CN102031593A - Method for preparing pitch-based carbon fiber - Google Patents
Method for preparing pitch-based carbon fiber Download PDFInfo
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- CN102031593A CN102031593A CN 201010567314 CN201010567314A CN102031593A CN 102031593 A CN102031593 A CN 102031593A CN 201010567314 CN201010567314 CN 201010567314 CN 201010567314 A CN201010567314 A CN 201010567314A CN 102031593 A CN102031593 A CN 102031593A
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Abstract
The invention discloses a method for preparing a pitch-based carbon fiber, relates to the carbon fiber and a preparation method thereof, and provides the method for preparing the pitch-based carbon fiber which has the advantages of high mechanical performance, simple production process, low cost, stable product performance and the like. The method comprises the following steps of: heating anisotropic pitch and isotropous pitch under the protection of inert gas; mechanically stirring in a molten state at a constant temperature; cooling to obtain a mixed pitch raw material; placing into a spinning barrel of a melt spinning machine; loading in a pitch carbon fiber forming device; heating under the protective gas to a melt spinning temperature to obtain a precursor fiber at a spinning nozzle; placing on a sample carrying table; placing in a high temperature furnace; setting a heating program; performing oxidation treatment and naturally cooling to obtain an oxidized fiber; and placing a cross-linked oxidized fiber on the sample carrying table, placing in the high temperature furnace, setting a heating program, introducing the inert gas for protection, performing carbonization treatment and then naturally cooling to obtain the pitch-based carbon fiber.
Description
Technical field
The present invention relates to carbon fiber and manufacture method thereof, especially relate to asphalt base carbon fiber of a kind of mixed material preparation that utilizes isotropic pitch and anisotropy pitch and preparation method thereof.
Background technology
Because a series of excellent properties such as carbon fiber and composite thereof have high specific strength, high ratio modulus, high temperature resistant, endurance, creep resistant, electrical and thermal conductivity performance is good and thermal coefficient of expansion is little, it not only can be used as the structural material bearing load, and can be used as functional material and play a role.Therefore in recent years, the development of carbon fiber and composite thereof is rapid, be widely used in aircraft, spaceship, automobile, the building, and exotic material, as brake block, rocket etc.
Consider only have polyacrylonitrile (PAN) base carbon fibre, viscose-based carbon fiber and asphalt base carbon fiber to realize industrialization on the international market from multiple combined factors such as the difficulty or ease of charcoal yield, production technology and technology cost.Wherein, be that raw material is made high strength with PAN, the PAN base carbon fibre of medium modulus, because its production technology is comparatively simple, and the good mechanical performance of product, so purposes is comparatively extensive.But, the cost of material height of PAN base carbon fibre, the graphitization difficulty makes its degree of graphitization be restricted, and is difficult to obtain the PAN base carbon fibre of high-modulus.Must be and produce the carbon fiber of strong mechanical performance through the drawing by high temperature graphitization from viscose, its carbonization yield is low, and technical difficulty is big, equipment is complicated, and cost is higher.
And the carbonization yield of asphalt base carbon fiber is than PAN base carbon fibre height, and the material asphalt price is also cheap more than PAN.The high-performance asphalt base carbon fiber is to be transformed by mesophase pitch, and in its preparation process, aligning that the mesophase pitch molecule is intrinsic is retained, and therefore, obtains easily degree of graphitization height, carbon fiber that modulus is high under lower heat treatment temperature.In addition, therefore advantage such as it also has the thermal conductivity factor height, conduct electricity very well and thermal coefficient of expansion is little brings into play its unique effect in military project and space industry.For example the elastic modelling quantity of the new product Thornel K-1100 of BPAmoco company has reached 965GPa, is 94.6% of theoretical modulus.
But the essence of above-mentioned mesophase pitch raw material is the liquid crystal state material, and the characteristic of liquid crystal itself makes the graphite flake layer in the fiber trend towards closely arranging and forms the radioactivity cross-sectional structure, thereby easily axially cracks when carbonization.Even without cracking, fiber weakness is also bigger, causes its knitting property poor, is unfavorable for the application of carbon fiber in composite.In order to improve carbon fiber strength and to keep its modulus, should under the prerequisite of not damaging its degree of graphitization, suitably reduce the orderly arrangement of graphite flake layer.
