right PAN/ one dimension high conductivity carbon composition polymer solution that directly adopts in-situ polymerization.Solid content in the spinning solution (gross mass of PAN and one dimension high conductivity carbon) concentration is 10%～40%, is preferably 15%～30%.If the total solids content in the setting solution is 100 parts, then wherein the umber of one dimension high conductivity carbon is 1～20 part.The condition during according to fiberizing and the difference of setting medium can adopt wet spinning, dry-wet spinning or dry spinning.So-called wet spinning, be meant that the spinning solution thread of extruding from spinneret orifice enters coagulating bath, because solvent makes polymer precipitation come out to form fiber with the counterdiffusion mutually of coagulating with agent, coagulating bath is generally mixed by the solvent and the coagulating agent of different proportion, and the most frequently used coagulating agent is a water.Dry-wet spinning is meant that the spinning solution thread of extruding from spinneret orifice enters to enter coagulating bath again behind the air layer of certain distance and make polymer precipitation come out to form fiber.And dry spinning is meant that the spinning solution thread of extruding from spinneret orifice enters that the hot-air path makes solvent evaporates and polymer precipitation comes out to form fiber, and the temperature of hot-air generally is higher than 10～50 ℃ of spinning solution solvent boiling point in the path.
In step (2), the spinning solution thread forms former silk fiber after overmolding, and is wound on the spinning tube.Consider follow-up pre-oxidation and carbonization technique, precursor silk tube adopts the high purity carbon cellulosic material, and carbon element tube diameter is about 12.0cm.Pre-oxidation can be put into precursor silk tube box pre-oxidation furnace integral body and carried out, and precursor is carried out continuously by the tubular type pre-oxidation furnace.Pre-oxidation is carried out in 190～300 ℃ oxidizing atmosphere, and preoxidation time is 1～48h.PAN in the process of pre-oxidation owing to molecule in and effects such as intermolecular generation cyclisation, oxidation form heat-resisting ladder-shaper structure, make it that fusion or doubling not take place in follow-up high-temperature heat treatment process.Carbonization can be put into preoxided thread silk tube box carbide furnace integral body and carried out, and preoxided thread is carried out continuously by the tubular type carbide furnace.Carbonization is carried out in 800～1500 ℃ inert atmosphere, and constant temperature 10～20min under final carburizing temperature can obtain the carbon fibre that diameter is 15～45 μ m.In carbonisation, elements such as the N among the PAN, H, O decompose volatilization, make it be transformed into carbon content greater than 95% fiber.Because one dimension high conductivity carbon has excellent heat conductivility, in pre-oxidation and carbonisation, help reducing the thermograde of fiber core and cortex, make the tissue of fiber and performance more even.In order further to improve conductance, the fiber after the carbonization need carry out graphitization processing under inert atmosphere protection, and graphitization temperature is 2300～2800 ℃, and graphitization time is 0.5～5s.At last the monofilament after the graphitization is used the coil winding machine after-combustion to the special-purpose silk axle of CVD, made the carbon core.The key property of the carbon core of the present invention preparation is referring to table 1:
Table 1
| Average diameter (μ m) resistivity (μ Ω m) tensile strength (MPa) continuous length (m) | 15～45(±2) ＜8.0 ＞900 ＞1500 |
The invention provides the CVD legal system and be equipped with the preparation method of continuous fibers with the PAN based carbon core, its advantage is that processing performance is good, intensity is high, electric conductivity and diameter can be controlled.Substitute with its that tungsten core can reduce cost and the density of SiC fiber, overcome the shortcoming that tungsten at high temperature causes fibre property to descend with the SiC reaction; Substitute the mesophase pitch based carbon core with it, can overcome mesophase pitch based carbon core raw material modulation difficulty, melt spinning poor continuity, the pre-oxidation process technical difficulty is big, cost is high shortcoming.The addition that this carbon core can be by regulating one dimension high conductivity carbon and the preparation technology of carbon core fibre obtain that resistivity is controlled, the fiber of controllable diameter, and the core of different-diameter is provided for CVD method fiber.This carbon core prepares the CVD method SiC fiber except being particularly suitable for, and also is applicable to the core that is equipped with boron fibre as the CVD legal system.