At present, had many by improving the carbon fiber cross section structure to regulate and control its Mechanical Properties.Mainly be to make its even contraction, avoid axial cracking by the spinning special-shaped carbon fiber.Comprise and use ribbon shape spinnerets spinning ribbon shape fiber (Japanese JP62078220 (A), U.S. Pat 5578330); Use C type spinnerets spinning hollow or C type carbon fiber (Chinese patent CN1584137, European patent EP 0443431A, U.S. Pat 5156831 (A)); Introduce particular atmosphere in the spinning process, obtain hollow carbon fiber (Japan Patent JP3279422 (A)) etc.Profiled filament evenly shrinks in carbonisation, can avoid stress cracking, therefore axial crack can not occur.But this series products has following problem usually:
(1) special-shaped carbon fiber is not suitable for the Application Areas that some needs traditional circular carbon fiber.
(2) craft precision requires height, and the spinnerets shape and size need precise design, and atmosphere composition, ratio and flow velocity need strict control, are difficult for fibre property is regulated and control.
Stir spinning material (Japan Patent JP62177222 and JP6112919) when in addition, utilizing spinning and screen pack (Japan Patent JP61186520 and JP6375119) is set above spinneret orifice and also can improve the arrangement of fiber graphite flake layer.These technology have been improved the fibre section structure, have avoided the generation of fiber axial crack, but carbon fiber still exists the low problem of toughness, and the experiment repeated relatively poor, be difficult to reach the purpose of eliminating axial crack fully.On the other hand, these methods have improved carbon fiber strength by weakening the order of molecular arrangement, have but destroyed the orientation of graphite flake layer along fiber axis, have reduced modulus of carbon fibres.
Summary of the invention
The present invention is intended to the deficiency that exists on the above-mentioned preparation asphalt base carbon fiber scheme, problems such as established technology complexity and properties of product instability, a kind of mechanical performance excellence of prepared asphalt base carbon fiber is provided, and has the preparation method of the asphalt base carbon fiber of advantages such as production technology is simple, cost is low, properties of product are stable.
Technical scheme of the present invention is that a kind of mesophase pitch and a kind of isotropic pitch are heated in mixing device with certain proportion, stirs a period of time under molten condition, and cooling obtains the mix asphalt raw material then.Raw material makes the high strength and modulus asphalt base carbon fiber through melt spinning, non-melt processed and carbonisation.
The present invention includes following steps:
1) preparation of mix asphalt raw material: anisotropy pitch and isotropic pitch are heated up under inert gas shielding, constant temperature mechanical agitation under molten condition, stirring is cooled to room temperature after finishing, and makes the mix asphalt raw material;
2) spinning: the mix asphalt raw material is put into melt spinning machine spray silk charging basket, and the asphalt-based carbon fiber shaped device of packing into is warming up to spinning temperature under protection gas, get precursor at the spinning nozzle place then;
3) the not fusion process of precursor: precursor is placed on the load sample platform, puts into high temperature furnace, heating schedule is set, bubbling air or oxygen carry out oxidation processes, finish back cooling naturally, promptly get oxidized fibre.
4) carbonisation of oxidation silk: the oxidized fibre of crossing through the step 3) crosslinking Treatment is placed on the load sample platform, puts into high temperature furnace, heating schedule is set, feed inert gas shielding, the beginning carbonization treatment finishes back cooling naturally, promptly gets asphalt base carbon fiber.
In step 1), described anisotropy pitch and isotropic pitch mixing quality ratio can be (9～1): 1, and the middle phase content of anisotropy pitch is preferably 100%, and the isotropism content of isotropic pitch is preferably 100%.Otherwise calculate the final mixing quality ratio of mix asphalt in proportion according to the content of actual anisotropy (or isotropism).Churned mechanically temperature can be 300～400 ℃ under the nitrogen protection, and mixing time can be 0.1～2h.
In step 2) in, the program that intensification is set can rise to 330 ℃ from room temperature with 2 ℃/min, rises to spinning temperature with 1 ℃/min again.The pitch-based fiber shaped device is provided with top cover labyrinth, push rod, spinnerets and lower sealing cover.Can be wrapped in after the spinning nozzle place gets precursor on the curled hair tube, regulate the rotating speed of curled hair tube, rotating speed can be 200～900m/min, makes the fiber uniform winding, but by regulating the also diameter of controlling fiber of extrusion speed, extrusion speed can be 1.9 * 10
-7～3.8 * 10
-7m
3/ min.