Using the PAN base carbon fibre is to improve conductance as the key of CVD method SiC fiber core, and the relevant report of this respect is not arranged at present as yet.Improving the effective method of conductance is the material that adds other high conductivity, but the material that requires to be added possesses following performance: chemical reaction at high temperature and does not take place in (1) between the carbon fiber, otherwise will cause change in resistance; (2) at high temperature, and chemical reaction not taking place between the SiC, otherwise will reduce the performance of SiC fiber; (3) approaching with the thermal coefficient of expansion of carbon fiber, otherwise will produce large interface stress and reduce the performance of SiC fiber.The present invention as adding material, can satisfy above-mentioned condition with one dimension high conductivity carbon.
In the spinning process, one dimension high conductivity carbon extrude with drawing process in therefore be subjected to the effect of shearing force and, will form the conductive channel of high conductivity along the precursor axial orientation, thereby the conductance of raising PAN base carbon fibre.In addition, therefore height-oriented one dimension high conductivity carbon can also improve the intensity of PAN base carbon fibre because itself TENSILE STRENGTH and elastic modelling quantity are higher than the PAN base carbon fibre far away, improves the processing performance of CVD.
The specific embodiment
Embodiment 1
10 parts of graphite whiskers (average diameter 0.5 μ m, average length 6 μ m) are disperseed 120min with powerful motor mechanical agitation (200r/min) in 90 parts dimethyl sulfoxide (DMSO)s (DMSO), be made into 10% graphite whisker solution.(the PAN molecular weight is about 240,000, is terpolymer, consists of acrylonitrile: methyl acrylate: acrylic acid=93: 6: 1) dissolving evenly obtains 10% PAN solution in 810 parts of DMSO with 90 parts of PAN.Divide 5 priorities to join in the graphite whisker solution this PAN solution, and stir (1500r/min) with powerful motor successively and disperse 60min, the addition of each time is respectively 20 parts, 60 parts, 120 parts, 240 parts and 370 parts, obtains 10% PAN/ graphite whisker spinning solution at last.Pour into this spinning solution in the spinning box and be warmed up to 60 ℃, carry out wet spinning through standing and defoaming, after filtering.Spinning condition is measuring pump quantity delivered 0.15ml/min, orifice diameter 0.20mm.Coagulating bath one bath composition is 60% the DMSO aqueous solution, and temperature is 10 ℃, and the spinneret draft ratio is 0.7; Two baths are 10% the DMSO aqueous solution, and temperature is 50 ℃, and draw ratio is 1.2; Three baths are stretching water-baths, 95 ℃ of temperature, and draw ratio is 1.5; Four baths are washing water-baths, 25 ℃ of temperature, and draw ratio is 1.05; Then enter air drying densification district, 200 ℃ of temperature, draw ratio 1.1; Be wound at last on the carbon element tube, carbon element tube diameter 12.0cm, winding speed is 7m/min, the about 52 μ m of the diameter of gained precursor.Precursor carbon element tube is placed box pre-oxidation furnace, rise to 220 ℃ and carry out oxidation processes at 220 ℃ of insulation 24h with the speed of 1 ℃/min, oxide isolation is an oxygen.Fiber tube after the pre-oxidation is placed box carbide furnace, rise to 1500 ℃ and carry out carbonization treatment at 1500 ℃ of insulation 20min with the speed of 20 ℃/min, carbonization is carried out under nitrogen protection.With the fiber after the carbonization in argon gas atmosphere in 2500 ℃ of following graphitization processing 5s, at last with the coil winding machine after-combustion to CVD with on the silk axle, make the carbon core of using for CVD.This carbon core diameter is about 35 ± 2 μ m, intensity 1100～1250MPa, and length is greater than 1500m, resistivity 3.2～3.8 μ Ω m.The diameter of fiber is averaged with 20 fibers of scanning electronic microscope (SEM) mensuration try to achieve at least; Carbon core intensity is measured at least 20 fibers with the monofilament strength electronic tester and is tried to achieve (sample marking distance is 25mm, and draw speed is 1mm/min); Carbon core resistivity is measured at least 10 fibers with the four point probe resistivity tester and is tried to achieve (outer electrode is apart from 3.5cm for room temperature, inter-electrode distance 2.5cm).