In step 3), oxidation cross-linked program is: precursor is placed on the wire netting, puts into high temperature furnace, be provided with and be warming up to 140～350 ℃, and insulation 1～5h, take out the cooling back.Put into preferably bubbling air of high temperature furnace back, air mass flow is preferably 200～300ml/min; The program that heats up preferably is raised to 180 ℃ with 5 ℃/min from room temperature, is raised to 180～280 ℃ with 1 ℃/min from 180 ℃.
In step 4), the program of intensification preferably is raised to 1800 ℃ with 40 ℃/min from room temperature, insulation 20min.
The present invention adopts the composition of isotropic pitch and mesophase pitch Compositing Change mesophase pitch, to reach the purpose of regulation and control asphalt base carbon fiber performance.It has following following characteristics: (1) fiber densification, and defective is few, obtains the high strength and modulus asphalt base carbon fiber; (2) technology is simple, and operating process is easy; (3) fibre diameter is easy to control; (4) make the carbon fiber stable performance, solved the low problem of intensity that asphalt base carbon fiber exists at present.
Description of drawings
Fig. 1 is the sem photograph of the carbon fiber that obtains in the embodiment of the invention one.
Fig. 2 is the sem photograph of the carbon fiber that obtains in the embodiment of the invention two.
Fig. 3 is the sem photograph of the carbon fiber that obtains in the embodiment of the invention three.
In Fig. 1～3, scale is 10 μ m.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
1) gets (sp:280 ℃ of the anisotropy naphthalene pitch that Mitsubishi aerochemistry Co., Ltd produces; middle phase content 100%) and (sp:280 ℃ of the isotropism coal tar pitch of Shanghai Dong Dao Co., Ltd production; middle phase content 0%) under nitrogen protection, was warming up to 360 ℃ with 1: 1 in there-necked flask; be incubated 1h under the mechanical agitation; be cooled to room temperature, obtain spinning material.The 15g raw material is put into melt spinning machine spray silk charging basket; the asphalt-based carbon fiber shaped device of packing into; the fiber forming device 2 ℃/min under protection gas that fills the solid asphalt raw material is warming up to 330 ℃ of spinning temperatures, the precursor of fusion is drawn out, be wrapped on the curled hair tube.Extrusion speed is 1.96 * 10
-7m
3/ min, winding speed is 300m/min, and precursor is evenly twined continuously.
2) precursor that makes is carried out preliminary treatment (oxidation cross-linked), sample is placed on the wire netting load sample platform, put into the temperature programming stove, bubbling air, flow is 200ml/min, 2 ℃/min is set is warming up to 180 ℃, 1 ℃/min is warming up to 280 ℃ again, insulation 20min, and take out the cooling back.
3) carry out carbonization treatment after the crosslinking Treatment: the oxidation silk of crossing through crosslinking Treatment is placed on the graphite paper load sample platform; put into high temperature furnace; vacuumize; the back feeds argon shield; flow is 200ml/min, and heating schedule is set: directly be raised to 1800 ℃ from room temperature with 40 ℃/min, insulation 20min; take out the cold back of nature stove, can make asphalt base carbon fiber.As shown in fig. 1, carbon fiber surface is zero defect almost, even compact, and thickness is even, and diameter is about 15 μ m.TENSILE STRENGTH is 1.6GPa, and stretch modulus is 200GPa, and elongation at break is 0.89%, and obtaining average fibre diameter is 15 μ m.
Embodiment 2
1) get that two kinds of raw materials were warming up to 360 ℃ in there-necked flask with 5: 1 among the embodiment one under nitrogen protection, be incubated 1h under the mechanical agitation,, obtain the black spinning material.At the spinning equipment that embodiment one describes, the control extrusion speed is 3.14 * 10
-7m
3/ min., winding speed is 200m/min, and precursor is evenly twined continuously.
2) precursor that makes is carried out preliminary treatment (oxidation cross-linked), sample is placed on the wire netting load sample platform, the load sample platform is converted into " W " shape, puts into the temperature programming stove, bubbling air, flow is 200ml/min, 2 ℃/min is set is warming up to 180 ℃, insulation 200min, 1 ℃/min is warming up to 280 ℃, insulation 20min, take out the cooling back.