Embodiment 2
15 parts of dried carbon nanotube/PAN composition polymers that obtain with in-situ polymerization are dissolved with 85 parts of DMF, be made into concentration and be 15% spinning solution.Composition polymer consist of 1 part of CNT (average diameter 0.015 μ m, average length 10 μ m), 93 parts of acrylonitrile, 5 parts of ethyl acrylates and 1 part of itaconic acid.Spinning solution is warmed up to 60 ℃, carries out dry-wet spinning after standing and defoaming, the filtration.Spinning condition is that pump is for amount 0.15ml/min, spinneret orifice footpath 0.12mm, spinning head is 5mm from the distance of liquid level, fiberizing condition such as embodiment 1, but two bath draw ratios are that 1.5, three bath draw ratios are 2, four bath draw ratios are 1.05, the draw ratio in hot-air dry densification district is 1.05, and the winding speed of carbon element tube is 44m/min, the about 26 μ m of gained precursor fibre diameter.Pre-oxidation is carried out in length is the tubular type pre-oxidation furnace of 10m continuously, and 4 flat-temperature zones are arranged in the pre-oxidation furnace, and temperature is respectively 190 ℃, 220 ℃, 260 ℃ and 300 ℃, and pre-oxidation atmosphere is air, the about 2m of each humidity province length, and winding speed is 0.05m/min.Continuous carbonization under tubular type carbide furnace, nitrogen protection atmosphere then.Carbide furnace length is 5m, and the flat-temperature zone temperature is 1500 ℃, and the about 3m of length, fiber winding speed are 0.2m/min, at last in argon gas atmosphere in 2800 ℃ of following graphitization processing 0.5s, and with the coil winding machine after-combustion to CVD with on the silk axle, make the carbon core of using for CVD.This carbon core diameter is 15 ± 2 μ m, intensity 1300～1500MPa, and resistivity 7.5～8.0 μ Ω m, continuous length is greater than 2500m.
Embodiment 3
30 parts of dry PAN/ graphite whisker composition polymers that obtain with in-situ polymerization are dissolved with 70 parts of DMF, be made into concentration and be 30% spinning solution.Composition polymer consist of 5 parts of graphite whiskers (average diameter 0.5 μ m, average length 6 μ m), 90 parts of acrylonitrile, 4 parts of ethyl acrylates and 1 part of acrylic acid.Spinning solution is warmed up to 60 ℃, carries out dry-wet spinning after standing and defoaming, the filtration.Spinning, pre-oxidation and carbonization condition such as embodiment 2, and in 2300 ℃ argon gas atmosphere graphitization processing 5s.Gained carbon core diameter is about 24 ± 2 μ m, intensity 1050～1150MPa, and length is greater than 1500m, resistivity 4.8～5.5 μ Ω m.
Embodiment 4
Directly the concentration that obtains with in-situ polymerization is that 25% PAN/ gas-phase growth of carbon fibre composition polymer solution is as spinning solution.Composition polymer consist of 8 parts of gas-phase growth of carbon fibre (average diameter 0.150 μ m, average length 10 μ m), 88 parts of acrylonitrile, 3 parts of ethyl acrylates and 1 part of acrylic acid.Spinning solution is warmed up to 60 ℃, carries out dry-wet spinning after standing and defoaming, the filtration.Spinning, pre-oxidation and carbonization condition such as embodiment 2, and in 2500 ℃ argon gas atmosphere graphitization processing 3s.This carbon core diameter is about 22 ± 2 μ m, intensity 1100～1150MPa, and length is greater than 1500m, resistivity 4.8～5.5 μ Ω m.