3) carry out carbonization treatment after the crosslinking Treatment: the oxidation silk of crossing through crosslinking Treatment is placed on the graphite paper load sample platform, carbonization under carbonizing plant of in embodiment one, describing and the carbodiimide procedure, take out the cold back of natural stove, can make asphalt base carbon fiber.As shown in Figure 2, carbon fiber surface is zero defect almost, even compact, and thickness is even, and diameter is about 25 μ m.TENSILE STRENGTH is 1.7GPa, and TENSILE STRENGTH is 180GPa, and elongation at break is 0.96%, and obtaining average fibre diameter is 25 μ m.
Embodiment 3
1) get that two kinds of raw materials were warming up to 360 ℃ in there-necked flask with 9: 1 among the embodiment one under nitrogen protection, be incubated 1h under the mechanical agitation,, after be cooled to room temperature, obtain the black spinning material.Under spinning equipment and spinning condition that embodiment one describes, spin precursor.
2) carry out preliminary treatment (oxidation cross-linked) under oxidation cross-linked device that the precursor that makes is described and the heating schedule in embodiment one, take out the cooling back.Obtain the oxidation silk.
3) carry out carbonization treatment after the crosslinking Treatment: the oxidation silk of crossing through crosslinking Treatment is placed on the graphite paper load sample platform, carbonization under carbonizing plant of in embodiment one, describing and the carbodiimide procedure, take out the cold back of natural stove, can make asphalt base carbon fiber.As shown in Figure 3, carbon fiber surface is zero defect almost, even compact, and thickness is even, and diameter is about 18 μ m.TENSILE STRENGTH is 2.0GPa, and stretch modulus is 240GPa, and elongation at break is 0.85%, and obtaining average fibre diameter is 18 μ m.
Claims (8)
1. the preparation method of an asphalt base carbon fiber is characterized in that may further comprise the steps:
1) preparation of mix asphalt raw material: anisotropy pitch and isotropic pitch are heated up under inert gas shielding, constant temperature mechanical agitation under molten condition, stirring is cooled to room temperature after finishing, and makes the mix asphalt raw material;
2) spinning: the mix asphalt raw material is put into melt spinning machine spray silk charging basket, and the asphalt-based carbon fiber shaped device of packing into is warming up to spinning temperature under protection gas, get precursor at the spinning nozzle place then;
3) the not fusion process of precursor: precursor is placed on the load sample platform, puts into high temperature furnace, heating schedule is set, bubbling air or oxygen carry out oxidation processes, finish back cooling naturally, promptly get oxidized fibre;
4) carbonisation of oxidation silk: the oxidized fibre of crossing through the step 3) crosslinking Treatment is placed on the load sample platform, puts into high temperature furnace, heating schedule is set, feed inert gas shielding, the beginning carbonization treatment finishes back cooling naturally, promptly gets asphalt base carbon fiber.
2. the preparation method of a kind of asphalt base carbon fiber as claimed in claim 1 is characterized in that in step 1), and described anisotropy pitch and isotropic pitch mixing quality ratio are 9～1: 1.
3. the preparation method of a kind of asphalt base carbon fiber as claimed in claim 2, the middle phase content that it is characterized in that described anisotropy pitch is 100%, the isotropism content of isotropic pitch is 100%.
4. the preparation method of a kind of asphalt base carbon fiber as claimed in claim 1 is characterized in that in step 1), and churned mechanically temperature is 300～400 ℃ under the described nitrogen protection, and mixing time is 0.1～2h.
5. the preparation method of a kind of asphalt base carbon fiber as claimed in claim 1 is characterized in that in step 2) in, the program that intensification is set rises to 330 ℃ with 2 ℃/min from room temperature, rises to spinning temperature with 1 ℃/min again.
6. the preparation method of a kind of asphalt base carbon fiber as claimed in claim 1, it is characterized in that in step 2) in, the pitch-based fiber shaped device is provided with top cover labyrinth, push rod, spinnerets and lower sealing cover, after getting precursor, the spinning nozzle place is wrapped on the curled hair tube, regulate the rotating speed of curled hair tube, rotating speed is 200～900m/min, makes the fiber uniform winding, but by regulating the also diameter of controlling fiber of extrusion speed, extrusion speed is 1.9 * 10
-7～3.8 * 10
-7m
3/ min.