Embodiment 5
40 parts of dried carbon nanotube/PAN composition polymers that obtain with in-situ polymerization are dissolved with 60 parts of DMF, be made into concentration and be 40% spinning solution.Composition polymer consist of 20 parts of CNTs (average diameter 0.015 μ m, average length 10 μ m), 74 parts of acrylonitrile, 5 parts of ethyl acrylates and 1 part of itaconic acid.Carry out dry spinning with being warmed up to 90 ℃ after this spinning solution standing and defoaming, the filtration.Spinning condition is that pump supplies amount 0.15ml/min, and spinneret orifice footpath 0.15mm enters the about 163 ℃ spinning shaft of temperature after dynamic analysis of spinning is extruded by spinneret orifice, batches the about 56 μ m of gained precursor fibre diameter with the speed of 24m/min.Precursor silk tube is taken off integral body from spinning machine put into box pre-oxidation furnace pre-oxidation, pre-oxidation is constant temperature 48h in 220 ℃ air atmosphere.Silk tube integral body after the pre-oxidation taken off put into carbide furnace, the speed with 20 ℃/min in nitrogen atmosphere rises to 800 ℃ of insulation 10min, rises to 1500 ℃ of insulation 10min with the speed of 20 ℃/min again and carries out carbonization treatment, and carbonization is carried out under nitrogen protection.In argon gas atmosphere, obtain graphitized fibre at last in 2500 ℃ of following graphitization processing 5s, with the coil winding machine after-combustion to CVD with making the carbon core of using for CVD on the silk axle.This carbon core diameter is 45 ± 2 μ m, intensity 900～1050MPa, and resistivity 0.8～1.2 μ Ω m, continuous length is greater than 1500m.
Embodiment 6
Adopt the spinning solution of embodiment 3 to carry out dry spinning, spinning condition is that pump supplies amount 0.15ml/min, and spinneret orifice footpath 0.15mm enters the about 180 ℃ spinning shaft of temperature after dynamic analysis of spinning is extruded by spinneret orifice, speed with 30m/min is batched, the about 44 μ m of gained precursor fibre diameter.Pre-oxidation, carbonization and graphitization condition such as embodiment 5.This carbon core diameter is 29 ± 2 μ m, intensity 1150～1250MPa, and length is greater than 1500m, resistivity 4.5～5.0 μ Ω m.
Embodiment 7
Adopt the spinning solution of embodiment 4 to carry out dry spinning, spinning condition is that pump supplies amount 0.15ml/min, and spinneret orifice footpath 0.15mm enters the about 203 ℃ spinning shaft of temperature after dynamic analysis of spinning is extruded by spinneret orifice, speed with 45m/min is batched, the about 33 μ m of gained precursor fibre diameter.Pre-oxidation, carbonization and graphitization condition such as embodiment 5.This carbon core diameter is 22 ± 2 μ m, intensity 1150～1250MPa, and length is greater than 1500m, resistivity 4.2～4.8 μ Ω m.
Claims (10)
1. the preparation method of polyacrylonitrile-based carbon core is characterized in that the steps include:
(1) preparation contains the PAN spinning solution of one dimension high conductivity carbon, and one dimension high conductivity carbon is meant that carbon content is greater than 95% The Fiber Shape Carbon Material;
(2) prepare precursor by the spinning solution spinning;
(3) crosslinked in oxidizing atmosphere, the preparation preoxided thread;
(4) carbonization in inert atmosphere, the preparation carbon fibre;
(5) graphitization under inert atmosphere, preparation graphitized carbon core.
2. the preparation method of polyacrylonitrile-based carbon core as claimed in claim 1 is characterized in that one dimension high conductivity carbon is selected from CNT, gas-phase growth of carbon fibre or graphite whisker.
3. the preparation method of polyacrylonitrile-based carbon core as claimed in claim 1 or 2, the diameter that it is characterized in that one dimension high conductivity carbon is 0.005～10 μ m, and length is 0.1～50 μ m, and draw ratio is greater than 5.