7. the preparation method of a kind of asphalt base carbon fiber as claimed in claim 1, it is characterized in that in step 3), oxidation cross-linked program is: precursor is placed on the wire netting, put into high temperature furnace, setting is warming up to 140～350 ℃, insulation 1～5h, and take out the cooling back, put into high temperature furnace back bubbling air, air mass flow is 200～300ml/min; The program that heats up is raised to 180 ℃ with 5 ℃/min from room temperature, is raised to 180～280 ℃ with 1 ℃/min from 180 ℃.
8. the preparation method of a kind of asphalt base carbon fiber as claimed in claim 1 is characterized in that in step 4), and the program of intensification is raised to 1800 ℃ with 40 ℃/min from room temperature, insulation 20min.
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| CN 201010567314 CN102031593B (en) | 2010-11-30 | 2010-11-30 | Method for preparing pitch-based carbon fiber |
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| CN102031593B CN102031593B (en) | 2013-04-17 |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560744A (en) * | 2011-12-21 | 2012-07-11 | 鞍山塞诺达碳纤维有限公司 | Method for preparing universal pitch-based carbon fiber |
| CN102704042A (en) * | 2012-07-09 | 2012-10-03 | 遇秉武 | Method for preparing pitch-based carbon fiber |
| CN103122503A (en) * | 2013-01-28 | 2013-05-29 | 江苏国正新材料科技有限公司 | Preparation method of high-strength and high-modulus pitch-based fiber |
| CN103980710A (en) * | 2014-06-02 | 2014-08-13 | 北京化工大学 | Heat-conducting type carbon fiber composite material and preparation method thereof |
| CN104195676A (en) * | 2014-08-12 | 2014-12-10 | 上海交通大学 | Mesophase pitch material for preparing high-performance carbon fibers and preparation method of mesophase pitch material |
| CN105177766A (en) * | 2015-09-28 | 2015-12-23 | 东华大学 | Preparation method of mesophase pitch continuous filaments |
| CN105220274A (en) * | 2015-11-09 | 2016-01-06 | 沈阳化工大学 | The preparation method of the brilliant material of a kind of asphalt base carbon fiber carbon |
| CN105315426A (en) * | 2015-11-06 | 2016-02-10 | 沈阳化工大学 | Composite asphalt-based carbon crystal material preparation method and carbon crystal plate prepared from composite asphalt-based carbon crystal material |
| CN106987926A (en) * | 2017-04-14 | 2017-07-28 | 河北民族师范学院 | Pitch based carbon fiber, preparation method and its application in lithium ion battery |
| CN107488892A (en) * | 2017-08-22 | 2017-12-19 | 安徽艾米伦特建材科技有限公司 | Asphalt base carbon fiber material and preparation method thereof |
| CN107904698A (en) * | 2017-11-07 | 2018-04-13 | 东华大学 | A kind of preparation method of asphalt base carbon fiber |
| CN108221089A (en) * | 2017-12-26 | 2018-06-29 | 宜兴市天宇世纪高新科技有限公司 | A kind of preparation method of asphalt base carbon fiber |
| CN108286088A (en) * | 2018-02-09 | 2018-07-17 | 西安天运新材料科技有限公司 | A kind of asphalt base carbon fiber and preparation method thereof that can be used for weaving |
| CN108486689A (en) * | 2018-03-08 | 2018-09-04 | 湖南东映碳材料科技有限公司 | A kind of preparation method of high-modulus high heat conduction pitch based carbon fiber continuous filament yarn |
| CN109234916A (en) * | 2018-06-21 | 2019-01-18 | 中国科学院山西煤炭化学研究所 | A kind of preparation method with cross-linked structure asphalt-based nano fabric nonwoven cloth |
| CN110629326A (en) * | 2019-10-29 | 2019-12-31 | 北京化工大学 | Preparation method of high-thermal-conductivity mesophase pitch-based carbon fiber |
| CN115466626A (en) * | 2022-09-21 | 2022-12-13 | 武汉科技大学 | Preparation method of high-quality isotropic asphalt |
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| US7018526B1 (en) * | 2001-11-30 | 2006-03-28 | The University Of Akron | Carbonized pitch moldings prepared from synthetic mesophase pitch and heat-soaked isotropic pitch |
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| US5037697A (en) * | 1986-01-22 | 1991-08-06 | Nitto Boseki Co., Ltd. | Carbon fiber and process for producing the same |
| US7018526B1 (en) * | 2001-11-30 | 2006-03-28 | The University Of Akron | Carbonized pitch moldings prepared from synthetic mesophase pitch and heat-soaked isotropic pitch |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560744A (en) * | 2011-12-21 | 2012-07-11 | 鞍山塞诺达碳纤维有限公司 | Method for preparing universal pitch-based carbon fiber |
| CN102560744B (en) * | 2011-12-21 | 2013-10-23 | 鞍山塞诺达碳纤维有限公司 | Method for preparing universal pitch-based carbon fiber |
| CN102704042A (en) * | 2012-07-09 | 2012-10-03 | 遇秉武 | Method for preparing pitch-based carbon fiber |
| CN102704042B (en) * | 2012-07-09 | 2013-11-27 | 遇秉武 | Method for preparing pitch-based carbon fiber |
| CN103122503A (en) * | 2013-01-28 | 2013-05-29 | 江苏国正新材料科技有限公司 | Preparation method of high-strength and high-modulus pitch-based fiber |
| CN103980710A (en) * | 2014-06-02 | 2014-08-13 | 北京化工大学 | Heat-conducting type carbon fiber composite material and preparation method thereof |
| CN104195676A (en) * | 2014-08-12 | 2014-12-10 | 上海交通大学 | Mesophase pitch material for preparing high-performance carbon fibers and preparation method of mesophase pitch material |
| CN105177766A (en) * | 2015-09-28 | 2015-12-23 | 东华大学 | Preparation method of mesophase pitch continuous filaments |
| CN105315426A (en) * | 2015-11-06 | 2016-02-10 | 沈阳化工大学 | Composite asphalt-based carbon crystal material preparation method and carbon crystal plate prepared from composite asphalt-based carbon crystal material |
| CN105220274A (en) * | 2015-11-09 | 2016-01-06 | 沈阳化工大学 | The preparation method of the brilliant material of a kind of asphalt base carbon fiber carbon |
| CN106987926A (en) * | 2017-04-14 | 2017-07-28 | 河北民族师范学院 | Pitch based carbon fiber, preparation method and its application in lithium ion battery |
| CN106987926B (en) * | 2017-04-14 | 2020-10-02 | 王立勇 | Asphalt-based carbon fiber, preparation method and application thereof in lithium ion battery |
| CN107488892A (en) * | 2017-08-22 | 2017-12-19 | 安徽艾米伦特建材科技有限公司 | Asphalt base carbon fiber material and preparation method thereof |
| CN107904698A (en) * | 2017-11-07 | 2018-04-13 | 东华大学 | A kind of preparation method of asphalt base carbon fiber |
| CN107904698B (en) * | 2017-11-07 | 2020-04-17 | 东华大学 | Preparation method of asphalt-based carbon fiber |
| CN108221089A (en) * | 2017-12-26 | 2018-06-29 | 宜兴市天宇世纪高新科技有限公司 | A kind of preparation method of asphalt base carbon fiber |
| CN108286088A (en) * | 2018-02-09 | 2018-07-17 | 西安天运新材料科技有限公司 | A kind of asphalt base carbon fiber and preparation method thereof that can be used for weaving |
| CN108486689A (en) * | 2018-03-08 | 2018-09-04 | 湖南东映碳材料科技有限公司 | A kind of preparation method of high-modulus high heat conduction pitch based carbon fiber continuous filament yarn |
| CN108486689B (en) * | 2018-03-08 | 2020-03-24 | 湖南东映碳材料科技有限公司 | Preparation method of high-modulus high-thermal-conductivity asphalt-based carbon fiber continuous filament |
| CN109234916A (en) * | 2018-06-21 | 2019-01-18 | 中国科学院山西煤炭化学研究所 | A kind of preparation method with cross-linked structure asphalt-based nano fabric nonwoven cloth |
| CN110629326A (en) * | 2019-10-29 | 2019-12-31 | 北京化工大学 | Preparation method of high-thermal-conductivity mesophase pitch-based carbon fiber |
| CN110629326B (en) * | 2019-10-29 | 2020-10-27 | 北京化工大学 | Preparation method of high-thermal-conductivity mesophase pitch-based carbon fiber |
| CN115466626A (en) * | 2022-09-21 | 2022-12-13 | 武汉科技大学 | Preparation method of high-quality isotropic asphalt |
| CN115466626B (en) * | 2022-09-21 | 2024-01-12 | 武汉科技大学 | Preparation method of high-quality isotropic asphalt |
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