4. the preparation method of polyacrylonitrile-based carbon core as claimed in claim 1, the method that it is characterized in that preparing the PAN spinning solution that contains one dimension high conductivity carbon is selected from the direct method of disperseing to sneak in the PAN solution of one dimension high conductivity carbon, PAN/ one dimension high conductivity carbon composition polymer is dissolved in method in the solvent, or directly adopts the method for the PAN/ one dimension high conductivity carbon composition polymer solution of in-situ polymerization.
5. the preparation method of polyacrylonitrile-based carbon core as claimed in claim 1 is characterized in that solid content in the spinning solution is that the total mass concentration of PAN and one dimension high conductivity carbon is 10%～40%.
6. the preparation method of polyacrylonitrile-based carbon core as claimed in claim 1 is characterized in that the total solids content in the spinning solution is 100 parts, and wherein the content of one dimension high conductivity carbon is 1～20 part.
7. the preparation method of polyacrylonitrile-based carbon core as claimed in claim 1 is characterized in that described spinning solution spinning is selected from wet spinning, dry-wet spinning or dry spinning.
8. the preparation method of polyacrylonitrile-based carbon core as claimed in claim 1 is characterized in that preparing preoxided thread and carries out in 190～300 ℃ oxidizing atmosphere, and preoxidation time is 1～48h, and oxidizing atmosphere is selected from air or oxygen atmosphere.
9. the preparation method of polyacrylonitrile-based carbon core as claimed in claim 1 is characterized in that preparing carbon fibre and carries out in 800～1500 ℃ inert atmosphere, constant temperature 10～20min under final carburizing temperature.
10. the preparation method of polyacrylonitrile-based carbon core as claimed in claim 1, the temperature that it is characterized in that preparing the graphitized carbon core is 2300～2800 ℃, graphitization time is 0.5～5s.
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| CN101545164B (en) * | 2008-03-28 | 2011-06-01 | 孙致明 | Method for producing incombustible acrylic yarn and incombustible acrylic yarn manufactured by method |
| CN102190756B (en) * | 2010-03-12 | 2013-06-05 | 财团法人工业技术研究院 | Polyacrylonitrile-based carbon fibers, and precursor material thereof |
| CN101922065B (en) * | 2010-09-16 | 2011-12-07 | 中国科学院西安光学精密机械研究所 | Method for pre-oxidizing polyacrylonitrile-based carbon fiber precursors |
| CN102465376A (en) * | 2010-11-09 | 2012-05-23 | 张孟福 | Preparation method of highly carbonized fiber woven filler |
| CN102220664B (en) * | 2011-05-09 | 2012-08-22 | 北京化工大学 | Preparation method and application of conducting polymer-based nanometer carbon fibers |
| CN102433614B (en) * | 2011-08-23 | 2013-10-09 | 东华大学 | Preparation method of low-shrinkage high-strength carbon nanofiber |
| CN104178935A (en) * | 2014-08-15 | 2014-12-03 | 上海电气钠硫储能技术有限公司 | Graphite carbon fiber felt for sodium-sulfur cell and preparation method of graphite carbon fiber felt |
| CN104630923A (en) * | 2015-01-26 | 2015-05-20 | 中复神鹰碳纤维有限责任公司 | Method for preparing carbon nano tube modified polyacrylonitrile fibers with solution in-situ polymerization technology |
| ES2861580T3 (en) * | 2016-08-18 | 2021-10-06 | Aksa Akrilik Kimya Sanayii Anonim Sirketi | Production method of acrylic or modacrylic fiber that has anti-odor effect |
| CN106222804B (en) * | 2016-08-31 | 2021-06-15 | 孙旭阳 | Micro-nano film-shaped carbon fiber and preparation method thereof |
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| CN109054375A (en) * | 2018-07-13 | 2018-12-21 | 余新军 | A kind of bamboo-plastic fastener and preparation method thereof |
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